JP2017035196A - Deodorant sheet - Google Patents
Deodorant sheet Download PDFInfo
- Publication number
- JP2017035196A JP2017035196A JP2015157082A JP2015157082A JP2017035196A JP 2017035196 A JP2017035196 A JP 2017035196A JP 2015157082 A JP2015157082 A JP 2015157082A JP 2015157082 A JP2015157082 A JP 2015157082A JP 2017035196 A JP2017035196 A JP 2017035196A
- Authority
- JP
- Japan
- Prior art keywords
- paper
- deodorant
- glass
- mol
- deodorizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002781 deodorant agent Substances 0.000 title claims abstract description 77
- 239000011521 glass Substances 0.000 claims abstract description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 28
- 230000001877 deodorizing effect Effects 0.000 claims description 64
- 239000000835 fiber Substances 0.000 claims description 18
- 239000005388 borosilicate glass Substances 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 239000006107 alkali alkaline earth silicate glass Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 24
- 239000000126 substance Substances 0.000 abstract description 21
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 12
- 239000000194 fatty acid Substances 0.000 abstract description 12
- 229930195729 fatty acid Natural products 0.000 abstract description 12
- 150000004665 fatty acids Chemical class 0.000 abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 235000013305 food Nutrition 0.000 abstract description 7
- 239000010813 municipal solid waste Substances 0.000 abstract description 7
- 208000035985 Body Odor Diseases 0.000 abstract description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 6
- 206010040904 Skin odour abnormal Diseases 0.000 abstract description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 235000009508 confectionery Nutrition 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 2
- 230000005923 long-lasting effect Effects 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 98
- 239000000203 mixture Substances 0.000 description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 11
- 235000019645 odor Nutrition 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- 238000004332 deodorization Methods 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- -1 silver ions Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 229920002620 polyvinyl fluoride Polymers 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- BSAIUMLZVGUGKX-BQYQJAHWSA-N (E)-non-2-enal Chemical compound CCCCCC\C=C\C=O BSAIUMLZVGUGKX-BQYQJAHWSA-N 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000000474 nursing effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 240000000249 Morus alba Species 0.000 description 2
- 235000008708 Morus alba Nutrition 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000025 natural resin Substances 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 241001265525 Edgeworthia chrysantha Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000010849 combustible waste Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004031 devitrification Methods 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
- 238000002845 discoloration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 238000005534 hematocrit Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011572 manganese 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
- 150000004667 medium chain fatty acids Chemical class 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004666 short chain fatty acids Chemical class 0.000 description 1
- 235000021391 short chain fatty acids Nutrition 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Paper (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Glass Compositions (AREA)
Abstract
Description
本発明は、ガラス質消臭剤を担持させた消臭紙に関するものである。 The present invention relates to a deodorizing paper carrying a glassy deodorant.
紙に特定の機能を付与する技術として、例えば、ダニの駆除に有効なB2O5を溶出する溶解性ガラスを微粉末としてバインダーと混合し、紙の表面にスプレーして、防虫機能を備えた紙を得る方法(特許文献1)や、消臭や抗菌等の機能を有する銀イオンを溶出する溶解性ガラスを微粉末としてバインダーおよび水と混合攪拌してスラリーとし、そこに紙シートを浸漬し、含浸、乾燥の各工程を経て消臭や抗菌等の機能を備えた紙を得る方法(特許文献2)が開示されている。 As a technique for imparting a specific function to paper, for example, soluble glass that dissolves B 2 O 5 effective for mite control is mixed as a fine powder with a binder and sprayed on the surface of the paper to provide an insect repellent function. A method to obtain a crumpled paper (Patent Document 1) and a soluble glass that elutes silver ions having functions such as deodorization and antibacterial as a fine powder mixed with a binder and water to make a slurry, and a paper sheet is immersed therein In addition, a method (Patent Document 2) is disclosed in which paper having functions such as deodorization and antibacterial is obtained through the steps of impregnation and drying.
しかし、特許文献1、2の技術は、溶解性ガラスから溶出させた成分により特定の機能を奏するものであるため、溶出が進行するとともに、その特定の機能(例えば、特許文献1では抗かび効果、特許文献2では消臭効果や抗菌効果)が低下することが避けられず、長期間に亘っての使用が想定される製品への応用には適さないという問題があった。 However, since the techniques of Patent Documents 1 and 2 exhibit a specific function by the components eluted from the soluble glass, the elution progresses and the specific function (for example, Patent Document 1 has an antifungal effect). In Patent Document 2, it is inevitable that the deodorizing effect and the antibacterial effect are reduced, and there is a problem that it is not suitable for application to a product that is expected to be used for a long period of time.
また、特許文献2に関し、銀イオンは抗菌効果があるために菌が生成する悪臭を防ぐ効果があるが、低級脂肪酸や体臭成分等の悪臭物質に対する消臭効果はなく、これらの臭気が主となる介護分野等で用いる製品への応用には適さないという問題があった。 Further, regarding Patent Document 2, silver ions have an antibacterial effect, and thus have an effect of preventing malodors produced by bacteria. However, there is no deodorizing effect on malodorous substances such as lower fatty acids and body odor components, and these odors are mainly used. There is a problem that it is not suitable for application to products used in the nursing field.
従って本発明の目的は上記した従来の問題点を解決し、消臭効果の持続性に優れ、硫化水素、メチルメルカプタン等の硫黄系悪臭物質のみならず、低級脂肪酸や体臭成分等の悪臭物質をも消臭する機能を備えた消臭紙を提供することである。 Therefore, the object of the present invention is to solve the above-mentioned conventional problems, have excellent deodorizing effect, and not only sulfur-based malodorous substances such as hydrogen sulfide and methyl mercaptan, but also malodorous substances such as lower fatty acids and body odor components. Another object is to provide a deodorizing paper having a function of deodorizing.
上記の課題を解決するためになされた本発明は、紙を構成する繊維間または紙の表面にガラス質消臭剤を担持させた消臭紙であって、このガラス質消臭剤は銅成分を含有するアルカリ−アルカリ土類−ホウケイ酸ガラスまたは銅成分を含有するアルカリ−アルカリ土類−ケイ酸塩ガラスからなり、ガラス中に保持された銅成分の触媒作用により、悪臭成分を分解する機能を有することを特徴とするものである。ここで「紙」とは、植物繊維その他の繊維を絡み合わせ、こう着させて作った紙の他、合成高分子物質を使用して作った合成紙、合成繊維紙、合成パルプ紙、古紙パルプ紙、繊維状無機材料を配合した紙も含むものとする。 The present invention made to solve the above problems is a deodorizing paper in which a glassy deodorant is supported between fibers constituting the paper or on the surface of the paper, and this glassy deodorant is a copper component. Of alkali-alkaline earth-borosilicate glass containing copper or alkali-alkaline earth-silicate glass containing copper component, and the function of decomposing malodorous components by the catalytic action of the copper component held in the glass It is characterized by having. Here, “paper” refers to paper made by interlacing and attaching plant fibers and other fibers, as well as synthetic paper, synthetic fiber paper, synthetic pulp paper, and waste paper pulp made using synthetic polymer substances. Paper and paper mixed with fibrous inorganic materials are also included.
なお請求項2に記載の通り、紙を構成する繊維間に担持させたガラス質消臭剤の含有量を、0.1〜10質量%とすることが好ましい。また請求項3に記載の通り、紙の表面に担持させたガラス質消臭剤の含有量を、0.1〜5g/m2とすることが好ましい。また請求項4に記載の通り、ガラス質消臭剤が、D96=40μm以下の粉体であることが好ましい。また請求項5に記載の通り、上記した消臭紙を積層して、もしくは、ガラス質消臭剤を含有しない紙と積層して、積層構造を持つ積層紙とすることもできる。 In addition, as described in claim 2, it is preferable that the content of the vitreous deodorant supported between the fibers constituting the paper is 0.1 to 10% by mass. Moreover, as described in claim 3, it is preferable that the content of the vitreous deodorant carried on the paper surface is 0.1 to 5 g / m 2 . Further, as described in claim 4, the vitreous deodorant is preferably a powder having a D 96 of 40 μm or less. Further, as described in claim 5, the above-mentioned deodorant paper can be laminated, or can be laminated with paper not containing a glassy deodorant to obtain a laminated paper having a laminated structure.
本発明の消臭紙は、銅成分を含有するアルカリ−アルカリ土類−ホウケイ酸ガラスまたは銅成分を含有するアルカリ−アルカリ土類−ケイ酸塩ガラスからなるガラス質消臭剤を紙に保持させ、ガラス中に保持された銅成分の触媒作用により、悪臭成分を分解する。 The deodorizing paper of the present invention holds a glassy deodorant composed of an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component on the paper. The malodorous component is decomposed by the catalytic action of the copper component held in the glass.
溶解性ガラスを用いた消臭剤は各種開発されていたが、それらは何れも、溶解性ガラスから溶出させた特定成分に悪臭成分を化学的もしくは物理的に吸着させるものであり、従来、「触媒作用による消臭効果を示すガラス剤」は知られていなかった。本発明者らは、長年による研究の結果、「上記組成のガラス中に含有させた銅成分が触媒として機能して、硫黄系悪臭物質の分解反応を促進し、硫黄系悪臭物質の消臭効果を奏する」という新たな知見を見出した。 Various deodorizers using soluble glass have been developed, but they all adsorb malodorous components chemically or physically to specific components eluted from the soluble glass. A “glass agent exhibiting a deodorizing effect by catalytic action” has not been known. As a result of many years of research, the present inventors have found that "the copper component contained in the glass having the above composition functions as a catalyst, promotes the decomposition reaction of the sulfur-based malodorous substance, and deodorizes the sulfur-based malodorous substance. We found a new finding that
本発明では、このように、ガラス中に含まれる銅成分を触媒として硫黄系悪臭物質の分解反応を促進するメカニズムを有するものであるため、化学吸着、物理吸着を利用した従来技術に比べて、消臭容量を増大させることができ、消臭効果を長期間に亘って安定して発揮することができる。すなわち、従来の化学吸着、物理吸着は何れも吸着剤の表面露出量に依存し、露出量によって消臭限界が決定されるのであるが、本発明では触媒反応を利用するため、露出量が少量であっても大きい消臭総量を得ることができる。このため消臭量のみに着目すればガラス質消臭剤の添加量は少量添加でもよいが、消臭スピードを加えるためには前記したように、紙を構成する繊維間に担持させたガラス質消臭剤の含有量は0.1〜10質量%とし、また紙の表面に担持させたガラス質消臭剤の含有量は0.1〜5g/m2とすることが好ましい。 In the present invention, as described above, since it has a mechanism for promoting the decomposition reaction of the sulfur-based malodorous substance using the copper component contained in the glass as a catalyst, compared to the conventional technology using chemical adsorption and physical adsorption, The deodorizing capacity can be increased, and the deodorizing effect can be exhibited stably over a long period of time. That is, both conventional chemical adsorption and physical adsorption depend on the surface exposure amount of the adsorbent, and the deodorization limit is determined by the exposure amount. However, in the present invention, since the catalytic reaction is used, the exposure amount is small. Even so, a large total deodorizing amount can be obtained. For this reason, if attention is paid only to the deodorizing amount, a small amount of the glassy deodorant may be added, but in order to add a deodorizing speed, as described above, the glassy material supported between the fibers constituting the paper. The content of the deodorant is preferably 0.1 to 10% by mass, and the content of the glassy deodorant supported on the paper surface is preferably 0.1 to 5 g / m 2 .
本発明で用いたガラス質消臭剤は、特にメチルメルカプタンに対し、優れたな消臭効果を発揮することができる。すなわちこのガラス質消臭剤は、メチルメルカプタンを触媒的に酸化分解し、二量体のジメチルジスルフィドを生成する。このときラジカルが発生し、酸化分解される。同様に、他のガスに対しても同様の酸化分解が可能である。しかし、消臭可能な悪臭は硫黄系悪臭物質に限られるものではない。具体的には、低級脂肪酸や、体臭(汗、足臭)として知られる酢酸、イソ吉草酸を始め、悪臭防止法で定められるプロピオン酸、ノルマル酪酸、ノルマル吉草酸や、中鎖脂肪酸のカプロン酸、エナント酸や、加齢臭として知られるトランス−2−ノネナールも消臭可能である。一般的に、炭素数2〜4個のものを短鎖脂肪酸(低級脂肪酸)というが、本明細書においては炭素数1個の酢酸、5個の吉草酸も低級脂肪酸として取り扱う。 The vitreous deodorant used in the present invention can exhibit an excellent deodorizing effect particularly with respect to methyl mercaptan. That is, this glassy deodorant catalytically oxidatively decomposes methyl mercaptan to produce dimeric dimethyl disulfide. At this time, radicals are generated and oxidatively decomposed. Similarly, similar oxidative decomposition is possible for other gases. However, the odor that can be deodorized is not limited to sulfur-based odor substances. Specific examples include lower fatty acids, acetic acid known as body odor (sweat, foot odor), isovaleric acid, propionic acid, normal butyric acid, normal valeric acid, and caproic acid, a medium chain fatty acid, as defined by the Malodor Control Law. Also, enanthic acid and trans-2-nonenal, known as an aging odor, can be deodorized. In general, those having 2 to 4 carbon atoms are referred to as short chain fatty acids (lower fatty acids), but in this specification, acetic acid having 1 carbon atom and 5 valeric acids are also treated as lower fatty acids.
なお、本発明の消臭紙は、食品包装用、ゴミ用、レジ袋、おむつ用などの消臭効果が望まれる用途に適したものである。おむつ臭の主成分は硫化水素、メチルメルカプタン、低級脂肪酸であり、介護分野においては低級脂肪酸の消臭効果が求められている。また生ゴミ臭の主成分も、硫化水素、メチルメルカプタン、低級脂肪酸の一種であるプロピオン酸であり、本発明の消臭紙はこれらの用途に好適である。さらに最近ではゴミの分別化が進んだことから、自治体等のゴミ焼却施設でゴミが燃えにくいという事例がある。本発明のガラス質消臭剤はラジカルによる酸化分解を促進することから、消臭効果のみならず、燃焼促進触媒としての機能も有している。つまり、可燃ゴミに分類される紙への利用に適している。 The deodorizing paper of the present invention is suitable for applications where a deodorizing effect is desired, such as food packaging, garbage, plastic bags, diapers, and the like. The main components of a diaper odor are hydrogen sulfide, methyl mercaptan, and lower fatty acids, and the deodorizing effect of lower fatty acids is required in the nursing field. The main component of the garbage odor is also hydrogen sulfide, methyl mercaptan, and propionic acid, which is one of lower fatty acids, and the deodorized paper of the present invention is suitable for these uses. Furthermore, there is a case where garbage is hard to burn in garbage incineration facilities such as local governments because of the recent separation of garbage. Since the vitreous deodorant of the present invention promotes oxidative decomposition by radicals, it has not only a deodorizing effect but also a function as a combustion promoting catalyst. That is, it is suitable for use on paper classified as combustible waste.
このほか、医薬品や電子部品・精密機器の技術分野でも悪臭成分の除去が求められることがある。すなわち、製造工程で使用される薬剤からのアウトガスで硫化水素や酢酸が発生することがあり、これらは悪臭であるのみならず、金属腐食、製品劣化につながる腐食ガスでもある。本発明の消臭紙を用いることにより、製品寿命の延長や製品品質の安定化に寄与することができる。上記したように、本発明の消臭紙(消臭多層紙)は、医療用包装紙、食品用包装紙、鮮度保持紙、紙製衣料、壁紙、ティッシュペーパー、トイレットペーパー、セパレートシート、段ボールなどの様々な用途に用いることができる。 In addition, removal of malodorous components may be required in the technical fields of pharmaceuticals, electronic parts and precision equipment. That is, hydrogen sulfide and acetic acid may be generated by outgas from chemicals used in the manufacturing process, and these are not only bad odors but also corrosive gases that lead to metal corrosion and product deterioration. By using the deodorizing paper of the present invention, it can contribute to the extension of product life and stabilization of product quality. As described above, the deodorant paper (deodorant multilayer paper) of the present invention is a medical wrapping paper, a food wrapping paper, a freshness preserving paper, a paper apparel, a wallpaper, a tissue paper, a toilet paper, a separate sheet, a cardboard, etc. It can be used for various applications.
以下に本発明の実施形態を説明する。
第1の実施形態の消臭紙は、図1に示すように、紙を構成する繊維1の間にガラス質消臭剤2の粉末を含有させたものであり、第2の実施形態の消臭紙は、紙の表面にガラス質消臭剤を含む消臭層3を形成したものである。ガラス質消臭剤は、銅成分を含有するアルカリ−アルカリ土類−ホウケイ酸ガラスまたは銅成分を含有するアルカリ−アルカリ土類−ケイ酸塩ガラスからなり、D96=40μm以下の粉体であることが望ましい。
Embodiments of the present invention will be described below.
As shown in FIG. 1, the deodorizing paper of the first embodiment is obtained by containing a glassy deodorant 2 powder between the fibers 1 constituting the paper, and the deodorizing paper of the second embodiment. The odor paper is obtained by forming a deodorizing layer 3 containing a glassy deodorant on the surface of the paper. The vitreous deodorant is composed of an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component, and is a powder having a D 96 of 40 μm or less. It is desirable.
ここでD96は粒度分布測定を行い、累積分布させたときの積分値が96%に当たる粒径を意味する。D96が40μmを超えるとガラス質消臭剤2が紙から脱落し易くなったり、平滑性が悪くなる。なお、粒径が1μm未満になるとガラスの粉砕や分級の効率が極端に低下するので、製造上好ましくない。1〜25μm程度の粒径が実用的である。このようなガラス質消臭剤は、調合原料を溶融したうえ急冷してプレ成形体を得た後、粉砕を行なう方法で製造することができる。粉砕には一般的に知られる粉砕機(例えば、ボールミル、ビーズミル、ジェットミル、CFミル等)を用いることができ、乾式でも湿式でも構わない。以下にガラス質消臭剤の組成について説明する。 Here, D 96 means a particle size at which the integral value when the particle size distribution measurement is performed and the cumulative distribution is 96%. Or vitreous deodorant 2 becomes liable to fall off from the paper when D 96 is more than 40 [mu] m, smoothness is deteriorated. When the particle size is less than 1 μm, the efficiency of pulverizing and classifying glass is extremely lowered, which is not preferable in production. A particle size of about 1 to 25 μm is practical. Such a vitreous deodorant can be produced by a method in which the raw material for preparation is melted and rapidly cooled to obtain a pre-molded product, and then pulverized. For the pulverization, a generally known pulverizer (for example, a ball mill, a bead mill, a jet mill, a CF mill, etc.) can be used, and it may be dry or wet. The composition of the glassy deodorant will be described below.
(アルカリ−アルカリ土類−ホウケイ酸ガラス)
上記した銅成分を含有するアルカリ−アルカリ土類−ホウケイ酸ガラスは、SiO2:46〜70モル%、B2O3+R2O(R:アルカリ金属):15〜50モル%、R´O(R´:アルカリ土類金属):0〜10モル%、Al2O3:0〜6%、CuO:0.01〜23モル%含有するガラスである。ここで、B2O3:5〜20モル%、R2O:10〜30モル%とすることができる。
(Alkali-alkaline earth-borosilicate glass)
The alkali-alkaline earth-borosilicate glass containing the above-described copper component is SiO 2 : 46 to 70 mol%, B 2 O 3 + R 2 O (R: alkali metal): 15 to 50 mol%, R′O. (R ′: alkaline earth metal): 0 to 10 mol%, Al 2 O 3 : 0 to 6%, CuO: 0.01 to 23 mol%. Here, B 2 O 3: 5~20 mol%, R 2 O: can be 10 to 30 mol%.
このガラス質消臭剤の好ましい組成は、SiO2:51〜63モル%、B2O3+R2O:21〜39モル%、R´O:2〜7モル%、Al2O3:0〜5.5%、CuO:1〜13モル%である。ここで、B2O3:8〜17モル%、R2O:13〜22モル%とすることができる。 A preferred composition of the vitreous deodorants, SiO 2: 51 to 63 mol%, B 2 O 3 + R 2 O: 21~39 mol%, R'O: 2 to 7 mol%, Al 2 O 3: 0 -5.5%, CuO: 1-13 mol%. Here, B 2 O 3: 8~17 mol%, R 2 O: can be 13 to 22 mol%.
またこのガラス質消臭剤の最も好ましい組成は、SiO2:53〜62モル%、B2O3:10〜17モル%、R2O:13〜19モル%、R´O:3〜6モル%、Al2O3:0〜4.5%、CuO:4〜13モル%である。以下に、各ガラス組成について詳細に説明する。 The most preferred composition of this vitreous deodorants, SiO 2: 53-62 mol%, B 2 O 3: 10~17 mol%, R 2 O: 13~19 mol%, R'O: 3 to 6 mol%, Al 2 O 3: 0~4.5 %, CuO: 4~13 are mole%. Below, each glass composition is demonstrated in detail.
(SiO2)
SiO2は、ガラスの構造骨格を形成する主成分であり、その含有量は46〜70モル%、好ましくは、51〜63モル%、更に好ましくは53〜62モル%とする。46モル%未満の場合、ガラスの化学的耐久性が不十分となり、またガラスが失透しやすくなり好ましくない。更に、46モル%未満の場合、ガラスの耐水性が不十分となり、水分存在下(大気中の水分を含む)で銅イオンが溶出しやすくなる結果、触媒作用による消臭効果よりも、イオン溶出によって起こる硫化反応による消臭効果が強くなるため好ましくない。70モル%を超える場合、融点が上昇することにより、ガラスの溶融性が困難となる他、粘度上昇も起こるため好ましくない。
(SiO 2 )
SiO 2 is a main component that forms the structural skeleton of glass, and its content is 46 to 70 mol%, preferably 51 to 63 mol%, and more preferably 53 to 62 mol%. If it is less than 46 mol%, the chemical durability of the glass becomes insufficient, and the glass tends to devitrify, which is not preferable. Furthermore, if it is less than 46 mol%, the water resistance of the glass becomes insufficient, and copper ions are more likely to elute in the presence of moisture (including moisture in the atmosphere). Since the deodorizing effect by the sulfurization reaction which occurs by this becomes strong, it is not preferable. If it exceeds 70 mol%, the melting point increases, which makes glass melting difficult and also causes an increase in viscosity.
(B2O3)
B2O3は、ガラスの溶解性、清澄性を向上させる成分であり、特定の組成においてはガラスの構造骨格を形成する成分ともなる。B2O3は、その含有量によって、ガラスの安定性を大きく左右するものであり、本願発明ではガラスの融剤としての意味合いが大きい。その含有量は、B2O3の揮発量を勘案して、5〜20モル%、好ましくは8〜17モル%、さらに好ましくは10〜17モル%とする。20モル%を超える場合、B2O3は溶融過程において揮発しやすく、組成制御が困難となるため好ましくない。
(B 2 O 3 )
B 2 O 3 is a component that improves the solubility and clarity of the glass, and in a specific composition, it also becomes a component that forms the structural skeleton of the glass. B 2 O 3 greatly affects the stability of the glass depending on its content, and in the present invention, the meaning as a flux of glass is large. Its content, in consideration of the volatilization amount of B 2 O 3, 5 to 20 mol%, preferably 8 to 17 mol%, further preferably 10 to 17 mol%. When it exceeds 20 mol%, B 2 O 3 is not preferred because it tends to volatilize in the melting process and the composition control becomes difficult.
(R2O)
R2O(R=Li、Na、K)は、ガラスの構造骨格におけるSiとOの結合を切断して非架橋酸素を形成し、その結果、ガラスの粘性を低下させ、成形性や溶解性を向上させる成分であり、B2O3同様の融剤である。その含有量は、R2Oの一種もしくは二種以上を、多成分との含有比も考慮しつつ、合計10〜30モル%、好ましくは13〜22モル%、更に好ましくは13〜19モル%とする。30モル%を超える場合、ガラスの化学的耐久性が不十分となる。具体的には、ガラス剤と大気中の水分が反応してブルームと称される白化現象が引き起こされる。ブルームが発生することにより、悪臭ガスとの接触面積が減少するため望ましくない。
(R 2 O)
R 2 O (R = Li, Na, K) breaks the bond between Si and O in the glass structure skeleton to form non-crosslinked oxygen, resulting in a decrease in glass viscosity, moldability and solubility. And a flux similar to B 2 O 3 . The content of one or more of R 2 O is 10 to 30 mol% in total, preferably 13 to 22 mol%, more preferably 13 to 19 mol%, considering the content ratio with multiple components. And When it exceeds 30 mol%, the chemical durability of the glass becomes insufficient. Specifically, a whitening phenomenon called bloom is caused by a reaction between the glass agent and moisture in the atmosphere. The occurrence of bloom is undesirable because it reduces the contact area with malodorous gas.
(B2O3+R2O)
前記のように、B2O3とR2Oは、共に、融剤として使用される。B2O3とR2Oの合計含有量が、15〜50モル%、好ましくは21〜39モル%の範囲が、安全に消臭効果を示す領域となる。15モル%未満の場合、ガラスの溶融性が不十分となり、成形の際に失透が発生しやすくなるため好ましくない。50モル%を超えると、ガラスの耐水性が不十分となり、水分存在下(大気中の水分を含む)で銅イオンが溶出しやすくなる結果、触媒作用による消臭効果よりも、イオン溶出によって起こる硫化反応による消臭効果が強くなるため好ましくない。また、50モル%を超えると、溶融の際に分相を起こしやすく、それに伴いガラス剤の消臭効果が不十分となるため好ましくない。
(B 2 O 3 + R 2 O)
As mentioned above, both B 2 O 3 and R 2 O are used as fluxing agents. The range in which the total content of B 2 O 3 and R 2 O is 15 to 50 mol%, preferably 21 to 39 mol%, is a region that safely exhibits the deodorizing effect. If it is less than 15 mol%, the meltability of the glass becomes insufficient, and devitrification tends to occur during molding, which is not preferable. If it exceeds 50 mol%, the water resistance of the glass becomes insufficient, and copper ions are likely to elute in the presence of moisture (including moisture in the atmosphere), resulting in ion elution rather than deodorizing effect due to catalysis. Since the deodorizing effect by a sulfurization reaction becomes strong, it is not preferable. On the other hand, if it exceeds 50 mol%, phase separation is likely to occur during melting, and the deodorizing effect of the glass agent becomes insufficient accordingly.
(R´O)
R´O(R´=Mg、Ca、Sr、Ba)は、ガラスの化学的耐久性を向上させる成分である。その含有量は、R´O(R´=Mg、Ca、Sr、Ba)の一種もしくは二種以上を、合計0〜10モル%、好ましくは2〜7モル%、更に好ましくは3〜6モル%とする。10モル%を超えると溶融時の粘性が高くなるとともに、ガラスが失透しやすくなるため好ましくない。なおR´Oは発明の消臭剤において必須成分ではなく、その含有量は0モル%でもよいが、2モル%以上とすることが好ましい。
(R'O)
R′O (R ′ = Mg, Ca, Sr, Ba) is a component that improves the chemical durability of the glass. The content is one or two or more of R′O (R ′ = Mg, Ca, Sr, Ba) in a total of 0 to 10 mol%, preferably 2 to 7 mol%, more preferably 3 to 6 mol. %. If it exceeds 10 mol%, the viscosity at the time of melting becomes high and the glass tends to be devitrified, which is not preferable. Note that R′O is not an essential component in the deodorant of the invention, and its content may be 0 mol%, but is preferably 2 mol% or more.
(Al2O3)
Al2O3は、ガラスの化学的耐久性を向上させ、結晶構造安定性に影響を与える成分である。また、Al2O3は、ガラスの分相を抑制しガラス剤の均質性を高める働きをする。粘性を上げること、添加によってガラス中の銅イオンの酸化還元状態に影響を与える可能性があることから、その含有量は、6モル%以下、好ましくは5.5モル%以下、最も好ましくは4.5モル%以下とする。
(Al 2 O 3 )
Al 2 O 3 is a component that improves the chemical durability of the glass and affects the crystal structure stability. Further, Al 2 O 3 functions to suppress the phase separation of the glass and increase the homogeneity of the glass agent. Since the viscosity and the addition may affect the redox state of copper ions in the glass, its content is 6 mol% or less, preferably 5.5 mol% or less, most preferably 4 .5 mol% or less.
(CuO)
CuOは、触媒として機能して、硫黄系悪臭物質の分解反応を促進し、硫黄系悪臭物質の消臭効果を奏するものである。その含有量は、0.01〜23モル%、好ましくは1〜13モル%、さらに好ましくは4〜13モル%とする。23モル%を超えると未溶解物が残留しやすくなる他、急冷の際や加工時に金属銅が析出しやすくなるため好ましくない。金属銅の析出に伴いガラスに変色を生じるため、ガラスの変色が問題となる用途には適さない。また、金属銅として析出した場合、被毒が進行してしまう。これに対し、CuOをガラス成分として含ませれば被毒が進行し難く、触媒機能を長期間に亘って安定して発揮することができる。
(CuO)
CuO functions as a catalyst, accelerates the decomposition reaction of the sulfurous malodorous substance, and exhibits the deodorizing effect of the sulfurous malodorous substance. The content is 0.01 to 23 mol%, preferably 1 to 13 mol%, more preferably 4 to 13 mol%. If it exceeds 23 mol%, undissolved material tends to remain, and metal copper tends to precipitate during rapid cooling or processing, which is not preferable. Since the glass is discolored with the deposition of metallic copper, it is not suitable for applications where discoloration of the glass is a problem. Moreover, when it precipitates as metallic copper, poisoning will advance. On the other hand, if CuO is included as a glass component, poisoning does not proceed easily, and the catalytic function can be stably exhibited over a long period of time.
(その他の微量成分)
上記成分以外にも、微量成分として、ZnO、SrO、BaO、TiO2、ZrO2、Nb2O5、P2O5、Cs2O、Rb2O、TeO2、BeO、GeO2、Bi2O3、La2O3、Y2O3、WO3、MoO3、またはFe2O3等も含めることができる。さらに、F、Cl、SO3、Sb2O3、SnO2、あるいはCe等を清澄剤として添加してもよい。
(Other trace components)
In addition to the above components, ZnO, SrO, BaO, TiO 2 , ZrO 2 , Nb 2 O 5 , P 2 O 5 , Cs 2 O, Rb 2 O, TeO 2 , BeO, GeO 2 , Bi 2 can be used as trace components. O 3 , La 2 O 3 , Y 2 O 3 , WO 3 , MoO 3 , Fe 2 O 3 or the like can also be included. Furthermore, F, Cl, SO 3 , Sb 2 O 3 , SnO 2 , Ce, or the like may be added as a clarifier.
(アルカリ−アルカリ土類−ケイ酸塩ガラス)
また本発明ではガラス質消臭剤として、銅成分を含有するアルカリ−アルカリ土類−ケイ酸塩ガラスを用いることもできる。このガラスは、SiO2:50〜70モル%、R2O:10〜33モル%、R´O:0〜15モル%、Al2O3:0〜6%、CuO:0.01〜23モル%含有するガラスである。
(Alkali-alkaline earth-silicate glass)
In the present invention, an alkali-alkaline earth-silicate glass containing a copper component can also be used as the vitreous deodorant. This glass, SiO 2: 50-70 mol%, R 2 O: 10~33 mol%, R'O: 0 to 15 mol%, Al 2 O 3: 0~6 %, CuO: 0.01~23 It is a glass containing mol%.
このガラス質消臭剤の好ましい組成は、SiO2:55〜70モル%、R2O:12〜24モル%、R´O:2〜10モル%、Al2O3:0〜5.5%、CuO:1〜20モル%である。またこのガラス質消臭剤の最も好ましい組成は、SiO2:55〜65モル%、R2O:12〜20モル%、R´O:3〜7モル%、Al2O3:0〜5%、CuO:4〜13モル%である。 A preferred composition of the vitreous deodorants, SiO 2: 55 to 70 mol%, R 2 O: 12~24 mol%, R'O: 2 to 10 mol%, Al 2 O 3: 0~5.5 %, CuO: 1 to 20 mol%. The most preferred composition of this vitreous deodorants, SiO 2: 55 to 65 mol%, R 2 O: 12~20 mol%, R'O: 3 to 7 mol%, Al 2 O 3: 0~5 %, CuO: 4 to 13 mol%.
アルカリ−アルカリ土類−ケイ酸塩ガラスは、上記したアルカリ−アルカリ土類−ホウケイ酸ガラスとは異なりB2O3を含有しないため組成の数値範囲が多少変化しているが、数値限定の理由はアルカリ−アルカリ土類−ホウケイ酸ガラスと同様である。 Unlike the alkali-alkaline earth-borosilicate glass described above, the alkali-alkaline earth-silicate glass does not contain B 2 O 3 , so the numerical range of the composition is slightly changed. Is the same as alkali-alkaline earth-borosilicate glass.
上記した銅成分を含有するアルカリ−アルカリ土類−ホウケイ酸ガラスまたは銅成分を含有するアルカリ−アルカリ土類−ケイ酸塩ガラスからなるガラス質消臭剤は、紙を構成する繊維間または紙の表面に含有される。紙の種類は、セルロース繊維を主成分とするものであることが好ましいが、特に限定されるものではなく、木材パルプ、非木材パルプ(藁、サトウキビ、ヨシ、ケナフ、クワ、コウゾ、ミツマタ、竹を由来とする)、合成パルプ(ポリプロピレン、ポリエチレン、ポリエチレンテレフタレート、ポリ塩化ビニル、ポリスチレン、アルミナ繊維、炭素繊維、ガラス繊維、ジルコニア繊維、アルミナ・シリカ繊維等)、古紙パルプから製造されるものであればよい。例えば、和紙、洋紙、中性紙、再生紙、合成紙など任意の紙とすることができる。 The glassy deodorant comprising the alkali-alkaline earth-borosilicate glass containing the copper component or the alkali-alkaline earth-silicate glass containing the copper component is used between the fibers constituting the paper or the paper. Contained on the surface. The type of paper is preferably cellulose fiber, but is not particularly limited. Wood pulp, non-wood pulp (wood, sugar cane, reed, kenaf, mulberry, mulberry, mitsumata, bamboo ), Synthetic pulp (polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, polystyrene, alumina fiber, carbon fiber, glass fiber, zirconia fiber, alumina / silica fiber, etc.), recycled pulp That's fine. For example, any paper such as Japanese paper, western paper, neutral paper, recycled paper, and synthetic paper can be used.
前記したように、紙を構成する繊維間に担持させる場合には、消臭紙中のガラス質消臭剤の含有量は0.1〜10質量%とし、また紙の表面に担持させる場合には、ガラス質消臭剤の含有量は0.1〜5g/m2とすることが好ましい。この範囲より少ないと消臭効果が不足し、逆にこの範囲を超えると、紙の特性、すなわち、柔軟性や平滑性が失われる可能性があるためである。本発明において、ガラス質消臭剤は触媒効果によって消臭機能を発揮するため、消臭量がガラス質消臭剤の露出量に依存しない。このため長期的には、少量が紙の表面に露出していればよく、上記の範囲を超えて含有させても消臭量の増加を見込むことができない。 As described above, when it is carried between the fibers constituting the paper, the content of the glassy deodorant in the deodorant paper is 0.1 to 10% by mass, and when it is carried on the surface of the paper. The glassy deodorant content is preferably 0.1 to 5 g / m 2 . This is because if it is less than this range, the deodorizing effect is insufficient, while if it exceeds this range, the characteristics of the paper, that is, flexibility and smoothness may be lost. In the present invention, since the vitreous deodorant exhibits a deodorizing function due to a catalytic effect, the deodorizing amount does not depend on the exposure amount of the vitreous deodorant. For this reason, in the long term, it is sufficient that a small amount is exposed on the surface of the paper, and even if the content exceeds the above range, an increase in deodorizing amount cannot be expected.
上記したように、第1の実施形態の消臭紙は紙を構成する繊維1の間にガラス質消臭剤2を含有させたものであり、第2の実施形態の消臭紙は紙の表面にガラス質消臭剤2を含有する消臭層3を形成したものである。第1の実施形態の場合には、ガラス質消臭剤を含ませたスラリー中に紙を含浸した後に絞って乾燥する方法で消臭紙を得ることができる。第2の実施形態の場合には、バインダー中にガラス質消臭剤を含ませ塗布、スプレーする方法で消臭紙を得ることができる。第2の実施形態の消臭紙のように、紙の表面にガラス質消臭剤を担持させたものでは、繊維の内部に埋没して消臭に寄与しないガラス質消臭剤を減少させることができるので、消臭効果をより高めることができる。バインダーとしては、例えば、以下のものがある。アクリル樹脂、ウレタン樹脂、エポキシ樹脂、セルロース系樹脂、アルキド樹脂、ポリアミド樹脂、スチレン樹脂、キシレン樹脂、スチレン樹脂、アミノ樹脂、フェノール樹脂、天然樹脂、天然樹脂誘導体、石油樹脂、塩化ゴム、ポリ塩化ビニル、塩化ビニル・酢酸ビニル共重合樹脂、ポリ酢酸ビニル、ポリビニルアルコール、ポリビニルブチラール、塩素化ポリプロピレンなどを使用することができる。 As described above, the deodorizing paper of the first embodiment includes the glassy deodorant 2 between the fibers 1 constituting the paper, and the deodorizing paper of the second embodiment is made of paper. The deodorizing layer 3 containing the glassy deodorant 2 is formed on the surface. In the case of the first embodiment, deodorized paper can be obtained by a method of impregnating paper in a slurry containing a vitreous deodorant and then squeezing and drying. In the case of the second embodiment, the deodorized paper can be obtained by a method in which a glassy deodorant is contained in a binder and applied and sprayed. In the case where a glassy deodorant is carried on the surface of the paper as in the deodorant paper of the second embodiment, the glassy deodorant that is buried in the fiber and does not contribute to deodorization is reduced. Therefore, the deodorizing effect can be further enhanced. Examples of the binder include the following. Acrylic resin, urethane resin, epoxy resin, cellulose resin, alkyd resin, polyamide resin, styrene resin, xylene resin, styrene resin, amino resin, phenol resin, natural resin, natural resin derivative, petroleum resin, chlorinated rubber, polyvinyl chloride , Vinyl chloride / vinyl acetate copolymer resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, chlorinated polypropylene, and the like can be used.
また、上記した消臭紙を積層して、もしくは、上記した消臭紙と、ガラス質消臭剤を含有しない紙とを積層して、積層構造を持つ積層紙とすることもできる。 Alternatively, the above-described deodorizing paper may be laminated, or the above-mentioned deodorizing paper and paper containing no vitreous deodorant may be laminated to obtain a laminated paper having a laminated structure.
本発明の消臭紙は、ガラス質消臭剤のガラス中に保持された銅成分の触媒作用により、悪臭成分を分解する機能を有するものである。溶解性ガラスとは異なり、銅成分はガラス中に保持されたままで触媒作用により悪臭成分を分解するため、長期間にわたり消臭効果が維持され、持続性に優れる。また、溶解性ガラスは酸性ガラスであるため酸性悪臭である低級脂肪酸に対する消臭効果はないが、本発明におけるガラス質消臭剤は、低級脂肪酸や体臭成分等の悪臭物質に対する消臭効果を持つ。 The deodorizing paper of this invention has a function which decomposes | disassembles a malodorous component by the catalytic action of the copper component hold | maintained in the glass of a vitreous deodorizing agent. Unlike the soluble glass, the copper component decomposes the malodorous component by the catalytic action while being retained in the glass, so that the deodorizing effect is maintained over a long period of time and the durability is excellent. Further, since the soluble glass is an acidic glass, it does not have a deodorizing effect on lower fatty acids that are acidic malodors, but the vitreous deodorant in the present invention has a deodorizing effect on malodorous substances such as lower fatty acids and body odor components. .
本発明の消臭紙はそのまま使用できることは勿論であるが、袋にして食品用袋、菓子袋、レジ袋、ゴミ袋など等として使用するに適している。ガラス質消臭剤は人体に対して無害であるから、食品包装用袋として使用することができる。また低級脂肪酸や体臭成分等の悪臭物質に対する消臭効果を持つので、介護分野におけるおむつ用袋等として使用することができる。また、トイレットペーパーやその芯材用紙としても適している。さらに障子紙、襖紙等として使用すれば、室内の臭気をなくす効果がある。 The deodorizing paper of the present invention can of course be used as it is, but is suitable for use as a bag for food, a confectionery bag, a shopping bag, a garbage bag, etc. Since the glassy deodorant is harmless to the human body, it can be used as a food packaging bag. Moreover, since it has a deodorizing effect on malodorous substances such as lower fatty acids and body odor components, it can be used as a diaper bag in the field of nursing care. It is also suitable as toilet paper and its core material paper. Furthermore, if it is used as shoji paper, paper, etc., it has the effect of eliminating indoor odors.
その他、ティッシュペーパー、塗工紙、非塗工紙、印刷用紙、画用紙、ラミネート紙、ペット用シート、靴箱、靴の包装紙、衣類用包装紙、新聞紙、セパレートシート、段ボールなど、広い用途に用いることができる。特にセパレートシートは、食品や食品容器の保管、運搬に繰返し使用されるため、用途として適している。また、特におむつ向け対し、密封容器内で紙と保持し消臭効果を高めることができる。水分で消臭効果が助長されるため、簡易トイレと併用して使用することも可能である。 Other uses such as tissue paper, coated paper, non-coated paper, printing paper, drawing paper, laminate paper, pet sheet, shoe box, shoe wrapping paper, clothing wrapping paper, newspaper, separate sheet, cardboard, etc. be able to. In particular, the separate sheet is suitable for use because it is repeatedly used for storage and transportation of food and food containers. Moreover, especially for diapers, the deodorizing effect can be enhanced by holding paper in a sealed container. Since the deodorizing effect is promoted by moisture, it can be used in combination with a simple toilet.
なお、上記した実施形態ではガラス質消臭剤を単独で使用したが、汎用のシリカゲル、ゼオライト、活性炭、粘土鉱物、光触媒(二酸化チタン)等の無機系消臭剤と複合使用することもできる。また銀を含有する溶解性ガラスとともに使用することもできる。このような複合使用により、消臭速度のスピードアップや対象ガス拡大、コストダウン等の効果を狙うことが可能となる。特に簡易トイレと併用して使用するような場合には、銀イオンを溶出させる溶解性ガラスとの複合使用により、抗菌・消臭効果をさらに高めることができる。
以下に本発明の実施例を示す。なお、表中のn.d.は未検出を意味する。
In the above-described embodiment, the vitreous deodorant is used alone, but it can also be used in combination with an inorganic deodorant such as general-purpose silica gel, zeolite, activated carbon, clay mineral, photocatalyst (titanium dioxide). It can also be used with soluble glass containing silver. Such combined use makes it possible to aim at effects such as speeding up the deodorization speed, expanding target gas, and reducing costs. In particular, when used in combination with a simple toilet, the combined use with soluble glass that elutes silver ions can further enhance the antibacterial and deodorizing effects.
Examples of the present invention are shown below. In the table, nd means not detected.
表1に示す組成となるようにガラス原料を調合し、びんガラスなどの汎用ガラス組成と同様の常法により溶融、成形、粉砕してガラス質消臭剤を製造した。得られたガラス質消臭剤を表2に示す条件で紙に含有させて消臭紙を得た。この消臭紙をテドラーバッグに封入し、消臭効果の確認試験を行った。なお、表2において「繊維の種類」とは、「紙を構成する繊維の主成分の種類」を意味する。ここで、主成分とは、当該主成分の機能を妨げない範囲で他の成分を含有することを許容する意を包含し、特に当該主成分の含有割合を特定するものではないが、主成分は最も多い含有割合を占めるものであり、好ましくは50質量%以上、更に好ましくは70質量%以上、特に好ましくは90質量%以上(100%含む)を占める意を包含するものである。 A glass raw material was prepared so as to have the composition shown in Table 1, and melted, molded, and pulverized in the same manner as general-purpose glass compositions such as bottle glass to produce a glassy deodorant. The obtained glassy deodorant was contained in paper under the conditions shown in Table 2 to obtain deodorized paper. This deodorizing paper was enclosed in a tedlar bag and a deodorizing effect confirmation test was performed. In Table 2, “type of fiber” means “type of main component of fiber constituting paper”. Here, the main component includes the intention to allow other components to be contained within a range that does not interfere with the function of the main component, and does not particularly specify the content ratio of the main component. Occupies the largest content, and preferably includes 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more (including 100%).
表2中の実施形態1は、木材パルプにガラス質消臭剤を添加し、JIS P 8222に基づいて手すき紙を調整したものであり、実施形態2は、古紙(100%)に対し、セルロール系バインダーを用いて両面にスプレーコートしたものである。いずれも、100×100mmに断裁し、テドラーバッグに悪臭成分と封入した。また表2に記載した含有量は、いずれも明細書中で示した含有量(実施形態1:○質量、実施形態2:○質量%/m2)を示しており、実験ではその条件に該当する試料を断裁した。 Embodiment 1 in Table 2 is one in which a glassy deodorant is added to wood pulp and handsheets are adjusted based on JIS P 8222. Embodiment 2 is a cell roll for waste paper (100%). This is spray-coated on both sides using a system binder. All were cut to 100 × 100 mm and sealed with malodorous components in a Tedlar bag. In addition, the contents shown in Table 2 indicate the contents shown in the specification (Embodiment 1: ○ mass, Embodiment 2: ○ mass% / m 2 ), and correspond to the conditions in the experiment. The sample to be cut was cut.
(実施例A)
表2の実験例1〜11、13〜22の紙を1Lのテドラーバッグに悪臭成分と封入し、室温で、経過時間に伴う袋内の悪臭濃度を測定した。硫化水素、メチルメルカプタンはガスクロマトグラフで、プロピオン酸、イソ吉草酸はガス検知管で、トランス−2‐ノネナールは高速液体クロマトグラフで測定した。比較として、表3に示す溶解性ガラス1〜3からなるガラス質消臭剤を製造し、第1の実施形態でガラス質消臭剤の含有率が1質量%の紙を作製し、同様に断裁した。なお、銅成分を含まないブランクは、実験例6、16に該当する。その結果、表4に示すように、いずれの悪臭に対しても消臭効果があることが確認された。
(Example A)
The papers of Experimental Examples 1 to 11 and 13 to 22 in Table 2 were sealed with malodorous components in a 1 L Tedlar bag, and the malodor concentration in the bag with the elapsed time was measured at room temperature. Hydrogen sulfide and methyl mercaptan were measured with a gas chromatograph, propionic acid and isovaleric acid were measured with a gas detector tube, and trans-2-nonenal was measured with a high performance liquid chromatograph. As a comparison, a glassy deodorant composed of the soluble glasses 1 to 3 shown in Table 3 was produced, and a paper with a glassy deodorant content of 1% by mass was prepared in the first embodiment. Cut out. In addition, the blank which does not contain a copper component corresponds to Experimental Examples 6 and 16. As a result, as shown in Table 4, it was confirmed that there was a deodorizing effect against any offensive odor.
(実施例B)
表2の実験例5、12の紙を1Lのテドラーバッグに悪臭成分と封入し、室温で、経過時間に伴う袋内の悪臭濃度をガスクロマトグラフで測定した。比較として、表3に示す溶解性ガラス2〜4からなるガラス質消臭剤を製造し、第1の実施形態で1質量%の紙を作製し、同様に断裁した。その結果、表5に示すように、溶解性ガラスは消臭限界に達したのに対し、実験例5は消臭総量が大きいことが確認された。溶解性ガラスは、露出量に応じて消臭限界が決定するのに対し、銅成分を含有させたガラス質消臭剤は、触媒作用を示すため、少量でも露出すれば消臭総量が期待できる。しかし、ガラスは組成によって連続的に変化し、その効果も触媒反応から溶解性ガラスの吸着反応まで連続的に変化する。実験例12は、耐久性が低下した組成のため、溶解性ガラス同様に吸着反応を示し、消臭限界に達したことが確認された。
(Example B)
The papers of Experimental Examples 5 and 12 in Table 2 were sealed with malodorous components in a 1 L Tedlar bag, and the malodor concentration in the bag with the elapsed time was measured at room temperature with a gas chromatograph. As a comparison, a vitreous deodorant composed of the soluble glasses 2 to 4 shown in Table 3 was produced, and 1% by mass of paper was prepared in the first embodiment, and cut similarly. As a result, as shown in Table 5, it was confirmed that the soluble glass reached the deodorization limit, whereas Experimental Example 5 had a large total deodorization amount. The deodorizing limit of the soluble glass is determined according to the exposure amount, whereas the vitreous deodorant containing a copper component shows a catalytic action, so that even if a small amount is exposed, the total deodorizing amount can be expected. . However, the glass changes continuously depending on the composition, and the effect also changes continuously from the catalytic reaction to the adsorption reaction of the soluble glass. Since Experimental Example 12 had a composition with reduced durability, it exhibited an adsorption reaction like the soluble glass, and it was confirmed that the deodorization limit was reached.
(実施例C:ガラス質消臭剤の基本特性・分解作用)
D50=4.2μmまで粉砕した表1の組成番号6からなるガラス1gとメチルメルカプタンを5Lのテドラーバッグに封入し、室温で、経過時間に伴う袋内のメチルメルカプタン、ジメチルジスルフィドをガスクロマトグラフで測定した。またブランクとして、ガラス質消臭剤なしで同様の操作を行った。なお、事前にガスクロマトグラフ質量分析計にて、袋内に存在するガス成分がこの二成分のみであることを確認していた。その結果、図3に示すように、本発明のガラス質消臭剤がメチルメルカプタンを分解し、ジメチルジスルフィドを生成する作用を示すことを確認した。ガラス質消臭剤の基本特性は、紙に含有させても、当然保持される。
(Example C: Basic characteristics and decomposition action of glassy deodorant)
D 50 = 4.2 μm ground glass 1g consisting of composition number 6 in Table 1 and methyl mercaptan were sealed in a 5 L Tedlar bag, and methyl mercaptan and dimethyl disulfide in the bag over time were measured with a gas chromatograph at room temperature. did. Moreover, the same operation was performed as a blank, without a glassy deodorant. In addition, it was confirmed in advance by a gas chromatograph mass spectrometer that the gas components present in the bag were only these two components. As a result, as shown in FIG. 3, it was confirmed that the vitreous deodorant of the present invention has an action of decomposing methyl mercaptan and generating dimethyl disulfide. The basic characteristics of the vitreous deodorant are naturally retained even when incorporated in paper.
(実施例D:ガラス質消臭剤の基本特性・ラジカル発生)
D50=5.0μmまで粉砕した表1の組成番号6、9、表3の溶解性ガラス1からなるガラス200mgに対し、pH=7.4の0.1mоl・L−1のリン酸緩衝溶液200μLを添加した。そこに9.2mоl・L−1のDMPO(LABOTEC.製、LM−2110)10μLを添加し、シェイクした。DMPO添加時点から10秒後、1分後、5分後にシェイクをやめ、溶液のみをヘマトクリット管で採取し、ESR(日本電子株式会社製、FR−30、Xバンド)測定を実施した。また、ガラスを除いたものをブランクとした。全て、室温、蛍光灯下で実施した。当手法は、ラジカル測定の一般的手法であるスピントラップ法に該当し、DMPOがラジカルを補足するとスピンアダクトが生成する。この生成物(DMPO−OH)をESRで検出した。なお、検出値の単位は、基準物質Mn2+に対するピーク面積値比率(エリアシングル/エリアマンガン、S/M)である。その結果を表6に示す。組成番号6のガラスはDMPO−OHの生成が確認されたのに対し、組成番号9、溶解性ガラス1はブランクと同様にバックグラウンドの値を示しただけであった。本発明のガラス質消臭剤がラジカルを発生する可能性が高いことが確認された。
(Example D: Basic characteristics of glassy deodorant / radical generation)
D 50 = 0.1 mol·L −1 phosphate buffer solution of pH = 7.4 with respect to 200 mg of the glass composed of the soluble glass 1 of composition numbers 6 and 9 and table 3 of Table 1 ground to 5.0 μm 200 μL was added. Thereto, 10 μL of 9.2 mol·L −1 DMPO (manufactured by LABOTEC, LM-2110) was added and shaken. Shake was stopped 10 seconds, 1 minute, and 5 minutes after DMPO addition, and only the solution was collected with a hematocrit tube, and ESR (manufactured by JEOL Ltd., FR-30, X band) measurement was performed. Moreover, the thing except glass was made into the blank. All were performed at room temperature under fluorescent light. This technique corresponds to the spin trap method, which is a general technique for measuring radicals, and spin adducts are generated when DMPO captures radicals. This product (DMPO-OH) was detected by ESR. The unit of the detected value is a peak area value ratio (area single / area manganese, S / M) with respect to the reference material Mn 2+ . The results are shown in Table 6. The composition No. 6 glass was confirmed to produce DMPO-OH, whereas the composition No. 9 and the soluble glass 1 only showed a background value as in the blank. It was confirmed that the vitreous deodorant of the present invention has a high possibility of generating radicals.
(実施例E:ガラス質消臭剤の基本特性・触媒劣化の抑制)
D50=4.2μmまで粉砕した表2の組成番号6からなるガラス0.1gとCuO試薬(平均粒径4μm)0.1gのそれぞれを1Lのテドラーバッグに封入し、室温で、経過時間に伴う袋内のメチルメルカプタン濃度をガスクロマトグラフで測定した。メチルメルカプタンの初期濃度は55ppmとし、繰返し10回まで実施した。また、ブランクとしてガラスなしで同様の操作を行った。その結果、表7に示すように、CuO試薬は、繰返しに伴い消臭効果が低減している。これは、一般的に知られるCuOの触媒劣化(硫黄吸着)である。それに対し、ガラスは消臭効果を維持しており、持続性が高いことが確認された。このメカニズム解明は課題が残るが、ガラス化することで触媒劣化が抑制されることが確認された。このときのガラス表面をXPS(アルバックファイ(株)製、PHI 5000 VersaProbe)で解析したところ、表8に示すように、確かに消臭後に硫黄の吸着がないことが確認された。ガラス質消臭剤の基本特性は、紙に含有させても、当然保持される。
(Example E: Basic characteristics of glassy deodorant and suppression of catalyst deterioration)
D 50 = 4.2 μm crushed glass of composition number 6 in Table 2 0.1 g and CuO reagent (average particle size 4 μm) 0.1 g each was sealed in a 1 L Tedlar bag at room temperature with time The methyl mercaptan concentration in the bag was measured with a gas chromatograph. The initial concentration of methyl mercaptan was 55 ppm and repeated up to 10 times. Moreover, the same operation was performed without glass as a blank. As a result, as shown in Table 7, the deodorizing effect of the CuO reagent is reduced with repetition. This is a generally known catalyst deterioration (sulfur adsorption) of CuO. On the other hand, it was confirmed that the glass maintained the deodorizing effect and was highly sustainable. Although elucidation of this mechanism remains, it has been confirmed that catalyst degradation is suppressed by vitrification. When the glass surface at this time was analyzed by XPS (manufactured by ULVAC-PHI Co., Ltd., PHI 5000 VersaProbe), as shown in Table 8, it was confirmed that there was certainly no sulfur adsorption after deodorization. The basic characteristics of the vitreous deodorant are naturally retained even when incorporated in paper.
1 繊維
2 ガラス質消臭剤
3 消臭層
1 fiber 2 glassy deodorant 3 deodorant layer
Claims (5)
このガラス質消臭剤は銅成分を含有するアルカリ−アルカリ土類−ホウケイ酸ガラスまたは銅成分を含有するアルカリ−アルカリ土類−ケイ酸塩ガラスからなり、
ガラス中に保持された銅成分の触媒作用により、悪臭成分を分解する機能を有することを特徴とする消臭紙。 A deodorizing paper carrying a glassy deodorant between fibers constituting the paper or on the surface of the paper,
This glassy deodorant consists of an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component,
A deodorizing paper characterized by having a function of decomposing malodorous components by the catalytic action of a copper component held in glass.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015157082A JP6422833B2 (en) | 2015-08-07 | 2015-08-07 | Deodorant paper |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015157082A JP6422833B2 (en) | 2015-08-07 | 2015-08-07 | Deodorant paper |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2017035196A true JP2017035196A (en) | 2017-02-16 |
JP6422833B2 JP6422833B2 (en) | 2018-11-14 |
Family
ID=58046796
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015157082A Active JP6422833B2 (en) | 2015-08-07 | 2015-08-07 | Deodorant paper |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6422833B2 (en) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0369695A (en) * | 1989-05-09 | 1991-03-26 | Ain:Kk | Paper having deodorizing, bactericidal, far-infrared radiating and antistatic properties |
JPH0381375A (en) * | 1989-08-25 | 1991-04-05 | Ain:Kk | Coating material with deodorizing, antimicrobial, far infrared radiating, acidic corrosion resistant and antistatic properties |
JPH04134008A (en) * | 1990-09-25 | 1992-05-07 | Nippon Sheet Glass Co Ltd | Bactericidal treating agent |
JP2003310725A (en) * | 2002-04-19 | 2003-11-05 | Pyramid:Kk | Method for preventing lowering of adsorption action of porous body, deodorizing sheet, product equipped therewith and manufacturing method for deodorizing sheet |
JP2004008518A (en) * | 2002-06-07 | 2004-01-15 | Kao Corp | Deodorant |
JP2005232654A (en) * | 2004-02-23 | 2005-09-02 | Kao Corp | Deodorizing, antibacterial fibrous product |
JP2008516944A (en) * | 2004-10-14 | 2008-05-22 | ディーエスエム アイピー アセッツ ビー.ブイ. | Composition comprising a binary mixture of melamine particles |
JP2010273698A (en) * | 2009-05-26 | 2010-12-09 | Jgc Catalysts & Chemicals Ltd | Antibacterial deodorant and method for producing the same |
JP2011104274A (en) * | 2009-11-20 | 2011-06-02 | Toagosei Co Ltd | Sulfur-based gas deodorant |
JP2014005194A (en) * | 2012-06-01 | 2014-01-16 | Ishizuka Glass Co Ltd | Antibacterial glass and manufacturing method of the same |
JP2014198094A (en) * | 2013-03-29 | 2014-10-23 | 大王製紙株式会社 | Production technique of toilet tissue paper, production technique of toilet roll, and toilet roll |
-
2015
- 2015-08-07 JP JP2015157082A patent/JP6422833B2/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0369695A (en) * | 1989-05-09 | 1991-03-26 | Ain:Kk | Paper having deodorizing, bactericidal, far-infrared radiating and antistatic properties |
JPH0381375A (en) * | 1989-08-25 | 1991-04-05 | Ain:Kk | Coating material with deodorizing, antimicrobial, far infrared radiating, acidic corrosion resistant and antistatic properties |
JPH04134008A (en) * | 1990-09-25 | 1992-05-07 | Nippon Sheet Glass Co Ltd | Bactericidal treating agent |
JP2003310725A (en) * | 2002-04-19 | 2003-11-05 | Pyramid:Kk | Method for preventing lowering of adsorption action of porous body, deodorizing sheet, product equipped therewith and manufacturing method for deodorizing sheet |
JP2004008518A (en) * | 2002-06-07 | 2004-01-15 | Kao Corp | Deodorant |
JP2005232654A (en) * | 2004-02-23 | 2005-09-02 | Kao Corp | Deodorizing, antibacterial fibrous product |
JP2008516944A (en) * | 2004-10-14 | 2008-05-22 | ディーエスエム アイピー アセッツ ビー.ブイ. | Composition comprising a binary mixture of melamine particles |
JP2010273698A (en) * | 2009-05-26 | 2010-12-09 | Jgc Catalysts & Chemicals Ltd | Antibacterial deodorant and method for producing the same |
JP2011104274A (en) * | 2009-11-20 | 2011-06-02 | Toagosei Co Ltd | Sulfur-based gas deodorant |
JP2014005194A (en) * | 2012-06-01 | 2014-01-16 | Ishizuka Glass Co Ltd | Antibacterial glass and manufacturing method of the same |
JP2014198094A (en) * | 2013-03-29 | 2014-10-23 | 大王製紙株式会社 | Production technique of toilet tissue paper, production technique of toilet roll, and toilet roll |
Also Published As
Publication number | Publication date |
---|---|
JP6422833B2 (en) | 2018-11-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6514595B2 (en) | Deodorant film and bag with deodorizing function | |
KR20170129120A (en) | Deodorizing glass | |
JP5191095B2 (en) | Aroma deodorizer and wicking volatilization member for aroma deodorizer | |
EP0021586B1 (en) | Controlled release air freshener using an absorbent generator | |
JP6422833B2 (en) | Deodorant paper | |
JP6441182B2 (en) | Masterbatch and method for producing deodorant resin composition | |
JP6441186B2 (en) | Deodorant spray | |
JP6514604B2 (en) | Deodorant fiber and deodorant cloth | |
JP6441185B2 (en) | Deodorant plate | |
JP6441187B2 (en) | Filter with deodorizing function | |
CN1189219C (en) | Absorption article containing cyclo dextrin | |
JP4873923B2 (en) | Deodorizing and / or sanitizing sheet | |
JP6408439B2 (en) | Deodorant resin container | |
JP6472727B2 (en) | Absorbent pad | |
JP6581845B2 (en) | Water absorption sheet | |
JP2006077367A (en) | Deodorant coating and deodorant decorative paper | |
JPWO2018185948A1 (en) | Material showing deodorant effect | |
GB2269587A (en) | Deodorising agent for paper mill effluents | |
JPH1133100A (en) | Photocatalyst fine grain containing solid porous silica particle, using method thereof, and photocatalyst containing polymer solid body | |
JP2017024749A (en) | Deodorant glass container | |
JPH0365239A (en) | Deodorizing agent | |
JP6408437B2 (en) | Deodorant organic composition, deodorant paint and deodorant print using the same | |
JP6670055B2 (en) | Glass film forming material and glass coated product using the same | |
WO2018002284A1 (en) | Device and method for treating matter | |
JPH0366900B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20171121 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180718 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180724 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180906 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20181009 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20181017 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6422833 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |