JP2011212522A - Method for inhibiting decomposition of isothiazolin-based compound in aqueous system and method for controlling microorganism in aqueous system - Google Patents
Method for inhibiting decomposition of isothiazolin-based compound in aqueous system and method for controlling microorganism in aqueous system Download PDFInfo
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本発明は、水系中のイソチアゾリン系化合物の分解抑制方法、及び、この方法を応用した水系の微生物制御方法に関する。 The present invention relates to a method for inhibiting decomposition of an isothiazoline compound in an aqueous system, and an aqueous microorganism control method to which this method is applied.
イソチアゾリン系化合物は抗菌スペクトルの広い殺菌剤として知られている。しかし、一部の粒状緑藻に対して殆ど効果を示さない。また、水系での分解が比較的早く、濃度を維持するのが困難あると云った問題があった。 Isothiazoline compounds are known as bactericides with a broad antibacterial spectrum. However, it has little effect on some granular green algae. In addition, there is a problem that decomposition in an aqueous system is relatively fast and it is difficult to maintain the concentration.
また、ヨーネンポリマは低毒性の殺菌剤であり、殺藻剤としても効果を発揮することが知られている。しかし、ヨーネンポリマ単独では効果が低く、高濃度の添加が必要であった。また、粒状緑藻に対しては十分な効果が得られないと云った問題があった。 Ionene polymer is a low-toxic fungicide and is known to exhibit an effect as an algicide. However, the ionene polymer alone has a low effect and needs to be added at a high concentration. Moreover, there was a problem that sufficient effects could not be obtained for granular green algae.
ここで、本発明者等はイソチアゾリン系化合物、および、ヨーネンポリマの両者の併用により得られる相乗効果に着目し、藻類抑制剤として提案している（特開２００９−１５５２２０公報（特許文献１））。 Here, the present inventors have focused on a synergistic effect obtained by the combined use of both an isothiazoline-based compound and an ionene polymer, and have proposed it as an algal inhibitor (Japanese Patent Laid-Open No. 2009-155220 (Patent Document 1)).
しかし、実際の冷却水系において、単にイソチアゾリン系化合物、および、ヨーネンポリマの両者を併用添加しただけでは、粒状緑藻の発生を抑えきれない場合があるばかりでなく、実験室レベルでは十分な抑制効果を発揮する細菌類に対しても、効果が不十分となる水系が存在することが明らかになった。 However, in the actual cooling water system, simply adding both the isothiazoline compound and the ionene polymer together may not be enough to suppress the generation of granular green algae. It has been clarified that there is an aqueous system that is insufficient in effect against bacteria.
本発明は、このようにイソチアゾリン系化合物を添加して微生物制御を行っている水系において、イソチアゾリン系化合物の持つ広い抗菌スペクトルと云う機能を、常に、そして、安定的に発揮させるための、水系の微生物制御方法を提供することを目的とする。 In the aqueous system in which the isothiazoline compound is added to control the microorganism as described above, the present invention provides an aqueous system for constantly and stably exhibiting the function of the broad antibacterial spectrum of the isothiazoline compound. An object is to provide a method for controlling microorganisms.
上記のように、イソチアゾリン系化合物、および、ヨーネンポリマの両者を併用添加していながら、粒状緑藻の発生を抑えきれなかった水系水を調査してみると、ヨーネンポリマは分解が遅く、添加した濃度を長期間維持していたのに対し、イソチアゾリン系化合物は分解が速く、そのために水系から失われていたことが判った。 As described above, when water-based water in which the generation of granular green algae was not suppressed while both the isothiazoline compound and the ionene polymer were added together, the ionene polymer was slow to decompose and the added concentration was long. It was found that the isothiazoline-based compound was rapidly decomposed and thus lost from the aqueous system, while maintaining the period.
さらに、種々の検討を行った結果、イソチアゾリン系化合物は、水系での分解が非常に速く、イソチアゾリン系化合物を単独使用している水系では、イソチアゾリン系化合物の水系中の濃度を維持するのが極めて困難である点、水系中でヨーネンポリマと共存させるとイソチアゾリン系化合物の分解速度を遅くすることができ、その結果、イソチアゾリン系化合物の水系中の濃度を維持するのが比較的容易となる点、更には、イソチアゾリン系化合物、および、ヨーネンポリマの両者を併用添加していながら、粒状緑藻の発生を抑えきれなかった水系において、水系中にイソチアゾリン系化合物が残存するように、イソチアゾリン系化合物の添加方法を変更することで、粒状緑藻の発生を抑制可能である点を見出し、本発明に至った。 Furthermore, as a result of various studies, isothiazoline-based compounds decompose very rapidly in aqueous systems, and in aqueous systems that use isothiazoline-based compounds alone, it is extremely important to maintain the concentration of isothiazoline-based compounds in the aqueous system. Difficult point, coexistence with ionene polymer in aqueous system can slow down decomposition rate of isothiazoline compound, and as a result, it is relatively easy to maintain the concentration of isothiazoline compound in aqueous system. Changed the addition method of isothiazoline compounds so that the isothiazoline compounds remain in the aqueous system in which the generation of granular green algae could not be suppressed even though both the isothiazoline compound and ionene polymer were added together As a result, it was found that the generation of granular green algae can be suppressed, and the present invention has been achieved.
すなわち、本発明は請求項１に記載の通り、イソチアゾリン系化合物を添加して微生物制御を行っている水系において、前記水系中のヨーネンポリマの濃度を所定濃度以上に維持することを特徴とするイソチアゾリン系化合物の分解抑制方法である。 That is, the present invention provides an isothiazoline system characterized in that, in an aqueous system in which an isothiazoline-based compound is added to perform microbial control, the concentration of the ionene polymer in the aqueous system is maintained at a predetermined level or more. This is a method for inhibiting the decomposition of a compound.
また、本発明のイソチアゾリン系化合物の分解抑制方法は請求項２に記載の通り、請求項１に記載のイソチアゾリン系化合物の分解抑制方法において、前記水系中の前記ヨーネンポリマの濃度を１ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下に維持することを特徴とする。 Further, the method for inhibiting decomposition of an isothiazoline compound according to the present invention is the method for inhibiting decomposition of an isothiazoline compound according to claim 1, wherein the concentration of the ionene polymer in the aqueous system is 1 mg / L or more and 100 mg. / L or less.
本発明の水系の微生物制御方法は請求項３に記載の通り、水系中のヨーネンポリマの濃度を所定濃度以上に維持すると共に、該水系中のイソチアゾリン系化合物の濃度が所定の濃度範囲となるように、該イソチアゾリン系化合物を該水系に添加することを特徴とする水系の微生物制御方法である。 According to the third aspect of the present invention, the aqueous microorganism control method maintains the concentration of the ionene polymer in the aqueous system at a predetermined concentration or more, and the concentration of the isothiazoline compound in the aqueous system is within a predetermined concentration range. A method for controlling an aqueous microorganism, which comprises adding the isothiazoline compound to the aqueous system.
また、本発明の水系の微生物制御方法は、請求項４に記載の通り、請求項３に記載の水系の微生物制御方法において、前記水系中の前記ヨーネンポリマの濃度を１ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下に維持し、かつ、該水系中の前記イソチアゾリン系化合物の前記所定の濃度範囲を０．１ｍｇ／Ｌ以上２０ｍｇ／Ｌ以下とすることを特徴とする。 The aqueous microorganism control method of the present invention is the aqueous microorganism control method according to claim 3, wherein the concentration of the ionene polymer in the aqueous system is 1 mg / L or more and 100 mg / L or less. And the predetermined concentration range of the isothiazoline compound in the aqueous system is 0.1 mg / L or more and 20 mg / L or less.
本発明の水系の微生物制御方法は、請求項５に記載の通り、請求項３または請求項４に記載の水系の微生物制御方法において、前記水系への補給水の水量に対して一定比率で、前記ヨーネンポリマを前記水系に添加することにより、該水系中の該ヨーネンポリマの濃度の維持を行うことを特徴とする。 The water-based microbial control method of the present invention is the water-based microbial control method according to claim 3 or claim 4 in a constant ratio to the amount of make-up water to the water system, as described in claim 5. By adding the ionene polymer to the aqueous system, the concentration of the ionene polymer in the aqueous system is maintained.
本発明の水系の微生物制御方法は、請求項６に記載の通り、請求項３または請求項４に記載の水系の微生物制御方法において、前記水系がブローを実施している水系であり、該ブローにおけるブロー水の水量に対して一定比率で、前記ヨーネンポリマを該水系に添加することにより、該水系中の該ヨーネンポリマの濃度の維持を行うことを特徴とする。 The water-based microorganism control method of the present invention is the water-based microorganism control method according to claim 3 or claim 4, wherein the water system is a water system in which the blow is performed. The ionene polymer is added to the water system at a constant ratio with respect to the amount of blow water in the water system to maintain the concentration of the ionene polymer in the water system.
本発明の水系の微生物制御方法は、請求項７に記載の通り、請求項３ないし請求項６のいずれか１項に記載の水系の微生物制御方法において、前記水系中の前記イソチアゾリン系化合物の濃度を測定し、該イソチアゾリン系化合物の濃度の測定結果に基づいて、該イソチアゾリン系化合物の該水系への添加を行うことを特徴とする。 The aqueous microorganism control method of the present invention is the aqueous microorganism control method according to any one of claims 3 to 6, wherein the concentration of the isothiazoline compound in the aqueous system is as described in claim 7. The isothiazoline-based compound is added to the aqueous system based on the measurement result of the concentration of the isothiazoline-based compound.
本発明の水系の微生物制御方法は、請求項８に記載の通り、請求項３ないし請求項７のいずれか１項に記載の水系の微生物制御方法において、前記ヨーネンポリマが、ポリ［オキシエチレン（ジメチルイミニオ）エチレン（ジメチルイミニオ）エチレンジクロライド］であることを特徴とする。 The water-based microorganism control method according to the present invention is the water-based microorganism control method according to any one of claims 3 to 7, wherein the ionene polymer is poly [oxyethylene (dimethyl). Iminio) ethylene (dimethyliminio) ethylene dichloride].
本発明のイソチアゾリン系化合物の分解抑制方法によれば、イソチアゾリン系化合物の分解を効果的に抑制することができ、このために、少量、低頻度の添加であっても、イソチアゾリン系化合物の濃度維持が容易となり、その結果、イソチアゾリン系化合物を添加して微生物制御を行っている水系において、イソチアゾリン系化合物の持つ広い抗菌スペクトルと云う機能を、常に、そして、安定的に発揮させることが可能となる。 According to the method for inhibiting decomposition of an isothiazoline compound of the present invention, the decomposition of the isothiazoline compound can be effectively suppressed. For this reason, the concentration of the isothiazoline compound can be maintained even with a small amount and low frequency addition. As a result, in an aqueous system in which an isothiazoline compound is added to control microorganisms, it is possible to always and stably exhibit the function of the broad antibacterial spectrum of an isothiazoline compound. .
また、本発明の水系の微生物制御方法は上記のイソチアゾリン系化合物の分解抑制方法を応用して、抗菌スペクトルの広いイソチアゾリン系化合物を水系中に常に存在させることで、該水系における細菌、真菌、藻類等、各種の微生物の増殖を効果的に抑制することができる。更に、本発明の水系の微生物制御方法は、水系中にイソチアゾリン系化合物とヨーネンポリマとを常に共存させることになるので、イソチアゾリン系化合物単独では効果を示さない一部の粒状緑藻に対しても有効であり、単にイソチアゾリン系化合物とヨーネンポリマとの両者を併用添加しただけでは、粒状緑藻の発生を抑えきれなかった水系においても、イソチアゾリン系化合物の濃度を維持することで、効果的に粒状緑藻の発生を防止することが可能となる。 In addition, the aqueous microorganism control method of the present invention applies the above-described method for inhibiting decomposition of an isothiazoline compound, and always has an isothiazoline compound having a wide antibacterial spectrum in the aqueous system, so that bacteria, fungi, and algae in the aqueous system are present. The growth of various microorganisms can be effectively suppressed. Furthermore, since the method for controlling an aqueous microorganism of the present invention always allows an isothiazoline compound and an ionene polymer to coexist in the aqueous system, it is effective even for some granular green algae that are not effective by the isothiazoline compound alone. Yes, by simply adding both an isothiazoline compound and an ionene polymer together, even in an aqueous system where the generation of granular green algae could not be suppressed, the generation of granular green algae can be effectively achieved by maintaining the concentration of the isothiazoline compound. It becomes possible to prevent.
本発明で用いるイソチアゾリン系化合物としては、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オン、１，２−ベンゾイソチアゾリン−３−オン、２−ｎ−オクチル−４−イソチアゾリン−３−オン等が挙げられ、これらのうちの１種、あるいは、２種以上を選択して用いる。ここで、特に好ましいイソチアゾリン系化合物としては５−クロロ−２−メチル−４−イソチアゾリン−３−オン、および、２−メチル−４−イソチアゾリン−３−オンが挙げられる。 The isothiazoline compounds used in the present invention include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazoline-3-one, 2 -N-octyl-4-isothiazolin-3-one etc. are mentioned, 1 type or 2 types or more of these are selected and used. Here, particularly preferred isothiazoline compounds include 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.
一方、ヨーネンポリマは、低毒性の薬剤で、特開平５−３３１００２号公報（特許文献２）、あるいは、特開平１０−４５５１４号公報（特許文献３）等により殺藻剤として用いられることが知られているが、単独ではいつくかの藻類、例えば粒状緑藻に対しては充分な抑制効果が得られない。本発明では、ヨーネンポリマはむしろ、水中で分解されやすいイソチアゾリン系化合物の分解を抑制させると云う、本発明者等により見出された機能の方が重要である。 On the other hand, ionene polymer is a low-toxic drug and is known to be used as an algicidal agent by JP-A-5-331002 (Patent Document 2) or JP-A-10-45514 (Patent Document 3). However, a sufficient inhibitory effect cannot be obtained on some algae alone, for example, granular green algae. In the present invention, the function found by the present inventors is more important in that the ionene polymer rather suppresses the decomposition of an isothiazoline-based compound that is easily decomposed in water.
本発明で用いるヨーネンポリマとしては、ポリ［オキシエチレン（ジメチルイミニオ）エチレン（ジメチルイミニオ）エチレンジクロライド］、ポリ（２−ヒドロキシプロピルジメチルアンモニウムクロライド）、ポリ（ヘキサメチレンビグアニド）またはその塩などが挙げられ、これらのうち、１種、あるいは、２種以上選択して用いる。ここで、特に好ましいヨーネンポリマとしては、ポリ［オキシエチレン（ジメチルイミニオ）エチレン（ジメチルイミニオ）エチレンジクロライド］が挙げられる。 Examples of the ionene polymer used in the present invention include poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride], poly (2-hydroxypropyldimethylammonium chloride), poly (hexamethylenebiguanide), and salts thereof. Of these, one type or two or more types are selected and used. Here, as a particularly preferable ionene polymer, poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride] may be mentioned.
ここで、水系で分解されやすいイソチアゾリン系化合物の分解を抑制させると云うヨーネンポリマの機能を有効に活用するためには、イソチアゾリン系化合物を添加して微生物制御を行っている水系において、水系中のヨーネンポリマの濃度を常に所定濃度以上に維持することが必要となる。 Here, in order to effectively utilize the function of an ionene polymer that suppresses the decomposition of an isothiazoline compound that is easily decomposed in an aqueous system, an ionene polymer in an aqueous system is added in an aqueous system in which an isothiazoline compound is added to control microorganisms. Therefore, it is necessary to always maintain the density of the liquid at a predetermined density or higher.
ここで、上記所定濃度としては、好ましくは１ｍｇ／Ｌであり、より好ましいヨーネンポリマの濃度は、１ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下である。この範囲よりも低いと本発明の効果が得られない恐れがあり、また、この範囲よりも高くても、添加濃度の向上に伴う効果の向上が少なく、また、ランニングコストが上昇するので好ましくない。 Here, the predetermined concentration is preferably 1 mg / L, and a more preferable ionene polymer concentration is 1 mg / L or more and 100 mg / L or less. If it is lower than this range, the effect of the present invention may not be obtained, and if it is higher than this range, the effect accompanying the improvement of the addition concentration is small and the running cost increases, which is not preferable. .
ここで、前述のようにヨーネンポリマは水系で分解されにくいので、イソチアゾリン系化合物を添加している水系が冷却水系などの補給水が補給される水系や、ブローが実施される水系の場合には、その補給水量やブロー水量に対して一定比率で、ヨーネンポリマの添加を行うことにより、該水系中のヨーネンポリマの濃度を所定の濃度、例えば、１ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下に容易に維持することができる。 Here, as described above, since the ionene polymer is not easily decomposed in an aqueous system, the aqueous system to which the isothiazoline-based compound is added is an aqueous system in which make-up water such as a cooling water system is supplied or an aqueous system in which blow is performed. By adding the ionene polymer at a constant ratio with respect to the replenishing water amount and the blow water amount, the concentration of the ionene polymer in the aqueous system can be easily maintained at a predetermined concentration, for example, 1 mg / L or more and 100 mg / L or less. it can.
本発明の水系の微生物制御方法において、イソチアゾリン系化合物は、添加されたイソチアゾリン系化合物が水系中で常に検出される濃度（通常０．１ｍｇ／Ｌが検出下限）となるように添加する必要がある。より好ましい濃度範囲は０．１ｍｇ／Ｌ以上２０ｍｇ／Ｌ以下である。この範囲以下であると本発明の効果が得られない恐れがあり、また、この範囲を越えて添加しても、添加量の増加に伴う効果の向上は少なく、ランニングコストを上昇させる。 In the aqueous microorganism control method of the present invention, it is necessary to add the isothiazoline-based compound so that the added isothiazoline-based compound has a concentration that is always detected in the aqueous system (usually 0.1 mg / L is the lower detection limit). . A more preferable concentration range is 0.1 mg / L or more and 20 mg / L or less. If the amount is less than this range, the effect of the present invention may not be obtained. Even if the amount exceeds this range, the improvement in the effect due to the increase in the amount added is small, and the running cost is increased.
イソチアゾリン系化合物の添加方法としては、上記ヨーネンポリマと同様、水系の補給水量や、ブロー水量に対して一定比率で添加してもよいが、水系の運転条件や水系中に存在する微生物量等に応じてイソチアゾリン系化合物の分解速度は変化するので、この方法では薬品の添加量に無駄や不足が生じる恐れがある。 As for the method of adding the isothiazoline compound, it may be added at a fixed ratio to the amount of supplemental water or blown water in the same manner as the above ionene polymer, but depending on the operating conditions of the aqueous system and the amount of microorganisms present in the aqueous system. Since the decomposition rate of the isothiazoline-based compound changes, this method may cause waste or shortage in the amount of chemical added.
このため、水系中のイソチアゾリン系化合物の濃度を適宜測定し、その測定結果に基づいて、該水系中のイソチアゾリン系化合物の濃度が所定の濃度範囲、例えば０．１〜２０ｍｇ／Ｌの範囲となるように、該水系に対してイソチアゾリン系化合物を添加することが、本発明の効果が確実に得られるので好ましい。 For this reason, the concentration of the isothiazoline compound in the aqueous system is appropriately measured, and based on the measurement result, the concentration of the isothiazoline compound in the aqueous system falls within a predetermined concentration range, for example, a range of 0.1 to 20 mg / L. Thus, it is preferable to add an isothiazoline-based compound to the aqueous system because the effects of the present invention can be obtained with certainty.
このように、ヨーネンポリマとイソチアゾリン系化合物を別々に添加するのが通常採られる方法であるが、ヨーネンポリマとイソチアゾリン系化合物を含む１液剤を水系の補給水量や、ブロー水量に対して一定比率で添加しておき、定期的あるいは不定期に水系中のイソチアゾリン系化合物の濃度を測定し、イソチアゾリン系化合物の測定濃度に応じてイソチアゾリン系化合物の不足分を別途添加する方法を採ってもよい。 In this way, it is a common practice to add the ionene polymer and the isothiazoline compound separately, but one liquid containing the ionene polymer and the isothiazoline compound is added at a constant ratio to the amount of the water-based makeup water and the amount of blow water. Alternatively, a method may be employed in which the concentration of the isothiazoline compound in the aqueous system is measured regularly or irregularly, and the shortage of the isothiazoline compound is separately added according to the measured concentration of the isothiazoline compound.
水系中のイソチアゾリン系化合物濃度の測定は、通常、高速液体クロマトグラフ分析装置を用いて行う。ここで、本発明ではイソチアゾリン系化合物をヨーネンポリマと常に共存させるので、イソチアゾリン系化合物の分解速度は、イソチアゾリン系化合物を単独使用している水系と比較して、明らかに遅くなる。このため、イソチアゾリン系化合物の濃度測定に１〜２日を要しても、その測定結果に基づいてイソチアゾリン系化合物を水系に補充添加することにより、十分にイソチアゾリン系化合物の水系中の濃度を０．１〜２０ｍｇ／Ｌの範囲に維持することが可能である。 Measurement of the concentration of an isothiazoline compound in an aqueous system is usually performed using a high performance liquid chromatograph analyzer. Here, in the present invention, since the isothiazoline-based compound always coexists with the ionene polymer, the decomposition rate of the isothiazoline-based compound is clearly slow compared to the aqueous system using the isothiazoline-based compound alone. Therefore, even if it takes 1 to 2 days to measure the concentration of the isothiazoline compound, the concentration of the isothiazoline compound in the aqueous system can be sufficiently reduced by adding the isothiazoline compound to the aqueous system based on the measurement result. It can be maintained in the range of 1-20 mg / L.
また、イソチアゾリン系化合物の迅速測定法として、発光スペクトルを測定する方法（特開平６−３１７５２２号公報（特許文献４））、モノクローナル抗体を利用する方法（特開平７−２９４５２２号公報（特許文献５））、遷移金属との化学発光反応を利用する方法（特開２０００−２７１５６４公報（特許文献６））等、各種方法が提案されており、このような方法を用いることで、サンプル採取現場でのイソチアゾリン系化合物の濃度測定が可能となるので、よりきめ細やかなイソチアゾリン系化合物の添加量調整が可能となる。 Further, as a rapid measurement method for isothiazoline-based compounds, a method for measuring an emission spectrum (JP-A-6-317522 (Patent Document 4)) and a method using a monoclonal antibody (JP-A-7-294522 (Patent Document 5)). )), A method using a chemiluminescence reaction with a transition metal (Japanese Patent Laid-Open No. 2000-271564 (Patent Document 6)) and the like, and various methods have been proposed. This makes it possible to measure the concentration of the isothiazoline-based compound, so that the addition amount of the isothiazoline-based compound can be adjusted more finely.
本発明の水系の微生物制御方法では、本発明の効果が損なわれない限り、例えば、アクリル酸系、マレイン酸系、メタクリル酸系、スルホン酸系、イタコン酸系、または、イソブチレン系の各重合体やこれらの共重合体、燐酸系重合体、有機ホスホン酸、有機ホスフィン酸、あるいはこれらの水溶性塩などのスケール防止剤、あるいは、グルタルアルデヒド、フタルアルデヒド等のアルデヒド類、過酸化水素、ヒドラジン、塩素系殺菌剤（次亜塩素酸ナトリウム等）、臭素系殺菌剤及びヨウ素系殺菌剤、ジチオール系化合物、メチレンビスチオシアネート等のチオシアネート系化合物、ピリチオン系化合物、ビス型四級アンモニウム塩、ビス型四級アンモニウム塩以外の四級アンモニウム塩、四級ホスホニウム塩等のポリマーでないカチオン系化合物などのスライム防止剤、更には、ベンゾトリアゾール、トリルトリアゾール等のアゾール類、エチレンジアミン、ジエチレントリアミン等のアミン系化合物、ニトリロ三酢酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸等のアミノカルボン酸系化合物、グルコン酸、クエン酸、シュウ酸、ギ酸、酒石酸、フィチン酸、琥珀酸、乳酸等の有機カルボン酸など、各種の水処理用の薬剤を併用することができ、その場合も本発明に含まれる。 In the aqueous microbial control method of the present invention, for example, acrylic acid, maleic acid, methacrylic acid, sulfonic acid, itaconic acid, or isobutylene polymers may be used as long as the effects of the present invention are not impaired. And copolymers of these, phosphoric acid polymers, organic phosphonic acids, organic phosphinic acids, or scale inhibitors such as water-soluble salts thereof, or aldehydes such as glutaraldehyde and phthalaldehyde, hydrogen peroxide, hydrazine, Chlorine fungicides (sodium hypochlorite, etc.), bromine fungicides and iodine fungicides, dithiol compounds, thiocyanate compounds such as methylenebisthiocyanate, pyrithione compounds, bis type quaternary ammonium salts, bis type four Non-polymeric cations such as quaternary ammonium salts and quaternary phosphonium salts other than quaternary ammonium salts Anti-slime agents such as compounds, azoles such as benzotriazole and tolyltriazole, amine compounds such as ethylenediamine and diethylenetriamine, aminocarboxylic acid compounds such as nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, gluconic acid Further, various water treatment agents such as citric acid, oxalic acid, formic acid, tartaric acid, phytic acid, succinic acid, and organic carboxylic acids such as lactic acid can be used in combination, and such cases are also included in the present invention.
以下に本発明の水系中のイソチアゾリン系化合物の分解抑制方法、及び、水系の微生物制御方法の実施例について具体的に説明する。 Examples of the method for inhibiting decomposition of an isothiazoline compound in an aqueous system and the method for controlling an aqueous microorganism will be described in detail below.
＜実施例１＞
逆浸透膜装置を用いて５倍濃縮したつくば市水道水（冷却水系水を想定）を７つの２Ｌビーカーに２Ｌずつ分注し、それぞれに表１に示す薬剤を表１に示す濃度で添加し、ラップフィルムで蓋をした後、３５℃に保ちながら６０ｒｐｍで攪拌、３０日間放置した。経時的にサンプリングを行い、カチオン系薬剤（ＰＯＥＤＩ、ＰＨＰＤＡ、ＰＨＭＢ、および、塩化ベンザルコニウム。また、略号は表１参照。以下同）の残存濃度、ＣＭＩの残存濃度、ＡＴＰ（アデノシン三リン酸）濃度、および、一般細菌数を調べた。結果を表２ないし表５に示した。
<Example 1>
Dispense 2 liters of Tsukuba City tap water (assuming cooling water system water) concentrated 5 times using a reverse osmosis membrane device into seven 2 liter beakers, and add the chemicals shown in Table 1 to the concentrations shown in Table 1. After covering with a wrap film, the mixture was stirred at 60 rpm while being kept at 35 ° C. and left for 30 days. Sampling was conducted over time, and the residual concentrations of cationic drugs (POEDI, PHPDA, PHMB, and benzalkonium chloride; see Table 1 for the abbreviations), CMI residual concentrations, ATP (adenosine triphosphate) ) Concentration and general bacterial count were examined. The results are shown in Tables 2 to 5.
表２〜表５により、ヨーネンポリマであるポリ［オキシエチレン（ジメチルイミニオ）エチレン（ジメチルイミニオ）エチレンジクロライド］、ポリ（２−ヒドロキシプロピルジメチルアンモニウムクロライド）、ポリ（ヘキサメチレンビグアニド）塩酸塩との共存によりイソチアゾリン系化合物である５−クロロ−２−メチル−４−イソチアゾリン−３−オンの分解が抑制されていることが、微生物活性を示すアデノシン三リン酸の濃度や、一般細菌数は、ヨーネンポリマの濃度には殆ど影響を受けず、その増減が、５−クロロ−２−メチル−４−イソチアゾリン−３−オンの残存濃度に依存していることが理解される。 According to Tables 2 to 5, the ionene polymer poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride], poly (2-hydroxypropyldimethylammonium chloride), poly (hexamethylene biguanide) hydrochloride The coexistence of the decomposition of 5-chloro-2-methyl-4-isothiazolin-3-one, which is an isothiazoline compound, suppresses the concentration of adenosine triphosphate exhibiting microbial activity and the number of general bacteria. It is understood that the increase or decrease depends on the residual concentration of 5-chloro-2-methyl-4-isothiazolin-3-one.
＜実施例２＞
保有水量１０ｍ3、冷凍能力１０００ＲＴ、補給水には水道水を使用し、５倍濃縮で濃縮管理をしている茨城県下のある工場の冷却水系において、以下の検討を行なった。
<Example 2>
The following examination was conducted in the cooling water system of a factory in Ibaraki Prefecture, which has 10m 3 of retained water, refrigeration capacity of 1000 RT, tap water is used as make-up water, and is concentrated and managed by 5-fold concentration.
当初、ＣＭＩを補給水に対して０．２ｍｇ／Ｌの濃度で連続的に添加していたが、一週間で上部水槽が粒状緑藻で覆われてしまうため、上部水槽の手清掃を月２回行っていた。このとき、冷却水中のＣＭＩ濃度は０．１ｍｇ／Ｌ未満（検出下限未満）であり、一般細菌数は１．５×１０6個／ｍＬであった。 Initially, CMI was continuously added to the makeup water at a concentration of 0.2 mg / L. However, since the upper tank is covered with granular green algae in one week, the upper tank is manually cleaned twice a month. I was going. At this time, the CMI concentration in the cooling water was less than 0.1 mg / L (below the lower limit of detection), and the number of general bacteria was 1.5 × 10 6 cells / mL.
次いで、上部水槽を手清掃した後、補給水に対してＣＭＩを０．２ｍｇ／Ｌ、ＰＯＥＤＩを２ｍｇ／Ｌの濃度で連続的に添加する処理に変更（条件変更（１））したが、１ヶ月後に粒状緑藻の発生が認められた。この期間の冷却水中のＰＯＥＤＩ濃度は９〜１１ｍｇ／Ｌ、ＣＭＩ濃度は、条件変更（１）の２週間後では０．１ｍｇ／Ｌ、１ヶ月後では０．１ｍｇ／Ｌ未満であった。また、一般細菌数は条件変更（１）の２週間後では８．３×１０3個／ｍＬ、１ヶ月後では２．３×１０6個／ｍＬであった。 Next, after manually cleaning the upper water tank, it was changed to a process of continuously adding CMI to the makeup water at a concentration of 0.2 mg / L and POEDI at a concentration of 2 mg / L (condition change (1)). The generation of granular green algae was observed after a month. During this period, the POEDI concentration in the cooling water was 9 to 11 mg / L, and the CMI concentration was 0.1 mg / L after 2 weeks of the condition change (1) and less than 0.1 mg / L after 1 month. Further, the number of general bacteria was 8.3 × 10 3 cells / mL after 2 weeks of the condition change (1), and 2.3 × 10 6 cells / mL after 1 month.
そこで、上記処理に加えて、２週間に一度、保有水量に対してＣＭＩを１０ｍｇ／Ｌの濃度で添加する処理を行った（条件変更（２））。条件変更前に発生していた粒状緑藻は条件変更（２）の１週間後には白色化し、以後３ヶ月間に亘って粒状緑藻は発生しなかった。条件変更（２）後の期間、冷却水中のＰＯＥＤＩ濃度は７〜１２ｍｇ／Ｌ、ＣＭＩ濃度は、２週間に１度の添加直前の測定で、０．２〜１．５ｍｇ／Ｌであった。また、一般細菌数は、１０2〜１０3個／ｍＬレベルが維持された。 Therefore, in addition to the above treatment, a treatment for adding CMI at a concentration of 10 mg / L to the amount of retained water was performed once every two weeks (condition change (2)). The granular green algae that had been generated before the condition change turned white one week after the condition change (2), and no granular green algae were generated over the next three months. During the period after the condition change (2), the POEDI concentration in the cooling water was 7 to 12 mg / L, and the CMI concentration was 0.2 to 1.5 mg / L as measured immediately before the addition once every two weeks. In general the number of bacteria is 10 2 to 10 3 cells / mL level was maintained.
３ヵ月後、ＣＭＩの添加はそのままで、ＰＯＥＤＩの添加のみ中止（条件変更（３））したところ、条件変更（３）の１ヶ月後には粒状緑藻が発生した。このときのＰＯＥＤＩの濃度は１ｍｇ／Ｌ未満、ＣＭＩ濃度は、２週間に１度の添加直前の測定で、０．１ｍｇ／Ｌ未満、一般細菌数は２．１×１０6個／ｍＬであった。 Three months later, the addition of CMI was maintained and only the addition of POEDI was stopped (condition change (3)), and granular green algae were generated one month after the condition change (3). At this time, the concentration of POEDI was less than 1 mg / L, the CMI concentration was less than 0.1 mg / L, and the number of general bacteria was 2.1 × 10 6 cells / mL, as measured immediately before addition every two weeks. It was.
そこで、２週間に一度のＣＭＩの添加を中止すると共に、ＰＯＥＤＩの添加を再開し、補給水に対してＣＭＩを０．５ｍｇ／Ｌ、ＰＯＥＤＩを１ｍｇ／Ｌの濃度で連続的に添加する処理にしたところ（条件変更（４））、発生していた粒状緑藻は２週間後には白色化し、その後、粒状緑藻の発生はなかった。この期間、ＰＯＥＤＩの濃度は４〜６ｍｇ／Ｌ、ＣＭＩ濃度は０．１〜０．３ｍｇ／Ｌ、一般細菌数は１０2〜１０3個／ｍＬレベルを推移した。 Therefore, the addition of CMI once every two weeks was stopped, and the addition of POEDI was resumed, and the CMI was continuously added to the makeup water at a concentration of 0.5 mg / L and POEDI at a concentration of 1 mg / L. As a result (condition change (4)), the generated granular green algae turned white after 2 weeks, and thereafter no granular green algae were generated. During this period, the concentration of POEDI is 4 to 6 mg / L, CMI concentration 0.1 to 0.3 mg / L, the number of general bacteria remained the 10 2 to 10 3 cells / mL level.
以上の結果から、ヨーネンポリマを所定濃度以上の濃度に維持している水系において、イソチアゾリン系化合物を検出下限以上の濃度となるように添加することで、微生物の効果的な抑制が可能となることが理解される。 From the above results, it is possible to effectively suppress microorganisms by adding an isothiazoline-based compound so that the concentration is higher than the lower limit of detection in an aqueous system in which the ionene polymer is maintained at a concentration higher than a predetermined concentration. Understood.
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