JP6439692B2 - Hydrogen peroxide aqueous solution for sterilization, method for producing the same, and sterilization method using the same - Google Patents
Hydrogen peroxide aqueous solution for sterilization, method for producing the same, and sterilization method using the same Download PDFInfo
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Description
本発明は、過酸化水素水溶液を加熱蒸発させ、そのミスト及び／又はガスを対象物と接触させ、対象物に付着している菌及び／又は対象物の近傍に浮遊している菌の数を減少させるために用いられる過酸化水素水溶液及びその製造方法、並びにそれを用いた殺菌方法に関する。 The present invention heats and evaporates an aqueous hydrogen peroxide solution, contacts the mist and / or gas with an object, and determines the number of bacteria attached to the object and / or floating in the vicinity of the object. The present invention relates to an aqueous hydrogen peroxide solution used for the reduction, a production method thereof, and a sterilization method using the same.
過酸化水素水溶液の高温ミスト或いは過酸化水素蒸気を対象物と接触させて、対象物に付着している菌の数を減少させる技術は、電子工業用のクリーンルームの殺菌や、飲料充填前のペットボトルの殺菌などに適用されている。とりわけ近年は、ペットボトルの普及と相まって、無菌充填に使用される過酸化水素水溶液にも高性能なものが求められるようになってきた。即ち、過酸化水素及び水を蒸発させた時の残渣が少ないものや、高温や金属製の貯蔵容器中での安定性が高いものが求められるようになってきている。無菌充填用に過酸化水素水溶液を使用する場合、過酸化水素水溶液を蒸発機で沸点以上に加熱気化させ、空気と共に過酸化水素の気体を噴霧して容器を殺菌する方法が知られている（特許文献１参照）。しかしながら、過酸化水素水溶液に添加されている安定剤の一部が、噴霧ノズル、蒸発機に付着し、配管部などを閉塞させ、無菌充填装置の安定した運転を阻害する問題があった。また、これまで顕在化していなかったが、過酸化水素水溶液をアルミニウム製やステンレス製のタンクに貯蔵すると、濃度変化は起きないものの、安定性が徐々に低下していく問題もあった。 The technology to reduce the number of bacteria adhering to the object by contacting the object with high temperature mist or hydrogen peroxide vapor of hydrogen peroxide solution is the sterilization of clean room for electronic industry and pet before filling beverage Applied to bottle sterilization. In particular, in recent years, in conjunction with the popularization of PET bottles, high-performance hydrogen peroxide aqueous solutions used for aseptic filling have been demanded. That is, there are demands for a material that has little residue when hydrogen peroxide and water are evaporated, and a material that has high stability in high temperature or metal storage containers. In the case of using an aqueous hydrogen peroxide solution for aseptic filling, a method is known in which the aqueous hydrogen peroxide solution is heated and vaporized to the boiling point or more with an evaporator, and the hydrogen peroxide gas is sprayed together with air to sterilize the container ( Patent Document 1). However, a part of the stabilizer added to the aqueous hydrogen peroxide solution adheres to the spray nozzle and the evaporator, obstructs the stable operation of the aseptic filling device by blocking the piping and the like. Further, although this has not been realized so far, when the aqueous hydrogen peroxide solution is stored in an aluminum or stainless steel tank, the concentration does not change, but the stability gradually decreases.
これまでに、上記の閉塞問題を解決する手段として、過酸化水素水溶液に添加する安定剤の添加量を低減することが提案されている。この場合、過酸化水素水溶液に含まれる分解活性物質量に応じて安定剤の添加量を決めるため、分解活性物質濃度の低い過酸化水素水溶液を使用する必要があった。
例えば、分解活性物質濃度が５ｐｐｂ以下のレベルにおいては、ピロリン酸ナトリウム及びオルトリン酸を安定剤として使用する場合、その総添加量が４０ｍｇ／ｋｇ以下にしても過酸化水素の安定性が確保できることが知られている（特許文献２参照）。
また、蒸発（乾燥）残渣を１０ｍｇ／ｋｇ以下にすることで、アミノトリスメチレンホスホン酸の添加量が５０ｍｇ／ｋｇ以下でも過酸化水素の安定性を確保することができたとの報告もある（特許文献３参照）。
前述のように閉塞問題を解決する手段は、幾つか提案されているものの、これまで顕在化していなかったタンク貯蔵中の過酸化水素の安定性の低下問題については、解決する手段が見出されていなかった。本発明者らによる最近の研究によって、過酸化水素水溶液に安定剤として添加されているリン酸などのキレート剤によって、金属製タンクより微量の金属が溶出し、過酸化水素の安定度が低下することが分かってきた。安定剤を多量に用いれば安定度の低下は回避出来るが、前述のノズル閉塞などの運転阻害が起こり易くなるため、当該用途では好ましくない。So far, as a means for solving the above-mentioned clogging problem, it has been proposed to reduce the amount of stabilizer added to the aqueous hydrogen peroxide solution. In this case, it is necessary to use a hydrogen peroxide aqueous solution having a low decomposition active substance concentration in order to determine the addition amount of the stabilizer according to the amount of the decomposition active substance contained in the hydrogen peroxide aqueous solution.
For example, when the decomposition active substance concentration is 5 ppb or less, when sodium pyrophosphate and orthophosphoric acid are used as stabilizers, the stability of hydrogen peroxide can be ensured even if the total addition amount is 40 mg / kg or less. It is known (see Patent Document 2).
There is also a report that by setting the evaporation (drying) residue to 10 mg / kg or less, the stability of hydrogen peroxide could be secured even when the amount of aminotrismethylenephosphonic acid added was 50 mg / kg or less (patent) Reference 3).
As described above, although several means for solving the blockage problem have been proposed, a means for solving the problem of deterioration in the stability of hydrogen peroxide during storage of the tank, which has not been revealed so far, has been found. It wasn't. According to recent research by the present inventors, a small amount of metal is eluted from a metal tank by a chelating agent such as phosphoric acid added as a stabilizer to an aqueous hydrogen peroxide solution, and the stability of hydrogen peroxide decreases. I understand that. If a stabilizer is used in a large amount, a decrease in stability can be avoided, but it is not preferable in the application because operation obstruction such as nozzle clogging is likely to occur.
また、閉塞問題対策として過酸化水素水溶液への安定剤添加量を低減しても、噴霧ノズル、蒸発機への付着物の残存は完全には解消できず、かつホスホン酸系の付着物が難溶性であることから、配管部を閉塞させ、無菌充填装置の安定した運転を阻害する問題は完全には解決できていなかった。 Moreover, even if the amount of stabilizer added to the aqueous hydrogen peroxide solution is reduced as a countermeasure against the clogging problem, the remaining deposits on the spray nozzle and evaporator cannot be completely eliminated, and phosphonic acid deposits are difficult. Since it is soluble, the problem of blocking the piping part and hindering stable operation of the aseptic filling device has not been completely solved.
本発明の目的は、従来技術における上記の課題を解決し、いわゆる蒸気殺菌に供せられる過酸化水素水溶液及びその製造方法、並びにそれを用いた殺菌方法を提供することにある。 An object of the present invention is to solve the above-mentioned problems in the prior art and to provide a hydrogen peroxide aqueous solution used for so-called steam sterilization, a method for producing the same, and a sterilization method using the same.
本発明者らは、過酸化水素水溶液の安定剤添加量、安定剤成分、蒸発残渣とその水洗性、含有不純物、貯蔵安定性、使用安全性などについて鋭意研究を重ねた結果、必須成分として過酸化水素、リン酸塩及びアルミニウム塩を含む過酸化水素水溶液を用いれば、噴霧ノズルおよび蒸発機に付着残存する過酸化水素水溶液の安定剤由来の付着物を低減し、かつ残渣を水洗により容易に除去することができ、無菌充填装置の安定した運転が可能な過酸化水素水溶液を提供し得ることを見出し本発明に到達した。
すなわち本発明は以下のとおりである。
＜１＞ 菌の数を減少させるために用いられる過酸化水素水溶液であって、必須成分として過酸化水素、リン酸塩及びアルミニウム塩を含むことを特徴とする過酸化水素水溶液である。
＜２＞ 前記リン酸塩がリン酸三カリウム、リン酸三マグネシウム、リン酸水素二アンモニウム、リン酸二水素アンモニウム、リン酸水素二カリウム、リン酸二水素カリウム、リン酸水素二ナトリウム、リン酸二水素ナトリウム、リン酸三ナトリウム、及びビス（リン酸水素）カルシウムからなる群より選ばれる少なくとも一種である上記＜１＞記載の過酸化水素水溶液である。
＜３＞ 前記リン酸塩がリン酸水素塩である上記＜１＞に記載の過酸化水素水溶液である。
＜４＞ 前記リン酸塩の添加濃度が１〜１８ｍｇ／ｋｇである上記＜１＞から＜３＞のいずれかに記載の過酸化水素水溶液である。
＜５＞ 前記アルミニウム塩が、硫酸アルミニウムカリウムである上記＜１＞から＜４＞のいずれかに記載の過酸化水素水溶液である。
＜６＞ 前記アルミニウム塩の添加濃度が１〜４ｍｇ／ｋｇである上記＜１＞から＜５＞のいずれかに記載の過酸化水素水溶液である。
＜７＞ Ｌ−アスコルビン酸及びその塩、エチレンジアミン四酢酸塩、クエン酸及びその塩、グルコン酸及びその塩、Ｌ−グルタミン酸及びその塩、ケイ酸塩、硝酸塩、炭酸塩、ピロリン酸塩、並びに硫酸塩からなる群より選ばれる少なくとも１種の酸及び／又は塩を含む上記＜１＞から＜６＞のいずれかに記載の過酸化水素水溶液である。
＜８＞ 前記酸及び／又は塩の添加濃度が２〜１２ｍｇ／ｋｇである上記＜７＞に記載の過酸化水素水溶液である。
＜９＞ 前記過酸化水素の濃度が３０重量％〜４０重量％である上記＜１＞から＜８＞のいずれかに記載の過酸化水素水溶液である。
＜１０＞ 上記＜１＞から＜９＞のいずれかに記載の過酸化水素水溶液を用いた殺菌剤である。
＜１１＞ 原料となる過酸化水素水溶液に、リン酸塩及びアルミニウム塩を添加することを特徴とする上記＜１＞から＜９＞のいずれかに記載の過酸化水素水溶液の製造方法である。
＜１２＞ 空気と、上記＜１＞から＜９＞のいずれかに記載の過酸化水素水溶液のミスト及び／又はガスを混合した後、対象物に接触させることを特徴とする殺菌方法である。
＜１３＞ 過酸化水素水溶液を対象物と接触させる際に、空気を加熱して過酸化水素水溶液のミスト及び／又はガスを同伴させる上記＜１２＞に記載の殺菌方法である。
＜１４＞ 過酸化水素水溶液を１００℃〜１５０℃に加熱して対象物に接触させる上記＜１２＞または＜１３＞に記載の殺菌方法である。
＜１５＞ 前記対象物が包装容器、食品機械、ペットボトル、又はペットボトルプリフォームである上記＜１２＞から＜１４＞のいずれかに記載の殺菌方法である。
＜１６＞ 前記対象物が閉鎖空間である上記＜１２＞から＜１４＞のいずれかに記載の殺菌方法である。
＜１７＞ 前記閉鎖空間が自動車、電子工業用のクリーンルーム、居住空間、医療スペース、厨房、調理場、車両、または航空機である上記＜１６＞に記載の殺菌方法である。
＜１８＞ 過酸化水素水溶液のミスト及び／又は過酸化水素蒸気の発生装置を施設内に持ち込み、過酸化水素水溶液のミスト及び／又は過酸化水素蒸気を発生させ、施設内の菌数を減らすこと特徴とする上記＜１２＞から＜１４＞のいずれかに記載の殺菌方法である。
＜１９＞ 前記施設がトイレタリー施設、廃棄物処理施設、または畜舎である上記＜１８＞に記載の殺菌方法である。As a result of extensive research on the amount of stabilizer added to the aqueous hydrogen peroxide solution, the stabilizer component, the evaporation residue and its water washability, impurities contained, storage stability, safety in use, etc. By using a hydrogen peroxide solution containing hydrogen oxide, phosphate and aluminum salt, the deposits derived from the stabilizer of the hydrogen peroxide solution remaining on the spray nozzle and the evaporator can be reduced, and the residue can be easily washed with water. It has been found that an aqueous hydrogen peroxide solution can be provided that can be removed and enables stable operation of an aseptic filling apparatus.
That is, the present invention is as follows.
<1> An aqueous hydrogen peroxide solution used for reducing the number of bacteria, wherein the aqueous hydrogen peroxide solution contains hydrogen peroxide, a phosphate and an aluminum salt as essential components.
<2> The phosphate is tripotassium phosphate, trimagnesium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, phosphoric acid The aqueous hydrogen peroxide solution according to <1>, which is at least one selected from the group consisting of sodium dihydrogen, trisodium phosphate, and bis (hydrogen hydrogen phosphate) calcium.
<3> The aqueous hydrogen peroxide solution according to <1>, wherein the phosphate is a hydrogen phosphate.
<4> The hydrogen peroxide aqueous solution according to any one of <1> to <3>, wherein an addition concentration of the phosphate is 1 to 18 mg / kg.
<5> The hydrogen peroxide solution according to any one of <1> to <4>, wherein the aluminum salt is potassium aluminum sulfate.
<6> The hydrogen peroxide aqueous solution according to any one of <1> to <5>, wherein an addition concentration of the aluminum salt is 1 to 4 mg / kg.
<7> L-ascorbic acid and its salt, ethylenediaminetetraacetate, citric acid and its salt, gluconic acid and its salt, L-glutamic acid and its salt, silicate, nitrate, carbonate, pyrophosphate, and sulfuric acid The aqueous hydrogen peroxide solution according to any one of <1> to <6> above, which contains at least one acid selected from the group consisting of salts and / or salts.
<8> The aqueous hydrogen peroxide solution according to <7>, wherein the addition concentration of the acid and / or salt is 2 to 12 mg / kg.
<9> The aqueous hydrogen peroxide solution according to any one of <1> to <8>, wherein the concentration of the hydrogen peroxide is 30% by weight to 40% by weight.
<10> A disinfectant using the aqueous hydrogen peroxide solution according to any one of <1> to <9>.
<11> The method for producing an aqueous hydrogen peroxide solution according to any one of <1> to <9>, wherein a phosphate and an aluminum salt are added to the aqueous hydrogen peroxide solution as a raw material.
<12> A sterilization method comprising mixing air and a mist and / or gas of the hydrogen peroxide aqueous solution according to any one of <1> to <9>, and then bringing the mixture into contact with an object.
<13> The sterilization method according to <12>, wherein when bringing the aqueous hydrogen peroxide solution into contact with the object, the air is heated to accompany the mist and / or gas of the aqueous hydrogen peroxide solution.
<14> The sterilization method according to <12> or <13>, wherein the hydrogen peroxide aqueous solution is heated to 100 ° C. to 150 ° C. and brought into contact with an object.
<15> The sterilization method according to any one of <12> to <14>, wherein the object is a packaging container, a food machine, a plastic bottle, or a plastic bottle preform.
<16> The sterilization method according to any one of <12> to <14>, wherein the object is a closed space.
<17> The sterilization method according to <16>, wherein the closed space is an automobile, a clean room for electronic industry, a living space, a medical space, a kitchen, a kitchen, a vehicle, or an aircraft.
<18> Reduce the number of bacteria in the facility by bringing a hydrogen peroxide solution mist and / or hydrogen peroxide vapor generator into the facility to generate a hydrogen peroxide solution mist and / or hydrogen peroxide vapor. The sterilization method according to any one of <12> to <14>, which is characterized in that
<19> The sterilization method according to <18>, wherein the facility is a toiletry facility, a waste disposal facility, or a barn.
本発明により、過酸化水素の安定性が向上し、噴霧ノズルや蒸発機などに付着残存する過酸化水素水溶液の安定剤由来の付着物を低減し、かつ残渣が水洗により容易に除去可能となる。 According to the present invention, the stability of hydrogen peroxide is improved, the deposits derived from the stabilizer of the aqueous hydrogen peroxide solution remaining on the spray nozzle or the evaporator are reduced, and the residue can be easily removed by washing with water. .
以下、本発明を詳細に説明する。
本発明の過酸化水素水溶液は、過酸化水素の安定化のための有効成分として、リン酸塩とアルミニウム塩を含む。更にノズルや蒸発機などに付着した蒸発残渣の水洗性を容易にするための添加剤として、その他の酸及び／又は塩を含んでもよい。
従来、過酸化水素水溶液に安定剤として添加されていたリン酸などのキレート剤によって、金属製タンクより微量の金属が溶出し、過酸化水素の安定度が低下する問題があったが、リン酸塩を用いることでこの問題を解消することができる。Hereinafter, the present invention will be described in detail.
The aqueous hydrogen peroxide solution of the present invention contains a phosphate and an aluminum salt as active ingredients for stabilizing hydrogen peroxide. Furthermore, other acid and / or salt may be included as an additive for facilitating water washing of the evaporation residue adhering to the nozzle or the evaporator.
Conventionally, a chelating agent such as phosphoric acid that has been added as a stabilizer to an aqueous hydrogen peroxide solution causes a trace amount of metal to elute from the metal tank, resulting in a decrease in the stability of hydrogen peroxide. This problem can be solved by using salt.
本発明で使用するリン酸塩は、例として具体的には、リン酸三カリウム、リン酸三マグネシウム、リン酸水素二アンモニウム、リン酸二水素アンモニウム、リン酸水素二カリウム、リン酸二水素カリウム、リン酸水素二ナトリウム、リン酸二水素ナトリウム、リン酸三ナトリウム、ビス（リン酸水素）カルシウムが好ましく、特にリン酸水素二ナトリウムが好ましい。また、本発明で使用するリン酸塩は、リン酸水素塩であることが好ましい。 Specific examples of the phosphate used in the present invention include tripotassium phosphate, trimagnesium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate. Disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, and bis (hydrogen hydrogen phosphate) calcium are preferable, and disodium hydrogen phosphate is particularly preferable. Moreover, it is preferable that the phosphate used by this invention is a hydrogen phosphate.
本発明で使用するアルミニウム塩は、アルミニウムを含む食品添加物であれば特に問題なく使用でき、例えば硫酸アルミニウムカリウムが好ましい。 The aluminum salt used in the present invention can be used without any problem as long as it is a food additive containing aluminum. For example, potassium aluminum sulfate is preferred.
本発明において、ノズルや蒸発機などに付着した蒸発残渣の水洗性を良好とする酸及び／又は塩も食品衛生法の指定添加物より選ぶことができる。具体的には、Ｌ−アスコルビン酸及び／又はその塩、エチレンジアミン四酢酸塩、クエン酸及び／又はその塩、グルコン酸及び／又はその塩、Ｌ−グルタミン酸及び／又はその塩、ケイ酸塩、硝酸塩、炭酸塩、ピロリン酸塩、硫酸塩が好ましく、特に硫酸塩が好ましい。 In the present invention, an acid and / or salt that improves the washing ability of the evaporation residue adhering to the nozzle or the evaporator can also be selected from designated additives of the Food Sanitation Law. Specifically, L-ascorbic acid and / or its salt, ethylenediaminetetraacetate, citric acid and / or its salt, gluconic acid and / or its salt, L-glutamic acid and / or its salt, silicate, nitrate , Carbonates, pyrophosphates and sulfates are preferable, and sulfates are particularly preferable.
本発明の過酸化水素水溶液において、リン酸塩の添加濃度は１〜１８ｍｇ／ｋｇが好ましく、１〜１２ｍｇ／ｋｇがより好ましい。リン酸塩の添加濃度が１〜１８ｍｇ／ｋｇであると、安定化効果が得られ、蒸発機やノズルに付着する蒸発残渣の量が抑制される。
本発明の過酸化水素水溶液において、アルミニウム塩の添加濃度は１〜４ｍｇ／ｋｇが好ましく、１〜３ｍｇ／ｋｇがより好ましい。アルミニウム塩の添加濃度が１〜４ｍｇ／ｋｇであると、安定化効果が得られ、蒸発機やノズルに付着する蒸発残渣の量が抑制される。
本発明の過酸化水素水溶液において、過酸化水素の濃度は３０〜４０重量％が好ましく、３３〜３７重量％がより好ましい。過酸化水素の濃度が３０〜４０重量％であると、殺菌力が適切な強さとなり好ましい。
本発明の過酸化水素水溶液において好ましく用いられるその他の酸及び／又は塩の添加濃度は２〜１２ｍｇ／ｋｇが好ましく、３〜１０ｍｇ／ｋｇがより好ましい。その他の酸及び／又は塩の添加濃度が２〜１２ｍｇ／ｋｇであると、蒸発残渣洗浄性が高くなり好ましい。
特に好ましくは、リン酸塩の添加濃度は２〜４ｍｇ／ｋｇであり、アルミニウム塩の添加濃度は２〜３ｍｇ／ｋｇであり、その他の酸及び／又は塩の添加濃度は３〜５ｍｇ／ｋｇである。 In the hydrogen peroxide solution of the present invention, the addition concentration of phosphate is preferably 1 to 18 mg / kg, and more preferably 1 to 12 mg / kg. When the addition concentration of phosphate is 1 to 18 mg / kg, a stabilizing effect is obtained, and the amount of evaporation residue adhering to the evaporator and the nozzle is suppressed.
In the aqueous hydrogen peroxide solution of the present invention, the addition concentration of the aluminum salt is preferably 1 to 4 mg / kg, more preferably 1 to 3 mg / kg. When the addition concentration of the aluminum salt is 1 to 4 mg / kg, a stabilizing effect is obtained, and the amount of evaporation residue adhering to the evaporator and the nozzle is suppressed.
In the hydrogen peroxide aqueous solution of the present invention, the concentration of hydrogen peroxide is preferably 30 to 40% by weight, and more preferably 33 to 37% by weight. It is preferable that the concentration of hydrogen peroxide is 30 to 40% by weight because the sterilizing power is appropriate.
The addition concentration of other acids and / or salts preferably used in the aqueous hydrogen peroxide solution of the present invention is preferably 2 to 12 mg / kg, more preferably 3 to 10 mg / kg. When the concentration of the other acid and / or salt added is 2 to 12 mg / kg, the evaporation residue cleaning property is increased, which is preferable.
Particularly preferably, the addition concentration of phosphate is 2 to 4 mg / kg, the addition concentration of aluminum salt is 2 to 3 mg / kg, and the addition concentration of other acids and / or salts is 3 to 5 mg / kg. is there.
過酸化水素の分解成分としては重金属類が知られているが、工業的に製造する過酸化水素水溶液に含有される分解成分としては、Ｆｅ、Ｃｒ、Ｎｉ、Ｐｄにほぼ限定される。本発明は、Ｎｉ、Ｐｄ濃度をそれぞれ０．１ｐｐｂ以下とし、Ｆｅ、Ｃｒ濃度をそれぞれ５ｐｐｂ以下とした過酸化水素水溶液を使用することが望ましい。 Heavy metals are known as hydrogen peroxide decomposition components, but the decomposition components contained in an aqueous hydrogen peroxide solution produced industrially are almost limited to Fe, Cr, Ni, and Pd. In the present invention, it is desirable to use an aqueous hydrogen peroxide solution in which the Ni and Pd concentrations are each 0.1 ppb or less and the Fe and Cr concentrations are each 5 ppb or less.
本発明の過酸化水素水溶液は、原料となる過酸化水素水溶液にリン酸塩及びアルミニウム塩、並びに付随的なその他の酸及び／又は塩を直接添加し製造することができる。 The aqueous hydrogen peroxide solution of the present invention can be produced by directly adding a phosphate and an aluminum salt and other accompanying acids and / or salts to the aqueous hydrogen peroxide solution used as a raw material.
ミスト及び／またはガス状の過酸化水素の生成方法は特に限定されない。超音波による方法、加熱による方法が例示される。過酸化水素水溶液を蒸発機で沸点以上に加熱気化させ、空気と共に過酸化水素の気体を噴霧することが好ましい。 The method for producing mist and / or gaseous hydrogen peroxide is not particularly limited. Examples include a method using ultrasonic waves and a method using heating. It is preferable to heat and vaporize the aqueous hydrogen peroxide solution above the boiling point with an evaporator and spray the hydrogen peroxide gas together with air.
本発明の過酸化水素水溶液を加熱蒸発させる装置は、特に制限はなく公知の装置を用いることができる。 The apparatus for heating and evaporating the aqueous hydrogen peroxide solution of the present invention is not particularly limited, and a known apparatus can be used.
加熱気化する温度は１００℃〜１５０℃がより望ましい。 As for the temperature which heat-vaporizes, 100 to 150 degreeC is more desirable.
過酸化水素水溶液を対象物と接触させる際に、空気も加熱して過酸化水素水溶液のミスト及び／又はガスを同伴させることがより望ましい。 When the aqueous hydrogen peroxide solution is brought into contact with the object, it is more desirable to heat the air to entrain the mist and / or gas of the aqueous hydrogen peroxide solution.
対象物としては、例えば包装容器、食品機械、ペットボトル及び／又はペットボトルプリフォーム、閉鎖空間などが挙げられる。 Examples of the object include a packaging container, a food machine, a PET bottle and / or a PET bottle preform, and a closed space.
閉鎖空間としては、例えば自動車、電子工業用のクリーンルーム、居住空間、医療スペース、厨房、調理場、車両、航空機などが挙げられる。 Examples of the closed space include automobiles, electronic industry clean rooms, living spaces, medical spaces, kitchens, kitchens, vehicles, and aircraft.
本発明では過酸化水素水溶液のミスト及び／又は過酸化水素蒸気の発生装置を施設内に持ち込み、過酸化水素水溶液のミスト及び／又は過酸化水素蒸気を発生させ、施設内の菌数を減らすこともできる。 In the present invention, a hydrogen peroxide aqueous solution mist and / or hydrogen peroxide vapor generator is brought into the facility to generate a hydrogen peroxide aqueous solution mist and / or hydrogen peroxide vapor to reduce the number of bacteria in the facility. You can also.
この施設として、トイレタリー施設、廃棄物処理施設、畜舎が例示される。 As this facility, a toiletry facility, a waste disposal facility, and a barn are exemplified.
次に、実施例および比較例により本発明をさらに具体的に説明する。但し本発明は以下の実施例により制限されるものではない。 Next, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited by the following examples.
＜サンプルの調製方法＞
過酸化水素の安定性は、(1)調合直後、(2)アルミニウムタンク貯蔵後想定、(3)アルミニウムタンク貯蔵に次いでステンレスタンク貯蔵されたことを想定した段階において調べた。
所定の過酸化水素水溶液を用い、所望量の添加剤を加えた後、過酸化水素濃度を３５重量％とした。添加剤の量は表１〜３に示したとおりである。
(2)の説明：本発明における過酸化水素水溶液３００ミリリットルにアルミニウム製のテストピース（３０ｍｍ×３０ｍｍ×２ｍｍ）２枚を入れ、４５℃にて２４時間静置した。
(3)の説明：(2)の後、アルミニウム製のテストピースを抜出し、代わりにＳＵＳ３０４製のテストピース（３０ｍｍ×３０ｍｍ×２ｍｍ）２枚を入れ、４５℃にて２４時間静置した。
なお、クエン酸3Naはクエン酸3ナトリウムを表し、同様にグルコン酸Naはグルコン酸ナトリウムを表す。また、カリミョウバンは硫酸アルミニウムカリウム（ＡｌＫ（ＳＯ４）２・１２Ｈ２Ｏ）を示す。<Sample preparation method>
The stability of hydrogen peroxide was examined at the stage assuming (1) immediately after compounding, (2) post-storage after storage of aluminum tank, and (3) storage of stainless steel tank after storage of aluminum tank.
After using a predetermined aqueous hydrogen peroxide solution and adding a desired amount of additives, the hydrogen peroxide concentration was set to 35% by weight. The amount of the additive is as shown in Tables 1-3.
Explanation of (2): Two test pieces (30 mm × 30 mm × 2 mm) made of aluminum were placed in 300 ml of the hydrogen peroxide solution in the present invention, and allowed to stand at 45 ° C. for 24 hours.
Explanation of (3): After (2), an aluminum test piece was extracted, and instead two test pieces (30 mm × 30 mm × 2 mm) made of SUS304 were placed and allowed to stand at 45 ° C. for 24 hours.
In addition, citrate 3Na represents trisodium citrate, and similarly, gluconate Na represents sodium gluconate. Potash alum indicates aluminum potassium sulfate (AlK (SO 4 ) 2 · 12H 2 O).
＜サンプルの測定方法＞
過酸化水素の安定性はＪＩＳ安定度により、蒸発残渣の物性については付着物水洗性により評価した。ＪＩＳ安定度は、ＪＩＳ−１４６３に規定された方法で行った。また付着物水洗性の評価は、１５０℃に加熱したホットプレート上にＳＵＳ３０４製のテストピース（３０ｍｍ×３０ｍｍ×２ｍｍ）を置き、テストピース上に過酸化水素水溶液を３ミリリットル滴下し、水分を蒸発させ付着物を析出させた。そのテストピースを流水にて水洗し、水洗前後の付着物の残渣の状況をSEMにより観察し、取れ残り量の多少で評価した。○＝取れ残り量が写真中の面積の40％以下、△＝取れ残り量が写真中の面積の40超〜70％未満、×＝取れ残り量が写真中の面積の70％以上。<Sample measurement method>
The stability of hydrogen peroxide was evaluated by the JIS stability, and the physical properties of the evaporation residue were evaluated by the adhering water washing property. The JIS stability was measured by the method specified in JIS-1463. In addition, the evaluation of the ability to wash the adhering matter was made by placing a SUS304 test piece (30 mm x 30 mm x 2 mm) on a hot plate heated to 150 ° C, dropping 3 ml of an aqueous hydrogen peroxide solution onto the test piece, and evaporating the water. And deposits were deposited. The test piece was washed with running water, the state of the deposit residue before and after washing was observed by SEM, and the remaining amount was evaluated. ○ = Remaining remaining amount is 40% or less of the area in the photograph, Δ = Remaining remaining amount is more than 40 to less than 70% of the area in the photograph, and X = Remaining remaining amount is 70% or more of the area in the photograph.
表１に本発明の必須成分を欠いた場合の結果を示す。
比較例１〜１１のようにアルミニウム塩（カリミョウバン）を添加しなかったり、比較例５、７及び１２のようにリン酸塩を添加しなかった場合、あるいは比較例１３のようにリン酸塩の代わりにリン酸を添加した場合には、ＪＩＳ安定度は満足のいくものではなく、残渣洗浄性も満足のいくものではないことがわかる。Table 1 shows the results when the essential components of the present invention are lacking.
When no aluminum salt (potash alum) was added as in Comparative Examples 1 to 11, or when phosphate was not added as in Comparative Examples 5, 7, and 12, or as in Comparative Example 13, It can be seen that when phosphoric acid is added instead of JIS, the JIS stability is not satisfactory, and the residue cleaning property is not satisfactory.
表２に本発明の必須成分を満たした場合の結果を示す。
表１の結果に比べ、ＪＩＳ安定度は向上し、残渣洗浄性も向上した。
特に実施例１４は残渣洗浄性に著しい効果が見られる。Table 2 shows the results when the essential components of the present invention are satisfied.
Compared with the results shown in Table 1, the JIS stability was improved and the residue washes were also improved.
In particular, Example 14 shows a remarkable effect on the residue cleaning property.
表３にはカリミョウバン、リン酸二水素ナトリウム、硫酸ナトリウムの添加量を変化させた場合の結果を示す。
なお、実施例４は表２からの再掲である。
実施例２０，２１はＪＩＳ安定性も高く、残渣洗浄性も著しく良い。Table 3 shows the results when the amounts of potassium alum, sodium dihydrogen phosphate, and sodium sulfate were changed.
In addition, Example 4 is a reproduction from Table 2.
Examples 20 and 21 have high JIS stability and remarkably good residue cleaning properties.
本発明により、過酸化水素の安定性が向上し、噴霧ノズルや蒸発機などに付着残存する過酸化水素水溶液の安定剤由来の付着物が低減され、かつ残渣が水洗により容易に除去可能となることから、ノズルなどの細い配管部を閉塞させることなく、無菌充填装置の安定した運転が可能となる。
According to the present invention, the stability of hydrogen peroxide is improved, the deposits derived from the stabilizer of the aqueous hydrogen peroxide solution remaining on the spray nozzle and the evaporator are reduced, and the residue can be easily removed by washing with water. For this reason, the aseptic filling apparatus can be stably operated without blocking a thin pipe portion such as a nozzle.
Claims (13)
ｂ）リン酸塩、
ｃ）硫酸アルミニウムカリウムであるアルミニウム塩、及び
ｄ）Ｌ−アスコルビン酸及びその塩、エチレンジアミン四酢酸塩、クエン酸及びその塩、グルコン酸及びその塩、Ｌ−グルタミン酸及びその塩、ケイ酸塩、硝酸塩、炭酸塩、ピロリン酸塩、並びに硫酸塩からなる群より選ばれる少なくとも１種の酸及び／又は塩
を含む殺菌用過酸化水素水溶液であって、
前記リン酸塩の添加濃度が６〜１８ｍｇ／ｋｇであり、前記アルミニウム塩の添加濃度が１．７〜３ｍｇ／ｋｇであり、前記酸及び／又は塩の添加濃度が２〜１２ｍｇ／ｋｇである、前記殺菌用過酸化水素水溶液。 a) hydrogen peroxide,
b) phosphate ,
c) an aluminum salt which is potassium aluminum sulfate , and
d) L-ascorbic acid and its salt, ethylenediaminetetraacetate, citric acid and its salt, gluconic acid and its salt, L-glutamic acid and its salt, silicate, nitrate, carbonate, pyrophosphate, and sulfate At least one acid and / or salt selected from the group consisting of
An aqueous hydrogen peroxide solution for sterilization, comprising
The phosphate concentration is 6-18 mg / kg, the aluminum salt concentration is 1.7-3 mg / kg, and the acid and / or salt concentration is 2-12 mg / kg. The aqueous hydrogen peroxide solution for sterilization .
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| WO2017135780A1 (en) | 2016-02-05 | 2017-08-10 | 한양대학교 산학협력단 | Apparatus and method for generating activated sterilization solution |
| CN117941706A (en) * | 2017-01-31 | 2024-04-30 | 三菱瓦斯化学株式会社 | Aqueous hydrogen peroxide solution for sterilization |
| WO2018151308A1 (en) | 2017-02-20 | 2018-08-23 | 大日本印刷株式会社 | Gasifying device for sterilization agent and method for cleaning gasifying device for sterilization agent |
| CN111372469A (en) * | 2017-11-27 | 2020-07-03 | 三菱瓦斯化学株式会社 | Method for producing peracetic acid composition used as food additive |
| KR102127417B1 (en) | 2018-12-10 | 2020-06-29 | 주식회사 코드스테리 | Compositions for sterilization and disinfection using hydrogen peroxide |
| US20220212966A1 (en) * | 2019-05-10 | 2022-07-07 | Kao Corporation | Method for removing biofilm |
| TW202301976A (en) * | 2021-03-08 | 2023-01-16 | 日商三菱瓦斯化學股份有限公司 | Aqueous hydrogen peroxide solution for sterilization, method for sterilizing object using same, and method for producing sterilized object |
| WO2022272257A1 (en) * | 2021-06-23 | 2022-12-29 | Evonik Corporation | A process for sterilization treatment using a residue-free hydrogen peroxide |
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| JPS5372799A (en) * | 1976-12-10 | 1978-06-28 | Tokuyama Soda Co Ltd | Storage method for aqueous solution of hydrogen peroxide |
| US4320102A (en) * | 1980-10-10 | 1982-03-16 | Air Products And Chemicals, Inc. | Method of stabilizing hydrogen peroxide solutions |
| US5667753A (en) * | 1994-04-28 | 1997-09-16 | Advanced Sterilization Products | Vapor sterilization using inorganic hydrogen peroxide complexes |
| JPH1135306A (en) * | 1997-07-17 | 1999-02-09 | Mitsubishi Gas Chem Co Inc | Hydrogen peroxide composition |
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| US7803315B2 (en) * | 2001-10-05 | 2010-09-28 | American Sterilizer Company | Decontamination of surfaces contaminated with prion-infected material with gaseous oxidizing agents |
| JP2006240969A (en) * | 2005-03-07 | 2006-09-14 | Mitsubishi Gas Chem Co Inc | Hydrogen peroxide water for aseptic packaging apparatus |
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