JP2012214389A - Microorganism controlling agent, and method for controlling microorganism - Google Patents

Microorganism controlling agent, and method for controlling microorganism Download PDF

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JP2012214389A
JP2012214389A JP2011079236A JP2011079236A JP2012214389A JP 2012214389 A JP2012214389 A JP 2012214389A JP 2011079236 A JP2011079236 A JP 2011079236A JP 2011079236 A JP2011079236 A JP 2011079236A JP 2012214389 A JP2012214389 A JP 2012214389A
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microorganism
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JP5735328B2 (en
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Masayo Ito
雅代 伊藤
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Aquas Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a microorganism controlling agent having high microorganism controlling performance even in the case of addition of a low concentration, while keeping sustainability of the effect, and to provide a method for controlling microorganism.SOLUTION: This microorganism controlling agent contains a tri-n-butyl-n-dodecyl phosphonium salt and 2-methyl-4-isothiazoline-3-one as active ingredients.

Description

本発明は、開放循環冷却水系などの水系水に対する微生物防除剤、及び、微生物防除方法に関する。   The present invention relates to a microbial control agent and a microbial control method for aqueous water such as an open circulation cooling water system.

開放循環冷却水系における微生物防除剤、特に細菌防除剤として、イソチアゾロン系化合物、特に5−クロロ−2−メチル−4−イソチアゾリン−3−オンは、抗菌スペクトルが広く、水溶性で取扱いが容易、かつ、低毒性なことから広く使われてきた(特公昭58−4682号公報(特許文献1))。   As a microorganism control agent in an open circulation cooling water system, particularly as a bacterial control agent, isothiazolone compounds, particularly 5-chloro-2-methyl-4-isothiazolin-3-one has a wide antibacterial spectrum, is water-soluble and easy to handle, and It has been widely used because of its low toxicity (Japanese Patent Publication No. 58-4682 (Patent Document 1)).

しかし、5−クロロ−2−メチル−4−イソチアゾリン−3−オンは不安定で分解速度が速いために効果の持続性には難点があり、この点を改善する長期間安定なスライムコントロ−ル剤として、2−メチル−4−イソチアゾリン−3−オンが提案されている(特開2002−193712公報(特許文献2))。   However, since 5-chloro-2-methyl-4-isothiazolin-3-one is unstable and has a high decomposition rate, there is a difficulty in sustaining the effect, and a long-term stable slime control that improves this point. 2-methyl-4-isothiazolin-3-one has been proposed as an agent (Japanese Patent Laid-Open No. 2002-193712 (Patent Document 2)).

この技術によれば、従来の問題点である効果の持続性には格段の改善は見られるものの、2−メチル−4−イソチアゾリン−3−オンは、5−クロロ−2−メチル−4−イソチアゾリン−3−オンと比較して殺菌力自体が弱いために、効果を発揮させるために多量の薬剤の添加が必要となるという問題が生じる。   According to this technique, although the improvement in the sustainability of the effect, which is a problem in the past, is markedly improved, 2-methyl-4-isothiazolin-3-one is a 5-chloro-2-methyl-4-isothiazoline. Since the sterilizing power itself is weak compared with -3-one, there arises a problem that a large amount of a drug needs to be added in order to exert the effect.

また、特開平11−71213号公報(特許文献3)では、ホスホニウム塩の一種である、テトラキス(ヒドロキシメチル)ホスホニウム塩と2−メチル−4−イソチアゾリン−3−オンとを併用する工業用殺菌剤が提案されているが、この技術では十分な殺菌効果は得られず、問題となっていた。   Japanese Patent Application Laid-Open No. 11-71213 (Patent Document 3) discloses an industrial disinfectant that uses a combination of tetrakis (hydroxymethyl) phosphonium salt and 2-methyl-4-isothiazolin-3-one, which is a kind of phosphonium salt. However, this technique has been problematic because a sufficient bactericidal effect cannot be obtained.

特公昭58−4682号公報Japanese Patent Publication No.58-4682 特開2002−193712公報JP 2002-193712 A 特開平11−71213号公報Japanese Patent Laid-Open No. 11-71213

本発明は、効果の持続性を維持しながら、低濃度での添加であっても、高い微生物防除性能を有する微生物防除剤、及び、微生物防除方法を提供することを目的とするものである。   An object of the present invention is to provide a microbial control agent and a microbial control method having high microbial control performance even when added at a low concentration while maintaining the sustainability of the effect.

本発明は、このような問題点を解決する、すなわち、特定のホスホニウム塩と2−メチル−4−イソチアゾリン−3−オンとを併用することにより相乗効果が得られ、効果の持続性を維持しながら低濃度の添加であっても高い微生物防除効果を示すことを見出し、本発明に至った。   The present invention solves such a problem, that is, a synergistic effect is obtained by using a specific phosphonium salt in combination with 2-methyl-4-isothiazolin-3-one, and the sustainability of the effect is maintained. However, even when added at a low concentration, the present inventors have found that a high microorganism control effect is exhibited, and the present invention has been achieved.

すなわち、本発明の微生物防除剤は上記課題を解決するため、請求項1に記載の通り、トリ−n−ブチル−n−ドデシルホスホニウム塩と2−メチル−4−イソチアゾリン−3−オンとを有効成分として含有することを特徴とする微生物防除剤である。   That is, in order to solve the above problems, the microorganism control agent of the present invention effectively uses tri-n-butyl-n-dodecylphosphonium salt and 2-methyl-4-isothiazolin-3-one as described in claim 1. It is a microorganism control agent characterized by containing as a component.

また、本発明の微生物防除方法は請求項2に記載の通り、トリ−n−ブチル−n−ドデシルホスホニウム塩と2−メチル−4−イソチアゾリン−3−オンとを有効成分として水系水に添加することを特徴とする微生物防除方法である。   Moreover, the microorganisms control method of the present invention adds tri-n-butyl-n-dodecylphosphonium salt and 2-methyl-4-isothiazolin-3-one as active ingredients to aqueous water as described in claim 2. This is a method for controlling microorganisms.

本発明は、トリ−n−ブチル−n−ドデシルホスホニウム塩を、2−メチル−4−イソチアゾリン−3−オンと併用することにより、優れた微生物防除効果を持続させることができ、これらを組み合わせて微生物防除対象水系水へ添加することにより、効果の持続性を維持しながら低濃度の添加であっても高い微生物防除効果を得ることができる。   The present invention can maintain an excellent microbial control effect by combining tri-n-butyl-n-dodecylphosphonium salt with 2-methyl-4-isothiazolin-3-one, and combining these By adding to the microbial control target water system water, a high microbial control effect can be obtained even with a low concentration while maintaining the sustainability of the effect.

本発明の微生物防除剤は上記の通り、トリ−n−ブチル−n−ドデシルホスホニウム塩と2−メチル−4−イソチアゾリン−3−オンとの両者を有効成分として含有することにより、単独使用では得られない相乗的で、優れた微生物防除効果を持続させることができ、これらを組み合わせて微生物防除対象水系水へ添加することにより、効果の持続性を維持しながら低濃度の添加であっても相乗的な高い微生物防除効果を得ることができる。   As described above, the microorganism control agent of the present invention contains both tri-n-butyl-n-dodecylphosphonium salt and 2-methyl-4-isothiazolin-3-one as active ingredients. Synergistic and superior microbial control effects can be sustained, and by combining them and adding them to the microbial control target water system water, it is possible to synergize even at low concentrations while maintaining the sustainability of the effects. High microbial control effect can be obtained.

本発明において、トリ−n−ブチル−n−ドデシルホスホニウム塩と2−メチル−4−イソチアゾリン−3−オンとは、重量比で1:100〜100:1(境界値含む。以下同)となるように用いることが高い効果が得られるので好ましい。さらに好ましい範囲は1:10〜10:1である。   In the present invention, tri-n-butyl-n-dodecylphosphonium salt and 2-methyl-4-isothiazolin-3-one are in a weight ratio of 1: 100 to 100: 1 (including boundary values; the same applies hereinafter). Since it is possible to obtain a high effect, it is preferable. A more preferred range is 1:10 to 10: 1.

本発明の微生物防除剤では上記2成分を1剤としても、あるいは、1成分ずつ2剤として水系水に添加し、両者を共存させてもよい。なお、これら薬剤は水に溶解して1剤としても安定している。   In the microorganism control agent of the present invention, the above-mentioned two components may be added as one agent, or two components may be added to the aqueous water one component at a time, and both may coexist. In addition, these chemical | medical agents melt | dissolve in water and are stable as one agent.

トリ−n−ブチル−n−ドデシルホスホニウム塩と2−メチル−4−イソチアゾリン−3−オンとは、微生物防除目的の水系水に対して、これら有効成分の合計添加濃度として2mg/L以上1000mg/L以下となるように添加することが好ましい。添加濃度が2mg/L未満であると充分な効果が得られないときがあり、また、 1000mg/Lを超えて添加しても、添加量の増加に見合う微生物防除効果の増加は得られにくい。最適な添加範囲は10mg/L以上100mg/L以下である。   Tri-n-butyl-n-dodecylphosphonium salt and 2-methyl-4-isothiazolin-3-one are 2 mg / L or more and 1000 mg / L as total addition concentration of these active ingredients with respect to aqueous water for the purpose of controlling microorganisms. It is preferable to add so that it may become L or less. If the addition concentration is less than 2 mg / L, a sufficient effect may not be obtained, and even if the addition concentration exceeds 1000 mg / L, it is difficult to obtain an increase in the microorganism control effect commensurate with the increase in the addition amount. The optimal addition range is 10 mg / L or more and 100 mg / L or less.

本発明の微生物防除剤では、本発明の効果が妨げられない範囲で、さらにその特性を改良するなどの目的で、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、ホスホン酸、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、例えば5-クロロ−2−メチル−4−イソチアゾリン−3−オン、1,2−ベンズイソチアゾリン−3−オン等の2−メチル−4−イソチアゾリン−3−オン以外のイソチアゾリン系化合物、グルタルアルデヒド、フタルアルデヒド等のアルデヒド系化合物、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)、臭素系殺菌剤およびヨウ素系殺菌剤、さらにピリチオン系化合物、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、四級アンモニウム塩系化合物、ピリジニウム塩系化合物、ヨーネンポリマー等のトリ−n−ブチル−n−ドデシルホスホニウム塩以外のカチオン系化合物などのスライム防止剤、例えば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、例えばエチレンジアミン、ジエチレントリアミン等のアミン系化合物、例えばニトリロ三酢酸、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、例えばグルコン酸、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、各種の水処理剤を添加することができ、その場合も本発明に含まれる。   In the microorganism control agent of the present invention, for the purpose of further improving the characteristics within the range where the effects of the present invention are not hindered, for example, acrylic acid-based, maleic acid-based, methacrylic acid-based, sulfonic acid-based, itaconic acid-based Or scale inhibitors such as isobutylene polymers, copolymers thereof, phosphoric acid polymers, phosphonic acid, phosphinic acid, or water-soluble salts thereof, such as 5-chloro-2-methyl-4 -Isothiazoline compounds other than 2-methyl-4-isothiazolin-3-one such as isothiazoline-3-one and 1,2-benzisothiazolin-3-one; aldehyde compounds such as glutaraldehyde and phthalaldehyde; hydrogen peroxide , Hydrazine, chlorine-based disinfectants (such as sodium hypochlorite), bromine-based and iodine-based disinfectants, and pyrithione compounds Products, dithiol compounds, thiocyanate compounds such as methylenebisthiocyanate, quaternary ammonium salt compounds, pyridinium salt compounds, cationic compounds other than tri-n-butyl-n-dodecylphosphonium salts such as ionene polymers, etc. Anti-slime agents, such as 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, such as gluconic acid, Various water treatment agents such as organic carboxylic acids such as acid, oxalic acid, formic acid, tartaric acid, phytic acid, succinic acid, and lactic acid can be added, and such cases are also included in the present invention.

<実施例1>
茨城県内にある工場の冷却水系より採取した冷却水を試験水として使用した。
<Example 1>
Cooling water collected from the cooling water system of a factory in Ibaraki Prefecture was used as test water.

上記試験水を30mLずつ50mLの振盪フラスコに採り、表1に示した薬剤(略号も併せて示す)を表2に示す濃度(表中単位はmg/L。表中、各空欄は「添加なし」を表す)で添加し、その後30℃、60rpmで振盪培養した。培養開始72時間後に試験水中の一般細菌数をJIS K0101 63.2に従って測定した。   Each 30 mL of the above test water was put into a 50 mL shake flask, and the concentrations shown in Table 1 (units are mg / L in Table 1). ”, And then cultured with shaking at 30 ° C. and 60 rpm. 72 hours after the start of the culture, the number of general bacteria in the test water was measured according to JIS K0101 63.2.

測定結果を表2に併せて示す(表中”<10”は10個/mL未満であることを示す)。なお、試験開始時の試験水の一般細菌数は5100個/mLであった。   The measurement results are also shown in Table 2 (“<10” in the table indicates less than 10 / mL). The number of general bacteria in the test water at the start of the test was 5100 cells / mL.

Figure 2012214389
Figure 2012214389

Figure 2012214389
Figure 2012214389

表2により、A〜Dの各種ホスホニウム塩のうち、本発明にかかるホスホニウム塩であるトリ−n−ブチル−n−ドデシルホスホニウムクロライドと2−メチル−4−イソチアゾリン−3−オンとの組み合わせからなる微生物防除剤が、他の組み合わせでの使用または単剤での使用と比較して、極めて高い相乗的な殺菌性能を有していることが判る。   According to Table 2, among various phosphonium salts A to D, the phosphonium salt according to the present invention is a combination of tri-n-butyl-n-dodecylphosphonium chloride and 2-methyl-4-isothiazolin-3-one. It can be seen that the microbial control agent has a very high synergistic bactericidal performance compared to use in other combinations or as a single agent.

<実施例2>
東京都内にあるビルの空調用の冷却水系より採取した冷却水を試験水として使用した。
<Example 2>
Cooling water collected from a cooling water system for air conditioning in a building in Tokyo was used as test water.

上記試験水を30mLずつ50mLの振盪フラスコに採り、表3に示した薬剤(略号も併せて示す)を表4に示す濃度(表中単位はmg/L。表中、各空欄は「添加なし」を表す)で添加し、その後30℃、60rpmで振盪培養した。培養開始24、72及び168時間後にそれぞれ試験水中の一般細菌数をJIS K0101 63.2に従って測定した。   Each 30 mL of the above test water was put into a 50 mL shake flask, and the concentrations shown in Table 3 (units are mg / L in Table). ”, And then cultured with shaking at 30 ° C. and 60 rpm. The number of general bacteria in the test water was measured according to JIS K0101 63.2, 24, 72 and 168 hours after the start of culture.

測定結果を表4に併せて示す(表中”<10”は10個/mL未満であることを示す)。なお、試験開始時の試験水の一般細菌数は58000個/mLであった。   The measurement results are also shown in Table 4 (“<10” in the table indicates less than 10 / mL). The general bacterial count of test water at the start of the test was 58,000 / mL.

Figure 2012214389
Figure 2012214389

Figure 2012214389
Figure 2012214389

表4により本発明にかかる微生物防除剤が、極めて高い相乗的な殺菌性能を有していること、さらに、その高い殺菌性能が長時間維持されることが判る。一方、トリ−n−ブチル−n−ドデシルホスホニウムクロライドと5−クロロ−2−メチル−4−イソチアゾリン−3−オンとの併用の場合、殺菌効果に即効性があり、相乗的な作用も認められるものの、効果に持続性がなく、1週間(168時間)経過後には細菌数の上昇が認められた。   It can be seen from Table 4 that the microorganism control agent according to the present invention has a very high synergistic sterilization performance and that the high sterilization performance is maintained for a long time. On the other hand, when tri-n-butyl-n-dodecylphosphonium chloride and 5-chloro-2-methyl-4-isothiazolin-3-one are used in combination, the bactericidal effect is immediate and a synergistic effect is also observed. However, the effect was not persistent and an increase in the number of bacteria was observed after one week (168 hours).

<実施例3>
埼玉県内にある工場の冷却水系より採取した緑藻を試験試料として使用した。
<Example 3>
Green algae collected from the cooling water system of a factory in Saitama Prefecture was used as a test sample.

滅菌済みのデトマー培地30mLの入った50mLの振盪フラスコに上記緑藻を接種し、トリ−n−ブチル−n−ドデシルホスホニウムクロライド(略号:A)と2−メチル−4−イソチアゾリン−3−オン(略号:E)とを表5に示す濃度(表中単位はmg/L。表中、各空欄は「添加なし」を表す)で添加した後、10000lxの光を照射しながら30℃、30rpmで7日間振盪培養した。7日後に培養液の色調を観察し、緑色が初期と同程度である場合を「+」、増殖して緑色が濃くなった場合を「++」、褪色して微黄白色となった場合を「−」と判定した。結果を表5に併せて示す。   The green algae was inoculated into a 50 mL shake flask containing 30 mL of sterilized detomer medium, and tri-n-butyl-n-dodecylphosphonium chloride (abbreviation: A) and 2-methyl-4-isothiazolin-3-one (abbreviation). : E) at a concentration shown in Table 5 (unit is mg / L. In the table, each blank represents “no addition”), and after irradiation with 10000 lx light, 7 at 30 ° C. and 30 rpm. Cultured with shaking for days. After 7 days, observe the color tone of the culture, “+” when the green color is the same as the initial level, “++” when the green color grows and becomes dark, It was determined as “−”. The results are also shown in Table 5.

Figure 2012214389
Figure 2012214389

表5により本発明にかかる微生物防除剤が、極めて高い相乗的な殺藻性能を有していることが判る。   Table 5 shows that the microorganism control agent according to the present invention has a very high synergistic algaecidal performance.

上記の通り、本発明の微生物防除剤は極めて高い殺菌性能と殺藻性能を有し、また、その効果が長時間維持される優れた微生物防除剤である。   As described above, the microorganism control agent of the present invention is an excellent microorganism control agent that has extremely high bactericidal performance and algicidal performance, and that the effect is maintained for a long time.

Claims (2)

トリ−n−ブチル−n−ドデシルホスホニウム塩と2−メチル−4−イソチアゾリン−3−オンとを有効成分として含有することを特徴とする微生物防除剤。   A microorganism control agent comprising tri-n-butyl-n-dodecylphosphonium salt and 2-methyl-4-isothiazolin-3-one as active ingredients. トリ−n−ブチル−n−ドデシルホスホニウム塩と2−メチル−4−イソチアゾリン−3−オンとを有効成分として水系水に添加することを特徴とする微生物防除方法。   A method for controlling microorganisms, comprising adding tri-n-butyl-n-dodecylphosphonium salt and 2-methyl-4-isothiazolin-3-one as active ingredients to aqueous water.
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