WO2010044194A1 - Alkaline cleaning water - Google Patents

Alkaline cleaning water Download PDF

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WO2010044194A1
WO2010044194A1 PCT/JP2009/004760 JP2009004760W WO2010044194A1 WO 2010044194 A1 WO2010044194 A1 WO 2010044194A1 JP 2009004760 W JP2009004760 W JP 2009004760W WO 2010044194 A1 WO2010044194 A1 WO 2010044194A1
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cao
cleaning water
alkaline cleaning
alkaline
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高平真弓
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株式会社イオンコマース
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/20Water-insoluble oxides
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/06Aluminium; Calcium; Magnesium; Compounds thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/10Salts
    • C11D7/16Phosphates including polyphosphates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/268Carbohydrates or derivatives thereof

Abstract

An alkaline cleaning water having an excellent bactericidal effect, wherein the pH can be maintained high (on the alkaline side) for a long time. Specifically, not less than 0.1% by weight of a cellulose is added into a saturated aqueous solution of CaO (calcium oxide) which is obtained by firing the shell of Sakhalin surf clam or the like at a temperature not less than 1000˚C.  Consequently, precipitation of CaCO3 rarely occurs in the saturated aqueous solution of CaO.

Description

アルカリ洗浄水Alkaline washing water
 本発明は、貝殻を焼成して得られるCaOを溶解したアルカリ洗浄水に関する。 The present invention relates to an alkaline washing water in which CaO obtained by firing a shell is dissolved.
 従来から、貝殻やサンゴを焼成して有用性を付加することが行われている。例えば、特許文献1には、牡蛎やホッキ貝の貝殻を不活性ガス雰囲気で最終到達温度850~1000℃で焼成して粉末状の抗菌剤を製造することが開示されている。即ち、焼成によってCaCOをCaOに変化させ、このCaOが水に接触してOHイオンを生成することで強アルカリによる殺菌効果を得ることが記載されている。 Conventionally, shells and corals are baked to add utility. For example, Patent Document 1 discloses that a powdery antibacterial agent is produced by firing oysters or seashell shells in an inert gas atmosphere at a final temperature of 850 to 1000 ° C. That is, it is described that CaCO 3 is changed to CaO by firing, and this CaO comes into contact with water to generate OH ions, thereby obtaining a bactericidal effect by a strong alkali.
 特許文献2には、活性炭槽を通して水道水中の微細なゴミを除去し、この水分子のクラスターを焼成ゼオライトを充填したカラムを通して細分化し、細分化した水にホッキ貝の焼成粉末とリン酸三カリウムを過飽和に添加して攪拌し、攪拌された混合水から飽和水溶液の部分を分離して洗浄殺菌水として用いることが記載されている。 In Patent Document 2, fine debris in tap water is removed through an activated carbon tank, and this water molecule cluster is subdivided through a column filled with calcined zeolite, and calcined powder of mussels and tripotassium phosphate in the subdivided water. Is added to supersaturation and stirred, and a portion of a saturated aqueous solution is separated from the stirred mixed water and used as washing sterilizing water.
 特許文献3には、アルカリイオン水からなる殺菌・除菌用の水溶液にリン酸カリウムを添加することが開示されている。 Patent Document 3 discloses that potassium phosphate is added to an aqueous solution for sterilization and sterilization made of alkaline ionized water.
特開2001-026508号公報JP 2001-026508 A 特開2005-306758号公報JP 2005-306758 A 特開2000-107265号公報JP 2000-107265 A
 特許文献1に開示される抗菌剤は水溶液として保存すると、Ca(OH)が再びCaCOに変化し抗菌能力が低下する。
 また、特許文献2に開示される水溶液は殺菌性に優れているが、経時的にpHを高く(アルカリ側)に維持することができず、殺菌効果が劣化してくる。これは時間とともに特許文献1と同様にCaCOが生成され、これが沈殿として固まってしまうからと思われる。
When the antibacterial agent disclosed in Patent Document 1 is stored as an aqueous solution, Ca (OH) 2 is changed again to CaCO 3 and the antibacterial ability is reduced.
Moreover, although the aqueous solution disclosed by patent document 2 is excellent in bactericidal property, pH cannot be maintained high (alkaline side) with time, and a bactericidal effect will deteriorate. This seems to be because CaCO 3 is produced with time as in Patent Document 1 and solidifies as a precipitate.
 また、特許文献3に開示される抗菌剤は殺菌・除菌効果の面において劣っている。 Moreover, the antibacterial agent disclosed in Patent Document 3 is inferior in terms of bactericidal and sterilizing effects.
 上記課題を解決するため本発明に係るアルカリ洗浄水は、貝殻を1000℃以上で焼成して得られたCaO(酸化カルシウム)の飽和水溶液中にセルロースが0.1重量%以上添加された構成とした。
 本発明のアルカリ洗浄水の原料となる貝殻としては、ホッキ貝、牡蛎などの二枚貝が考えられるが、特にホッキ貝がCaCOの含有割合が最も優れている。
 また焼成温度を1000℃にしているのは、貝殻中に微量に含まれる重金属を除去するためである。尚、重金属は貝殻の表面に結合している場合が多いため、焼成する前に貝殻の表面をNaOHで洗浄したものを用いるのが好ましい。
In order to solve the above problems, the alkaline washing water according to the present invention has a structure in which 0.1% by weight or more of cellulose is added to a saturated aqueous solution of CaO (calcium oxide) obtained by baking shells at 1000 ° C. or higher. did.
As the shell used as the raw material for the alkaline cleaning water of the present invention, bivalves such as sea shells and oysters are conceivable. In particular, sea shells have the highest CaCO 3 content.
The reason why the firing temperature is set to 1000 ° C. is to remove heavy metals contained in trace amounts in the shell. Since heavy metals are often bonded to the surface of the shell, it is preferable to use a material obtained by washing the surface of the shell with NaOH before firing.
 また、0.3重量%以上のゼオライト粉末及び0.3重量%以上のKPO(リン酸三カリウム)を添加することが好ましい。ゼオライト粉末は脱臭効果があり、KPO(リン酸三カリウム)は水溶液中で加水分解を起こしてアルカリ性を示すため、pHの維持に効果がある。
 また、粒径が1μm以下(ナノレベル)のAg粉体を0.1~1.0wt%の割合で添加することも好ましい。Ag粉体を添加することで抗菌性が更に高まる。
Further, it is preferable to add 0.3% by weight or more of zeolite powder and 0.3% by weight or more of K 3 PO 4 (tripotassium phosphate). Zeolite powder has a deodorizing effect, and K 3 PO 4 (tripotassium phosphate) is hydrolyzed in an aqueous solution to show alkalinity, and is therefore effective in maintaining pH.
It is also preferable to add Ag powder having a particle size of 1 μm or less (nano level) at a ratio of 0.1 to 1.0 wt%. Antibacterial properties are further enhanced by adding Ag powder.
 本発明に係るアルカリ洗浄水は、CaO(酸化カルシウム)の飽和水溶液中にセルロースが0.1重量%以上添加されているため、CaCOの生成が抑制される。このため、CaO(酸化カルシウム)の飽和状態を長期間持続することができ、pH値を高く(11.9以上)維持し、殺菌力が低下しない。 In the alkaline cleaning water according to the present invention, since 0.1% by weight or more of cellulose is added to a saturated aqueous solution of CaO (calcium oxide), generation of CaCO 3 is suppressed. For this reason, the saturated state of CaO (calcium oxide) can be maintained for a long time, the pH value is maintained high (11.9 or more), and the bactericidal power is not reduced.
 尚、CaO(酸化カルシウム)の溶解度は低温ほど大きくなる(0℃付近が最大)ので、アルカリ洗浄水はなるべく低温にして使用することが好ましい。 In addition, since the solubility of CaO (calcium oxide) increases as the temperature decreases (around 0 ° C. is the maximum), it is preferable to use the alkaline cleaning water at a temperature as low as possible.
本発明に係るアルカリ洗浄水の製造工程を説明したブロック図The block diagram explaining the manufacturing process of the alkaline washing water based on this invention
 以下に本発明を実施するための実施の形態を図面に基づいて説明する。図1は本発明に係るアルカリイオン水の製造工程を説明したブロック図である。
先ず、ホッキ貝などの貝殻をNaOH水溶液で洗浄し、表面に形成されている被膜を除去する。この被膜には重金属などの不純物が補足されていることがあり、この被膜を除去することで、高純度のCaCOが得られる。
Embodiments for carrying out the present invention will be described below with reference to the drawings. FIG. 1 is a block diagram illustrating a process for producing alkaline ionized water according to the present invention.
First, shells such as sea shells are washed with an aqueous NaOH solution to remove the film formed on the surface. This coating may be supplemented with impurities such as heavy metals. By removing this coating, high-purity CaCO 3 can be obtained.
 次いで貝殻を粉砕し、1000℃以上で焼成することで1μm以下のCaOの粉体を得る。1000℃以上で焼成することで重金属の割合を1ppm以下に低減することができる。 Next, the shell is pulverized and fired at 1000 ° C. or higher to obtain CaO powder of 1 μm or less. By baking at 1000 ° C. or higher, the ratio of heavy metals can be reduced to 1 ppm or lower.
 上記のCaO粉体に0.1重量%以上のセルロースを加える。また、必要に応じて、0.3重量%以上のゼオライト粉末及び0.3重量%以上のKPO(リン酸三カリウム)を加える。 Add 0.1% by weight or more of cellulose to the CaO powder. If necessary, 0.3% by weight or more of zeolite powder and 0.3% by weight or more of K 3 PO 4 (tripotassium phosphate) are added.
 上記によって得られた混合粉末に水を加えて飽和水溶液(アルカリ洗浄水)とする。この飽和水溶液には過剰の混合粉末を添加しているため、一部は溶解せずに残っている。 水 Water is added to the mixed powder obtained above to obtain a saturated aqueous solution (alkaline washing water). Since an excessive mixed powder is added to this saturated aqueous solution, a part remains without being dissolved.
 表1は財団法人日本食品分析センターが行った本発明に係るアルカリ洗浄水のウィルス不活性試験の結果(第607010054-001号)を示す。 Table 1 shows the results of virus inactivation test (No. 607010054-001) of alkaline washing water according to the present invention conducted by the Japan Food Analysis Center.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 試験方法は、精製水を用いて検体希釈液を調整し、試験液とした。試験液にネコカリシウィルス(ノロウィルスの代替ウィルス)のウィルス浮遊液を添加、混合し、作用液とした。室温で作用させ、30秒並びに1、5、10及び30分間作用後にウィルス感染価を測定した。なお、予め予備試験を行い、ウィルス感染価の測定方法について検討した。また試験液(150倍希釈)のpHをガラス電極法で測定したところ11.9であった。 The test method was to prepare a test solution by adjusting the sample dilution with purified water. A virus suspension of feline calicivirus (norovirus substitute virus) was added to the test solution and mixed to obtain a working solution. The virus infectivity was measured after 30 seconds and after 1, 5, 10, and 30 minutes of action at room temperature. A preliminary test was conducted in advance to examine a method for measuring the virus infectivity titer. Moreover, it was 11.9 when pH of the test liquid (150 times dilution) was measured by the glass electrode method.
 また使用細胞はCRFK細胞(大日本製薬株式会社)を使用し、細胞増殖培地は、Eagle MEM(0.06mg/mlカナマイシン含有)に新生コウシ血清を10%加えたものを使用し、細胞維持培地は新生コウシ血清2%添加Eagle MEMを使用した。 The cells used were CRFK cells (Dainippon Pharmaceutical Co., Ltd.), the cell growth medium was Eagle MEM (containing 0.06 mg / ml kanamycin) with 10% newborn calf serum, and the cell maintenance medium was Eagle MEM supplemented with 2% newborn calf serum was used.
 表2は財団法人日本食品分析センターが行った本発明に係るアルカリ洗浄水のカルシウムイオンの濃度の測定結果(第607010054-002号)を示す。 Table 2 shows the measurement results (No. 607010054-002) of the calcium ion concentration of the alkaline cleaning water according to the present invention conducted by the Japan Food Analysis Center.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 試験方法は検体1(本発明に係るアルカリ洗浄水)3mlにイオン交換水を加えて450ml(150倍希釈)にしたものを遠心分離(3500回転/分、10分間)した後、ろ過(No.5A[東洋濾紙株式会社])し、試験溶液とした。
また検体2(水道水)10mlにイオン交換水を加えて100ml(10倍希釈)にしたものを遠心分離(3500回転/分、10分間)した後、ろ過(No.5A[東洋濾紙株式会社])し、試験溶液とした。
 それぞれ得られた試験溶液をICP発光分析装置に導入し、カルシウムの濃度を測定し、カルシウム含量をカルシウムイオンとして算出した。
In the test method, 3 ml of specimen 1 (alkaline washing water according to the present invention) added with ion exchange water to 450 ml (diluted 150 times) was centrifuged (3500 rpm / minute, 10 minutes), and then filtered (No. 5A [Toyo Filter Paper Co., Ltd.]) and used as a test solution.
Further, 10 ml of sample 2 (tap water) added with ion exchange water to make 100 ml (diluted 10 times) was centrifuged (3500 rpm / minute, 10 minutes), and then filtered (No. 5A [Toyo Roshi Kaisha, Ltd.] And used as a test solution.
The obtained test solutions were introduced into an ICP emission analyzer, the calcium concentration was measured, and the calcium content was calculated as calcium ions.
 (表1)及び(表2)から、本発明に係るアルカリ洗浄水は殺菌効果に優れており、しかも持続時間が長いことが分かる。 (Table 1) and (Table 2) show that the alkaline cleaning water according to the present invention is excellent in sterilizing effect and has a long duration.
 (表3)はCaO粉体にセルロースを加えた場合の水溶液の沈降速度を比較した表である。(表3)中、試料1はCaO粉体1gを水道水1リットルに添加し、3分間攪拌し、一度沈殿させ落ち着いた後に溶液を1分間マドラーでかき混ぜたものであり、試料2はCaO粉体1g及びセルロース1gを水道水1リットルに添加し、3分間攪拌し、一度沈殿させ落ち着いた後に溶液を1分間マドラーでかき混ぜたものであり、試料3はCaO粉体1g及びセルロース2gを水道水1リットルに添加し、3分間攪拌し、一度沈殿させ落ち着いた後に溶液を1分間マドラーでかき混ぜたものである。 (Table 3) is a table comparing the sedimentation rates of aqueous solutions when cellulose is added to CaO powder. In Table 3, sample 1 is obtained by adding 1 g of CaO powder to 1 liter of tap water, stirring for 3 minutes, once settled and settled, and then stirring the solution with a mudler for 1 minute, and sample 2 is CaO powder. 1 g of body and 1 g of cellulose were added to 1 liter of tap water, stirred for 3 minutes, once settled and settled, the solution was stirred for 1 minute with a Madler. Sample 3 was obtained by adding 1 g of CaO powder and 2 g of cellulose to tap water. The solution was added to 1 liter, stirred for 3 minutes, once settled and settled, and then the solution was stirred for 1 minute with a mudler.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 沈降速度が遅いと、水とCaO粉体とが接触している時間が長くなり、水溶液はCaOが飽和状態で溶解している時間が長くなり、その結果pHを高く維持でき、殺菌効果が持続する。 If the sedimentation rate is slow, the time during which the water and CaO powder are in contact with each other becomes longer, and the aqueous solution takes longer to dissolve CaO in a saturated state. As a result, the pH can be maintained high, and the bactericidal effect is maintained. To do.
 本発明に係るアルカリ洗浄水は、野菜、肉、穀物などの食品の洗浄水として利用することができる。特に臭いが強い食品についてはゼオライトを混ぜることで脱臭効果も発揮でき、pHを更に維持するためにはリン酸三カリウムを添加すればよい。 The alkaline washing water according to the present invention can be used as washing water for foods such as vegetables, meat, and grains. For foods with particularly strong odors, mixing with zeolite can also exert a deodorizing effect, and tripotassium phosphate may be added to further maintain the pH.

Claims (4)

  1. 貝殻を1000℃以上で焼成して得られたCaO(酸化カルシウム)の飽和水溶液中にセルロースが0.1重量%以上添加されていることを特徴とするアルカリ洗浄水。 1. Alkaline washing water, characterized in that 0.1% by weight or more of cellulose is added to a saturated aqueous solution of CaO (calcium oxide) obtained by baking shells at 1000 ° C. or higher.
  2. 請求項1に記載のアルカリ洗浄水において、0.3重量%以上のゼオライト粉末及び0.3重量%以上のKPO(リン酸三カリウム)が添加されていることを特徴とするアルカリ洗浄水。 2. The alkaline cleaning water according to claim 1, wherein 0.3% by weight or more of zeolite powder and 0.3% by weight or more of K 3 PO 4 (tripotassium phosphate) are added. water.
  3. 請求項1または請求項2に記載のアルカリ洗浄水において、前記貝殻は予め表面をNaOHで洗浄したものを用いたことを特徴とするアルカリ洗浄水。 3. The alkaline cleaning water according to claim 1, wherein the shell has a surface that has been previously cleaned with NaOH.
  4. 請求項1乃至請求項3の何れかに記載のアルカリ洗浄水において、
    粒径が1μm以下のAg粉体が0.1~1.0wt%の割合で添加されていることを特徴とするアルカリ洗浄水。
    In the alkaline cleaning water according to any one of claims 1 to 3,
    An alkaline cleaning water, wherein Ag powder having a particle size of 1 μm or less is added at a ratio of 0.1 to 1.0 wt%.
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JP5618218B2 (en) * 2012-07-11 2014-11-05 国立大学法人東京農工大学 Bactericidal water, antiviral agents, cleaning water for sterilization in fresh food processing systems and insecticides for poultry farming
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