JP2010273698A - Antibacterial deodorant and method for producing the same - Google Patents
Antibacterial deodorant and method for producing the same Download PDFInfo
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- JP2010273698A JP2010273698A JP2009126062A JP2009126062A JP2010273698A JP 2010273698 A JP2010273698 A JP 2010273698A JP 2009126062 A JP2009126062 A JP 2009126062A JP 2009126062 A JP2009126062 A JP 2009126062A JP 2010273698 A JP2010273698 A JP 2010273698A
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- antibacterial deodorant
- antibacterial
- silica
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- silver
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 180
- 239000002781 deodorant agent Substances 0.000 title claims abstract description 149
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 161
- 239000002245 particle Substances 0.000 claims abstract description 113
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 80
- 229910052709 silver Inorganic materials 0.000 claims abstract description 56
- 239000004332 silver Substances 0.000 claims abstract description 52
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 43
- -1 silver ions Chemical class 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 61
- 239000006185 dispersion Substances 0.000 claims description 58
- 239000007864 aqueous solution Substances 0.000 claims description 48
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 36
- 238000005342 ion exchange Methods 0.000 claims description 28
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 17
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 239000011135 tin Substances 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 14
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical group [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 12
- 229940100890 silver compound Drugs 0.000 claims description 12
- 150000003379 silver compounds Chemical class 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003242 anti bacterial agent Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract 1
- 235000012054 meals Nutrition 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 230000001877 deodorizing effect Effects 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000004332 deodorization Methods 0.000 description 14
- 239000012528 membrane Substances 0.000 description 14
- 238000000108 ultra-filtration Methods 0.000 description 14
- 239000011734 sodium Substances 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 235000019645 odor Nutrition 0.000 description 11
- 229910001961 silver nitrate Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 239000008399 tap water Substances 0.000 description 8
- 235000020679 tap water Nutrition 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 241000588724 Escherichia coli Species 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000003729 cation exchange resin Substances 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 208000035985 Body Odor Diseases 0.000 description 1
- 206010006326 Breath odour Diseases 0.000 description 1
- 206010016952 Food poisoning Diseases 0.000 description 1
- 208000019331 Foodborne disease Diseases 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 206010036790 Productive cough Diseases 0.000 description 1
- 206010040904 Skin odour abnormal Diseases 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Colloid Chemistry (AREA)
- Silicon Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
本発明は、抗菌消臭成分とシリカ系複合酸化物粒子とからなる抗菌消臭剤であって、抗菌消臭成分として銀イオンを含み、シリカ系複合酸化物粒子がアルカリ金属イオンを含む抗菌消臭剤とその製造方法とに関する。
さらに詳しくは、シリカ系複合酸化物粒子がアルカリ金属をイオンとして所定量含有し、このアルカリ金属イオンと抗菌消臭成分である銀イオンとをイオン交換して担持することにより銀イオンが効率的に、安定に担持され、このため水道水などの塩素含有水に接しても変色したり、性能が低下することなく長期に抗菌消臭性能を発揮することができる抗菌消臭剤とその製造方法とに関する。
The present invention is an antibacterial deodorant composed of an antibacterial deodorant component and silica-based composite oxide particles, which contains silver ions as the antibacterial deodorant component, and the silica-based composite oxide particles include an alkali metal ion. The present invention relates to an odorant and a method for producing the same.
More specifically, the silica-based composite oxide particles contain a predetermined amount of alkali metal ions, and the silver ions are efficiently supported by ion-exchanged and supported between the alkali metal ions and silver ions that are antibacterial deodorizing components. An antibacterial deodorant that can be stably supported and can exhibit long-term antibacterial and deodorant performance without contact with chlorine-containing water such as tap water, or performance degradation, and a method for producing the same About.
従来、居住環境において種々の問題が指摘されている。高温多湿の我が国に於いては、細菌による食中毒が多発したり、住空間における細菌、ウィルス、黴、悪臭の他、シックハウス症候群が問題となっている。さらに、ダニ（ヒト、動物）、花粉等のハウスダストによるアレルギー性疾患等も挙げられる。
さらに、近年、ヒトあるいはペット等について、清潔志向、衛生志向が高まり、具体的には、汗、体臭、口臭、加齢臭、足臭、脇の下臭等、臭気の発生部位を除菌したり、発生する臭気を抑制したり除去することが求められている。これらは、単に居住環境にとどまらずヒトの集合する公共施設、民間施設に於いても同様である。
Conventionally, various problems have been pointed out in the living environment. In Japan, which is hot and humid, food poisoning due to bacteria frequently occurs, and sick house syndrome is a problem in addition to bacteria, viruses, sputum and foul odors in living spaces. In addition, allergic diseases caused by house dust such as mites (human, animal) and pollen are also included.
Furthermore, in recent years, with regard to humans or pets, the desire for cleanliness and hygiene has increased. Specifically, sweat, body odor, bad breath, aging odor, foot odor, armpit odor, etc. There is a need to suppress or eliminate the odor that occurs. The same applies not only to residential environments but also to public facilities and private facilities where people gather.
このため、抗菌剤として、シリカゲル、複合酸化物、酸化チタン等の粉末、あるいはコロイド粒子に抗菌性を有する銀、銅、亜鉛等の金属成分を担持した抗菌性組成物が知られている。
具体例として、ゼオライト粉末に抗菌性を有する銀、銅、亜鉛等の金属成分を担持した抗菌性組成物が知られている（特開平２−２２５４０２号公報：特許文献１）。
For this reason, as an antibacterial agent, an antibacterial composition in which a metal component such as silver, copper or zinc having antibacterial properties is supported on a powder such as silica gel, composite oxide, titanium oxide or colloidal particles is known.
As a specific example, an antibacterial composition is known in which a zeolite powder is loaded with a metal component such as silver, copper, or zinc having antibacterial properties (JP-A-2-225402: Patent Document 1).
また、本願出願人は無機酸化物コロイド粒子に抗菌性金属成分を付着せしめた抗菌剤（特開平６−８０５２７号公報：特許文献２）あるいはメタ珪酸アルミン酸マグネシウムに抗菌性を有する金属イオンをイオン交換した抗菌剤（特開平３−２７５６２７号公報：特許文献３）を開示している。 Further, the applicant of the present application ionizes an antibacterial agent in which an antibacterial metal component is adhered to the inorganic oxide colloidal particles (Japanese Patent Laid-open No. Hei 6-80527: Patent Document 2) or metal ions having antibacterial properties to magnesium metasilicate aluminate. An exchanged antibacterial agent (JP-A-3-275627: Patent Document 3) is disclosed.
また、本願出願人は、金属成分と該金属成分以外の無機酸化物とから構成される無機酸化物微粒子であって、前記無機酸化物が酸化チタンとシリカおよび／またはジルコニアとを含んでなり、該酸化チタンが結晶性酸化チタンである抗菌性消臭剤を開示している（特開２００５−３１８９９９号公報：特許文献４）。
さらに、本願出願人は、抗菌性金属成分と該抗菌性金属成分以外の無機酸化物とから構成される微粒子を配合した化粧料（スキンパウダー）がイソ吉草酸等の悪臭を消臭できることを開示している（特開２００２−１４５７１７号公報：特許文献５）。
The applicant of the present invention is an inorganic oxide fine particle composed of a metal component and an inorganic oxide other than the metal component, and the inorganic oxide comprises titanium oxide and silica and / or zirconia. An antibacterial deodorant in which the titanium oxide is crystalline titanium oxide is disclosed (Japanese Patent Laid-Open No. 2005-318999: Patent Document 4).
Further, the applicant of the present application discloses that a cosmetic (skin powder) containing fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component can deodorize malodor such as isovaleric acid. (Japanese Patent Laid-Open No. 2002-145717: Patent Document 5).
これら従来の消臭抗菌組成物は、食器、まな板、箸、食品包装材料等の生活用品、インテリア家具、カーテン、壁、襖、障子、タイル、カーペット、ソファー等の生活環境用品、あるいは化粧品等に用いられている。
しかしながら、上記した従来の抗菌剤、消臭剤、特に、シリカ・アルミナ等の無機複合酸化物コロイド粒子に抗菌性金属成分をイオン交換樹脂の存在下で付着せしめた抗菌剤は、塩素含有する水道水等に曝されると変色したり、抗菌消臭性能が低下する問題があった。
These conventional deodorant antibacterial compositions can be used in household goods such as tableware, cutting boards, chopsticks, food packaging materials, interior furniture, curtains, walls, bags, shoji, tiles, carpets, sofas, and other living environment goods, or cosmetics. It is used.
However, the above-mentioned conventional antibacterial agents and deodorizers, in particular, antibacterial agents in which an antibacterial metal component is adhered to inorganic composite oxide colloidal particles such as silica / alumina in the presence of an ion exchange resin, are water containing chlorine. When exposed to water or the like, there were problems of discoloration or a decrease in antibacterial deodorizing performance.
本発明者等は、従来の抗菌消臭剤の製造方法について鋭意検討した結果、アルカリ金属イオンを含むシリカ系複合酸化物粒子を調製し、イオン交換樹脂を用いることなく銀化合物を添加しても銀の沈殿が生じることはなく、得られた銀イオンとアルカリ金属イオンを含むシリカ系複合酸化物コロイド粒子は、塩素を含有する水道水等に曝されても変色することがなく、長期にわたって抗菌消臭性能を維持することを見出して本発明を完成するに至った。 As a result of intensive studies on a conventional method for producing an antibacterial deodorant, the present inventors prepared silica-based composite oxide particles containing alkali metal ions, and added a silver compound without using an ion exchange resin. Silver precipitation does not occur, and the resulting silica-based composite oxide colloidal particles containing silver ions and alkali metal ions do not change color even when exposed to chlorine-containing tap water, etc. The inventors have found that the deodorizing performance can be maintained and have completed the present invention.
本発明の目的は、抗菌性能、消臭性能に優れ、変色することなく長期にわたって抗菌性能、消臭性を維持することのできる抗菌消臭剤およびその製造方法を提供することを目的としている。 An object of the present invention is to provide an antibacterial deodorant which is excellent in antibacterial performance and deodorization performance and can maintain the antibacterial performance and deodorization performance for a long time without discoloring, and a method for producing the same.
本発明に係る抗菌消臭剤は、抗菌消臭成分とシリカ系複合酸化物粒子とからなる抗菌消臭剤であって、抗菌消臭成分として銀イオンをＡｇ2Ｏとして０．１〜２５重量％含み、シリカ系複合酸化物粒子がアルカリ金属イオンを含むことを特徴としている。
前記シリカ系複合酸化物粒子中のアルカリ金属イオンの含有量がＭ2Ｏ（Ｍ：アルカリ金属を表す）として１〜２０重量％の範囲にあることが好ましい。
前記アルカリ金属イオンがＮａイオンであることが好ましい。
Antibacterial deodorant according to the present invention, 0.1 to 25 weight an antimicrobial deodorant composed of the antibacterial deodorant component and silica composite oxide particles, the silver ions as Ag 2 O as an antimicrobial deodorant component %, And the silica-based composite oxide particles contain an alkali metal ion.
The content of alkali metal ions in the silica-based composite oxide particles is preferably in the range of 1 to 20% by weight as M 2 O (M represents an alkali metal).
It is preferable that the alkali metal ion is Na ion.
前記シリカ系複合酸化物粒子のシリカ以外の酸化物がＡｌ2Ｏ3、Ｂ2Ｏ3、ＺｒＯ2、ＴｉＯ2、ＭｇＯ、ＣａＯ、ＣｅＯ2、ＳｎＯ2、Ｓｂ2Ｏ5、ＺnＯ、Ｆｅ2Ｏ3、Ｐ2Ｏ5からから選ばれる１種または２種以上の酸化物であることが好ましい。
前記シリカ系複合酸化物粒子のシリカ以外の酸化物（ＭＯｘ）含有量が、ＳｉＯ2・ＭＯｘ中に１０〜５０重量％の範囲であることが好ましい。
前記抗菌消臭成分が銀以外の抗菌消臭成分として銅、亜鉛、錫から選ばれる１種または２種以上を含むことが好ましい。
平均粒子径が２〜３００ｎｍの範囲にあることが好ましい。
アルカリ金属イオンの含有量がＭ2Ｏ（Ｍ：アルカリ金属を表す）として１〜１５重量％の範囲にあることが好ましい。
Oxides other than silica of the silica-based composite oxide particles are Al 2 O 3 , B 2 O 3 , ZrO 2 , TiO 2 , MgO, CaO, CeO 2 , SnO 2 , Sb 2 O 5 , ZnO, Fe 2 O. 3 and one or more oxides selected from P 2 O 5 are preferable.
The content of oxide (MOx) other than silica of the silica-based composite oxide particles is preferably in the range of 10 to 50% by weight in SiO 2 · MOx.
It is preferable that the antibacterial deodorant component contains one or more selected from copper, zinc, and tin as an antibacterial deodorant component other than silver.
The average particle diameter is preferably in the range of 2 to 300 nm.
The content of alkali metal ions is preferably in the range of 1 to 15% by weight as M 2 O (M represents an alkali metal).
本発明に係る抗菌消臭剤の製造方法は、下記の工程（ａ）〜（ｃ）からなることを特徴としている。
（ａ）珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液とを、ｐＨを９〜１３に維持しながら、得られるシリカ系複合酸化物粒子中のシリカ以外の元素の酸化物（ＭＯｘ）含有量が、ＳｉＯ2・ＭＯｘ中に１０〜５０重量％の範囲となるように混合する工程
（ｂ）工程（ａ）で得られたシリカ系複合酸化物粒子分散液を洗浄する工程
（ｃ）前記シリカ系複合酸化物粒子分散液に銀化合物を添加して銀イオン交換する工程
The method for producing an antibacterial deodorant according to the present invention is characterized by comprising the following steps (a) to (c).
(A) Content of oxide (MOx) of elements other than silica in the obtained silica-based composite oxide particles while maintaining an aqueous solution of alkali silicate and a compound aqueous solution of elements other than silicon at a pH of 9 to 13. Step of mixing in SiO 2 · MOx so as to be in the range of 10 to 50% by weight (b) Step of washing the silica-based composite oxide particle dispersion obtained in step (a) (c) The silica-based Step of silver ion exchange by adding silver compound to composite oxide particle dispersion
前記工程（ａ）において、平均粒子径１〜５０ｎｍの金属酸化物粒子（シード）分散液に珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液とを、ｐＨを９〜１３に維持しながら、添加することが好ましい。
前記珪素以外の元素がＡｌ、Ｂ、Ｚｒ、Ｔｉ、Ｍｇ、Ｃａ、Ｃｅ、Ｓｎ、Ｓｂ、Ｚn、Ｆｅ、Ｐからから選ばれる１種または２種以上であるすることが好ましい。
前記工程（ｃ）において、銀化合物以外に銅、亜鉛、錫から選ばれる１種または２種以上の元素の化合物を添加することが好ましい。
前記工程（ｃ）についで、銅、亜鉛、錫から選ばれる１種または２種以上の元素の化合物を添加してイオン交換してもよい。
In the step (a), an alkali silicate aqueous solution and a compound aqueous solution of an element other than silicon are added to a metal oxide particle (seed) dispersion having an average particle size of 1 to 50 nm while maintaining the pH at 9 to 13. It is preferable.
The element other than silicon is preferably one or more selected from Al, B, Zr, Ti, Mg, Ca, Ce, Sn, Sb, Zn, Fe, and P.
In the step (c), it is preferable to add a compound of one or more elements selected from copper, zinc and tin in addition to the silver compound.
Following the step (c), ion exchange may be performed by adding a compound of one or more elements selected from copper, zinc, and tin.
本発明によれば、シリカ系複合酸化物粒子がアルカリ金属をイオンとして所定量含有し、このアルカリ金属イオンと抗菌消臭成分である銀イオンとをイオン交換して担持することにより銀イオンが効率的に、安定に担持され、このため水道水などの塩素含有水に接しても変色したり、性能が低下することなく長期にわたって抗菌消臭性能を発揮することができる抗菌消臭剤とその製造方法とを提供することができる。
According to the present invention, silica-based composite oxide particles contain a predetermined amount of alkali metal ions as ions, and silver ions are efficiently supported by ion-exchanged and supported on the alkali metal ions and silver ions that are antibacterial deodorizing components. In addition, antibacterial deodorants that can be stably supported and can exhibit antibacterial and deodorant performance for a long period of time without contact with chlorine-containing water such as tap water or deterioration in performance. A method can be provided.
［１］抗菌消臭剤
本発明に係る抗菌消臭剤は、抗菌消臭成分とシリカ系複合酸化物粒子とからなる抗菌消臭剤であって、抗菌消臭成分として銀イオンをＡｇ2Ｏとして０．１〜２５重量％含み、シリカ系複合酸化物粒子がアルカリ金属イオンを含むことを特徴としている。
[1] Antibacterial deodorant The antibacterial deodorant according to the present invention is an antibacterial deodorant composed of an antibacterial deodorant component and silica-based composite oxide particles, and silver ions are added as an antibacterial deodorant component to Ag 2 O. And 0.1 to 25% by weight, and the silica-based composite oxide particles contain alkali metal ions.
本発明の抗菌消臭剤を構成するシリカ系複合酸化物粒子は、シリカとシリカ以外の酸化物としてＡｌ2Ｏ3、Ｂ2Ｏ3、ＺｒＯ2、ＴｉＯ2、ＭｇＯ、ＣａＯ、ＣｅＯ2、ＳｎＯ2、Ｓｂ2Ｏ5、ＺnＯ、Ｆｅ2Ｏ3、Ｐ2Ｏ5からから選ばれる１種または２種以上の酸化物を含んでいる。
なかでもＡｌ2Ｏ3は、安定で均一な粒子径分布のコロイド粒子を得ることができ、また、抗菌消臭成分である銀イオンのイオン交換容量が高く、且つ安定な抗菌消臭剤を得ることができるので好ましい。
また、ＺｒＯ2、ＴｉＯ2、ＺnＯが含まれているとこれらが紫外線を吸収するので銀成分の変色を防止する効果が得られる。
The silica-based composite oxide particles constituting the antibacterial deodorant of the present invention are Al 2 O 3 , B 2 O 3 , ZrO 2 , TiO 2 , MgO, CaO, CeO 2 , SnO as oxides other than silica and silica. 2 , one or more oxides selected from Sb 2 O 5 , ZnO, Fe 2 O 3 , and P 2 O 5 are included.
Among them, Al 2 O 3 can obtain colloidal particles having a stable and uniform particle size distribution, and can obtain a stable antibacterial deodorant having a high ion exchange capacity of silver ions as an antibacterial deodorant component. This is preferable.
If ZrO 2 , TiO 2 , or ZnO is contained, they absorb ultraviolet rays, so that the effect of preventing discoloration of the silver component can be obtained.
シリカ系複合酸化物粒子のシリカ以外の酸化物（ＭＯｘ）含有量は、ＳｉＯ2・ＭＯｘ中に１０〜５０重量％、さらには２０〜４０重量％の範囲にあることが好ましい。
ＳｉＯ2・ＭＯｘ中のＭＯｘの含有量が１０重量％未満の場合は、抗菌消臭成分である銀イオンの交換量が不充分となり、銀イオンの含有量が不充分となり、充分な抗菌消臭効果が得られない場合がある。
ＳｉＯ2・ＭＯｘ中のＭＯｘの含有量が５０重量％を越えると、シリカ以外の酸化物の種類によっても異なるが、銀イオンの交換量が不充分となり充分な抗菌消臭効果が得られない場合があり、また、シリカ以外の酸化物の種類によっては、抗菌消臭成分である銀イオンが不安定となり、遊離したり変色等が生じる場合がある。
The content of oxide (MOx) other than silica in the silica-based composite oxide particles is preferably in the range of 10 to 50% by weight, more preferably 20 to 40% by weight in SiO 2 · MOx.
When the content of MOx in SiO 2 · MOx is less than 10% by weight, the exchange amount of silver ions as an antibacterial deodorant component becomes insufficient, the content of silver ions becomes insufficient, and sufficient antibacterial deodorization The effect may not be obtained.
When the content of MOx in SiO 2 · MOx exceeds 50% by weight, the amount of exchange of silver ions is insufficient and sufficient antibacterial deodorizing effect cannot be obtained, although it depends on the type of oxide other than silica. Depending on the type of oxide other than silica, silver ions, which are antibacterial deodorizing components, may become unstable and may be liberated or discolored.
上記シリカ系複合酸化物粒子は、さらにアルカリ金属イオンを含んでいる。
アルカリ金属イオンとしては、通常Ｎａイオン、Ｋイオンであるが、使用する原料の点からＮａイオンが多く用いられる。
The silica-based composite oxide particles further contain alkali metal ions.
Alkali metal ions are usually Na ions and K ions, but Na ions are often used from the viewpoint of raw materials used.
シリカ系複合酸化物粒子中のアルカリ金属イオンの含有量はＭ2Ｏ（Ｍ：アルカリ金属を表す）として１〜２０重量％、さらには２〜１５重量％、特に５〜１５重量％の範囲にあることが好ましい。
シリカ系複合酸化物粒子中のアルカリ金属イオンの含有量がＭ2Ｏとして１重量％未満の場合は、抗菌消臭成分である銀イオンの交換量が不充分となり、銀イオンの含有量が不充分となり、充分な抗菌消臭効果が得られない場合がある。また、アルカリ金属イオンの含有量がＭ2Ｏとして１重量％未満の場合に、後述するイオン交換法（本願方法）以外の方法で銀イオンを多く付着させても、銀イオンが不安定となり、遊離したり、変色等が生じやすく、特に水道水などの塩素含有水に接した場合に変色したり、性能が大きく低下する場合がある。
The content of alkali metal ions in the silica-based composite oxide particles is in the range of 1 to 20% by weight, further 2 to 15% by weight, particularly 5 to 15% by weight as M 2 O (M: represents alkali metal). Preferably there is.
When the content of alkali metal ions in the silica-based composite oxide particles is less than 1% by weight as M 2 O, the exchange amount of silver ions that are antibacterial deodorizing components is insufficient, and the content of silver ions is insufficient. In some cases, sufficient antibacterial and deodorant effects cannot be obtained. In addition, when the content of alkali metal ions is less than 1% by weight as M 2 O, even if a large amount of silver ions are deposited by a method other than the ion exchange method (the method of the present application) described later, the silver ions become unstable, It is likely to be liberated or discolored, and in particular, when it comes into contact with chlorine-containing water such as tap water, it may be discolored or the performance may be greatly reduced.
シリカ系複合酸化物粒子中のアルカリ金属イオンの含有量がＭ2Ｏとして２０重量％を越えてもさらに銀イオンの交換量が増加することもなく、抗菌消臭効果が向上することもない。
また、銀イオンの交換量が少ない場合にはアルカリ金属イオンが多く残存することになり、用途、用法によっては、具体的には染料を含むことの多い繊維に使用すると退色したり、風合いが低下する場合があり、塗料に用いると得られる塗膜の強度が低下したり、剥離しやすいといったアルカリ金属イオンの悪影響が出ることがあるので好ましくない。
Even if the content of alkali metal ions in the silica-based composite oxide particles exceeds 20% by weight as M 2 O, the exchange amount of silver ions does not increase and the antibacterial deodorizing effect does not improve.
In addition, when the exchange amount of silver ions is small, a large amount of alkali metal ions will remain, and depending on the application and usage, the color may fade or the texture may deteriorate when used for fibers that often contain dyes. If it is used in a paint, the strength of the resulting coating film may be reduced or the alkali metal ions may be easily peeled off, which is not preferable.
このようなシリカ系複合酸化物粒子と抗菌消臭成分である銀イオンとからなる抗菌消臭剤中の銀イオンの含有量はＡｇ2Ｏとして０．１〜２５重量％、さらには０．５〜１０重量％、特に１〜８重量％の範囲にあることが好ましい。
抗菌消臭剤中の銀イオンの含有量がＡｇ2Ｏとして０．１重量％未満の場合は充分な抗菌消臭効果が得られない場合がある。
抗菌消臭剤中の銀イオンの含有量がＡｇ2Ｏとして２５重量％を越えてもさらに抗菌消臭効果が向上することもなく、場合によっては銀イオンが不安定となり、遊離したり、変色等が生じやすくなる。
The content of silver ions in the antibacterial deodorant composed of such silica-based composite oxide particles and silver ions as the antibacterial deodorant component is 0.1 to 25% by weight as Ag 2 O, and further 0.5 It is preferably in the range of 10 to 10% by weight, particularly 1 to 8% by weight.
When the content of silver ions in the antibacterial deodorant is less than 0.1% by weight as Ag 2 O, a sufficient antibacterial deodorant effect may not be obtained.
Even if the content of silver ions in the antibacterial deodorant exceeds 25% by weight as Ag 2 O, the antibacterial deodorant effect is not further improved, and in some cases, the silver ions become unstable and are liberated or discolored. Etc. are likely to occur.
本発明の抗菌消臭剤には、銀以外の抗菌消臭成分として銅、亜鉛、錫から選ばれる１種または２種以上の金属イオンを含んでいてもよい。
銀以外の抗菌消臭成分の含有量は、金属イオンの種類によっても異なるが、酸化物として０．１〜２０重量％の範囲にあり、且つ、Ａｇ2Ｏとの合計が０．１〜２５重量％の範囲にあることが好ましい。
銀以外の抗菌消臭成分を含有していると、銀のみを含有する場合に比して消臭性能が向上する傾向がある。
なお、前記銀、銅、亜鉛、錫は全てがイオンである必要はなく、金属あるいは酸化物、水酸化物等であってもよい。
The antibacterial deodorant of the present invention may contain one or more metal ions selected from copper, zinc and tin as an antibacterial deodorant component other than silver.
The content of antibacterial deodorizing components other than silver varies depending on the type of metal ion, but is in the range of 0.1 to 20% by weight as an oxide, and the total amount with Ag 2 O is 0.1 to 25. It is preferably in the range of wt%.
When antibacterial deodorizing components other than silver are contained, the deodorizing performance tends to be improved as compared with the case of containing only silver.
The silver, copper, zinc, and tin do not have to be ions, and may be metals, oxides, hydroxides, or the like.
このような抗菌消臭剤は平均粒子径が２〜３００ｎｍ、さらには５〜２００ｎｍの範囲にあることが好ましい。
抗菌消臭剤の平均粒子径が２ｎｍ未満のものは、シリカ系複合酸化物粒子自体の分散安定性が低く、凝集しやすいために分散安定性に優れた抗菌消臭剤を得ることが困難であり、得られたとしても、用途によって凝集するため用途に制限がある。
抗菌消臭剤の平均粒子径が３００ｎｍを越えると、透明性が低下し、抗菌消臭剤を用いる基材の意匠性を損なう場合がある。また、抗菌消臭効果が不充分となる場合がある。
本発明の抗菌消臭剤の平均粒子径は、レーザー散乱粒子径測定装置（ＮＩＫＫＩＳＯ社製）を使用して測定することができる。
Such an antibacterial deodorant preferably has an average particle size in the range of 2 to 300 nm, more preferably 5 to 200 nm.
When the average particle size of the antibacterial deodorant is less than 2 nm, it is difficult to obtain an antibacterial deodorant having excellent dispersion stability because the dispersion stability of the silica-based composite oxide particles itself is low and the particles are likely to aggregate. Yes, even if it is obtained, there is a limit to the use because it aggregates depending on the use.
When the average particle diameter of the antibacterial deodorant exceeds 300 nm, the transparency is lowered and the design of the substrate using the antibacterial deodorant may be impaired. In addition, the antibacterial deodorizing effect may be insufficient.
The average particle size of the antibacterial deodorant of the present invention can be measured using a laser scattering particle size measuring device (manufactured by NIKKISO).
本発明の抗菌消臭剤中のアルカリ金属イオンの含有量（残存量）はＭ2Ｏ（Ｍ：アルカリ金属を表す）として１〜１５重量％、さらには１〜１０重量％、特に２〜１０重量％の範囲にあることが好ましい。
抗菌消臭剤中のアルカリ金属イオンの含有量（残存量）がＭ2Ｏ（Ｍ：アルカリ金属を表す）として１重量％未満の場合は、銀イオンの安定性が低下するためか、塩素を含む水道水等に接触した場合沈殿を生じ、変色するとともに、抗菌性能、消臭性能が低下し、長期にわたって抗菌消臭性能を維持できない場合がある。
The content (residual amount) of alkali metal ions in the antibacterial deodorant of the present invention is 1 to 15% by weight, more preferably 1 to 10% by weight, particularly 2 to 10% as M 2 O (M: represents alkali metal). It is preferably in the range of wt%.
If the content (residual amount) of alkali metal ions in the antibacterial deodorant is less than 1% by weight as M 2 O (M: represents alkali metal), the stability of silver ions may decrease, When it comes into contact with tap water, etc., it precipitates and discolors, and the antibacterial performance and deodorization performance may be reduced, and the antibacterial deodorization performance may not be maintained for a long time.
抗菌消臭剤中のアルカリ金属イオンの含有量が１５重量％を越えると、本発明では、抗菌消臭剤中抗菌消臭性金属成分の含有量とアルカリ金属イオンの含有量は、シリカ系複合酸化物粒子中のアルカリ金属イオンと抗菌消臭性金属イオンとがイオン交換するため、逆相関の関係にあり、このことから抗菌消臭性金属成分の含有量が少ないことを意味し、抗菌消臭効果が高くないことに加え、用途、用法によっては、具体的には染料を含むことの多い繊維に使用すると退色したり、風合いが低下する場合があり、塗料に用いると得られる塗膜の強度が低下したり、剥離しやすいといったアルカリ金属イオンの悪影響がでることがあるので好ましくない。 When the content of alkali metal ions in the antibacterial deodorant exceeds 15% by weight, in the present invention, the content of the antibacterial deodorant metal component and the content of the alkali metal ion in the antibacterial deodorant Since the alkali metal ions and antibacterial deodorant metal ions in the oxide particles are ion-exchanged, there is an inverse correlation, which means that the content of the antibacterial deodorant metal component is low, In addition to not having a high odor effect, depending on the application and usage, specifically, it may fade when used in fibers that often contain dyes, and the texture may decrease. This is not preferred because the adverse effect of alkali metal ions such as reduced strength and easy peeling can occur.
［２］抗菌消臭剤の製造方法
本発明に係る抗菌消臭剤の製造方法は、下記の工程（ａ）〜（ｃ）からなることを特徴としている。
（ａ）珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液とを、ｐＨを９〜１３に維持しながら、得られるシリカ系複合酸化物粒子中のシリカ以外の元素の酸化物（ＭＯｘ）含有量が、ＳｉＯ2・ＭＯｘ中に１０〜５０重量％の範囲となるように混合する工程
（ｂ）工程（ａ）で得られたシリカ系複合酸化物粒子分散液を洗浄する工程
（ｃ）前記シリカ系複合酸化物粒子分散液に銀化合物を添加して銀イオン交換する工程
[2] Manufacturing method of antibacterial deodorant The manufacturing method of the antibacterial deodorant according to the present invention is characterized by comprising the following steps (a) to (c).
(A) Content of oxide (MOx) of elements other than silica in the obtained silica-based composite oxide particles while maintaining an aqueous solution of alkali silicate and a compound aqueous solution of elements other than silicon at a pH of 9 to 13. Step of mixing in SiO 2 · MOx so as to be in the range of 10 to 50% by weight (b) Step of washing the silica-based composite oxide particle dispersion obtained in step (a) (c) The silica-based Step of silver ion exchange by adding silver compound to composite oxide particle dispersion
工程（ａ）
珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液とを、ｐＨを９〜１３に維持しながら、得られるシリカ系複合酸化物粒子中のシリカ以外の元素の酸化物（ＭＯｘ）含有量が、ＳｉＯ2・ＭＯｘ中に１０〜５０重量％の範囲となるように混合する。
珪酸アルカリ水溶液としては、珪酸ナトリウム水溶液、珪酸カリウム水溶液等が用いられる。この時の珪酸アルカリ水溶液の濃度はＳｉＯ2として０．１〜１０重量％、さらには０．５〜５．０重量％の範囲にあることが好ましい。
Step (a)
The oxide (MOx) content of elements other than silica in the silica-based composite oxide particles obtained while maintaining the pH of the aqueous solution of an alkali silicate solution and an element compound other than silicon at 9 to 13 is SiO 2. -Mix so that it may become the range of 10 to 50 weight% in MOx.
Examples of the alkali silicate aqueous solution include a sodium silicate aqueous solution and a potassium silicate aqueous solution. The concentration of the aqueous alkali silicate solution at this time is preferably in the range of 0.1 to 10% by weight, more preferably 0.5 to 5.0% by weight as SiO 2 .
珪素以外の元素の化合物水溶液としては、Ａｌ、Ｂ、Ｚｒ、Ｔｉ、Ｍｇ、Ｃａ、Ｃｅ、Ｓｎ、Ｓｂ、Ｚn、Ｆｅ、Ｐからから選ばれる１種または２種以上の元素の化合物の水溶液が用いられる。例えば、塩化アルミニウム、硫酸アルミニウム、アルミン酸ナトリウム等のアルミニウム化合物水溶液、ホウ酸、ホウ酸ナトリウム、塩化ジルコニウム、硫酸チタニル、塩化錫、塩化アンチモン、塩化鉄等が挙げられる。
珪素以外の元素の化合物水溶液の濃度はＭＯｘとして０．１〜５．０重量％、さらには０．２〜２．０重量％の範囲にあることが好ましい。
As the compound aqueous solution of elements other than silicon, an aqueous solution of a compound of one or more elements selected from Al, B, Zr, Ti, Mg, Ca, Ce, Sn, Sb, Zn, Fe, and P is used. Used. Examples thereof include aqueous aluminum compound solutions such as aluminum chloride, aluminum sulfate, and sodium aluminate, boric acid, sodium borate, zirconium chloride, titanyl sulfate, tin chloride, antimony chloride, and iron chloride.
The concentration of the compound aqueous solution of elements other than silicon is preferably 0.1 to 5.0% by weight, more preferably 0.2 to 2.0% by weight as MOx.
珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液とを、ｐＨを９〜１３に維持しながら混合するが、この時、必要に応じてｐＨ調整剤として苛性ソーダ水溶液、苛性カリ水溶液、アンモニア水、テトラアンモニウムハイドロオキサイド等の有機塩基を用いることができる。
前記ｐＨが９未満の場合は、得られるシリカ系複合酸化物粒子の抗菌性消臭成分である銀イオン交換容量が不充分となったり、分散安定性が不充分となる場合がある。
前記ｐＨが１３を越えてもさらに、イオン交換容量、分散安定性が向上することもなく、珪素以外の元素の化合物の種類によっては低下する場合がある。
An alkali silicate aqueous solution and a compound aqueous solution of an element other than silicon are mixed while maintaining the pH at 9 to 13. At this time, as necessary, a caustic soda aqueous solution, a caustic potassium aqueous solution, ammonia water, tetraammonium hydro as a pH adjuster. An organic base such as oxide can be used.
When the pH is less than 9, the silver ion exchange capacity, which is an antibacterial deodorant component of the resulting silica-based composite oxide particles, may be insufficient, or the dispersion stability may be insufficient.
Even if the pH exceeds 13, the ion exchange capacity and the dispersion stability are not improved, and it may be lowered depending on the type of compound of an element other than silicon.
珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液との混合比率は、得られるシリカ系複合酸化物粒子中のシリカ以外の元素の酸化物（ＭＯｘ）含有量が、ＳｉＯ2・ＭＯｘ中に１０〜５０重量％、さらには２０〜４０重量％の範囲となるように混合する。
ＳｉＯ2・ＭＯｘ中のＭＯｘの含有量が１０重量％未満の場合は、抗菌消臭成分である銀イオンの交換容量が不充分となり、銀イオンの含有量が不充分となり、充分な抗菌消臭効果が得られない場合がある。
ＳｉＯ2・ＭＯｘ中のＭＯｘの含有量が５０重量％を越えると、シリカ以外の酸化物の種類によっても異なるが、銀イオンの交換容量が不充分となり充分な抗菌消臭効果が得られない場合があり、また、シリカ以外の酸化物の種類によっては、抗菌消臭成分である銀イオンが不安定となり、遊離したり変色等が生じる場合がある。
The mixing ratio of the alkali silicate aqueous solution and the compound aqueous solution of elements other than silicon is such that the oxide (MOx) content of elements other than silica in the obtained silica-based composite oxide particles is 10 to 50 in SiO 2 · MOx. It mixes so that it may become the range of 20 weight% further 20weight%.
When the content of MOx in SiO 2 · MOx is less than 10% by weight, the exchange capacity of silver ions, which are antibacterial deodorant components, becomes insufficient, the content of silver ions becomes insufficient, and sufficient antibacterial deodorization The effect may not be obtained.
When the content of MOx in SiO 2 · MOx exceeds 50% by weight, although it depends on the type of oxide other than silica, the exchange capacity of silver ions is insufficient and sufficient antibacterial deodorizing effect cannot be obtained. Depending on the type of oxide other than silica, silver ions, which are antibacterial deodorizing components, may become unstable and may be liberated or discolored.
珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液との混合濃度は、ＳｉＯ2・ＭＯｘとして０．２〜１５重量％、さらには０．５〜１０重量％の範囲にあることが好ましい。
珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液との混合濃度がＳｉＯ2・ＭＯｘとして０．２重量％未満の場合は、収率、生産効率が低く、経済性が低下する。
珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液との混合濃度がＳｉＯ2・ＭＯｘとして１５重量％を越えると、凝集したシリカ系複合酸化物粒子が生成する場合がある。
The mixed concentration of the alkali silicate aqueous solution and the compound aqueous solution of elements other than silicon is preferably 0.2 to 15% by weight, more preferably 0.5 to 10% by weight as SiO 2 · MOx.
When the mixed concentration of the alkali silicate aqueous solution and the compound aqueous solution of elements other than silicon is less than 0.2% by weight as SiO 2 · MOx, the yield and production efficiency are low, and the economic efficiency is lowered.
When the mixed concentration of the alkali silicate aqueous solution and the compound aqueous solution of an element other than silicon exceeds 15 wt% as SiO 2 · MOx, aggregated silica-based composite oxide particles may be generated.
前記工程（ａ）において、平均粒子径１〜５０ｎｍの金属酸化物粒子（シード）分散液に珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液とを、ｐＨを９〜１３に維持しながら、添加することが好ましい。
前記金属酸化物粒子としては、ＳｉＯ2、Ａｌ2Ｏ3、ＺｒＯ2、ＴｉＯ2等の金属酸化物粒子を用いることができる。
金属酸化物粒子の平均粒子径は、得ようとする抗菌消臭剤の粒子径によっても異なるが、１〜５０ｎｍ、さらには２〜３０ｎｍの範囲にあることが好ましい。金属酸化物粒子の平均粒子径が前記範囲にあれば均一な平均粒子径を有し、単分散（非凝集）のシリカ系複合酸化物粒子が得られる。
In the step (a), an alkali silicate aqueous solution and a compound aqueous solution of an element other than silicon are added to a metal oxide particle (seed) dispersion having an average particle size of 1 to 50 nm while maintaining the pH at 9 to 13. It is preferable.
Examples of the metal oxide particles can be used SiO 2, Al 2 O 3, ZrO 2, TiO 2 or the like of the metal oxide particles.
The average particle size of the metal oxide particles varies depending on the particle size of the antibacterial deodorant to be obtained, but is preferably in the range of 1 to 50 nm, more preferably 2 to 30 nm. If the average particle diameter of the metal oxide particles is within the above range, monodispersed (non-aggregated) silica-based composite oxide particles having a uniform average particle diameter can be obtained.
珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液の添加、混合時間は、原料各水溶液の濃度、温度等によって異なるが、所望の平均粒子径が得られるまで添加する。
この時の温度は、概ね３０〜９５℃、好ましくは５０〜９０℃の範囲である。
添加時の温度が３０℃未満では、粒子成長が遅く、生産性が低下する。添加時の温度が９５℃を越えると、凝集したシリカ系複合酸化物粒子が得られる場合がある。
The addition and mixing time of the alkali silicate aqueous solution and the compound aqueous solution of elements other than silicon vary depending on the concentration, temperature, etc. of each raw material aqueous solution, but are added until a desired average particle size is obtained.
The temperature at this time is generally in the range of 30 to 95 ° C, preferably 50 to 90 ° C.
When the temperature at the time of addition is less than 30 ° C., particle growth is slow and productivity is lowered. When the temperature at the time of addition exceeds 95 ° C., aggregated silica-based composite oxide particles may be obtained.
なお、添加終了後は、必要に応じて熟成することができる。熟成温度は、添加時の温度より高くてもよく、低くてもよい。熟成することによってより均一な粒子径分布を有するシリカ系複合酸化物粒子が得られる。 In addition, after completion | finish of addition, it can age | cure | ripen as needed. The aging temperature may be higher or lower than the temperature at the time of addition. By aging, silica-based composite oxide particles having a more uniform particle size distribution can be obtained.
工程（ｂ）
次いで、工程（ａ）で得られたシリカ系複合酸化物粒子分散液を洗浄する。
本発明に用いる洗浄する方法としては、限外濾過膜法が好ましい。洗浄することによって、原料に由来する陰イオン、あるいはシリカ系複合酸化物粒子にイオン的に結合してないアルカリ金属イオン（フリーのアルカリ金属イオン）を除去することができる。フリーのアルカリ金属イオンが多く残存すると前記銀イオンの利用効率が低下する他、所望量の銀イオン交換が困難になる場合がある。なお、工程（ｂ）では、洗浄と同時に濃度調整をすることもできる。
Step (b)
Next, the silica-based composite oxide particle dispersion obtained in step (a) is washed.
The washing method used in the present invention is preferably an ultrafiltration membrane method. By washing, an anion derived from the raw material or an alkali metal ion (free alkali metal ion) that is not ionically bonded to the silica-based composite oxide particles can be removed. When a large amount of free alkali metal ions remain, the utilization efficiency of the silver ions is lowered, and a desired amount of silver ion exchange may be difficult. In step (b), the concentration can be adjusted simultaneously with cleaning.
工程（ｃ）
次いで、前記シリカ系複合酸化物粒子分散液に銀化合物を添加して銀イオン交換する。
銀化合物としては、硝酸銀が好適に用いられる。なお、銀化合物として、本願出願人の出願による特開平６−８０５２７号公報等に開示した銀アミン錯体も使用することができるが、抗菌消臭成分の安定性の点から硝酸銀が好ましい。
銀化合物の添加量は、得られる抗菌消臭剤中の銀イオンの含有量がＡｇ2Ｏとして０．１〜２５重量％となるように添加する。
Step (c)
Next, a silver compound is added to the silica-based composite oxide particle dispersion to exchange silver ions.
As the silver compound, silver nitrate is preferably used. A silver amine complex disclosed in Japanese Patent Application Laid-Open No. 6-80527 filed by the applicant of the present application can be used as the silver compound, but silver nitrate is preferred from the viewpoint of the stability of the antibacterial deodorant component.
The silver compound is added so that the content of silver ions in the resulting antibacterial deodorant is 0.1 to 25% by weight as Ag 2 O.
本発明では、銀化合物と同時に銅、亜鉛、錫から選ばれる１種または２種以上の金属の化合物を添加してイオン交換することもできる。
銅、亜鉛、錫の化合物としては、塩酸塩、硝酸塩、硫酸塩、酢酸塩および銅、亜鉛、錫の錯イオン等があげられるが、抗菌消臭成分の安定性の点から塩酸塩、硝酸塩、硫酸塩、酢酸塩が好ましい。
これら銀化合物以外の化合物の添加量は、得られる抗菌消臭剤中の酸化物としての含有量がＡｇ2Ｏとの合計で０．１〜２５重量％の範囲にあることが好ましい。
In the present invention, ion exchange can be performed by adding a compound of one or more metals selected from copper, zinc, and tin simultaneously with the silver compound.
Examples of copper, zinc, and tin compounds include hydrochloride, nitrate, sulfate, acetate, and complex ions of copper, zinc, and tin. From the viewpoint of the stability of antibacterial deodorizing ingredients, hydrochloride, nitrate, Sulfate and acetate are preferred.
As for the addition amount of compounds other than these silver compounds, it is preferable that the content as an oxide in the obtained antibacterial deodorant is in the range of 0.1 to 25% by weight in total with Ag 2 O.
シリカ系複合酸化物粒子分散液の濃度は銀イオン交換できれば特に制限はないが、通常固形分として０．１〜１０重量％である。
銀イオン交換時の分散液のｐＨは６〜１３、さらには８〜１０の範囲にあることが好ましい。
分散液のｐＨが６未満の場合は、シリカ系複合酸化物粒子が不安定となり、凝集した抗菌消臭剤が得られる場合がある。
分散液のｐＨが１３を越えると、シリカ系複合酸化物粒子のシリカ成分、シリカ以外の酸化物成分のいずれかの溶解が起こるとともに、銀イオン交換が不十分となる場合がある。
The concentration of the silica-based composite oxide particle dispersion is not particularly limited as long as silver ion exchange can be performed, but is usually 0.1 to 10% by weight as a solid content.
The pH of the dispersion during silver ion exchange is preferably in the range of 6 to 13, more preferably 8 to 10.
When the pH of the dispersion is less than 6, the silica-based composite oxide particles may become unstable, and an aggregated antibacterial deodorant may be obtained.
If the pH of the dispersion exceeds 13, dissolution of either the silica component of the silica-based composite oxide particles or the oxide component other than silica may occur, and silver ion exchange may be insufficient.
銀イオン交換時の温度は特に制限はないが、通常３０〜９５℃の範囲であり、イオン交換時間は１時間以内で充分である。
銀イオン交換終了後、前記と同様に限外濾過膜法で洗浄することができる。さらに、必要に応じて、銀の含有量を高めるために、繰り返し銀イオン交換してもよい。また、銅、亜鉛、錫から選ばれる１種または２種以上の金属の化合物を添加してイオン交換することもできる。
The temperature at the time of silver ion exchange is not particularly limited, but is usually in the range of 30 to 95 ° C., and the ion exchange time is sufficient within 1 hour.
After completion of the silver ion exchange, it can be washed by the ultrafiltration membrane method as described above. Further, if necessary, silver ion exchange may be repeated to increase the silver content. Moreover, the ion exchange can also be performed by adding a compound of one or more metals selected from copper, zinc and tin.
このようにして得られる抗菌消臭剤は、銀イオンの含有量が０．１〜２５重量％の範囲にあり、前記銀以外の抗菌消臭成分の含有量は酸化物として０．１〜２０重量％の範囲にあり、且つ、Ａｇ2Ｏとの合計が０．１〜２５重量％の範囲にあることが好ましい。
また、アルカリ金属イオンの含有量（残存量）は、Ｍ2Ｏ（Ｍ：アルカリ金属を表す）として１〜１５重量％、さらには２〜１０重量％の範囲にあることが好ましい。
抗菌消臭剤中のアルカリ金属イオンの含有量が酸化物として１重量％未満の場合は、銀イオンの安定性が低下するためか、塩素を含む水道水等に接触した場合沈殿を生じ、変色するとともに、抗菌性能、消臭性能が低下し、長期にわたって抗菌消臭性能を維持できない場合がある。
The antibacterial deodorant thus obtained has a silver ion content of 0.1 to 25% by weight, and the content of the antibacterial deodorant component other than silver is 0.1 to 20 as an oxide. It is preferably in the range of wt%, and the total with Ag 2 O is preferably in the range of 0.1 to 25 wt%.
The content of alkali metal ions (remaining amount), M 2 O: 1 to 15% by weight (M an alkali metal represents a), more preferably in the range of 2 to 10 wt%.
If the content of alkali metal ions in the antibacterial deodorant is less than 1% by weight as an oxide, the stability of silver ions may decrease, or precipitation may occur when contacted with tap water containing chlorine. In addition, the antibacterial performance and deodorant performance may be reduced, and the antibacterial deodorization performance may not be maintained for a long time.
抗菌消臭剤中のアルカリ金属イオンの含有量が１５重量％を越えると、本発明では、抗菌消臭剤中抗菌消臭性金属成分の含有量とアルカリ金属イオンの含有量は、シリカ系複合酸化物粒子中のアルカリ金属イオンと抗菌消臭性金属イオンとがイオン交換するため、逆相関の関係にあり、このことから抗菌消臭性金属成分の含有量が少ないことを意味し、抗菌消臭効果が高くないことに加え、用途、用法によっては、具体的には染料を含むことの多い繊維に使用すると退色したり、風合いが低下する場合があり、塗料に用いると得られる塗膜の強度が低下したり、剥離しやすいといったアルカリ金属イオンの悪影響がでることがあるので好ましくない。 When the content of alkali metal ions in the antibacterial deodorant exceeds 15% by weight, in the present invention, the content of the antibacterial deodorant metal component and the content of the alkali metal ion in the antibacterial deodorant Since the alkali metal ions and antibacterial deodorant metal ions in the oxide particles are ion-exchanged, there is an inverse correlation, which means that the content of the antibacterial deodorant metal component is low, In addition to not having a high odor effect, depending on the application and usage, specifically, it may fade when used in fibers that often contain dyes, and the texture may decrease. This is not preferred because the adverse effect of alkali metal ions such as reduced strength and easy peeling can occur.
本発明では、抗菌消臭剤中のアルカリ金属イオンの含有量（残存量）を１５重量％以下、好ましくは１０重量％以下とするために、予めシリカ系複合酸化物粒子のアルカリ金属イオンの含有量を一部除去して使用することができる。
除去する方法としては、Ｈ型あるいはＮＨ4型イオン交換樹脂等を用いて一部をイオン交換除去する方法、限外濾過膜法にて、ＮＨ4イオンを含む薬液を用いて一部をイオン交換除去する方法等が挙げられる。
得られた抗菌消臭剤は水分散液として用いてもよく、有機溶媒に置換して用いてもよく、さらに乾燥して粉体として用いてもよい。
In the present invention, in order to make the content (residual amount) of alkali metal ions in the antibacterial deodorant 15% by weight or less, preferably 10% by weight or less, the content of alkali metal ions in the silica-based composite oxide particles in advance. A part of the amount can be removed and used.
As a removal method, a part of the ion exchange is performed using an H-type or NH 4 -type ion exchange resin or the like, and a part of the ion-exchange is performed using a chemical solution containing NH 4 ions by an ultrafiltration membrane method. The method of removing etc. are mentioned.
The obtained antibacterial deodorant may be used as an aqueous dispersion, may be used after being replaced with an organic solvent, or may be further dried and used as a powder.
［３］抗菌消臭剤の使用方法
本発明の抗菌消臭剤の使用方法は、従来公知の抗菌剤、消臭剤、抗菌消臭剤等と同様に使用することができる。
例えば、抗菌消臭剤粉体を直接塗布する方法、抗菌消臭剤分散液を直接塗布する方法、抗菌消臭剤塗料を塗布して塗膜を形成する方法、抗菌消臭剤をマスターバッチ樹脂に含有させた樹脂基材として使用する方法、抗菌消臭剤分散液を繊維、不織布、フィルター等に付着あるいは担持して使用する方法等が挙げられるがこれらに限定するものではない。
[3] Method of using antibacterial deodorant The method of using the antibacterial deodorant of the present invention can be used in the same manner as conventionally known antibacterial agents, deodorants, antibacterial deodorants and the like.
For example, a method of directly applying antibacterial deodorant powder, a method of directly applying an antibacterial deodorant dispersion, a method of forming a coating film by applying an antibacterial deodorant paint, and an antibacterial deodorant as a masterbatch resin. Examples thereof include, but are not limited to, a method of using as a resin base material contained in a resin, a method of using an antibacterial deodorant dispersion liquid attached to or carrying a fiber, nonwoven fabric, filter or the like.
以下に実施例を示し、本発明を更に具体的に説明するが、本発明はこれら実施例に限定されるものではない。 Examples Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
［実施例１］
抗菌消臭剤(1)分散液の調製
ＳｉＯ2濃度２０重量％のコロイド溶液（コロイド粒子平均粒子径：５ｎｍ）２０ｇと純水３８０ｇの混合物を８０℃に加温した。この反応母液のｐＨは１０．７であり、同母液にＳｉＯ2として濃度１．５重量％の珪酸ソーダ水溶液１５００ｇとＡｌ2Ｏ3として濃度０．５重量％のアルミン酸ソーダ水溶液１５００ｇとを同時に添加し、添加終了後、９０℃で１時間熟成した。この時の分散液のｐＨは１２．３であった。
ついで、限外濾過膜で洗浄し、濃縮して固形分濃度２２．２重量％、ｐＨ１０．６のシリカ・アルミナ複合酸化物粒子(1)分散液を調製した。
シリカ・アルミナ複合酸化物粒子(1)の平均粒子径は１５ｎｍ、組成はＳｉＯ2：６０．２重量％、Ａｌ2Ｏ3：２５．５重量％、Ｎａ2Ｏ：１４．３重量％であった。
[Example 1]
Preparation of antibacterial deodorant (1) dispersion A mixture of 20 g of a colloidal solution (colloidal particle average particle size: 5 nm) having a SiO 2 concentration of 20% by weight and 380 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor is 10.7, and 1500 g of a sodium silicate aqueous solution with a concentration of 1.5 wt% as SiO 2 and 1500 g of a sodium aluminate aqueous solution with a concentration of 0.5 wt% as Al 2 O 3 are simultaneously added to the mother liquor. After the addition, the mixture was aged at 90 ° C. for 1 hour. The pH of the dispersion at this time was 12.3.
Subsequently, it was washed with an ultrafiltration membrane and concentrated to prepare a dispersion of silica / alumina composite oxide particles (1) having a solid content of 22.2% by weight and a pH of 10.6.
The average particle diameter of the silica-alumina composite oxide particles (1) was 15 nm, the composition was SiO 2 : 60.2 wt%, Al 2 O 3 : 25.5 wt%, Na 2 O: 14.3 wt%. It was.
室温にて、陽イオン交換樹脂（三菱化学社製ダイヤイオン、ＳＫ１ＢＨ）をｐＨが７．０になるまで添加、その後、５％アンモニアにて、ｐＨ９．０まで添加、ついで、濃度１．０重量％の硝酸銀水溶液２０７．４ｇを添加し、９０℃で１時間撹拌してイオン交換を行った。この時、ｐＨは８．８であった。
ついで、限外濾過膜で洗浄し、濃縮して固形分濃度１．５重量％の抗菌消臭剤(1)分散液を調製した。
得られた抗菌消臭剤(1)の平均粒子径は１５ｎｍ、組成はＳｉＯ2：６４．８重量％、Ａｌ2Ｏ3：２２．５重量％、Ｎａ2Ｏ：８．７重量％、Ａｇ2Ｏ：４．０重量％であった。
At room temperature, a cation exchange resin (Mitsubishi Chemical Corporation Diaion, SK1BH) was added until the pH reached 7.0, then 5% ammonia was added until pH 9.0, and then a concentration of 1.0 wt. A 20% silver nitrate aqueous solution was added, and the mixture was stirred at 90 ° C. for 1 hour for ion exchange. At this time, the pH was 8.8.
Subsequently, it was washed with an ultrafiltration membrane and concentrated to prepare an antibacterial deodorant (1) dispersion having a solid content of 1.5% by weight.
The obtained antibacterial deodorant (1) has an average particle size of 15 nm, a composition of SiO 2 : 64.8% by weight, Al 2 O 3 : 22.5% by weight, Na 2 O: 8.7% by weight, Ag 2 O: 4.0% by weight.
安定性テスト （水道水添加：沈殿）
抗菌消臭剤(1)分散液を水道水（塩素濃度：２ｐｐｍ）に加えて１０分の１に稀釈し、目視にて変色状態、沈殿生成の有無を次の評価基準で観察した。
変色も沈殿も無し ：◎
変色したが沈殿無し ：○
変色は無いが沈殿あり：△
変色し、沈殿も生成 ：×
Stability test (tap water addition: precipitation)
The antibacterial deodorant (1) dispersion was added to tap water (chlorine concentration: 2 ppm), diluted to 1/10, and visually observed for discoloration and precipitation, according to the following evaluation criteria.
No discoloration or precipitation: ◎
Discolored but no precipitation: ○
No discoloration but precipitation: △
Discoloration and formation of precipitates: ×
耐光性テスト
抗菌消臭剤(1)分散液に等量のメタノールを添加して、ＵＶランプにて５時間照射し、目視にて変色の有無を次の評価基準で観察した。
変色有り ：○
変色無し ：×
Light resistance test Antibacterial deodorant (1) An equal amount of methanol was added to the dispersion, irradiated with a UV lamp for 5 hours, and visually observed for the presence or absence of discoloration according to the following evaluation criteria.
Discoloration: ○
No discoloration: ×
抗菌性能テスト
（１）大腸菌試験
１００ｍｌのリン酸緩衝液に大腸菌（Escherichia coli IFO 3972）を懸濁させ、安定性テストを実施した抗菌消臭剤(1)分散液０．１ｇを添加し、室温で１時間、３３０ｒｐｍで攪拌した後、生菌数（Ｂ）を測定した。
別途、上記において抗菌消臭剤(1)分散液を添加しない空試験として、大腸菌添加１時間後の生菌数（Ａ）を測定したところ、Ａ＝３ｘ１０6であった。抗菌性能を増減値差（ＬｏｇＡ−ＬｏｇＢ）として評価し、結果を表１に示した。
なお、前記リン酸緩衝液とは、リン酸２水素カリウム３４ｇを１０００ｍｌの精製水に溶解し、水酸化ナトリウムでｐＨを７．２に調製した液を濃度０．８５重量％の塩化ナトリウム水溶液で８００倍に希釈した溶液である。
Antibacterial performance test (1) Escherichia coli test Suspend E. coli (Escherichia coli IFO 3972) in 100 ml of phosphate buffer solution, add 0.1 g of antibacterial deodorant (1) dispersion that was subjected to stability test, and After stirring at 330 rpm for 1 hour, the viable cell count (B) was measured.
Separately, as a blank test in which the antibacterial deodorant (1) dispersion was not added in the above, the viable cell count (A) after 1 hour of addition of E. coli was measured, and A = 3 × 10 6 . The antibacterial performance was evaluated as an increase / decrease value difference (LogA−LogB), and the results are shown in Table 1.
The phosphate buffer is a solution prepared by dissolving 34 g of potassium dihydrogen phosphate in 1000 ml of purified water and adjusting the pH to 7.2 with sodium hydroxide with a 0.85 wt% sodium chloride aqueous solution. It is a solution diluted 800 times.
（２）黄色ぶどう球菌試験
大腸菌に代えて黄色ぶどう球菌（Staphylococcus aureuse IFO 12732）を用いた以外は前記（１）大腸菌試験と同様にして評価し、結果を表１に示した。なお、空試験における黄色ぶどう球菌添加１時間後の生菌数（Ａ）は、２ｘ１０6であった。
(2) Staphylococcus aureus test Evaluation was made in the same manner as in the (1) Escherichia coli test, except that Staphylococcus aureuse IFO 12732 was used instead of Escherichia coli. The results are shown in Table 1. The addition Staphylococcus aureus in blank test number of viable bacteria after 1 hour (A) was 2x10 6.
消臭性能テスト
臭気成分としてアセトアルデヒド、アンモニアおよび硫化水素を用いた。
（１）アセトアルデヒド
安定性テストを実施した抗菌消臭剤(1)分散液を１０５℃で２時間乾燥した後、２０℃、相対湿度６５％で２４時間湿度調整した。ついで、湿度調整した抗菌消臭剤(1)分散液粉末１ｇを５Ｌのテトラバッグに入れ、濃度１４ｐｐｍのアセトアルデヒド臭気ガス３Ｌを封入し、２時間後に検知管（ガステック社製：９２Ｌ）にてアセトアルデヒド濃度を測定し、アセトアルデヒドの減少率を消臭率として表１に示した。
Deodorization performance test Acetaldehyde, ammonia and hydrogen sulfide were used as odor components.
(1) Acetaldehyde Antibacterial deodorant subjected to stability test (1) The dispersion was dried at 105 ° C. for 2 hours, and then the humidity was adjusted at 20 ° C. and relative humidity of 65% for 24 hours. Next, 1 g of the antibacterial deodorant (1) with the humidity adjusted was put in a 5 L tetrabag, filled with 3 L of acetaldehyde odor gas with a concentration of 14 ppm, and 2 hours later, with a detector tube (92 G manufactured by GASTEC). The concentration of acetaldehyde was measured, and the reduction rate of acetaldehyde is shown in Table 1 as the deodorization rate.
（２）アンモニア
安定性テストを実施した抗菌消臭剤(1)分散液を１０５℃で２時間乾燥した後、２０℃、相対湿度６５％で２４時間湿度調整した。ついで、湿度調整した抗菌消臭剤(1)分散液粉末１ｇを５Ｌのテトラバッグに入れ、濃度１００ｐｐｍのアンモニア臭気ガス３Ｌを封入し、２時間後に検知管（ガステック社製：３ＬＡ）にてアンモニア濃度を測定し、アンモニアの減少率を消臭率として表１に示した。
(2) Ammonia Antibacterial deodorant subjected to stability test (1) The dispersion was dried at 105 ° C. for 2 hours, and then the humidity was adjusted at 20 ° C. and relative humidity of 65% for 24 hours. Next, 1 g of the antibacterial deodorant (1) with adjusted humidity was put in a 5 L tetrabag, 3 L of ammonia odor gas with a concentration of 100 ppm was sealed, and 2 hours later, with a detector tube (manufactured by GASTECH: 3LA) The ammonia concentration was measured, and the ammonia reduction rate is shown in Table 1 as the deodorization rate.
（３）硫化水素
安定性テストを実施した抗菌消臭剤(1)分散液を１０５℃で２時間乾燥した後、２０℃、相対湿度６５％で２４時間湿度調整した。ついで、湿度調整した抗菌消臭剤(1)分散液粉末１ｇを５Ｌのテトラバッグに入れ、濃度４ｐｐｍの硫化水素臭気ガス３Ｌを封入し、２時間後に検知管（ガステック社製：４ＬＴ）にて硫化水素濃度を測定し、硫化水素の減少率を消臭率として表１に示した。
(3) Hydrogen sulfide Antibacterial deodorant (1) subjected to the stability test (1) The dispersion was dried at 105 ° C. for 2 hours, and then the humidity was adjusted at 20 ° C. and a relative humidity of 65% for 24 hours. Next, 1 g of the antibacterial deodorant (1) with adjusted humidity was put in a 5 L tetrabag, 3 L of hydrogen sulfide odor gas with a concentration of 4 ppm was sealed, and after 2 hours, it was placed in a detector tube (Gastech Co., Ltd .: 4LT). The hydrogen sulfide concentration was measured, and the reduction rate of hydrogen sulfide is shown in Table 1 as the deodorization rate.
［実施例２］
抗菌消臭剤(2)分散液の調製
実施例１と同様にしてシリカ・アルミナ複合酸化物粒子(1)分散液を調製した。
ついで、濃度１．０重量％の硝酸銀水溶液１０３．７ｇを添加し、９０℃で１時間撹拌してイオン交換を行った。この時、ｐＨは９．５であった。
ついで、限外濾過膜で洗浄し、濃縮して固形分濃度１．５重量％の抗菌消臭剤(2)分散液を調製した。
得られた抗菌消臭剤(2)の平均粒子径は１５ｎｍ、組成はＳｉＯ2：６１．３重量％、Ａｌ2Ｏ3：２２．７重量％、Ｎａ2Ｏ：１４．０重量％、Ａｇ2Ｏ：２．０重量％であった。
ついで、抗菌消臭剤(2)について、安定性、耐光性、抗菌性能および消臭性能を評価し、結果を表に示す。
[Example 2]
Preparation of antibacterial deodorant (2) dispersion A silica / alumina composite oxide particle (1) dispersion was prepared in the same manner as in Example 1.
Next, 103.7 g of an aqueous silver nitrate solution having a concentration of 1.0% by weight was added and the mixture was stirred at 90 ° C. for 1 hour for ion exchange. At this time, the pH was 9.5.
Subsequently, it was washed with an ultrafiltration membrane and concentrated to prepare an antibacterial deodorant (2) dispersion having a solid concentration of 1.5% by weight.
The average particle diameter of the obtained antibacterial deodorant (2) was 15 nm, the composition was SiO 2 : 61.3% by weight, Al 2 O 3 : 22.7% by weight, Na 2 O: 14.0% by weight, Ag 2 O: 2.0% by weight.
Next, the antibacterial deodorant (2) was evaluated for stability, light resistance, antibacterial performance and deodorization performance, and the results are shown in the table.
［実施例３］
抗菌消臭剤(3)分散液の調製
実施例１と同様にしてシリカ・アルミナ複合酸化物粒子(1)分散液を調製した。
ついで、室温にて、陽イオン交換樹脂（三菱化学社製ダイヤイオン、ＳＫ１ＢＨ）をｐＨが５．０になるまで添加、その後、５％アンモニアにて、ｐＨ９．０まで添加、ついで、濃度１．０重量％の硝酸銀水溶液３１５ｇを添加し、９０℃で１時間撹拌してイオン交換を行った。この時、ｐＨは８．８であった。
ついで、限外濾過膜で洗浄し、濃縮して固形分濃度１．５重量％の抗菌消臭剤(3)分散液を調製した。
得られた抗菌消臭剤(3)の平均粒子径は１５ｎｍ、組成はＳｉＯ2：６７．２重量％、Ａｌ2Ｏ3：２１．６重量％、Ｎａ2Ｏ：５．２重量％、Ａｇ2Ｏ：６．０重量％であった。
ついで、抗菌消臭剤(3)について、安定性、耐光性、抗菌性能および消臭性能を評価し、結果を表に示す。
[Example 3]
Preparation of antibacterial deodorant (3) dispersion A silica / alumina composite oxide particle (1) dispersion was prepared in the same manner as in Example 1.
Next, at room temperature, a cation exchange resin (Diaion, SK1BH, manufactured by Mitsubishi Chemical Corporation) was added until the pH reached 5.0, and then added to pH 9.0 with 5% ammonia, and then a concentration of 1. Ion exchange was performed by adding 315 g of a 0 wt% aqueous silver nitrate solution and stirring at 90 ° C. for 1 hour. At this time, the pH was 8.8.
Subsequently, it was washed with an ultrafiltration membrane and concentrated to prepare an antibacterial deodorant (3) dispersion having a solid concentration of 1.5% by weight.
The average particle diameter of the obtained antibacterial deodorant (3) was 15 nm, the composition was SiO 2 : 67.2% by weight, Al 2 O 3 : 21.6% by weight, Na 2 O: 5.2% by weight, Ag 2 O: 6.0% by weight.
The antibacterial deodorant (3) was then evaluated for stability, light resistance, antibacterial performance and deodorant performance, and the results are shown in the table.
［実施例４］
抗菌消臭剤(4)分散液の調製
実施例１において、濃度１．０重量％の硝酸銀水溶液１０３．７ｇおよび濃度１．０重量％の硝酸亜鉛水溶液４９６ｇを添加した以外は同様にして、固形分濃度１．５重量％の抗菌消臭剤(4)分散液を調製した。
得られた抗菌消臭剤(4)の平均粒子径は１５ｎｍ、組成はＳｉＯ2：６５．３重量％、Ａｌ2Ｏ3：２１．２重量％、Ｎａ2Ｏ：７．５重量％、Ａｇ2Ｏ：２．０重量％、ＺｎＯ：４．０重量％であった。
ついで、抗菌消臭剤(4)について、安定性、耐光性、抗菌性能および消臭性能を評価し、結果を表に示す。
[Example 4]
Preparation of Antibacterial Deodorant (4) Dispersion In Example 1, a solid solution was prepared in the same manner except that 103.7 g of a silver nitrate aqueous solution having a concentration of 1.0% by weight and 496 g of a zinc nitrate aqueous solution having a concentration of 1.0% by weight were added. An antibacterial deodorant (4) dispersion having a partial concentration of 1.5% by weight was prepared.
The average particle diameter of the obtained antibacterial deodorant (4) was 15 nm, the composition was SiO 2 : 65.3% by weight, Al 2 O 3 : 21.2% by weight, Na 2 O: 7.5% by weight, Ag 2 O: 2.0% by weight, ZnO: 4.0% by weight.
Next, the antibacterial deodorant (4) was evaluated for stability, light resistance, antibacterial performance and deodorization performance, and the results are shown in the table.
［実施例５］
抗菌消臭剤(5)分散液の調製
実施例１において、濃度１．０重量％の硝酸銀水溶液１０３．７ｇおよび濃度１．０重量％の硝酸銅水溶液４１４ｇを添加した以外は同様にして、固形分濃度１．５重量％の抗菌消臭剤(5)分散液を調製した。
得られた抗菌消臭剤(5)の平均粒子径は１５ｎｍ、組成はＳｉＯ2：６４．６重量％、Ａｌ2Ｏ3：２１．８重量％、Ｎａ2Ｏ：７．６重量％、Ａｇ2Ｏ：２．０重量％、ＣｕＯ：４．０重量％であった。
ついで、抗菌消臭剤(5)について、安定性、耐光性、抗菌性能および消臭性能を評価し、結果を表に示す。
[Example 5]
Preparation of Antibacterial Deodorant (5) Dispersion In Example 1, a solid solution was prepared in the same manner except that 103.7 g of an aqueous silver nitrate solution having a concentration of 1.0 wt% and 414 g of an aqueous copper nitrate solution having a concentration of 1.0 wt% were added. An antibacterial deodorant (5) dispersion having a partial concentration of 1.5% by weight was prepared.
The average particle diameter of the obtained antibacterial deodorant (5) was 15 nm, the composition was SiO 2 : 64.6 wt%, Al 2 O 3 : 21.8 wt%, Na 2 O: 7.6 wt%, Ag 2 O: 2.0% by weight, CuO: 4.0% by weight.
The antibacterial deodorant (5) was then evaluated for stability, light resistance, antibacterial performance and deodorant performance, and the results are shown in the table.
［実施例６］
抗菌消臭剤(6)分散液の調製
ＳｉＯ2濃度２０重量％のコロイド溶液（コロイド粒子平均粒子径：５ｎｍ）２０ｇと純水３８０ｇの混合物を８０℃に加温した。この反応母液のｐＨは１０．７であり、同母液にＳｉＯ2として濃度１．３重量％の珪酸ソーダ水溶液１５００ｇとＡｌ2Ｏ3として濃度０．７重量％のアルミン酸ソーダ水溶液１５００ｇとを同時に添加し、添加終了後、９０℃で1時間熟成した。この時の分散液のｐＨは１２．１であった。
ついで、限外濾過膜で洗浄し、濃縮して固形分濃度２２．２重量％、ｐＨ１０．５のシリカ・アルミナ複合酸化物粒子(2)分散液を調製した。
シリカ・アルミナ複合酸化物粒子(2)の平均粒子径は１５ｎｍ、組成はＳｉＯ2：５２．３重量％、Ａｌ2Ｏ3：３５．７重量％、Ｎａ2Ｏ：１２．０重量％であった。
[Example 6]
Preparation of antibacterial deodorant (6) dispersion A mixture of 20 g of a colloidal solution (colloid particle average particle size: 5 nm) having a SiO 2 concentration of 20% by weight and 380 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor is 10.7, and 1500 g of a sodium silicate aqueous solution with a concentration of 1.3 wt% as SiO 2 and 1500 g of a sodium aluminate aqueous solution with a concentration of 0.7 wt% as Al 2 O 3 are simultaneously added to the mother liquor. After the addition, the mixture was aged at 90 ° C. for 1 hour. The pH of the dispersion at this time was 12.1.
Subsequently, it was washed with an ultrafiltration membrane and concentrated to prepare a dispersion of silica / alumina composite oxide particles (2) having a solid content of 22.2% by weight and a pH of 10.5.
The average particle diameter of the silica / alumina composite oxide particles (2) was 15 nm, the composition was SiO 2 : 52.3% by weight, Al 2 O 3 : 35.7% by weight, and Na 2 O: 12.0% by weight. It was.
室温にて、陽イオン交換樹脂（三菱化学社製ダイヤイオン、ＳＫ１ＢＨ）をｐＨが７．０になるまで添加、その後、５％アンモニアにて、ｐＨ９．０まで添加、ついで、濃度１．０重量％の硝酸銀水溶液２０７．４ｇを添加し、９０℃で１時間撹拌してイオン交換を行った。この時、ｐＨは８．７であった。
ついで、限外濾過膜で洗浄し、濃縮して固形分濃度１．５重量％の抗菌消臭剤(6)分散液を調製した。
得られた抗菌消臭剤(6)の平均粒子径は１５ｎｍ、組成はＳｉＯ2：５２．０重量％、Ａｌ2Ｏ3：３５．５重量％、Ｎａ2Ｏ：８．５重量％、Ａｇ2Ｏ：４．０重量％であった。
ついで、抗菌消臭剤(6)について、安定性、耐光性、抗菌性能および消臭性能を評価し、結果を表に示す。
At room temperature, a cation exchange resin (Mitsubishi Chemical Corporation Diaion, SK1BH) was added until the pH reached 7.0, then 5% ammonia was added until pH 9.0, and then a concentration of 1.0 wt. A 20% silver nitrate aqueous solution was added, and the mixture was stirred at 90 ° C. for 1 hour for ion exchange. At this time, the pH was 8.7.
Subsequently, it was washed with an ultrafiltration membrane and concentrated to prepare an antibacterial deodorant (6) dispersion having a solid content of 1.5% by weight.
The obtained antibacterial deodorant (6) has an average particle size of 15 nm, a composition of SiO 2 : 52.0 wt%, Al 2 O 3 : 35.5 wt%, Na 2 O: 8.5 wt%, Ag 2 O: 4.0% by weight.
Next, the antibacterial deodorant (6) was evaluated for stability, light resistance, antibacterial performance and deodorization performance, and the results are shown in the table.
［実施例７］
抗菌消臭剤(7)分散液の調製
ＳｉＯ2濃度２０重量％のコロイド溶液（コロイド粒子平均粒子径：５ｎｍ）２０ｇと純水３８０ｇの混合物を８０℃に加温した。この反応母液のｐＨは１０．７であり、同母液にＳｉＯ2として濃度１．５重量％の珪酸ソーダ水溶液１５００ｇとＡｌ2Ｏ3として濃度０．２５重量％のアルミン酸ソーダ水溶液１５００ｇと、ＺｒＯ2として濃度０．２５重量％の炭酸ジルコニウム水溶液１５００ｇとを同時に添加し、添加終了後、９０℃で1時間熟成した。この時の分散液のｐＨは１２．１であった。
ついで、限外濾過膜で洗浄し、濃縮して固形分濃度２２．２重量％、ｐＨ１０．５のシリカ・アルミナ・ジルコニア複合酸化物粒子(3)分散液を調製した。
シリカ・アルミナ・ジルコニア複合酸化物粒子(3)の平均粒子径は１６ｎｍ、組成はＳｉＯ2：６０．５重量％、Ａｌ2Ｏ3：２３．１重量％、ＺｒＯ2：６．４重量％、Ｎａ2Ｏ：１０．０重量％であった。
[Example 7]
Preparation of Antibacterial Deodorant (7) Dispersion A mixture of 20 g of a colloidal solution (colloid particle average particle size: 5 nm) having a SiO 2 concentration of 20% by weight and 380 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.7. In the mother liquor, 1500 g of a 1.5 wt% sodium silicate aqueous solution as SiO 2 , 1500 g of a 0.25 wt% sodium aluminate aqueous solution as Al 2 O 3 , ZrO 2 , 1500 g of an aqueous zirconium carbonate solution having a concentration of 0.25 wt% was added at the same time, and after the addition was completed, the mixture was aged at 90 ° C. for 1 hour. The pH of the dispersion at this time was 12.1.
Subsequently, it was washed with an ultrafiltration membrane and concentrated to prepare a dispersion of silica / alumina / zirconia composite oxide particles (3) having a solid content of 22.2% by weight and a pH of 10.5.
The average particle size of the silica / alumina / zirconia composite oxide particles (3) is 16 nm, the composition is SiO 2 : 60.5 wt%, Al 2 O 3 : 23.1 wt%, ZrO 2 : 6.4 wt%, Na 2 O: 10.0% by weight.
室温にて、陽イオン交換樹脂（三菱化学社製ダイヤイオン、ＳＫ１ＢＨ）をｐＨが７．０になるまで添加、その後、５％アンモニアにて、ｐＨ９．０まで添加、ついで、濃度１．０重量％の硝酸銀水溶液２０７．４ｇを添加し、９０℃で１時間撹拌してイオン交換を行った。この時、ｐＨは８．８であった。
ついで、限外濾過膜で洗浄し、濃縮して固形分濃度１．５重量％の抗菌消臭剤(7)分散液を調製した。
得られた抗菌消臭剤(7)の平均粒子径は１６ｎｍ、組成はＳｉＯ2：６０．０重量％、Ａｌ2Ｏ3：２２．１重量％、ＺｒＯ2：６．４重量％、Ｎａ2Ｏ：７．５重量％、Ａｇ2Ｏ：４．０重量％であった。
At room temperature, a cation exchange resin (Mitsubishi Chemical Corporation Diaion, SK1BH) was added until the pH reached 7.0, then 5% ammonia was added until pH 9.0, and then a concentration of 1.0 wt. A 20% silver nitrate aqueous solution was added, and the mixture was stirred at 90 ° C. for 1 hour for ion exchange. At this time, the pH was 8.8.
Subsequently, it was washed with an ultrafiltration membrane and concentrated to prepare an antibacterial deodorant (7) dispersion having a solid concentration of 1.5% by weight.
The average particle diameter of the obtained antibacterial deodorant (7) was 16 nm, the composition was SiO 2 : 60.0 wt%, Al 2 O 3 : 22.1 wt%, ZrO 2 : 6.4 wt%, Na 2 O: 7.5 wt%, Ag 2 O: 4.0 was wt%.
［比較例１］
抗菌消臭剤(R1)分散液の調製
実施例１と同様にして固形分濃度２２．２重量％、ｐＨ１０．６のシリカ・アルミナ複合酸化物粒子(1)分散液を調製した。
ついで、室温にて、陽イオン交換樹脂（三菱化学社製ダイヤイオン、ＳＫ１ＢＨ）をｐＨが４．５になるまで添加、その後、５％アンモニアにて、ｐＨ９．０まで添加した。
別途、酸化銀（試薬特級）０．８６ｇを約８４．８７ｇの水に懸濁し、次いで１５重量％のアンモニア水を酸化銀が溶解するまで加えて、銀アンミン錯塩水溶液を調製した。
この銀アンミン錯塩水溶液をシリカ・アルミナ複合酸化物粒子(1)に添加して十分に撹拌した後、限外濾過膜で洗浄し、濃縮して、固形分濃度１．５重量％の抗菌消臭剤(R1)分散液を調製した。
得られた抗菌消臭剤(R1)の平均粒子径は１５ｎｍ、組成はＳｉＯ2：７０．７重量％、Ａｌ2Ｏ3：２４．７重量％、Ｎａ2Ｏ：０．６重量％、Ａｇ2Ｏ：４．０重量％であった。
[Comparative Example 1]
Preparation of antibacterial deodorant (R1) dispersion A silica / alumina composite oxide particle (1) dispersion having a solid content of 22.2% by weight and a pH of 10.6 was prepared in the same manner as in Example 1.
Next, at room temperature, a cation exchange resin (Diaion, SK1BH, manufactured by Mitsubishi Chemical Corporation) was added until the pH reached 4.5, and then 5% ammonia was added until pH 9.0.
Separately, 0.86 g of silver oxide (special grade reagent) was suspended in about 84.87 g of water, and then 15% by weight of ammonia water was added until the silver oxide was dissolved to prepare an aqueous silver ammine complex salt solution.
This silver ammine complex salt aqueous solution is added to the silica-alumina composite oxide particles (1) and stirred sufficiently, then washed with an ultrafiltration membrane and concentrated to an antibacterial deodorant having a solid content of 1.5% by weight. An agent (R1) dispersion was prepared.
The average particle diameter of the obtained antibacterial deodorant (R1) was 15 nm, the composition was SiO 2 : 70.7 wt%, Al 2 O 3 : 24.7 wt%, Na 2 O: 0.6 wt%, Ag 2 O: 4.0% by weight.
［比較例２］
抗菌消臭剤(R2)分散液の調製
比較例１において、陽イオン交換樹脂（三菱化学社製ダイヤイオン、ＳＫ１ＢＨ）をｐＨが４．０になるまで添加、次いで１５％アンモニアでｐＨを９．０に調整後、濃度１．０重量％の硝酸銀水溶液２０７．４ｇを添加し、９０℃で１時間撹拌してイオン交換を行った。この時、ｐＨは８．５であった。次いで、このコロイド溶液を限外濾過膜で洗浄し、濃縮して、固形分濃度１．５重量％の抗菌消臭剤(R2)分散液を調製した。
得られた抗菌消臭剤(R2)の平均粒子径は１５ｎｍ、組成はＳｉＯ2：７０．５重量％、Ａｌ2Ｏ3：２５．３重量％、Ｎａ2Ｏ：０．１重量％、Ａｇ2Ｏ：４．０重量％であった。
[Comparative Example 2]
Preparation of antibacterial deodorant (R2) dispersion In Comparative Example 1, a cation exchange resin (Diaion, SK1BH, manufactured by Mitsubishi Chemical Corporation) was added until the pH reached 4.0, and then the pH was adjusted to 9. with 15% ammonia. After adjusting to 0, 207.4 g of an aqueous silver nitrate solution having a concentration of 1.0% by weight was added, and the mixture was stirred at 90 ° C. for 1 hour for ion exchange. At this time, the pH was 8.5. Next, this colloidal solution was washed with an ultrafiltration membrane and concentrated to prepare an antibacterial deodorant (R2) dispersion having a solid content concentration of 1.5% by weight.
The obtained antibacterial deodorant (R2) has an average particle size of 15 nm, a composition of SiO 2 : 70.5% by weight, Al 2 O 3 : 25.3% by weight, Na 2 O: 0.1% by weight, Ag 2 O: 4.0% by weight.
［比較例３］
抗菌消臭剤(R3)分散液の調製
比較例１において、シリカ・アルミナ複合酸化物粒子(1)の陽イオン樹脂をｐＨが４．５になるまで添加、次いで１５％アンモニアでｐＨを９．０に調整後、濃度１．０重量％の硝酸銀水溶液１０３．７ｇを添加し、９０℃で１時間撹拌してイオン交換を行った。この時、ｐＨは８．７であった。次いで、このコロイド溶液を限外濾過膜で洗浄し、濃縮して、１．５重量％の抗菌消臭剤(R3)分散液を調製した。
得られた抗菌消臭剤(R3)の平均粒子径は１５ｎｍ、組成はＳｉＯ2：７１．７重量％、Ａｌ2Ｏ3：２５．６重量％、Ｎａ2Ｏ：０．７重量％、Ａｇ2Ｏ：２．０重量％であった。
[Comparative Example 3]
Preparation of antibacterial deodorant (R3) dispersion In Comparative Example 1, a cation resin of silica / alumina composite oxide particles (1) was added until the pH reached 4.5, and then the pH was adjusted to 9. with 15% ammonia. After adjusting to 0, 103.7 g of a silver nitrate aqueous solution having a concentration of 1.0% by weight was added, and the mixture was stirred at 90 ° C. for 1 hour for ion exchange. At this time, the pH was 8.7. The colloidal solution was then washed with an ultrafiltration membrane and concentrated to prepare a 1.5 wt% antibacterial deodorant (R3) dispersion.
The obtained antibacterial deodorant (R3) has an average particle size of 15 nm, a composition of SiO 2 : 71.7% by weight, Al 2 O 3 : 25.6% by weight, Na 2 O: 0.7% by weight, Ag 2 O: 2.0% by weight.
Claims (13)
（ａ）珪酸アルカリ水溶液と珪素以外の元素の化合物水溶液とを、ｐＨを９〜１３に維持しながら、得られるシリカ系複合酸化物粒子中のシリカ以外の元素の酸化物（ＭＯｘ）含有量が、ＳｉＯ2・ＭＯｘ中に１０〜５０重量％の範囲となるように混合する工程
（ｂ）工程（ａ）で得られたシリカ系複合酸化物粒子分散液を洗浄する工程
（ｃ）前記シリカ系複合酸化物粒子分散液に銀化合物を添加して銀イオン交換する工程 The manufacturing method of the antibacterial deodorant characterized by including the following process (a)-(c).
(A) Content of oxide (MOx) of elements other than silica in the obtained silica-based composite oxide particles while maintaining an aqueous solution of alkali silicate and a compound aqueous solution of elements other than silicon at a pH of 9 to 13. Step of mixing in SiO 2 · MOx so as to be in the range of 10 to 50% by weight (b) Step of washing the silica-based composite oxide particle dispersion obtained in step (a) (c) The silica-based Step of silver ion exchange by adding silver compound to composite oxide particle dispersion
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| CN114797829A (en) * | 2022-03-30 | 2022-07-29 | 郑州轻工业大学 | Visible light catalytic nano antibacterial material and manufacturing method thereof |
| CN114797829B (en) * | 2022-03-30 | 2023-06-16 | 郑州轻工业大学 | Visible light catalytic nano antibacterial material and manufacturing method thereof |
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