JP6260077B2 - Antibacterial coating agent - Google Patents
Antibacterial coating agent Download PDFInfo
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- JP6260077B2 JP6260077B2 JP2012217640A JP2012217640A JP6260077B2 JP 6260077 B2 JP6260077 B2 JP 6260077B2 JP 2012217640 A JP2012217640 A JP 2012217640A JP 2012217640 A JP2012217640 A JP 2012217640A JP 6260077 B2 JP6260077 B2 JP 6260077B2
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- Prior art keywords
- cellulose
- fine
- antibacterial
- fine cellulose
- coating agent
- 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.)
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- 230000000844 anti-bacterial effect Effects 0.000 title claims description 43
- 239000011248 coating agent Substances 0.000 title claims description 25
- 229920002678 cellulose Polymers 0.000 claims description 88
- 239000001913 cellulose Substances 0.000 claims description 88
- 239000010419 fine particle Substances 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 229910052709 silver Inorganic materials 0.000 claims description 25
- 239000004332 silver Substances 0.000 claims description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 239000000835 fiber Substances 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 230000000845 anti-microbial effect Effects 0.000 claims description 5
- 238000002834 transmittance Methods 0.000 claims description 4
- 229910001111 Fine metal Inorganic materials 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 description 77
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000006185 dispersion Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 16
- 229920002201 Oxidized cellulose Polymers 0.000 description 14
- 229940107304 oxidized cellulose Drugs 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 239000002131 composite material Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 9
- -1 silver ions Chemical class 0.000 description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical group CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- SFXHWRCRQNGVLJ-UHFFFAOYSA-N 4-methoxy-TEMPO Chemical group COC1CC(C)(C)N([O])C(C)(C)C1 SFXHWRCRQNGVLJ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920002749 Bacterial cellulose Polymers 0.000 description 1
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- 241001478802 Valonia Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000402 conductometric titration Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000002542 deteriorative effect 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
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052811 halogen oxide Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000004670 tapping atomic force microscopy Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001258 titanium gold Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paints Or Removers (AREA)
- Powder Metallurgy (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Description
本発明は、抗菌性微細セルロース、その製造方法ならびに抗菌性コーティング剤に関する。 The present invention relates to antibacterial fine cellulose, a method for producing the same, and an antibacterial coating agent.
環境配慮型として注目されている機能性材料にセルロースがある。セルロースは植物の細胞壁や微生物の体外分泌物、ホヤの外套膜などに含まれており、地球上でもっとも多く存在する多糖類である。生分解性を有し、結晶性が高く、安定性や安全性に優れており、様々な分野へ応用展開が期待されている。 Cellulose is a functional material that is attracting attention as an environmentally friendly type. Cellulose is contained in plant cell walls, microbial exocrine secretions, and sea squirt mantles, and is the most abundant polysaccharide on earth. It has biodegradability, high crystallinity, excellent stability and safety, and is expected to be applied in various fields.
また、セルロースフィブリルを２，２，６，６−ｔｅｔｒａｍｅｔｈｙｌｐｉｐｅｒｉｄｉｎｅ １−ｏｘｙｌ（ＴＥＭＰＯ）触媒系によって酸化反応を行うことで得られる酸化セルロースフィブリルは、結晶表面のセルロースの持つ３つの水酸基のうち、Ｃ６位のアルコール性一級炭素のみ選択的に酸化することができ、アルデヒド基を経てカルボキシル基まで変換することができ、さらに水系、常温、常圧などの温和な条件下で反応を行うことが可能であるため、非常に注目されている。 The oxidized cellulose fibril obtained by oxidizing cellulose fibrils with a 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) catalyst system is C6-position among the three hydroxyl groups of cellulose on the crystal surface. It is possible to selectively oxidize only alcoholic primary carbon, and to convert it to a carboxyl group via an aldehyde group, and it is possible to carry out the reaction under mild conditions such as aqueous, normal temperature, and normal pressure. Because of that, it has attracted a lot of attention.
また、得られた酸化セルロースフィブリルは、水に懸濁させ軽微な機械的処理を加えるだけで、容易に微細セルロースを水分散させることができることが知られている。微細セルロースは高い結晶性と低い線膨張率により高強度で、表面に高密度にカルボキシル基を有していることから多くの分野への応用が期待されている。 In addition, it is known that the obtained oxidized cellulose fibrils can be easily dispersed in water by simply suspending them in water and applying a slight mechanical treatment. Fine cellulose has high strength due to its high crystallinity and low linear expansion coefficient, and has a high density of carboxyl groups on its surface, so it is expected to be applied in many fields.
一方、銀や亜鉛、銅等の金属は抗菌・消臭作用があることを古くから経験的に知られており、近年それらのイオンやナノ粒子の抗菌・消臭効果を利用した多くの製品が販売されている。銀等の金属は必ずしも強力な抗菌性を示すわけではないが、人体に対する害もなく広範囲な細菌およびカビ等への持続的抗菌および防カビ性を有している。抗菌剤として銀を利用し、一般的に流通している製品の製法としては、ゼオライトやシリカゲル等の吸着剤に銀イオンを担持させる方法が広く知られている。 On the other hand, metals such as silver, zinc, and copper have long been empirically known to have antibacterial and deodorizing effects, and in recent years many products that utilize the antibacterial and deodorant effects of these ions and nanoparticles have been developed. Sold. Metals such as silver do not necessarily exhibit strong antibacterial properties, but they have sustained antibacterial and antifungal properties against a wide range of bacteria and fungi without harm to the human body. As a method for producing a generally distributed product using silver as an antibacterial agent, a method of supporting silver ions on an adsorbent such as zeolite or silica gel is widely known.
抗菌剤が用いられる分野としては、繊維、洗濯機、塗料、ワニス、流しや衛生セラミックス、消毒剤、防臭剤、台所用品、化粧品、身体手入れ用品、乳幼児製品などから傷や火傷の処置、医療器具消毒等様々な応用範囲に拡大している。 Fields where antibacterial agents are used include textiles, washing machines, paints, varnishes, sinks and sanitary ceramics, disinfectants, deodorants, kitchenware, cosmetics, body care products, infant products, etc. It has been expanded to various applications such as disinfection.
例えば、特許文献１では、微細繊維状セルロース懸濁液と酸化アルミニウム、二酸化珪素、二酸化チタン、金などの無機化合物微粒子からなるコロイドを混合し、多孔性の基材の上でろ過により脱水し、乾燥させることで微細繊維状セルロースと無機化合物微粒子を複合化しているが、微細繊維状セルロースと微粒子を単純に混合し、乾燥させただけでは、微細繊維状セルロースおよび微粒子間の密着が悪く、脱離が生じたり、均一に数ｎｍオーダーの微粒子が分散しない等の問題が生じる恐れがある。 For example, in Patent Document 1, a fine fibrous cellulose suspension and a colloid composed of inorganic compound fine particles such as aluminum oxide, silicon dioxide, titanium dioxide, and gold are mixed and dehydrated by filtration on a porous substrate. Although fine fibrous cellulose and inorganic compound fine particles are combined by drying, the fine fibrous cellulose and fine particles are simply mixed and dried, resulting in poor adhesion between the fine fibrous cellulose and fine particles. There is a risk that separation will occur, or fine particles of the order of several nanometers may not be uniformly dispersed.
これまでの金属微粒子担持抗菌剤では、金属微粒子が凝集してしまい均一に分散できない、効果を発現させるために必要以上の金属微粒子を添加する必要があるなど問題があった。 Conventional anti-bacterial agents supporting metal fine particles have problems that the metal fine particles aggregate and cannot be uniformly dispersed, and that it is necessary to add more metal fine particles than necessary to achieve the effect.
本発明は、上記事情を鑑みてなされたものであり、低添加量で金属微粒子を高密度に微細セルロース上に担持させた材料、その製造方法、抗菌性コーティング剤を提供することを課題とする。 The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a material in which metal fine particles are supported on fine cellulose at high density with a low addition amount, a production method thereof, and an antibacterial coating agent. .
請求項１に記載の発明は、下記の抗菌性微細セルロースを用いたことを特徴とする抗菌性コーティング剤である。
前記抗菌性微細セルロース：木材を由来とする微細セルロースの表面上に、銀またはその化合物からなる金属微粒子が担持されてなる抗菌性微細セルロースであって、前記微細セルロースは、少なくともその結晶表面にカルボキシル基を有し、前記金属微粒子は、前記微細セルロースの結晶表面のカルボキシル基上に析出したものであることを特徴とする抗菌性微細セルロース。
請求項２に記載の発明は、該抗菌性コーティング剤の６００ｎｍにおける透過率が８０％以上であることを特徴とする請求項１に記載の抗菌性コーティング剤である。
請求項３に記載の発明は、該微細セルロースのカルボキシル基量が０．１ｍｍｏｌ／ｇ以上３．０ｍｍｏｌ／ｇ以下であることを特徴とする請求項１または２に記載の抗菌性コーティング剤である。
請求項４に記載の発明は、該微細セルロースは数平均繊維幅が１ｎｍ以上５０ｎｍ以下であり、且つ数平均繊維長が数平均繊維幅の１００倍以上１００００倍以下であることを特徴とする請求項１〜３のいずれかに記載の抗菌性コーティング剤である。
請求項５に記載の発明は、該微細セルロースは結晶化度が５０％以上であり、かつ、セルロースＩ型の結晶構造を有することを特徴とする請求項１〜４のいずれかに記載の抗菌性コーティング剤である。
請求項６に記載の発明は、該金属微粒子の粒子径が１ｎｍ以上２０ｎｍ以下であることを特徴とする請求項１〜５のいずれかに記載の抗菌性コーティング剤である。
The invention described in claim 1 is an antibacterial coating agent characterized by using the following antibacterial fine cellulose.
Antibacterial fine cellulose: antibacterial fine cellulose obtained by carrying fine metal particles made of silver or a compound thereof on the surface of fine cellulose derived from wood, and the fine cellulose is carboxylated on at least the crystal surface thereof. An antibacterial fine cellulose having a group, wherein the metal fine particles are precipitated on a carboxyl group on a crystal surface of the fine cellulose.
The invention according to claim 2 is the antibacterial coating agent according to claim 1 , wherein the transmittance of the antibacterial coating agent at 600 nm is 80% or more.
The invention according to claim 3 is the antibacterial coating agent according to claim 1 or 2 , wherein the amount of carboxyl groups of the fine cellulose is 0.1 mmol / g or more and 3.0 mmol / g or less. .
The invention according to claim 4 is characterized in that the fine cellulose has a number average fiber width of 1 nm to 50 nm and a number average fiber length of 100 times to 10,000 times the number average fiber width. Item 4. The antibacterial coating agent according to any one of Items 1 to 3 .
Invention of claim 5, the fine cellulose is a crystallinity of 50% or more, and antimicrobial according to claim 1, characterized by having a crystalline structure of cellulose I type Coating agent .
The invention according to claim 6 is the antibacterial coating agent according to any one of claims 1 to 5 , wherein the metal fine particles have a particle diameter of 1 nm or more and 20 nm or less.
本発明の抗菌性微細セルロースは、低添加量で高密度に金属微粒子を担持させ得る材料として用いることができる。
また本発明の製造方法によれば、微細セルロースと金属微粒子を別々で混合する工程なく、静電的な相互作用を利用し、微細セルロースのカルボキシル基上に選択的に金属微粒子を還元析出することができるため、金属微粒子の凝集がなく、かつ高密度に微細セルロース上に金属微粒子を担持することが可能になる。分散性よく金属微粒子を微細セルロース上に担持させることができることから、透明性が高く、さらには抗菌性を低下させることなく金属微粒子の量を減少させることが可能になり、低コスト化を実現することが可能になる。
さらに溶媒中で金属微粒子を微細セルロース上に還元析出可能であるため、そのままコーティング剤として用いることも可能である。また、分散液はチキソトロピー性を有することからスプレーコーティングも可能であり、立体的な構造体にもコーティングすることも可能である。
本発明の抗菌性コーティング剤を例えば衣類にコートした場合、優れた抗菌性や消臭性を示し、クリーニング等によって適度に衣類から脱離をすることから硬くこわばることもない衣類を提供することも可能になる。
The antibacterial fine cellulose of the present invention can be used as a material capable of supporting metal fine particles at a high density with a low addition amount.
Further, according to the production method of the present invention, the metal fine particles are selectively reduced and deposited on the carboxyl groups of the fine cellulose by using electrostatic interaction without separately mixing the fine cellulose and the metal fine particles. Therefore, the metal fine particles are not aggregated, and the metal fine particles can be supported on the fine cellulose at a high density. Since the metal fine particles can be supported on the fine cellulose with good dispersibility, the transparency is high, and further, the amount of the metal fine particles can be reduced without deteriorating the antibacterial property, thereby realizing cost reduction. It becomes possible.
Furthermore, since metal fine particles can be reduced and deposited on fine cellulose in a solvent, it can be used as it is as a coating agent. Further, since the dispersion has thixotropic properties, it can be spray-coated and can also be coated on a three-dimensional structure.
For example, when the antibacterial coating agent of the present invention is coated on clothing, it is possible to provide a clothing that exhibits excellent antibacterial properties and deodorization properties, and that does not stiffen because it is appropriately detached from the clothing by cleaning or the like. It becomes possible.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
（結晶表面にカルボキシル基を有する微細セルロースとその製造方法）
本発明の微細セルロースは結晶表面にカルボキシル基を有し、カルボキシル基量が０．１ｍｍｏｌ／ｇ以上３．０ｍｍｏｌ／ｇ以下が好ましい。０．５ｍｍｏｌ／ｇ以上２．０ｍｍｏｌ／ｇ以下がより好ましい。カルボキシル基量が０．１ｍｍｏｌ／ｇ未満であると、静電的な反発が起こらずに微細セルロースを均一に分散させることは難しい。また、３．０ｍｍｏｌ／ｇを超えると、微細セルロースの結晶性が低下してしまうおそれがある。また、本発明の微細セルロースは数平均繊維幅が１ｎｍ以上５０ｎｍ以下であり、且つ数平均繊維長が数平均繊維幅の１００倍以上１００００倍以下であることが好ましい。数平均繊維幅が１ｎｍ未満ではセルロースがナノファイバー状態にならず、５０ｎｍを超えると本発明の抗菌性微細セルロースにおいて十分な抗菌機能が得られないおそれがある。また、数平均繊維長が数平均繊維幅の１００倍未満の場合、微細セルロース上に金属微粒子を析出した際に粘度が低いため、沈殿してしまうおそれがあり、反対に１００００倍を超えると分散液の粘度が高くなり、分散性に問題が生じる可能性がある。
なお、上記のカルボキシル基量、微細セルロースのサイズは、下記で説明するセルロースを酸化する工程、微細化し分散液化する工程における諸条件を適宜調節することにより、所望の値に設定可能である。
また、微細セルロースは結晶化度が５０％以上であり、かつ、セルロースＩ型の結晶構造を有することが好ましい。結晶化度が５０％以上であることにより、内部に結晶構造を維持したまま微細な構造をとることができるため好ましく、セルロースＩ型の結晶構造を有することにより、結晶性の高い天然物由来のセルロースを用いることができるため好ましい。
(Fine cellulose having a carboxyl group on the crystal surface and production method thereof)
The fine cellulose of the present invention has a carboxyl group on the crystal surface, and the amount of carboxyl group is preferably 0.1 mmol / g or more and 3.0 mmol / g or less. 0.5 mmol / g or more and 2.0 mmol / g or less is more preferable. When the carboxyl group amount is less than 0.1 mmol / g, it is difficult to uniformly disperse the fine cellulose without causing electrostatic repulsion. Moreover, when it exceeds 3.0 mmol / g, there exists a possibility that the crystallinity of a fine cellulose may fall. The fine cellulose of the present invention preferably has a number average fiber width of 1 nm to 50 nm and a number average fiber length of 100 times to 10,000 times the number average fiber width. If the number average fiber width is less than 1 nm, the cellulose will not be in a nanofiber state, and if it exceeds 50 nm, sufficient antibacterial function may not be obtained in the antibacterial fine cellulose of the present invention. In addition, when the number average fiber length is less than 100 times the number average fiber width, the viscosity is low when the metal fine particles are deposited on the fine cellulose, which may cause precipitation. The viscosity of the liquid is increased, which may cause a problem in dispersibility.
The amount of the carboxyl group and the size of the fine cellulose can be set to desired values by appropriately adjusting various conditions in the step of oxidizing cellulose and the step of refining and dispersing the cellulose described below.
The fine cellulose preferably has a crystallinity of 50% or more and has a cellulose I type crystal structure. When the crystallinity is 50% or more, it is preferable because a fine structure can be obtained while maintaining the crystal structure inside, and by having a cellulose I type crystal structure, it is derived from a highly crystalline natural product. Since cellulose can be used, it is preferable.
本発明の結晶表面にカルボキシル基を有する微細セルロースを製造する方法について説明する。 A method for producing fine cellulose having a carboxyl group on the crystal surface of the present invention will be described.
本発明で用いられる結晶表面にカルボキシル基を有する微細セルロースは、セルロースを酸化する工程と微細化し分散液化する工程により得られる。 The fine cellulose having a carboxyl group on the crystal surface used in the present invention is obtained by a step of oxidizing cellulose and a step of refining and forming a dispersion liquid.
（セルロースを酸化する工程）
酸化されるセルロースの原料としては、木材パルプ、非木材パルプ、古紙パルプ、コットン、バクテリアセルロース、バロニアセルロース、ホヤセルロース、微結晶セルロース等を用いることができる。
(Step of oxidizing cellulose)
As raw materials for cellulose to be oxidized, wood pulp, non-wood pulp, waste paper pulp, cotton, bacterial cellulose, valonia cellulose, squirt cellulose, microcrystalline cellulose, and the like can be used.
セルロースを酸化する方法としては、水系の比較的温和な条件で、可能な限り構造を保ちながら、アルコール性一級炭素の酸化に対する選択性が高い、Ｎ−オキシル化合物の存在下、共酸化剤を用いた手法が望ましい。前記のＮ−オキシル化合物としては、Ｎ−オキシル化合物としては、２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル（ＴＥＭＰＯ）のほか、２，２，６，６−テトラメチル−４−ヒドロキシピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−フェノキシピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−ベンジルピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−アクリロイルオキシピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−ベンゾイルオキシピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−シンナモイルオキシピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−アセチルアミノピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−アクリロイルアミノピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−メタクリロイルアミノピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−ベンゾイルアミノピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−シンナモイルアミノピペリジン−１−オキシル、４−プロピオニルオキシ−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル、４−メトキシ−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル、４−エトキシ−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル、４−アセトアミド−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル、４−オキソ−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル、２，２，４，４−テトラメチルアゼチジン−１−オキシル、２，２−ジメチル−４，４−ジプロピルアゼチジン−１−オキシル、２，２，５，５−テトラメチルピロリジン−Ｎ−オキシル、２，２，５，５−テトラメチル−３−オキソピロリジン−１−オキシル、２，２，６，６−テトラメチル−４−アセトキシピペリジン−１−オキシル、ジｔｅｒｔ−ブチルアミン−Ｎ−オキシル、ポリ［（６−［１，１，３，３−テトラメチルブチル］アミノ）−ｓ−トリアジン−２，４−ジイル］［（２，２，６，６−テトラメチル−４−ピペリジル）イミノ］ヘキサメチレン［（２，２，６，６−テトラメチル−４−ピペリジル）イミノ等が挙げられる。２，２，６，６−テトラメチル−１−ピペリジン−Ｎ−オキシルなどが好ましく用いられる。 As a method for oxidizing cellulose, a co-oxidant is used in the presence of an N-oxyl compound that is highly selective to the oxidation of alcoholic primary carbon while maintaining the structure as much as possible under relatively mild conditions in water. The method was desirable. Examples of the N-oxyl compound include 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and 2,2,6,6-tetramethyl-4- Hydroxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-phenoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-benzylpiperidine-1-oxyl, 2,2 , 6,6-tetramethyl-4-acryloyloxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-methacryloyloxypiperidine-1-oxyl, 2,2,6,6-tetramethyl- 4-benzoyloxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-cinnamoyloxypiperidine-1-oxyl, 2,2,6 6-tetramethyl-4-acetylaminopiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-acryloylaminopiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-methacryloyl Aminopiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-benzoylaminopiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-cinnamoylaminopiperidine-1-oxyl, 4-propionyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-ethoxy-2,2,6 , 6-tetramethylpiperidine-N-oxyl, 4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl, 4- Xo-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,4,4-tetramethylazetidine-1-oxyl, 2,2-dimethyl-4,4-dipropylazetidine- 1-oxyl, 2,2,5,5-tetramethylpyrrolidine-N-oxyl, 2,2,5,5-tetramethyl-3-oxopyrrolidine-1-oxyl, 2,2,6,6-tetramethyl -4-acetoxypiperidine-1-oxyl, ditert-butylamine-N-oxyl, poly [(6- [1,1,3,3-tetramethylbutyl] amino) -s-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino and the like. 2,2,6,6-tetramethyl-1-piperidine-N-oxyl and the like are preferably used.
また、前記の共酸化剤としては、ハロゲン、次亜ハロゲン酸、亜ハロゲン酸や過ハロゲン酸、またはそれらの塩、ハロゲン酸化物、窒素酸化物、過酸化物など、酸化反応を推進することが可能であれば、いずれの酸化剤も用いることができる。入手の容易さや反応性から次亜塩素酸ナトリウムが好ましい。 The co-oxidant may promote an oxidation reaction such as halogen, hypohalous acid, halous acid or perhalogen acid, or a salt thereof, halogen oxide, nitrogen oxide, or peroxide. Any oxidant can be used if possible. Sodium hypochlorite is preferred because of its availability and reactivity.
さらに、臭化物やヨウ化物の共存下で行うと、酸化反応を円滑に進行させることができ、カルボキシル基の導入効率を改善することができる。 Furthermore, when carried out in the presence of bromide or iodide, the oxidation reaction can proceed smoothly, and the introduction efficiency of the carboxyl group can be improved.
Ｎ−オキシル化合物としてはＴＥＭＰＯが好ましく、触媒として機能する量があれば十分である。また臭化物としては臭化ナトリウムまたは臭化リチウムを用いた系が好ましく、コストや安定性から臭化ナトリウムがより好ましい。共酸化剤、臭化物またはヨウ化物の使用量は、酸化反応を促進することができる量があれば十分である。反応はｐＨ９〜１１がより望ましいが、酸化が進行するにつれて、カルボキシル基が生成されて系内のｐＨが低下してしまうため、系内をｐＨ９〜１１に保つ必要がある。 As the N-oxyl compound, TEMPO is preferable, and an amount that functions as a catalyst is sufficient. As the bromide, a system using sodium bromide or lithium bromide is preferable, and sodium bromide is more preferable from the viewpoint of cost and stability. The amount of the co-oxidant, bromide or iodide used is sufficient if there is an amount capable of promoting the oxidation reaction. The reaction is more preferably pH 9 to 11, but as the oxidation proceeds, carboxyl groups are generated and the pH in the system is lowered, so the inside of the system needs to be maintained at pH 9 to 11.
系内をアルカリ性に保つためにはｐＨを一定にスタットしながらアルカリ水溶液を添加していくことで調製することができる。アルカリ水溶液としては、水酸化ナトリウム、水酸化リチウム、水酸化カリウム、アンモニア水溶液、さらには水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラブチルアンモニウム、水酸化ベンジルトリメチルアンモニウムなどの有機アルカリなどが用いられるが、コストなどから水酸化ナトリウムが好ましい。 In order to keep the inside of the system alkaline, it can be prepared by adding an alkaline aqueous solution while keeping the pH constant. Examples of the alkaline aqueous solution include sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia solution, and organic alkalis such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide. Although used, sodium hydroxide is preferred in view of cost.
酸化反応を終了させるためには系内のｐＨを保ちながら他のアルコールを添加し共酸化剤を完全に反応し終える必要がある。添加するアルコールとしては反応をすばやく終了させるためメタノール、エタノール、プロパノールなどの低分子量のアルコールが望ましい。反応により生成される副産物の安全性などからエタノールがより好ましい。 In order to complete the oxidation reaction, it is necessary to add the other alcohol while maintaining the pH in the system and complete the reaction of the co-oxidant. As the alcohol to be added, a low molecular weight alcohol such as methanol, ethanol or propanol is desirable in order to quickly terminate the reaction. Ethanol is more preferable from the viewpoint of safety of by-products generated by the reaction.
酸化し終わったセルロース（酸化セルロース）の洗浄方法としては、アルカリと塩を形成したまま洗浄する方法、酸を添加してカルボン酸にして洗浄する方法、有機溶剤を添加して不要化して洗浄する方法等がある。ハンドリング性や収率等から酸を添加してカルボン酸にして洗浄する方法が好ましい。なお洗浄溶媒としては水が好ましい。 Washing method of oxidized cellulose (oxidized cellulose) includes washing with alkali and salt formed, washing with carboxylic acid by adding acid, washing with unnecessary addition of organic solvent There are methods. In view of handling properties and yield, a method of adding an acid to obtain a carboxylic acid and washing it is preferred. The washing solvent is preferably water.
（酸化セルロースを微細化し分散液化する工程）
酸化セルロースを微細化する方法としてはまず、酸化セルロースを水やアルコールをはじめとした各種有機溶媒やそれらの混合溶媒中に懸濁させる。必要とあれば、分散性を上げるために分散液のｐＨ調整を行ってもよい。ｐＨ調整に用いられるアルカリ水溶液としては、水酸化ナトリウム、水酸化リチウム、水酸化カリウム、アンモニア水溶液、さらには水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラブチルアンモニウム、水酸化ベンジルトリメチルアンモニウムなどの有機アルカリなどが挙げられる。コストや入手のしやすさなどから水酸化ナトリウムが好ましい。
(Step of making oxidized cellulose fine and dispersing liquid)
As a method for refining oxidized cellulose, first, oxidized cellulose is suspended in various organic solvents such as water and alcohol, or a mixed solvent thereof. If necessary, the pH of the dispersion may be adjusted to increase dispersibility. Examples of the alkaline aqueous solution used for pH adjustment include sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia aqueous solution, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, etc. And organic alkalis. Sodium hydroxide is preferred because of cost and availability.
続いて物理的に解繊する方法としては、高圧ホモジナイザー、超高圧ホモジナイザー、ボールミル、ロールミル、カッターミル、遊星ミル、ジェットミル、アトライター、グラインダー、ジューサーミキサー、ホモミキサー、超音波ホモジナイザー、ナノジナイザー、水中対向衝突などを用いることで微細化することができる。これらのような微細化処理を任意の時間や回数行うことで表面にカルボキシル基を有する微細セルロース（酸化微細セルロース）の分散水溶液を得ることができる。 Subsequent physical defibration methods include high pressure homogenizer, ultra high pressure homogenizer, ball mill, roll mill, cutter mill, planetary mill, jet mill, attritor, grinder, juicer mixer, homomixer, ultrasonic homogenizer, nanogenizer, underwater It can be miniaturized by using an opposing collision or the like. By carrying out such a refining treatment for an arbitrary time or number of times, a dispersed aqueous solution of fine cellulose (oxidized fine cellulose) having a carboxyl group on the surface can be obtained.
酸化微細セルロースの分散液（以下は、水分散液を例として説明する）は、必要に応じて、本発明の効果を損なわない範囲で、セルロースおよびｐＨ調整に用いた成分以外の他の成分を含有してもよい。該他の成分としては、特に限定されず、当該微細セルロースの用途等に応じて、公知の添加剤のなかから適宜選択できる。具体的には、アルコキシシラン等の有機金属化合物またはその加水分解物、無機層状化合物、無機針状鉱物、レベリング剤、消泡剤、水溶性高分子、合成高分子、無機系粒子、有機系粒子、潤滑剤、帯電防止剤、紫外線吸収剤、染料、顔料、安定剤、磁性粉、配向促進剤、可塑剤、架橋剤等が挙げられる。 The dispersion of oxidized fine cellulose (hereinafter described as an example of an aqueous dispersion) may contain other components other than the components used for cellulose and pH adjustment within a range that does not impair the effects of the present invention. You may contain. The other components are not particularly limited, and can be appropriately selected from known additives according to the use of the fine cellulose. Specifically, organometallic compounds such as alkoxysilanes or hydrolysates thereof, inorganic layered compounds, inorganic needle minerals, leveling agents, antifoaming agents, water-soluble polymers, synthetic polymers, inorganic particles, organic particles , Lubricants, antistatic agents, ultraviolet absorbers, dyes, pigments, stabilizers, magnetic powders, orientation promoters, plasticizers, crosslinking agents and the like.
（酸化微細セルロース表面に金属またはそれらの化合物からなる金属微粒子を担持させる工程）
酸化微細セルロース表面に担持させる金属微粒子としては、特に限定しないが、抗菌性を有する金属微粒子が好ましく、例えば、金、銀、白金、パラジウム、ルテニウム、イリジウム、ロジウム、オスミウム、レニウム、鉄、鉛、銅、亜鉛、クロム、コバルト、ニッケル、マンガン、バナジウム、モリブデン、ガリウム、アルミニウム、チタンなどの金属又はこれらの合金、または酸化物、複酸化物等が挙げられる。中でも、銀またはその化合物、例えば酸化銀、塩化銀等が好ましい。また、金属微粒子の粒子径が１ｎｍ以上２０ｎｍ以下であれば、酸化微細セルロース表面においてより緻密に金属微粒子を担持することが可能になり、抗菌性の効率を向上させることが可能になる点から好ましい。また、酸化微細セルロース表面に金属微粒子を担持させる方法としては、特に限定しないが、酸化微細セルロース表面上に高密度に金属微粒子を担持させるため、前記金属または合金、酸化物、複酸化物等の溶液と酸化微細セルロースの水分散液を混合し、酸化微細セルロース表面のアニオン性のカルボキシル基と前記金属または合金、酸化物、複酸化物のカチオンを静電的に相互作用させ、還元し析出させることが好ましい。前記金属または合金、酸化物、複酸化物を還元させる方法としては、特に限定しないが、弱い還元剤を用いる方が粒径を小さく均一に制御しやすく、かつ簡便で好ましい。還元剤としては、水素化ホウ素ナトリウム、水素化ホウ素カリウム、水素化アルミニウムリチウム、シアノ化水素化ホウ素ナトリウム、トリアルコキシ水素化アルミニウムリチウム、ジイソブチル水素化アルミニウム等の水素化金属が挙げられ、安全性や汎用性から水素化ホウ素ナトリウムが好ましい。
このようにして、本発明の抗菌性微細セルロースの分散液、上記の形態では抗菌性微細セルロースの水分散液が得られる。
(Step of supporting metal fine particles made of metal or a compound thereof on the surface of oxidized fine cellulose)
The metal fine particles supported on the oxidized fine cellulose surface are not particularly limited, but antibacterial metal fine particles are preferable, for example, gold, silver, platinum, palladium, ruthenium, iridium, rhodium, osmium, rhenium, iron, lead, Examples thereof include metals such as copper, zinc, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, aluminum, and titanium, alloys thereof, oxides, and double oxides. Of these, silver or a compound thereof such as silver oxide and silver chloride is preferable. Moreover, if the particle diameter of the metal fine particles is 1 nm or more and 20 nm or less, it is preferable because the metal fine particles can be more densely supported on the surface of the oxidized fine cellulose and the antibacterial efficiency can be improved. . Further, the method for supporting the metal fine particles on the surface of the oxidized fine cellulose is not particularly limited. However, in order to support the metal fine particles at a high density on the surface of the oxidized fine cellulose, the metal or alloy, oxide, double oxide, etc. A solution and an aqueous dispersion of oxidized fine cellulose are mixed, and the anionic carboxyl groups on the oxidized fine cellulose surface are electrostatically interacted with the cations of the metal, alloy, oxide or double oxide, and reduced and precipitated. It is preferable. The method for reducing the metal, alloy, oxide, or double oxide is not particularly limited, but it is preferable to use a weak reducing agent because it is easy to control the particle size uniformly and is simple and convenient. Examples of the reducing agent include metal hydrides such as sodium borohydride, potassium borohydride, lithium aluminum hydride, sodium cyanide borohydride, lithium trialkoxy aluminum hydride, and diisobutyl aluminum hydride. Sodium borohydride is preferred because of its versatility.
Thus, the antimicrobial fine cellulose dispersion of the present invention, and in the above-described form, the antimicrobial fine cellulose aqueous dispersion can be obtained.
（抗菌性コーティング剤）
本発明では、上記のようにして得られた抗菌性微細セルロースの分散液、例えば抗菌性微細セルロースの水分散液を、そのまま抗菌性コーティング剤として用いることができる。このとき該水分散液の６００ｎｍにおける透過率は８０％以上となり、透明性に優れる。
本発明の抗菌性コーティング剤は、様々な基材上に塗工し、コーティング膜を形成することが可能である。
本発明の抗菌性微細セルロースを含む分散液を基材上に塗工する場合の方法としては、コンマコーター、ロールコーター、リバースロールコーター、ダイレクトグラビアコーター、リバースグラビアコーター、オフセットグラビアコーター、ロールキスコーター、リバースキスコーター、キスグラビアコーター、リバースキスグラビアコーター、エアドクターコーター、ナイフコーター、バーコーター、ワイヤーバーコーター、ダイコーター、リップコーター、ディップコーター、ブレードコーター、ブラシコーター、カーテンコーター、ダイスロットコーター等のいずれかもしくは二つ以上の塗工方法を組み合わせて用いることができる。また立体に塗工する場合の方法としては、スプレーコーター、ディップコーター等のいずれかもしくは二つ以上の塗工方法を組み合わせて用いることできる。塗工方法はバッチ式、連続式によらない。
(Antimicrobial coating agent)
In the present invention, the antibacterial fine cellulose dispersion obtained as described above, for example, an antibacterial fine cellulose aqueous dispersion, can be used as it is as an antibacterial coating agent. At this time, the transmittance of the aqueous dispersion at 600 nm is 80% or more, and the transparency is excellent.
The antibacterial coating agent of the present invention can be applied on various substrates to form a coating film.
As a method for coating the dispersion containing the antibacterial fine cellulose of the present invention on a substrate, a comma coater, roll coater, reverse roll coater, direct gravure coater, reverse gravure coater, offset gravure coater, roll kiss coater , Reverse kiss coater, kiss gravure coater, reverse kiss gravure coater, air doctor coater, knife coater, bar coater, wire bar coater, die coater, lip coater, dip coater, blade coater, brush coater, curtain coater, die slot coater, etc. Any one of these methods or a combination of two or more coating methods can be used. In addition, as a method for coating three-dimensionally, any one of spray coater and dip coater or a combination of two or more coating methods can be used. The coating method does not depend on the batch type or continuous type.
以下、本発明を実施例に基づいて詳細に説明するが、本発明の技術範囲はこれらの実施形態に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, the technical scope of this invention is not limited to these embodiment.
＜セルロースのＴＥＭＰＯ酸化＞
針葉樹晒クラフトパルプ３０ｇを蒸留水１８００ｇに懸濁し、蒸留水２００ｇにＴＥＭＰＯを０．３ｇ、臭化ナトリウムを３ｇ溶解させた溶液を加え、２０℃まで冷却した。ここに２ｍｏｌ／ｌ、密度１．１５ｇ／ｍｌの次亜塩素酸ナトリウム水溶液１７２ｇを滴下により添加し、酸化反応を開始した。系内の温度は常に２０℃に保ち、反応中のｐＨの低下は０．５Ｎの水酸化ナトリウム水溶液を添加することでｐＨ１０に保ち続けた。セルロースの質量に対して、水酸化ナトリウムが２．８５ｍｍｏｌ／ｇになったところで十分量のエタノールを添加し反応を停止させた。その後、ｐＨ１になるまで塩酸を添加した後、蒸留水で十分洗浄を繰り返し、酸化セルロースを得た。
<TEMPO oxidation of cellulose>
30 g of softwood bleached kraft pulp was suspended in 1800 g of distilled water, a solution in which 0.3 g of TEMPO and 3 g of sodium bromide were dissolved in 200 g of distilled water was added and cooled to 20 ° C. To this, 172 g of a sodium hypochlorite aqueous solution having a concentration of 2 mol / l and a density of 1.15 g / ml was added dropwise to initiate an oxidation reaction. The temperature in the system was always kept at 20 ° C., and the decrease in pH during the reaction was kept at pH 10 by adding a 0.5N aqueous sodium hydroxide solution. When sodium hydroxide reached 2.85 mmol / g based on the mass of cellulose, a sufficient amount of ethanol was added to stop the reaction. Thereafter, hydrochloric acid was added until pH 1 was obtained, and then washing was sufficiently repeated with distilled water to obtain oxidized cellulose.
・酸化セルロースのカルボキシル基測定
上記ＴＥＭＰＯ酸化で得た酸化セルロースを固形分重量で０．１ｇ量りとり、１％濃度で水に分散させ、塩酸を加えてｐＨを３とした。その後０．５Ｎ水酸化ナトリウム水溶液を用いて電導度滴定法により、カルボキシル基量（ｍｍｏｌ／ｇ）を求めた。結果は１．６ｍｍｏｌ／ｇであった。
Measurement of carboxyl group of oxidized cellulose Oxidized cellulose obtained by the above TEMPO oxidation was weighed by 0.1 g in terms of solid content, dispersed in water at a concentration of 1%, and hydrochloric acid was added to adjust the pH to 3. Thereafter, the amount of carboxyl groups (mmol / g) was determined by conductometric titration using a 0.5N aqueous sodium hydroxide solution. The result was 1.6 mmol / g.
＜酸化セルロースの微細化＞
上記ＴＥＭＰＯ酸化で得た酸化セルロース１ｇを９９ｇの蒸留水に分散させ、水酸化ナトリウム水溶液を用いてｐＨ１０に調製した。調製した分散液をジューサーミキサーで６０分間微細化処理し、１％濃度の酸化微細セルロースの水分散液を得た。
<Refining of oxidized cellulose>
1 g of oxidized cellulose obtained by the TEMPO oxidation was dispersed in 99 g of distilled water and adjusted to pH 10 using an aqueous sodium hydroxide solution. The prepared dispersion was refined with a juicer mixer for 60 minutes to obtain an aqueous dispersion of oxidized fine cellulose having a concentration of 1%.
上記酸化微細セルロースの形状観察は原子間力顕微鏡（ＡＦＭ）を用いて観察した。繊維高さを１０点計測し平均を数平均繊維幅とした。また、繊維長さについては同様にタッピングＡＦＭで観察し、繊維の長方向の長さを１０点計測し、平均を数平均繊維長さとした。数平均繊維幅は３．５ｎｍ、数平均繊維長さは１．３μｍであった。 The shape of the oxidized fine cellulose was observed using an atomic force microscope (AFM). The fiber height was measured at 10 points and the average was taken as the number average fiber width. Further, the fiber length was similarly observed by tapping AFM, the length in the longitudinal direction of the fiber was measured at 10 points, and the average was taken as the number average fiber length. The number average fiber width was 3.5 nm, and the number average fiber length was 1.3 μm.
＜微細セルロース−金属微粒子複合体の作製＞
上記酸化微細セルロースの水分散液と５ｍＭ硝酸銀水溶液を混合し、十分攪拌した。その後、１０ｍＭ水素化ホウ素ナトリウムを添加し、銀イオンを還元し酸化微細セルロース上に銀微粒子を担持させ、微細セルロース−銀微粒子複合体水分散液を作製した。
<Preparation of fine cellulose-metal fine particle composite>
The aqueous dispersion of oxidized fine cellulose and a 5 mM aqueous silver nitrate solution were mixed and sufficiently stirred. Thereafter, 10 mM sodium borohydride was added, silver ions were reduced, and silver fine particles were supported on oxidized fine cellulose to prepare a fine cellulose-silver fine particle composite aqueous dispersion.
上記銀微粒子の大きさの観察としては、透過型電子顕微鏡（ＴＥＭ）を用いて観察したところ、粒子径２ｎｍであった。 The size of the silver fine particles was observed using a transmission electron microscope (TEM) and found to have a particle diameter of 2 nm.
前記実施例１のセルロースのＴＥＭＰＯ酸化において、水酸化ナトリウムの添加量を１．５ｍｍｏｌ／ｇとし、得られた酸化セルロースのカルボキシル基量を１．３ｍｍｏｌ／ｇとした以外は同様の方法で、実施例２の微細セルロース−銀微粒子複合体水分散液を作製した。 In the TEMPO oxidation of the cellulose of Example 1, the same procedure was performed except that the amount of sodium hydroxide added was 1.5 mmol / g and the amount of carboxyl groups of the obtained oxidized cellulose was 1.3 mmol / g. The fine cellulose-silver fine particle composite aqueous dispersion of Example 2 was prepared.
前記実施例１のセルロースのＴＥＭＰＯ酸化において、水酸化ナトリウムの添加量を４．０ｍｍｏｌ／ｇとし、得られた酸化セルロースのカルボキシル基量を１．９ｍｍｏｌ／ｇとした以外は同様の方法で、実施例３の微細セルロース−銀微粒子複合体水分散液を作製した。 In the TEMPO oxidation of the cellulose of Example 1, the same procedure was performed except that the amount of sodium hydroxide added was 4.0 mmol / g and the amount of carboxyl groups of the obtained oxidized cellulose was 1.9 mmol / g. The fine cellulose-silver fine particle composite aqueous dispersion of Example 3 was prepared.
前記実施例１の微細セルロース−銀微粒子複合体水分散液の作製において、硝酸銀水溶液の濃度を２．５ｍＭとし、担持した銀微粒子の大きさを１ｎｍとした以外は同様の方法で、実施例４の微細セルロース−銀微粒子複合体水分散液を作製した。 In the preparation of the fine cellulose-silver fine particle composite aqueous dispersion of Example 1, Example 4 was carried out in the same manner except that the concentration of the silver nitrate aqueous solution was 2.5 mM and the size of the supported silver fine particles was 1 nm. A fine cellulose-silver fine particle composite aqueous dispersion was prepared.
前記実施例１の微細セルロース−銀微粒子複合体水分散液の作製において、硝酸銀水溶液の濃度を１０ｍＭとし、担持した銀微粒子の大きさを４ｎｍとした以外は同様の方法で、実施例５の微細セルロース−銀微粒子複合体水分散液を作製した。
[比較例１]
The fine cellulose-silver fine particle composite aqueous dispersion of Example 1 was prepared in the same manner as in Example 5 except that the concentration of the aqueous silver nitrate solution was 10 mM and the size of the supported silver fine particles was 4 nm. A cellulose-silver fine particle composite aqueous dispersion was prepared.
[Comparative Example 1]
５ｍＭ硝酸銀水溶液に１０ｍＭ水素化ホウ素ナトリウム水溶液を添加し、充分攪拌し予め銀イオンを還元した。得られた液に実施例１の酸化微細セルロース水分散液を添加し比較例１の微細セルロース−銀微粒子複合体水分散液を作製した。 A 10 mM sodium borohydride aqueous solution was added to a 5 mM silver nitrate aqueous solution, and stirred sufficiently to reduce silver ions in advance. To the obtained liquid, the oxidized fine cellulose aqueous dispersion of Example 1 was added to prepare a fine cellulose-silver fine particle composite aqueous dispersion of Comparative Example 1.
上記銀微粒子の大きさの観察としては、ＴＥＭを用いて観察したところ、粒子径４５ｎｍであった。 As the observation of the size of the silver fine particles, the particle diameter was 45 nm when observed using a TEM.
・抗菌性能評価
上記実施例１〜５および比較例１の微細セルロース−銀微粒子複合体水分散液をＪＩＳ Ｌ１９０２の菌液吸収法に基づき実施し、黄色ぶどう球菌の静菌活性値で評価した。
-Antibacterial performance evaluation The fine cellulose-silver fine particle composite aqueous dispersions of Examples 1 to 5 and Comparative Example 1 were carried out based on the bacterial solution absorption method of JIS L1902, and evaluated by the bacteriostatic activity value of Staphylococcus aureus.
・透明性評価
上記実施例１〜５および比較例１の微細セルロース−銀微粒子複合体水分散液の６００ｎｍにおける透過率をＵＶ−ｖｉｓ分光光度計を用いて測定した。
結果を表１に示す。
-Transparency evaluation The transmittance | permeability in 600 nm of the fine cellulose-silver fine particle composite aqueous dispersion of the said Examples 1-5 and the comparative example 1 was measured using the UV-vis spectrophotometer.
The results are shown in Table 1.
表１の結果から、分散性よく金属微粒子を微細セルロース上に担持させることができることから、透明性が高く、さらには抗菌性を低下させることなく金属微粒子の量を減少させることが可能になり、少ない担持量で効率的に抗菌性を発現させることが可能になった。 From the results of Table 1, since the metal fine particles can be supported on the fine cellulose with good dispersibility, it is possible to reduce the amount of the metal fine particles without increasing the transparency and further reducing the antibacterial properties. Antibacterial properties can be efficiently expressed with a small loading.
Claims (6)
前記抗菌性微細セルロース：木材を由来とする微細セルロースの表面上に、銀またはその化合物からなる金属微粒子が担持されてなる抗菌性微細セルロースであって、前記微細セルロースは、少なくともその結晶表面にカルボキシル基を有し、前記金属微粒子は、前記微細セルロースの結晶表面のカルボキシル基上に析出したものであることを特徴とする抗菌性微細セルロース。 An antibacterial coating agent characterized by using the following antibacterial fine cellulose.
Antibacterial fine cellulose: antibacterial fine cellulose obtained by carrying fine metal particles made of silver or a compound thereof on the surface of fine cellulose derived from wood, and the fine cellulose is carboxylated on at least the crystal surface thereof. An antibacterial fine cellulose having a group, wherein the metal fine particles are precipitated on a carboxyl group on a crystal surface of the fine cellulose.
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