JP5438458B2 - Gel chlorine dioxide sterilizer - Google Patents
Gel chlorine dioxide sterilizer Download PDFInfo
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- JP5438458B2 JP5438458B2 JP2009238847A JP2009238847A JP5438458B2 JP 5438458 B2 JP5438458 B2 JP 5438458B2 JP 2009238847 A JP2009238847 A JP 2009238847A JP 2009238847 A JP2009238847 A JP 2009238847A JP 5438458 B2 JP5438458 B2 JP 5438458B2
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims description 72
- 239000004155 Chlorine dioxide Substances 0.000 title claims description 36
- 235000019398 chlorine dioxide Nutrition 0.000 title claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 14
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000661 sodium alginate Substances 0.000 claims description 11
- 235000010413 sodium alginate Nutrition 0.000 claims description 11
- 229940005550 sodium alginate Drugs 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000002781 deodorant agent Substances 0.000 claims description 10
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 8
- 229960002218 sodium chlorite Drugs 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 230000000844 anti-bacterial effect Effects 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 229960004543 anhydrous citric acid Drugs 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 14
- 229910001919 chlorite Inorganic materials 0.000 description 13
- 229910052619 chlorite group Inorganic materials 0.000 description 13
- 239000000499 gel Substances 0.000 description 12
- 230000007774 longterm Effects 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000005068 transpiration Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 239000003349 gelling agent Substances 0.000 description 5
- 229920001817 Agar Polymers 0.000 description 4
- 239000004113 Sepiolite Substances 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 229910052624 sepiolite Inorganic materials 0.000 description 4
- 235000019355 sepiolite Nutrition 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- -1 alkali metal chlorites Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- QXIKMJLSPJFYOI-UHFFFAOYSA-L calcium;dichlorite Chemical compound [Ca+2].[O-]Cl=O.[O-]Cl=O QXIKMJLSPJFYOI-UHFFFAOYSA-L 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
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- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Description
本発明は、ゲル状にして取り扱い容易な希薄な二酸化塩素ガスを放散する殺菌消臭剤に関するものである。 The present invention relates to a bactericidal deodorant that diffuses a thin chlorine dioxide gas that is gelled and easy to handle.
二酸化塩素ガスは、強力な酸化剤であるので、その酸化作用により、滅菌したり、また、悪臭成分を分解したりすることが知られており、特に他の物質と反応して有害物を作り出すことが少なく安全であるため、二酸化塩素ガスを発生する物質を殺菌剤、消臭剤等として使用している。 Chlorine dioxide gas is a powerful oxidant, and is known to sterilize and decompose malodorous components due to its oxidizing action, and reacts with other substances to produce harmful substances. Therefore, substances that generate chlorine dioxide gas are used as disinfectants and deodorants.
また二酸化塩素ガスの発生物質（安定化二酸化塩素水溶液）を殺菌剤、消臭剤等として取り扱いやすいようにゲル状物質とし、所定の容器に収納して、車両室内用や、冷蔵庫用として使用することが提案されている（特許文献１：特開昭５７−２２１０２号公報、特開昭６１−１８１５３２号公報）。また前記特許文献１には、ゲル化剤として寒天を使用することが開示されている。 In addition, the substance that generates chlorine dioxide gas (stabilized chlorine dioxide aqueous solution) is made into a gel-like substance so that it can be easily handled as a disinfectant, deodorant, etc., stored in a predetermined container, and used for vehicle interior or refrigerator (Patent Document 1: Japanese Patent Laid-Open Nos. 57-22102 and 61-181532). Patent Document 1 discloses using agar as a gelling agent.
しかし安定化二酸化塩素水溶液をゲル状組成物とした場合は、二酸化塩素ガスの発生が極めて少ないとして、特許文献２（特開平１１−２７８８０８号公報）には、亜塩素酸塩を水に溶解した亜塩素酸塩水溶液と、二酸化塩素ガスを水中にバブリングして溶解させた二酸化塩素水溶液と、亜塩素酸塩水溶液にｐＨ調整剤（クエン酸等）等を適宜量混合し室温で十分に攪拌して調製した純粋二酸化塩素液剤を高吸水樹脂に含有させてゲル化したゲル状組成物が提案されている。 However when the stabilized chlorine dioxide solution with a gel-like composition, and a generated chlorine dioxide gas is very small, Patent Document 2 (JP-A-11-278808), a chlorite is dissolved in water Mix chlorite aqueous solution, chlorine dioxide aqueous solution in which chlorine dioxide gas is dissolved in water, and chlorite aqueous solution with appropriate amount of pH adjuster (citric acid, etc.) and mix well at room temperature. There has been proposed a gel composition in which a pure chlorine dioxide solution prepared in this manner is contained in a highly water-absorbing resin and gelled.
また特許文献３（特開２００５−２９４３０号公報）には、固形亜塩素酸塩と固形有機酸と粉状のガス発生調節剤と吸水性樹脂とを混合し、使用前に水を添加してゲル化させて二酸化塩素ガスを持続的に発生させる場合に、二酸化塩素ガスの蒸散速度の調整が困難であるとして、蒸散ガスの吸収・放出をなすガス発生調整剤（セピオライトのような多孔質材料）を含めることが提案されている。 In Patent Document 3 (Japanese Patent Laid-Open No. 2005-29430), a solid chlorite, a solid organic acid, a powdered gas generation regulator and a water absorbent resin are mixed, and water is added before use. Gas generation regulator (porous material such as sepiolite) that absorbs and releases transpiration gas because it is difficult to adjust the transpiration rate of chlorine dioxide gas when chlorine dioxide gas is generated continuously by gelation. ) Is proposed.
また特許文献４（特開２００６−３２１６６６号公報）には、亜塩素酸塩水溶液に、活性化剤としてさらし粉またはイソシアヌル酸類と、ガス発生調節剤（セピオライト）と、吸水性樹脂とを添加し、ゲル化させて得られるゲル状組成物が開示されている。 Patent Document 4 (Japanese Patent Application Laid-Open No. 2006-321666) adds bleaching powder or isocyanuric acid as an activating agent, a gas generation regulator (sepiolite), and a water absorbent resin to a chlorite aqueous solution, A gel composition obtained by gelation is disclosed.
一般の冷蔵庫のような食品収納の場所や、要介護者の居室のような場所に使用される殺菌消臭剤は、使用部材の安全性、適度の希薄放散性、長期安定性などが求められるので、二酸化塩素ガス発生物質をゲル状化することが前記文献で開示されているが、特許文献１に記載されているようにゲル化剤として寒天を使用する場合には、当然二酸化塩素発生溶液が、寒天溶解温度（同文献では８０℃以上）状態として混合する必要があり、各家庭での使用する商品には不適当である。 Bactericidal deodorants used in food storage areas such as general refrigerators and places where care recipients need to be used are required to be safe, moderately dilute, and long-term stable. Therefore, it is disclosed in the above-mentioned document that the chlorine dioxide gas generating substance is gelled. However, as described in Patent Document 1, when using agar as a gelling agent, naturally a chlorine dioxide generating solution is used. However, it is necessary to mix in the agar melting temperature state (80 ° C. or higher in the same document), which is unsuitable for products used in each home.
そこで常温でもゲル化が可能な高給水樹脂を採用することが、特許文献２，３，４で提案されているが、高吸水性樹脂は、乳幼児や要介護者が誤って口にした場合の安全性に問題あり、特に特許文献２記載の高吸水性樹脂のみでゲル化した場合には、蒸散速度の調節が難しく、例えば温度の上昇によって蒸散速度が大きくなるという問題点もあり、特許文献３，４に開示されているようにガス発生調整剤を添加混合する必要がある。
Therefore, it has been proposed in
但し特許文献２に記載されているように、単に粉状のガス発生調節剤（セピオライト等）を混入することで二酸化塩素ガス発生の安定性を高めたとしても、その実施例からは７日間程度のガス発生量の安定性しか裏付けられていない。 However, as described in Patent Document 2, even if the stability of the generation of chlorine dioxide gas is improved by simply mixing a powdery gas generation regulator (such as sepiolite), it takes about 7 days from the examples. Only the stability of the amount of gas generated is supported.
二酸化塩素の長期安定性として、使用期間を１カ月（３０日：７２０時間）とすることを目安とした場合、特許文献４に開示されている実施例においては、実施例９，１０，１１が長期の安定性を認めることができるが、やや低濃度の蒸散である。
As the long-term stability of chlorine dioxide, when the usage period is set to one month (30 days: 720 hours), in Examples disclosed in
これは吸水樹脂の性質上、ゲル中からの安定気体放散機能（長期安定放出）の点で劣るためで、セピオライトのようなガス発生調整剤を必要とし、前記ガス発生調整剤を混入しないと混合当初のガス発生濃度が高くなってしまい、ガス発生濃度の減少率が高くなり、安定放出とは程遠いことになり、必然的にガス放散濃度を低くする必要がある。 This is because the properties of the water-absorbing resin are inferior in terms of the stable gas emission function (long-term stable release) from the gel, so a gas generation regulator such as sepiolite is required, and mixing is necessary without mixing the gas generation regulator The initial gas generation concentration becomes higher, the rate of decrease of the gas generation concentration becomes higher, and it is far from stable release, and it is inevitably necessary to lower the gas emission concentration.
そこで本発明は、特定のゲル化剤（アルギン酸ナトリウム）を採用することで、ガス発生調整剤を使用することなく、適度の濃度による放散性と、長期安定性と、安全性を兼ね備えることを見出し、新規な二酸化塩素ガスを放散する殺菌消臭剤を提案したものである。 Therefore, the present invention has found that by adopting a specific gelling agent (sodium alginate), it has both diffusibility at an appropriate concentration, long-term stability, and safety without using a gas generation regulator. A new bactericidal deodorant that releases chlorine dioxide gas is proposed.
本発明に係るゲル状二酸化塩素系殺菌消臭剤は、適宜容量の容器に適宜濃度の亜塩素酸塩水溶液を充填した第一液剤と、適宜量のアルギン酸ナトリウムと食品添加可能な無水クエン酸を混合した第二混合部とからなり、第一液剤に第二混合部を加えて混合攪拌してなることを特徴とするものである。 The gel-like chlorine dioxide-based disinfectant and deodorant according to the present invention comprises a first solution in which an appropriate volume of a container is filled with an aqueous solution of an appropriate concentration of chlorite, an appropriate amount of sodium alginate, and anhydrous citric acid to which food can be added. It consists of a mixed second mixing part, and the second mixing part is added to the first liquid agent and mixed and stirred.
第一液剤に第二混合部を混合攪拌すると、亜塩素酸塩と有機酸が反応して二酸化塩素が発生するが、アルギン酸ナトリウムによって水溶液全体がゲル状となり、前記のガス発生反応が徐々に進行することになり、長期間（１５〜３０日間程度）安定してガスが発生する。 When the second mixing part is mixed and stirred with the first liquid agent, chlorite reacts with the organic acid to generate chlorine dioxide, but the entire aqueous solution becomes gelled by sodium alginate, and the gas generation reaction proceeds gradually. Therefore, gas is stably generated for a long period (about 15 to 30 days).
また本発明（請求項２）に係るゲル状二酸化塩素系殺菌消臭剤は、前記第一液剤の水溶液に、マグネシウムイオン又はカルシウムイオン源となる物質を添加混合してなるもので、前記マグネシウムイオン又はカルシウムイオンは、アルギン酸ナトリウムの球状ゲル化を促進し、二酸化塩素の蒸散濃度を高める作用を有するものである。 Further, the gel-like chlorine dioxide-based bactericidal deodorant according to the present invention (invention 2) is obtained by adding and mixing a magnesium ion or a substance serving as a calcium ion source to the aqueous solution of the first liquid agent. Or calcium ion has the effect | action which accelerates | stimulates spherical gelatinization of sodium alginate and raises the transpiration | evaporation density | concentration of chlorine dioxide.
本発明は、上記のとおりの構成であって、亜塩素酸塩に酸を反応させて二酸化塩素ガスを発生させる周知手段において、特にゲル化剤としてアルギン酸ナトリウムを採用することで、ガス発生調整剤を使用することなく、適度の濃度の二酸化塩素ガスを蒸散し、且つ長期の安定放散性を備えることになる。また食品添加物として使用できる亜塩素酸と有機酸と、アルギン酸ナトリウムを使用することで、使用時の安全性も確保できたものである。 The present invention is configured as described above, and in a well-known means for generating chlorine dioxide gas by reacting an acid with chlorite, particularly by employing sodium alginate as a gelling agent, a gas generation regulator Without using a gas, a suitable concentration of chlorine dioxide gas is evaporated and long-term stable emission is provided. Moreover, by using chlorous acid and organic acid that can be used as food additives, and sodium alginate, safety during use can be secured.
本発明の実施形態となるゲル状二酸化塩素系殺菌消臭剤は、第一液剤と第二混合部とを備え、使用に際して第一液剤（容器充填）に第二混合部を添加し、混合攪拌して使用するものである。 The gel-like chlorine dioxide sterilizing deodorant according to the embodiment of the present invention includes a first liquid agent and a second mixing part, and in use, the second mixing part is added to the first liquid agent (filled in a container) and mixed and stirred. To use.
第一液剤は、所定の容器に、所定濃度の亜塩素酸塩水溶液及び必要に応じて適宜量のゲル化促進剤（Ｍｇ，Ｃａイオン源）を充填したもので、容器は、取り扱いの利便さや、使用対象空間（８畳程度の居室、靴箱、冷蔵庫等）に対応して定められる容量で、密封蓋と小透孔を穿った中蓋を備えたものである。 The first solution is a predetermined container filled with a predetermined concentration of a chlorite aqueous solution and an appropriate amount of a gelation accelerator (Mg, Ca ion source) as required. The volume is determined in accordance with the space to be used (a room of about 8 tatami mats, a shoe box, a refrigerator, etc.), and includes a sealing lid and an inner lid with a small through hole.
亜塩素酸塩水溶液は、１０〜１８％（好ましくは１２〜１６％）濃度の水溶液である。濃度が低いと二酸化塩素ガスの蒸散濃度が低すぎて、所望の殺菌消臭作用を達成できない。 The chlorite aqueous solution is an aqueous solution having a concentration of 10 to 18% (preferably 12 to 16%). If the concentration is low, the transpiration concentration of chlorine dioxide gas is too low to achieve the desired sterilizing and deodorizing action.
亜塩素酸塩としては、亜塩素酸ナトリウム、亜塩素酸カリウム、亜塩素酸カルシウム等の亜塩素酸アルカリ金属塩や亜塩素酸アルカリ土類金属塩が使用できる。 As the chlorite, alkali metal chlorites such as sodium chlorite, potassium chlorite, calcium chlorite and alkaline earth metal chlorites can be used.
また前記の亜塩素酸塩水溶液に、塩化マグネシウムや塩化カルシウム等のゲル化を促進するマグネシウムイオン又はカルシウムイオン源となる物質を適宜添加混合しても良い。 Moreover, you may add suitably the substance used as a magnesium ion or calcium ion source which accelerates | stimulates gelatinization, such as magnesium chloride and calcium chloride, to the said chlorite aqueous solution.
第二混合部は、前記の第一液剤の液量に対応したアルギン酸ナトリウムと、クエン酸、リンゴ酸、乳酸等の食品添加可能な固形有機酸とを、適宜な密封袋内に充填し、揉むようにして良く混合したものである。 The second mixing part is filled with sodium alginate corresponding to the amount of the first liquid and a solid organic acid to which food can be added such as citric acid, malic acid and lactic acid in an appropriate sealed bag, Mixed well.
而して容器内の第一液剤に、第二混合部を添加し、混合攪拌すると十数秒で全体がゲル状化すると共に、亜塩素酸塩と有機酸が反応して二酸化塩素を発生させ、中蓋の小透孔から二酸化塩素ガスが放散される。この二酸化塩素ガスの強力な酸化力で、殺菌消臭を実現するものである。 Thus, when the second mixing part is added to the first liquid agent in the container, and the mixture is stirred, the whole gels in a few dozen seconds, and the chlorite and the organic acid react to generate chlorine dioxide, Chlorine dioxide gas is emitted from the small through hole in the inner lid. The strong oxidizing power of this chlorine dioxide gas realizes sterilization and deodorization.
次にその具体的な実施について説明する。実施例に使用した容器は、市販されている内径５０ｍｍ、高さ９０ｍｍのネジ蓋式中蓋付き褐色ポリ容器で、予め中蓋中心近くに直径１ｍｍの穴を３個開口したものである。 Next, the specific implementation will be described. The container used in the examples is a brown plastic container with a screw lid type inner lid having an inner diameter of 50 mm and a height of 90 mm, and has three holes with a diameter of 1 mm previously opened near the center of the inner lid.
＜第一実施例＞
第一液剤は、前記容器に１２．５％濃度の亜塩素酸ナトリウム水溶液８０ｍｌを充填しておくものである。第二混合部は、アルギン酸ナトリウム（片山化学工業製品）４ｇと無水クエン酸３ｇを、チャック付きポリ袋に充填し、全体を揉むようにして混ぜ合わせたものである。
<First Example>
The first liquid is one in which the container is filled with 80 ml of a 12.5% sodium chlorite aqueous solution. The second mixing part is obtained by filling 4 g of sodium alginate (Katayama Chemical Co., Ltd.) and 3 g of anhydrous citric acid into a plastic bag with a chuck and mixing them so as to hold the whole.
前記の第一液剤に第二混合部を添加し、容器の中で第一液剤と第二混合部が良く混ざるように円を描く様に回転させて混合すると、約１５秒で全体がゲル状となる。この状態で小透孔を穿っている中蓋を装着し、小透孔の１０ｍｍ上方位置で北川式検知管にて二酸化塩素ガスの濃度を計測した。 When the second mixing part is added to the first liquid and mixed by rotating in a circle so that the first liquid and the second mixing part are well mixed in the container, the whole is gelled in about 15 seconds. It becomes. In this state, an inner lid having a small through hole was attached, and the concentration of chlorine dioxide gas was measured with a Kitagawa type detection tube at a position 10 mm above the small through hole.
計測結果は、図１の表のとおりで、ガス濃度は２時間後から４８０時間（２０日間）は４７〜４２ｐｐｍの範囲（減少率８９％）で放散するもので、長期間安定した放散がなされることが認められた。特許文献４で開示されているガス調整剤を使用した最適実施例（実施例１１）の減少率（８６％）よりも優れ、而も前記文献の平均的な減少率（６０％）に比較しても著しい放散安定性が認められるものである。
The measurement results are as shown in the table of FIG. 1. The gas concentration is radiated in the range of 47 to 42 ppm (reduction rate 89%) from 2 hours to 480 hours (20 days), and stable emission is made for a long time. It was recognized that It is superior to the reduction rate (86%) of the optimal example (Example 11) using the gas regulator disclosed in
＜第二実施例＞
第二実施例は、第一液剤が前記容器に１６％濃度の亜塩素酸ナトリウム水溶液８０ｍｌを充填し、第一実施例と同様の第二混合部を使用したもので、第一液剤に第二混合部を添加し、混合攪拌すると、約２０秒で全体がゲル状となり、第一実施例と同様に二酸化塩素ガスの濃度を計測した。
<Second Example>
In the second embodiment, the first liquid is filled with 80 ml of a 16% strength aqueous sodium chlorite solution in the container, and the same second mixing section as in the first embodiment is used. When the mixing part was added and mixed and stirred, the whole became a gel in about 20 seconds, and the concentration of chlorine dioxide gas was measured as in the first example.
計測結果は、図２の表のとおりで、ガス濃度は２時間後から４８０時間（２０日間）は５０〜４４ｐｐｍの範囲であり、第一実施例と同様に長期安定放散性が認められた。 The measurement results are as shown in the table of FIG. 2, and the gas concentration was in the range of 50 to 44 ppm from 2 hours to 480 hours (20 days), and a long-term stable release property was observed as in the first example.
＜第三実施例＞
第三実施例は、第一液剤として１２．５％濃度の亜塩素酸ナトリウム水溶液８０ｍｌにも塩化カルシウム３ｇを添加して溶解させたものである。前記各実施例と同様に容器の中で第一液剤と第二混合部を混合攪拌すると、約１５秒で全体が前記第一、二実施例のゲル状とはやや異なる状態のゲル状物となった。
<Third embodiment>
In the third example, 3 g of calcium chloride was added to and dissolved in 80 ml of a 12.5% sodium chlorite aqueous solution as the first solution. When the first liquid agent and the second mixing part are mixed and stirred in the container in the same manner as in each of the above examples, the whole gel gel in a state slightly different from the gel in the first and second examples in about 15 seconds became.
前記ゲル状物の二酸化塩素ガスの濃度を、前記各実施例と同様の手段で計測した結果が図３の表のとおりで、ガス濃度は２時間後から７２０時間（３０日間）は５０〜４２ｐｐｍの範囲であり、前記各実施例と同様に長期安定放散性が認められた。 The result of measuring the concentration of chlorine dioxide gas in the gel material by the same means as in the above examples is shown in the table of FIG. 3, and the gas concentration is 50 to 42 ppm from 2 hours to 720 hours (30 days). In the same manner as in the above examples, long-term stable radiation was observed.
＜第四実施例＞
第四実施例は、前記第三実施例において、塩化カルシウム３ｇに替えて塩化マグネシウム３．５ｇを添加して１２％濃度の亜塩素酸ナトリウム水溶液に溶解させたもので、その他は全て前記格実施例と同様に処置したもので、生成されたゲル状物の二酸化塩素ガスの濃度は、図４に示したとおりで、ガス濃度は２時間後から７２０時間（３０日間）は５０〜４０ｐｐｍの範囲であり、前記各実施例と同様に長期安定放散性が認められた。
<Fourth embodiment>
The fourth embodiment is the same as the third embodiment except that 3.5 g of magnesium chloride is added instead of 3 g of calcium chloride and dissolved in a 12% sodium chlorite aqueous solution. In the same manner as in the example, the concentration of chlorine dioxide gas in the produced gel was as shown in FIG. 4, and the gas concentration ranged from 50 to 40 ppm after 2 hours to 720 hours (30 days). In the same manner as in each of the above examples, long-term stable radiation was observed.
尚本発明はゲル状化に際して、吸水樹脂を採用せずにアルギン酸ナトリウムを採用したものであり、同様に自然物のゲル化剤として知られている小麦粉や寒天パウダーを使用してみたが、常温ではゲル状態に至らず、当然８０℃以上の加熱が必要であり、使用時の加熱は、亜塩素酸ナトリウムと有機酸の反応が加速し、瞬時に多量の二酸化塩素ガスを発生させ、またゲル剤の分解も起こし、使用することができない。 In the present invention, when gelling, sodium alginate was adopted without adopting a water-absorbing resin, and similarly, using wheat flour and agar powder known as a natural product gelling agent, It does not reach the gel state and naturally requires heating at 80 ° C. or higher. Heating during use accelerates the reaction between sodium chlorite and organic acid, instantly generates a large amount of chlorine dioxide gas, and gel agent Can also be decomposed and cannot be used.
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| CN107568208A (en) * | 2017-08-25 | 2018-01-12 | 南京斯泰尔医药科技有限公司 | A kind of sustained-release gel composition containing zinc and chlorine dioxide |
| CN108658339A (en) * | 2018-06-20 | 2018-10-16 | 南京海洛阿姆生物科技有限公司 | A kind of purifier and application method of the sterilizing deodorization of municipal sewage pond |
| KR102178392B1 (en) * | 2020-02-14 | 2020-11-13 | 이동희 | Hand dryer providing sterilizing effact |
| KR102380517B1 (en) * | 2020-05-19 | 2022-03-29 | 유숙정 | Chlorine dioxide diffusing pack |
| KR102478578B1 (en) * | 2020-05-19 | 2022-12-15 | 유숙정 | Chlorine dioxide diffusing gel |
| US20220071216A1 (en) * | 2020-09-08 | 2022-03-10 | The Hong Kong University Of Science And Technology | Disinfectant-dosing microgel and method of using the same |
| CN114403157B (en) * | 2022-02-11 | 2022-11-29 | 山东大学 | Double-component gel slow-release chlorine dioxide disinfectant and preparation method and application thereof |
| CN115399335A (en) * | 2022-08-31 | 2022-11-29 | 中国疾病预防控制中心病毒病预防控制所 | Chlorine dioxide sustained-release gel and preparation method and application thereof |
| CN117401649B (en) * | 2023-12-15 | 2024-03-08 | 山东华实药业有限公司 | Pure activation-free stable chlorine dioxide solution |
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| JPS59223201A (en) * | 1983-06-02 | 1984-12-15 | Hakugen:Kk | Gelled product of chlorine dioxide and its manufacture |
| JPH0251581A (en) * | 1988-08-12 | 1990-02-21 | Takasugi Seiyaku Kk | Gel-like instantaneous cold storage freshness retentive |
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