JP2018052994A - Bactericidal composition - Google Patents
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本発明は主に食品・清涼飲料水の分野で、製造装置や容器・包装資材等の殺菌・洗浄等の目的で幅広く使用される殺菌組成物に関する。 The present invention relates to a sterilizing composition that is widely used mainly for the purpose of sterilizing and washing production equipment, containers, packaging materials, and the like in the field of food and soft drinks.
過酸化水素と過酢酸は、殺菌力があり、環境に優しい過酸化物として、これまでにさまざまな殺菌用途で用いられてきた。特に、過酢酸製剤は低濃度でも殺菌力が強く即効性があり、抗菌スペクトルが広く、細菌芽胞、カビ、酵母等にも優れた殺菌効果を示す事から、近年、過酸化水素に代わって、殺菌処置が必要とされる食品・飲料産業場面で広く使用されている。 Hydrogen peroxide and peracetic acid are sterilizing power and have been used in various sterilization applications as environmentally friendly peroxides. In particular, peracetic acid formulations have strong bactericidal activity even at low concentrations, have immediate effects, have a wide antibacterial spectrum, and show excellent bactericidal effects on bacterial spores, molds, yeasts, etc. Widely used in food and beverage industry where sterilization is required.
しかし、従来の過酢酸製剤を用いても、耐薬品性の高い芽胞形成菌であるバチルス・セレウス（Ｂａｃｉｌｌｕｓ ｃｅｒｅｕｓ）や過酢酸耐性菌であるパエニバチルス（Ｐａｅｎｉｂａｃｉｌｌｕｓ）属細菌に関しては、一般的に用いられる過酢酸濃度では殺菌能力が不十分であるため、高い濃度の過酢酸系殺菌剤を用いることで殺菌能力を高めることが報告されている（特許文献１）。しかし、食品・清涼飲料水の製造装置や容器・包装資材等の殺菌・洗浄分野では、そのために過酸化水素の濃度も高まり、結果として残留する過酸化水素の濃度が高くなる問題を生じる。 However, even if a conventional peracetic acid preparation is used, it is generally used for Bacillus cereus which is a highly chemical-resistant spore-forming bacterium and Paenibacillus genus which is a peracetic acid-resistant bacterium. Since the sterilizing ability is insufficient at the concentration of peracetic acid, it has been reported to increase the sterilizing ability by using a high concentration of peracetic acid-based disinfectant (Patent Document 1). However, in the field of sterilization / cleaning of food / soft drink manufacturing equipment, containers / packaging materials, etc., the concentration of hydrogen peroxide increases, resulting in a problem that the concentration of residual hydrogen peroxide increases.
特許文献２および非特許文献１には、バチルス・セレウスに対し、過酢酸組成物中の過酢酸濃度を５００〜３０００ｐｐｍとし、かつ過酸化水素／過酢酸比率を０．７以下に低く抑えた過酢酸組成物が、有効な殺菌性を示す事が開示されている。特許文献２では、一般的な過酢酸１０質量％、過酸化水素１５質量％を含む過酢酸系殺菌剤を水で希釈して過酢酸濃度が５００〜３０００ｐｐｍのものを調製すると記載されている。しかし、パエニバチルス属細菌は、過酸化水素が共存すると過酢酸が効かなくなることが知られており、単なる希釈では相対的に過酸化水素の濃度が高いままであり、これを殺減することはできない。 In Patent Document 2 and Non-Patent Document 1, a peracetic acid concentration in a peracetic acid composition is set to 500 to 3000 ppm and a hydrogen peroxide / peracetic acid ratio is suppressed to 0.7 or less with respect to Bacillus cereus. It is disclosed that an acetic acid composition exhibits effective bactericidal properties. Patent Document 2 describes that a peracetic acid fungicide containing 10% by mass of general peracetic acid and 15% by mass of hydrogen peroxide is diluted with water to prepare a peracetic acid concentration of 500 to 3000 ppm. However, it is known that bacteria belonging to the genus Paenibacillus do not work with peracetic acid in the presence of hydrogen peroxide, and by simple dilution, the concentration of hydrogen peroxide remains relatively high and cannot be killed. .
このパエニバチルスに対して、過酢酸／過酸化水素比率を１〜２５まで高めた過酢酸組成物（特許文献３）や、組成中の過酸化水素を分解酵素で分解して過酢酸／過酸化水素比を高めた過酢酸組成物（特許文献４）を用いて殺菌を行なうという報告がなされている。しかし、特許文献３の方法では、平衡反応の範囲で過酢酸／過酸化水素比を高めたに過ぎず、なお過酢酸の効果を阻害する十分な濃度の過酸化水素が残っている。過酢酸／過酸化水素比を高める技術として、特許文献４、５では、生体抽出物である酵素を利用したものが報告されているが、それによるコストアップ、また殺菌・洗浄工程にタンパク質を入れることによる容器や設備の汚染が懸念される。 For this Paenibacillus, a peracetic acid composition in which the ratio of peracetic acid / hydrogen peroxide was increased from 1 to 25 (Patent Document 3), or hydrogen peroxide in the composition was decomposed with a decomposing enzyme to produce peracetic acid / hydrogen peroxide. It has been reported that sterilization is performed using a peracetic acid composition (Patent Document 4) with an increased ratio. However, in the method of Patent Document 3, the ratio of peracetic acid / hydrogen peroxide is only increased within the range of the equilibrium reaction, and a sufficient concentration of hydrogen peroxide remains to inhibit the effect of peracetic acid. As technologies for increasing the peracetic acid / hydrogen peroxide ratio, Patent Documents 4 and 5 report the use of enzymes, which are biological extracts, but this increases costs and puts proteins into the sterilization / washing process. There is concern about contamination of containers and equipment.
一方、亜塩素酸塩の一種である亜塩素酸ナトリウムは、日本国内で食品添加物として認められており、酸と混合して使用する方法が知られている。また、米国では、これをクエン酸などの酸存在下で酸性化亜塩素酸ナトリウムとしたものが間接食品添加物として認められており、食用肉や野菜類の殺菌料として使われている。ＦＤＡ２１ＣＦＲ（Ｆｏｏｄ ａｎｄ Ｄｒｕｇ Ａｄｍｉｎｉｓｔｒａｔｉｏｎ／Ｃｏｄｅ ｏｆ Ｆｅｄｅｒａｌ Ｒｅｇｕｌａｔｉｏｎｓ Ｔｉｔｌｅ２１）には、一般的に安全とされる酸、ＧＲＡＳ酸（Ａｃｉｄ（ｓ），Ｇｅｎｅｒａｌｌｙ Ｒｅｃｏｇｎｉｚｅｄ Ａｓ Ｓａｆｅ）と亜塩素酸ナトリウムを混合させ、家禽処理用の抗菌薬として使用することが記載されている。しかし、過酢酸などへの耐薬品性があるパエニバチルス属細菌等に対する殺菌効果が示されていない。 On the other hand, sodium chlorite, a kind of chlorite, is recognized as a food additive in Japan, and a method of using it by mixing with an acid is known. In the United States, acidified sodium chlorite in the presence of acids such as citric acid is recognized as an indirect food additive and is used as a sterilizer for edible meat and vegetables. FDA21CFR (Food and Drug Administration / Code of Federal Regulations Title 21) is a generally safe acid, GRAS acid (Acid (s), General Recognized As Safe) and sodium chlorite mixture. It is described as an antibacterial agent. However, the bactericidal effect against Paenibacillus bacteria having chemical resistance to peracetic acid and the like has not been shown.
本発明は、過酢酸耐性菌であるバチルス・セレウスやパエニバチルス属細菌などの芽胞形成菌に対して、短時間でも高い殺菌効果を示す環境に優しい殺菌組成物を提供する。 The present invention provides an environmentally friendly bactericidal composition that exhibits a high bactericidal effect even in a short time against spore-forming bacteria such as Bacillus cereus and Paenibacillus bacteria that are peracetic acid resistant bacteria.
本発明者らは、耐薬品性の高い芽胞形成菌であるバチルス・セレウスやパエニバチルス属細菌に対し、酸性化亜塩素酸ナトリウムと過酸化水素や過酢酸などの過酸化物との混合組成物が、きわめて有効に殺菌作用を示すことを発見した。さらに、鋭意努力の結果、食品・清涼飲料水の製造装置や容器・包装資材等の殺菌・洗浄分野での実用的な作用時間で殺菌を行なえる組成液の濃度等を見出し、発明を完成させた。 The present inventors have prepared a mixed composition of acidified sodium chlorite and peroxides such as hydrogen peroxide and peracetic acid against Bacillus cereus and Paenibacillus bacteria, which are highly chemical-resistant spore-forming bacteria. It was found that it exhibits a bactericidal action extremely effectively. Furthermore, as a result of diligent efforts, we have found the concentration of the composition liquid that can be sterilized in a practical working time in the field of sterilization / washing of food / soft drink manufacturing equipment, containers / packaging materials, etc., and completed the invention. It was.
すなわち、本発明は以下の構成を有する。 That is, the present invention has the following configuration.
［１］少なくとも、酸と、亜塩素酸塩と、過酸化水素を含有する殺菌組成物であって、該組成物全量に対して、前記酸の含有量が０．１０質量％〜３．００質量％、前記亜塩素酸塩の含有量が０．０１質量％〜１．００質量％、前記過酸化水素の含有量が０．１０質量％〜１．７０質量％であることを特徴とする殺菌組成物。
［２］前記酸が、前記亜塩素酸塩と混合してｐＨが２．０〜４．０となる酸であることを特徴とする殺菌組成物。
［３］前記亜塩素酸塩が亜塩素酸ナトリウムであることを特徴とする殺菌組成物。
［４］前記の殺菌組成物がさらに過酢酸を含有し、該組成物全量に対する前記過酢酸の含有量が０．０５質量％〜１．００質量％であることを特徴とする殺菌組成物。
［５］前記の殺菌組成物を用いて、パエニバチルス属細菌およびバチルス・セレウスの殺菌処理を行うことを特徴とする殺菌方法。
［６］前記殺菌処理を３０℃〜９５℃で行うことを特徴とする殺菌方法。
［７］前記殺菌処理を５秒〜１０分間で行うことを特徴とする殺菌方法。
[1] A sterilizing composition containing at least an acid, a chlorite, and hydrogen peroxide, wherein the acid content is 0.10% by mass to 3.00 with respect to the total amount of the composition. The content of the chlorite is 0.01% by mass to 1.00% by mass, and the content of the hydrogen peroxide is 0.10% by mass to 1.70% by mass. Bactericidal composition.
[2] The bactericidal composition, wherein the acid is an acid that is mixed with the chlorite to have a pH of 2.0 to 4.0.
[3] The bactericidal composition, wherein the chlorite is sodium chlorite.
[4] The sterilizing composition, wherein the sterilizing composition further contains peracetic acid, and the content of the peracetic acid is 0.05% by mass to 1.00% by mass with respect to the total amount of the composition.
[5] A sterilization method comprising performing sterilization of Paenibacillus bacteria and Bacillus cereus using the sterilizing composition.
[6] The sterilization method, wherein the sterilization treatment is performed at 30 ° C to 95 ° C.
[7] The sterilization method, wherein the sterilization treatment is performed for 5 seconds to 10 minutes.
本発明による殺菌組成物は、酸性化亜塩素酸塩と過酸化水素・過酢酸などの過酸化物との相乗効果により、優れた殺菌力を示し、パエニバチルス属細菌やバチルス・セレウスを含む菌類・微生物の汚染・混入が問題となる分野・用途で使用でき、たとえば、食品関連、無菌包装容器、設備機器・容器類、室内環境殺菌、医療関連、高水準消毒・内視鏡・透析ライン・その他医療機器類・院内環境殺菌、リネン関連、農・漁業関連設備器具類、病原菌殺菌などで用いることが出来る。 The bactericidal composition according to the present invention exhibits excellent bactericidal power due to the synergistic effect of acidified chlorite and peroxides such as hydrogen peroxide and peracetic acid, and fungi containing Paenibacillus genus bacteria and Bacillus cereus Can be used in fields and applications where contamination or contamination of microorganisms is a problem. For example, food-related, aseptic packaging containers, equipment / containers, indoor environment sterilization, medical-related, high-level disinfection / endoscope / dialysis line, etc. It can be used for medical equipment / in-hospital environment sterilization, linen-related, agricultural / fishery-related equipment, pathogen sterilization, etc.
以下、本発明を詳しく説明する。
清涼飲料水用のペットボトルの殺菌などで広く用いられている過酢酸製剤は、過酸化水素と酢酸との平衡反応により生成される。そのため、その組成中に必ず原料である過酸化水素と酢酸を含む混合組成物である。近年、こうした食品・清涼飲料水分野で問題となってきたバチルス・セレウスやパエニバチルス属細菌は、原因が詳しく解明されていないが、過酢酸製剤中の過酸化水素が阻害要因となって、過酢酸に対して耐薬品性を有していることが分かってきた。一般的に市販されている過酢酸製剤は、過酢酸濃度が１０００〜３０００ｐｐｍになるよう希釈して用いるが、その中に含有される過酸化水素が阻害要因となっているため、当該過酢酸製剤でこれらの耐薬品性菌を殺滅することはたいへん困難である。
The present invention will be described in detail below.
Peracetic acid preparations widely used in the sterilization of plastic bottles for soft drinks are produced by an equilibrium reaction between hydrogen peroxide and acetic acid. Therefore, it is a mixed composition which always contains hydrogen peroxide and acetic acid as raw materials in its composition. The causes of Bacillus cereus and Paenibacillus spp., Which have been problematic in the food and soft drink field in recent years, have not been elucidated in detail. It has been found that it has chemical resistance. A commercially available peracetic acid preparation is used by diluting it so that the concentration of peracetic acid is 1000 to 3000 ppm. However, since the hydrogen peroxide contained therein is an inhibiting factor, the peracetic acid preparation is used. It is very difficult to kill these chemical-resistant bacteria.
また、亜塩素酸塩単独では、これらの耐薬品性菌に対する殺菌性を示さない。クエン酸、酢酸などの酸と混合して、酸性化亜塩素酸塩とすると、ある程度の殺菌性を示すが、食品・清涼飲料水の製造装置や容器・包装資材等の殺菌・洗浄分野では実用性において不十分である。
本願発明では、酸性化亜塩素酸塩と、過酸化水素あるいは過酢酸製剤を混合した組成物はバチルス・セレウスやパエニバチルス属細菌に対する顕著な殺菌効果を示すことを見出した。なお、酸性化していない亜塩素酸塩と過酸化水素との組合せでは、こうした殺菌性が見られなかった。また、過酢酸は単独では存在せず、過酢酸製剤は必ず過酸化水素、酢酸、過酢酸が共存するため、過酢酸単独と亜塩素酸塩との混合物の殺菌力は評価できないが、過酸化水素の場合と同様、過酢酸単独と亜塩素酸塩との混合物は殺菌効果がない（あるいは不十分）と考えられる。しかし、亜塩素酸塩と酸と過酸化水素の混合物、あるいは過酢酸製剤と亜塩素酸塩の混合物では殺菌性がある。したがって、この優れた殺菌効果は、酸性化亜塩素酸塩と過酸化水素や過酢酸との相乗効果であると確信した。
Further, chlorite alone does not show bactericidal properties against these chemical-resistant bacteria. When mixed with acids such as citric acid and acetic acid to make acidified chlorite, it shows a certain degree of bactericidal properties, but is practical in the field of sterilization and washing of food and soft drink manufacturing equipment, containers and packaging materials. Inadequate in sex.
In this invention, it discovered that the composition which mixed acidified chlorite, hydrogen peroxide, or a peracetic acid formulation showed the remarkable bactericidal effect with respect to Bacillus cereus and Paenibacillus genus bacteria. In addition, such a bactericidal property was not seen in the combination of the non-acidified chlorite and hydrogen peroxide. In addition, peracetic acid does not exist alone, and peracetic acid preparations always contain hydrogen peroxide, acetic acid, and peracetic acid, so the bactericidal power of a mixture of peracetic acid alone and chlorite cannot be evaluated, but As with hydrogen, a mixture of peracetic acid alone and chlorite is considered to have no (or insufficient) bactericidal effect. However, a mixture of chlorite and acid and hydrogen peroxide or a mixture of peracetic acid preparation and chlorite is bactericidal. Therefore, it was convinced that this excellent bactericidal effect was a synergistic effect of acidified chlorite and hydrogen peroxide or peracetic acid.
また、上述したように、一般的な過酢酸製剤では、必ず共存する過酸化水素が過酢酸の殺菌効果に対して阻害的に働くことが知られている。しかし、本願発明では、過酸化水素が共存している過酢酸製剤でも、亜塩素酸塩との混合で高い殺菌性を示し、さらに、過酸化水素自身も、酸性化亜塩素酸塩との混合によって、殺菌効果を示す。こうしたことから、酸の存在によりなる酸性化亜塩素酸塩は、単なる殺菌剤としての効果だけではなく、バチルス・セレウスやパエニバチルス属細菌の、過酸化水素の阻害作用による過酢酸への耐薬品性（および、おそらくは過酸化水素そのものへの耐薬品性）を何らかの形で打破するものと思われる。 In addition, as described above, it is known that in a general peracetic acid preparation, the coexisting hydrogen peroxide necessarily acts to inhibit the bactericidal effect of peracetic acid. However, in the present invention, even a peracetic acid preparation coexisting with hydrogen peroxide exhibits high bactericidal properties when mixed with chlorite, and hydrogen peroxide itself is also mixed with acidified chlorite. Shows the bactericidal effect. For this reason, acidified chlorite in the presence of acid is not only effective as a bactericidal agent, but also has chemical resistance to peracetic acid by the inhibitory action of hydrogen peroxide of Bacillus cereus and Paenibacillus bacteria. (And possibly chemical resistance to hydrogen peroxide itself).
本願発明は少なくとも酸と亜塩素酸塩と過酸化水素を含有する殺菌組成物であり、ここで用いる亜塩素酸塩には、亜塩素酸ナトリウムや亜塩素酸カリウムなどがあるが、特にこれらに限定されない。酸性化亜塩素酸塩の調製に関し、前記酸を亜塩素酸塩と混合してｐＨが２．０〜４．０程度にできれば好ましく、殺菌用途・対象物を考慮して前記酸を選定すればよい。殺菌対象が食料・飲料等であれば、一般的に安全とされている酸（ＧＲＡＳ酸）が好ましい、酢酸やクエン酸がより好ましい、さらに酢酸がより好ましい。 The present invention is a sterilizing composition containing at least an acid, a chlorite, and hydrogen peroxide. Examples of the chlorite used herein include sodium chlorite and potassium chlorite. It is not limited. Regarding the preparation of acidified chlorite, it is preferable that the acid is mixed with chlorite to have a pH of about 2.0 to 4.0, and if the acid is selected in consideration of sterilization use / objects Good. If the object of sterilization is food / beverage or the like, generally safe acid (GRAS acid) is preferable, acetic acid or citric acid is more preferable, and acetic acid is more preferable.
また、過酢酸については、過酸化水素と酢酸を混合して作成することもできるが、市販されている過酢酸製剤（過酢酸・過酸化水素・酢酸・水の混合物）を用いてもよい。また、過酢酸製剤と混合する場合、上記したとおり、過酢酸製剤には常に酢酸が含まれていることから、特にほかの酸を加えることなく、亜塩素酸塩と過酢酸製剤との混合によって酸性化亜塩素酸塩が形成され、それがそのままで過酢酸との相乗殺菌効果を示す。 The peracetic acid can be prepared by mixing hydrogen peroxide and acetic acid, but a commercially available peracetic acid preparation (a mixture of peracetic acid / hydrogen peroxide / acetic acid / water) may be used. In addition, when mixed with peracetic acid preparations, as described above, peracetic acid preparations always contain acetic acid. Therefore, by adding chlorite and peracetic acid preparations without adding any other acids. Acidified chlorite is formed, which as such exhibits a synergistic bactericidal effect with peracetic acid.
一方、亜塩素酸塩は過酸化水素と混合する際には、酸性化亜塩素酸塩を調製するため、酢酸、クエン酸等のＧＲＡＳ酸を添加する必要がある。 On the other hand, when chlorite is mixed with hydrogen peroxide, it is necessary to add GRAS acid such as acetic acid and citric acid to prepare acidified chlorite.
本願発明の殺菌組成物中の各成分の濃度に関しては、
（１）酸濃度は０．１０質量％以上３．００質量％以下が好ましく、より好ましくは０．２０質量％以上３．００質量％以下、さらに好ましいのは０．３０質量％以上３．００質量％以下、
（２）亜塩素酸塩濃度は０．０１質量％以上１．００質量％以下が好ましく、より好ましくは０．０３質量％以上１．００質量％以下、さらに好ましいのは０．０５質量％以上１．００質量％以下、
（３）過酸化水素濃度は、０．１０質量％以上１．７０質量％以下が好ましく、より好ましくは０．２０質量％以上１．７０質量％以下、
または、
（４）過酢酸濃度は、０．０５質量％以上１．００質量％以下が好ましく、より好ましくは０．１０質量％以上１．００質量％以下、
である。
Regarding the concentration of each component in the sterilizing composition of the present invention,
(1) The acid concentration is preferably from 0.10% by mass to 3.00% by mass, more preferably from 0.20% by mass to 3.00% by mass, and still more preferably from 0.30% by mass to 3.00% by mass. Mass% or less,
(2) The chlorite concentration is preferably 0.01% by mass or more and 1.00% by mass or less, more preferably 0.03% by mass or more and 1.00% by mass or less, and further preferably 0.05% by mass or more. 1.00 mass% or less,
(3) The hydrogen peroxide concentration is preferably 0.10% by mass or more and 1.70% by mass or less, more preferably 0.20% by mass or more and 1.70% by mass or less,
Or
(4) The concentration of peracetic acid is preferably 0.05% by mass or more and 1.00% by mass or less, more preferably 0.10% by mass or more and 1.00% by mass or less,
It is.
また、本願発明の殺菌組成物で実施する殺菌方法は、３０℃〜９５℃の温度条件で行なうことができる。一般的に、処理温度は高いほど殺菌効果が高まるが、ＰＥＴボトル等のプラスチック容器の耐熱性に懸念がある。本願発明の殺菌方法は、３０℃〜７０℃という比較的低い温度でも、十分な殺菌力を発揮することができる。 Moreover, the sterilization method implemented with the sterilization composition of this invention can be performed on 30 degreeC-95 degreeC temperature conditions. In general, the higher the treatment temperature, the higher the bactericidal effect, but there is concern about the heat resistance of plastic containers such as PET bottles. The sterilization method of the present invention can exhibit a sufficient sterilizing power even at a relatively low temperature of 30 ° C to 70 ° C.
また、本願発明の殺菌組成物で実施する殺菌方法は、５秒〜１０分で行なうことができる。特に、ペットボトルの殺菌処理など、１５秒程度のきわめて短時間での殺菌処理が求められる用途でも、適用することができる。 Moreover, the sterilization method implemented with the sterilization composition of this invention can be performed in 5 second-10 minutes. In particular, the present invention can also be applied to uses that require a sterilization treatment in an extremely short time of about 15 seconds, such as a sterilization treatment of a PET bottle.
過酢酸製剤として、市販の過酢酸製剤オキシペール１００（製品名、保土谷化学工業）を用いた。本製剤の組成は、過酢酸１０質量％、過酸化水素１７質量％、酢酸２１質量％である。これを蒸留水で希釈し、所望の濃度として使用した。なお、過酢酸製剤の組成は平衡反応によるもので、蒸留水等で希釈し放置すると、当初の濃度比率から、別の平衡状態の比率に移行する。したがって、作り置きはせず、希釈後速やかに使用した。 As a peracetic acid formulation, a commercially available peracetic acid formulation Oxyper 100 (product name, Hodogaya Chemical Co., Ltd.) was used. The composition of this preparation is 10% by mass of peracetic acid, 17% by mass of hydrogen peroxide, and 21% by mass of acetic acid. This was diluted with distilled water and used as the desired concentration. Note that the composition of the peracetic acid preparation is based on an equilibrium reaction, and when diluted with distilled water or the like and left to stand, the initial concentration ratio shifts to another equilibrium ratio. Therefore, it was used immediately after dilution without preparation.
この過酢酸製剤を、過酢酸濃度が０．２０質量％になるよう希釈した。また、当該希釈過酢酸製剤中の過酸化水素濃度及び酢酸濃度は各組成物中にほぼ同じになるよう、過酸化水素の濃度が０．３４質量％、酢酸の濃度が０．４２質量％であり、それらの混合物等を調製した。亜塩素酸ナトリウムは０．０５質量％とした。実験に使われた組成物は下記のような組成で殺菌実験を行なった。
比較例１ 過酢酸製剤（過酢酸濃度０．２０質量％）
比較例２ 亜塩素酸ナトリウム（濃度０．０５質量％）
比較例３ 過酸化水素（濃度０．３４質量％）
比較例４ 酢酸（濃度０．４２質量％）
比較例５ 過酸化水素（濃度０．３４質量％）及び酢酸（濃度０．４２質量％）
比較例６ 過酸化水素（濃度０．３４質量％）及び亜塩素酸ナトリウム（濃度０．０５質量％）
比較例７ 酢酸（濃度０．４２質量％）及び亜塩素酸ナトリウム（濃度０．０５質量％）
実施例１ 過酸化水素（濃度０．３４質量％）、酢酸（濃度０．４２質量％）及び亜塩素酸ナトリウム（濃度０．０５質量％）
The peracetic acid preparation was diluted so that the peracetic acid concentration was 0.20% by mass. In addition, the hydrogen peroxide concentration and the acetic acid concentration are 0.44% by mass and 0.32% by mass, respectively, so that the hydrogen peroxide concentration and the acetic acid concentration in the diluted peracetic acid preparation are almost the same in each composition. There was a mixture of them. Sodium chlorite was 0.05% by mass. The composition used for the experiment was sterilized by the following composition.
Comparative Example 1 Peracetic acid preparation (peracetic acid concentration 0.20% by mass)
Comparative Example 2 Sodium chlorite (concentration 0.05% by mass)
Comparative Example 3 Hydrogen peroxide (concentration 0.34% by mass)
Comparative Example 4 Acetic acid (concentration 0.42% by mass)
Comparative Example 5 Hydrogen peroxide (concentration 0.34 mass%) and acetic acid (concentration 0.42 mass%)
Comparative Example 6 Hydrogen peroxide (concentration 0.34 mass%) and sodium chlorite (concentration 0.05 mass%)
Comparative Example 7 Acetic acid (concentration 0.42% by mass) and sodium chlorite (concentration 0.05% by mass)
Example 1 Hydrogen peroxide (concentration 0.34 mass%), acetic acid (concentration 0.42 mass%) and sodium chlorite (concentration 0.05 mass%)
パエニバチルス菌に対する各種組成物の殺菌効果を検討した。これらの組成物（液）にパエニバチルス属細菌（Ｐａｅｎｉｂａｃｉｌｌｓ ｃｈｉｂｅｎｓｉｓ ＮＢＲＣ １５９５８）の胞子を６５℃で表１に記載した時間まで接触させ、その後、胞子を栄養寒天培地に塗布して、生菌数を確認した。その結果を表１に示す。また、全ての組成液に接触していない胞子も同じ方法で生菌数を確認し、接触時間０秒の生菌数として表１に記入した。 The bactericidal effect of various compositions against Paenibacillus was investigated. These compositions (liquid) were contacted with spores of Paenibacillus chinbensis NBRC 15958 at 65 ° C. for the time indicated in Table 1, and then the spores were applied to a nutrient agar medium to confirm the viable cell count. did. The results are shown in Table 1. Further, the number of viable bacteria was also confirmed by the same method for all spores not in contact with the composition solution, and the number of viable bacteria with a contact time of 0 seconds was entered in Table 1.
上記の結果より、比較例１〜６は、いずれもＰａｅｎｉｂａｃｉｌｌｓ ｃｈｉｂｅｎｓｉｓ ＮＢＲＣ １５９５８の胞子に対して、殺菌効果がないものと判断された。また、比較例７は酸性化亜塩素酸ナトリウムが生成しているため、ある程度の殺菌能力を示した。ただ、1分間の接触では殺菌効果は不十分であった。実施例１では、酸性化亜塩素酸ナトリウムと過酸化水素の相乗効果により、１分間で十分な殺菌効果が得られた。 From the above results, it was determined that Comparative Examples 1 to 6 had no bactericidal effect on the spores of Paenibacils chibensis NBRC 15958. Moreover, since the acidified sodium chlorite produced | generated in the comparative example 7, some sterilization ability was shown. However, the bactericidal effect was insufficient with 1-minute contact. In Example 1, a sufficient bactericidal effect was obtained in 1 minute due to the synergistic effect of acidified sodium chlorite and hydrogen peroxide.
次に、パエニバチルス菌に対する、過酢酸及び亜塩素酸ナトリウムの濃度の殺菌効果への影響に関して検討した。過酢酸製剤と亜塩素酸ナトリウムを用いて、十分な殺菌能力を持つ殺菌組成物の組成濃度を調べた。組成物中過酢酸の濃度を０．０１質量％〜０．２０質量％、亜塩素酸ナトリウムの濃度を０．０５質量％〜０．２０質量％として、それらの組合せでＰａｅｎｉｂａｃｉｌｌｓ ｃｈｉｂｅｎｓｉｓ ＮＢＲＣ １５９５８の胞子に対する６５℃での殺菌力を確認した。結果を表２に示し、各組成の濃度単位は質量％である。 Next, it examined about the influence on the bactericidal effect of the density | concentration of a peracetic acid and sodium chlorite with respect to Paenibacillus. Using a peracetic acid preparation and sodium chlorite, the composition concentration of a sterilizing composition having sufficient sterilizing ability was examined. In a composition, the concentration of peracetic acid is 0.01 mass% to 0.20 mass%, the concentration of sodium chlorite is 0.05 mass% to 0.20 mass%, and combinations thereof, spores of Paenibacils chibensis NBRC 15958 The bactericidal power at 65 ° C. was confirmed. The results are shown in Table 2, and the concentration unit of each composition is mass%.
上記の結果より、いずれの濃度の過酢酸及び亜塩素酸ナトリウムにおいても、Ｐａｅｎｉｂａｃｉｌｌｓ ｃｈｉｂｅｎｓｉｓ ＮＢＲＣ １５９５８に対する殺菌力が示された。これらは、いずれも過酢酸製剤中の酢酸と亜塩素酸ナトリウムにより酸性化亜塩素酸ナトリウムが生成し、それと過酢酸製剤中の過酢酸との相乗効果によるものと考えられる。なお、ペットボトルの殺菌などで求められる１５秒間の殺菌能力については、実施例３、４に示した過酢酸濃度０．１０質量％と亜塩素酸ナトリウム０．１０質量％以上の組合せか、あるいは実施例５、６、８、９に示した過酢酸濃度０．１５質量％以上と亜塩素酸ナトリウム０．０５質量％以上の組合せが好ましいと示した。 From the above results, the bactericidal power against Paenibacils chibensis NBRC 15958 was shown at any concentration of peracetic acid and sodium chlorite. These are considered to be due to the synergistic effect of acidified sodium chlorite produced by acetic acid and sodium chlorite in the peracetic acid preparation, and peracetic acid in the peracetic acid preparation. As for the sterilization ability for 15 seconds required for sterilization of PET bottles, the combination of the peracetic acid concentration of 0.10% by mass and sodium chlorite of 0.10% by mass or more shown in Examples 3 and 4 or It was shown that the combination of peracetic acid concentration of 0.15% by mass or more and sodium chlorite of 0.05% by mass or more shown in Examples 5, 6, 8, and 9 was preferable.
また、過酢酸濃度０．２０質量％の過酢酸製剤及び濃度０．０５質量％の亜塩素酸ナトリウムの混合物はバチルス・セレウス（Ｂａｃｉｌｌｓ ｃｅｒｅｕｓ ＡＴＣＣ９１３９）に対する殺菌効果も同様に確認した、なお接触温度は４０℃とした。バチルス・セレウスに対する殺菌効果は表３に示し、各組成の濃度単位は質量％である。 Moreover, the mixture of the peracetic acid concentration of 0.20 mass% peracetic acid preparation and the sodium chlorite density | concentration of 0.05 mass% confirmed the bactericidal effect with respect to Bacillus cereus (Bacilles cereus ATCC9139) similarly. The temperature was 40 ° C. The bactericidal effect against Bacillus cereus is shown in Table 3, and the concentration unit of each composition is mass%.
表３の結果より、過酢酸製剤に亜塩素酸ナトリウムを添加することで、バチルス・セレウスに対しても、著しい殺菌効果を示した。 From the result of Table 3, the remarkable bactericidal effect was shown also with respect to Bacillus cereus by adding sodium chlorite to a peracetic acid formulation.
本発明による殺菌組成物は、食品関連、無菌包装容器、設備機器・容器類、室内環境殺菌、医療関連、高水準消毒・内視鏡・透析ライン・その他医療機器類・院内環境殺菌、リネン関連、農・漁業関連設備器具類、病原菌殺菌などの分野・用途で、パエニバチルス属細菌やバチルス・セレウスを含む有害菌の殺菌操作に有効な組成物である。 The sterilizing composition according to the present invention is food-related, aseptic packaging containers, equipment / containers, indoor environment sterilization, medical-related, high-level disinfection / endoscope / dialysis line / other medical equipment / in-hospital environment sterilization, linen-related It is an effective composition for sterilization of harmful bacteria including Paenibacillus spp. And Bacillus cereus in fields / uses such as agricultural / fishery-related equipment and sterilization of pathogens.
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