JP4279956B2 - Industrial sterilization composition and sterilization method - Google Patents
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Description
【０００１】
【産業上の利用分野】
本発明は、主に工業上の用水関係で発生する微生物障害の防止、また工業用製品の除菌に使用する工業用殺菌組成物、及び殺菌方法に関する。
【０００２】
【従来の技術】
製紙の抄紙工程や金属加工の切削油、一般の工業用冷却水などの循環用水系では用水に混入している有機物を栄養源として細菌、酵母、糸状菌等の種々の微生物が増殖する。微生物管理が十分でなければ、これら微生物が分泌する粘性物質に系内の微小な繊維、浮遊物が取り込まれ、流速が緩やかになった個所にスライム層が徐々に形成されていく。
【０００３】
一旦スライム層が形成されると、殺菌物質の浸透が非常に緩慢となりこの中に存在する微生物の殺菌が不充分となり、結果として耐性菌の出現や、さらにはこのスライム層が汚染源となって用水系全体がひどく汚染される事になる。
【０００４】
このスライム層形成による直接的な損害は配管の目詰まりであり、冷却水ならば冷却効率が低下し、さらにはスライム層の剥離−循環用水系への混入で製品の品質低下や操業停止が引き起こされる。また用水系にもよるが不快臭の発生で間接的に作業環境の悪化などのトラブルも発生する場合もある。
【０００５】
また各種水性の工業製品や製紙工場で塗工液等の加工原料として使用される澱粉スラリー、糊化液、ラテックス等は各種の微生物に汚染されやすく腐敗臭の発生や、腐敗による成分変化でその製品のみならず最終製品の品質までもが大きく低下する。この様な被害を最小限に抑えるためには、循環用水系や殺菌防腐対象物に生息する細菌、酵母、糸状菌等の生菌をある一定のレベル以下で制御しておく必要があり、この様な用途には広い殺菌スペクトラムを有する殺菌防腐成分の使用が望ましい。
【０００６】
従来このような用途に各種の有機系殺菌成分が使用されている。本発明の工業用殺菌組成物に使用される２，２−ジブロモ−３−ニトリロプロピオンアミド、テトラハロゲン化イソフタロニトリル化合物、ハロゲン化酢酸エステル化合物は特公昭４２−１０３８６号、特公昭４１−１１３５８号、特公昭５２−１２２４７号で単剤としての抗微生物物質として既に公知である。
【０００７】
これらの抗微生物物質はいずれも単独で使用することが可能であるが、最近では２剤を混合／或いは同時添加する方法で殺菌スペクトラムの広域化や相乗効果を意図した製剤や殺菌方法をとる場合がある。例えば、特公平５−３８４１号、特公平６−６８２号には２，２−ジブロモ−３−ニトリロプロピオンアミドとテトラハロゲン化イソフタロニトリル化合物との混合製剤、特公昭５２−４６２８５号には２，２−ジブロモ−３−ニトリロプロピオンアミドとハロゲン化酢酸エステル化合物との混合製剤が開示されている。
【０００８】
詳しくは２，２−ジブロモ−３−ニトリロプロピオンアミドの生物特性として、主に細菌への卓越した速効的な殺菌力が挙げられ、テトラハロゲン化イソフタロニトリル化合物とハロゲン化酢酸エステル化合物の生物特性としては、糸状菌への卓越した殺菌効力が挙げられる。前述の特公平５−３８４１号、特公平６−６８２号及び特公昭５２−４６２８５号はこれらの組合せにより、細菌から糸状菌までの広い殺菌スペクトラムと速効的な効果が期待でき、用水系におけるスライム抑制に好適な組合せである。
【０００９】
一方、特許２６３１１１９号に開示されたテトラハロゲン化イソフタロニトリル化合物とハロゲン化酢酸エステル化合物との組合せは、各薬剤の生物特性から糸状菌に対する殺菌効果は期待できるものの、細菌に対する速効的な殺菌効果は全く期待できない。つまり細菌と糸状菌が混在している用水系では効力が不充分であり、このような用水系でのスライム抑制に適する組合せとは言えない。
【００１０】
【発明が解決しようとする課題】
最近の用水のクローズド化に伴う用水の高温化、製品に高機能を具備させるために使用される各種の添加物による高栄養化、製紙白水の場合には還元性物質の高濃縮や中性抄造への移行は、用水系内における細菌、酵母、糸状菌等、種々の微生物の繁殖を容易にさせており、極めてスライムが発生し易い状況であると言える。
【００１１】
前述した各混合製剤の意図している所の殺菌スペクトラムの広域化や相乗効果は、単剤と比較すれば性能の向上が認められるものの、昨今のユーザー側から求められている環境負荷の低減、低コスト化、即ち薬剤使用量の低減化に十分対応しているとは言い難い。
【課題を解決するための手段】
【００１２】
本発明者らは上記課題に鑑み、鋭意研究した結果、２，２−ジブロモ−３−ニトリロプロピオンアミド、テトラハロゲン化イソフタロニトリル化合物、ハロゲン化酢酸エステル化合物の３種の殺菌成分を所定の配合比で組合せて使用する殺菌組成物及び殺菌方法は各殺菌成分単独での効力はもとより、前述した２者配合の混合剤では到底達成し得ない極めて強力な相乗的殺菌効果を示すことを見出し、この知見に基づき本発明を成すに至った。
【００１３】
すなわち本発明は、
（１）２，２−ジブロモ−３−ニトリロプロピオンアミドと1種類以上のテトラハロゲン化イソフタロニトリル化合物と1種類以上のハロゲン化酢酸エステル化合物とを有効成分として含有して成る工業用殺菌組成物。
【００１４】
（２）２，２−ジブロモ−３−ニトリロプロピオンアミドと５−クロロ−２，４，６−トリフルオロイソフタロニトリル、２，４，５，６−テトラフルオロイソフタロニトリルから選択される1種類以上のテトラハロゲン化イソフタロニトリル化合物と１，４−ビス（ブロモアセトキシ）−２−ブテン、１，２−ビス（ブロモアセトキシ）エタンから選択される1種類以上のハロゲン化酢酸エステル化合物とを有効成分として含有して成る工業用殺菌組成物。
【００１５】
（３）２，２−ジブロモ−３−ニトリロプロピオンアミド１重量部に対して、テトラハロゲン化イソフタロニトリル化合物０．０２〜２０重量部、ハロゲン化酢酸エステル化合物０．０５〜４０重量部を有効成分として含有して成る工業用殺菌組成物。
【００１６】
（４）２，２−ジブロモ−３−ニトリロプロピオンアミド１重量部に対して、５−クロロ−２，４，６−トリフルオロイソフタロニトリル０．１〜１０重量部、１，４−ビス（ブロモアセトキシ）−２−ブテン、又は１，２−ビス（ブロモアセトキシ）エタン０．１〜１０重量部を有効成分として含有して成る工業用殺菌組成物。
【００１７】
（５）殺菌防腐対象系に２，２−ジブロモ−３−ニトリロプロピオンアミド１重量部に対して、テトラハロゲン化イソフタロニトリル化合物０．０２〜２０重量部、ハロゲン化酢酸エステル化合物０．０５〜４０重量部の割合で同時に及び／又は別々に添加して対象系を殺菌、防腐する方法。
【００１８】
（６）殺菌防腐対象系に２，２−ジブロモ−３−ニトリロプロピオンアミド１重量部に対して、５−クロロ−２，４，６−トリフルオロイソフタロニトリル０．１〜１０重量部、１，４−ビス（ブロモアセトキシ）−２−ブテン、又は１，２−ビス（ブロモアセトキシ）エタン０．１〜１０重量部の割合で同時に及び／又は別々に添加して対象系を殺菌、防腐する方法である。
【００１９】
【発明の実施の形態】
本発明は２，２−ジブロモ−３−ニトリロプロピオンアミドと１種類以上のテトラハロゲン化イソフタロニトリル化合物と１種類以上のハロゲン化酢酸エステル化合物とを配合させた組成物、或いはこれらの有効成分を同時に及び／又は別々に添加して対象系を殺菌、防腐する方法である。
【００２０】
詳しくは２，２−ジブロモ−３−ニトリロプロピオンアミド１重量部に対し、テトラハロゲン化イソフタロニトリル化合物０．０２〜２０重量部、ハロゲン化酢酸エステル化合物０．０５〜４０重量部の配合から構成され、好ましくは２，２−ジブロモ−３−ニトリロプロピオンアミド１重量部に対し、テトラハロゲン化イソフタロニトリル化合物０．１〜１０重量部、ハロゲン化酢酸エステル化合物０．１〜１０重量部、さらに２，２−ジブロモ−３−ニトリロプロピオンアミド１重量部に対し、テトラハロゲン化イソフタロニトリル化合物０．２〜５重量部、ハロゲン化酢酸エステル化合物０．２〜５重量部がより好ましい配合である。
【００２１】
配合するテトラハロゲン化イソフタロニトリル化合物は、５−クロロ−２，４，６−トリフルオロイソフタロニトリル、２，４，５，６−テトラフルオロイソフタロニトリル、２，４，５，６−テトラクロロイソフタロニトリルから選択される１種類以上が挙げられ、特に５−クロロ−２，４，６−トリフルオロイソフタロニトリルの適用が効力と一液剤とした時の製剤安定性、さらには環境への配慮の点で好ましい。
【００２２】
また配合するハロゲン化酢酸エステル化合物は、１，４−ビス（ブロモアセトキシ）−２−ブテン、１，２−ビス（ブロモアセトキシ）エタン、１，２−ビス（ブロモアセトキシ）プロパンから選択される１種類以上が挙げられ、特に１，２−ビス（ブロモアセトキシ）エタンの適用が効力と一液剤とした時の製剤安定性の点で好ましい。
【００２３】
本発明は有効成分のほかに溶剤、水、界面活性剤、増粘剤、防錆剤、その他の補助剤を添加して水溶性液剤、乳化性液剤、フロアブル剤、粒剤、水和剤とすることが出来る。水溶性液剤として製剤する場合には各有効成分を十分に溶解できる溶剤を選択し、必要に応じて界面活性剤を配合することで水への分散性を向上させる事が出来る。
【００２４】
好適な溶剤としては、例えばエチレングリコール、ジエチレングリコール、ポリエチレングリコール２００、プロピレングリコール、ジプロピレングリコール、カルビトール類、セロソルブ類等の多価アルコールとその誘導体、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリジノン、炭酸プロピレン、γ−ブチロラクトン、フタル酸ジメチル、マレイン酸ジメチル等の非プロトン性溶媒が挙げられる。また耐寒性の向上や粘度調整を目的として２種類以上の溶剤の混合使用も可能である。界面活性剤はアニオン系界面活性剤、ノニオン系界面活性剤、或いはこれらを併用することができ、使用する溶剤により選択適用する。
【００２５】
乳化性液剤として製剤する場合にはトルエン、キシレン等の芳香族炭化水素やクロロベンゼン等のハロゲン化炭化水素の溶剤を使用し、アニオン系界面活性剤やノニオン系界面活性剤を配合する。フロアブル剤、粒剤、水和剤として製剤する場合には、クレー、炭酸カルシウム、ホワイトカーボン等の固体増量剤と界面活性剤を配合した後に微粉砕し、それぞれの剤型に製剤する。
【００２６】
本発明の殺菌組成物は一液タイプの混合剤として使用するのが最も簡便であるが、添加場所の制限や長期の保存安定性の点で有効成分を個別に製剤した方が良い場合もある。このように一液タイプではない場合でも使用時において各有効成分を殺菌対象系で所定の割合になるように添加すれば、一液タイプの混合剤と何ら変わることのない効果が得られる。
【００２７】
【発明の効果】
本発明の工業用殺菌組成物及び殺菌方法は、２，２−ジブロモ−３−ニトリロプロピオンアミド、テトラハロゲン化イソフタロニトリル化合物から選択される化合物、ハロゲン化酢酸エステル化合物から選択される化合物から構成される有効成分を所定の比率の組合せで使用する事により、単剤や２者配合剤では到底達成し得ない極めて強力な相乗的殺菌効果を達成できるとともに、細菌から酵母や糸状菌までの広い殺菌スペクトラムを有せしめることができる。
この優れた殺菌効果は循環用水のスライム防除や水性の工業製品の防腐、特に製紙白水や切削油、工業用冷却水のスライム防除の用途に好適である。
【００２８】
【実施例】
本発明を実施例に基づき、さらに詳細に説明する。下記の配合（重量％）により本発明の殺菌組成物を得た。使用される有効成分の２，２−ジブロモ−３−ニトリロプロピオンアミドはＤＢＮＰＡ、５−クロロ−２，４，６−トリフルオロイソフタロニトリルはＣＦＰＮ、２，４，５，６−テトラフルオロイソフタロニトリルはＴＦＰＮ、１，４−ビス（ブロモアセトキシ）−２−ブテンはＢＢＡＢ、１，２−ビス（ブロモアセトキシ）エタンはＢＢＡＥと略号を用いて表記する。
【００２９】
実施例１〜８、比較例１〜７、試験例１、試験例２で用いたＤＢＮＰＡ、ＣＦＰＮ、ＢＢＡＢ、ＢＢＡＥは容易に入手できる工業用グレード（純度９０〜９８％）を利用し、ケイ・アイ化成株式会社でさらに精製工程を経て純度を９９．５％以上とした標品を使用した。またＴＦＰＮについてはケイ・アイ化成株式会社で室内合成と精製を行い、純度を９９．０％以上とした標品を前述の各試験に使用した。
【００３０】
【表１】
【表２】
【試験例１】
（スライム抑制試験）
５〜１０°の傾斜で固定したプラスチック製の樋（Ｌ１００cm×Ｈ４cm×Ｗ５cm）、循環ポンプ、薬液添加用精密定量ポンプ、リザーバーから構成される５連の用水循環装置を用いスライム抑制試験を行った。樋には流速を抑える抵抗板を４枚装着し、この樋に付着したスライム湿重量の多寡をもってスライム抑制効果を判定した。
【００３３】
循環させる用水は３０℃に温調された人工白水（パルプ５０ｐｐｍ、炭酸カルシウム２００ｐｐｍ、ＰＡＭ１００ｐｐｍ、ペプトン５００ｐｐｍをそれぞれ含有し、ｐＨ６〜７に調整した）とし、製紙工場白水より単離した細菌２菌株（未同定）、酵母２菌株（未同定）、糸状菌１菌株（未同定）を接種し試験を開始した。５連の循環ポンプはそれぞれ約１０Ｌ／時で運転を行い、オーバーフローは約２Ｌ／時、薬液の添加は８時間ごとに０．５ｍｌ（系内濃度約２５ｐｐｍ）と設定した。
【００３４】
試験開始７日後において樋に付着したスライムを全て掻き取り、１２メッシュの網ふるいに広げ、恒温恒湿槽に１時間静置して湿重量を計測、これを付着スライム量とした。実施例のスライム抑制効果を表３〜表５に示す。
【００３５】
【表３】
【表４】
【表５】
細菌、酵母、糸状菌で複合的に汚染された水系におけるスライム抑制試験の結果から、本発明の実施例は比較例より良好なスライム抑制効果を有することが示される。つまり比較例に示される２成分の相乗的殺菌効果以上に、３成分が配合された実施例の強力な相乗的殺菌効力で、このような種々の微生物で複合的に汚染された循環用水系に対し効果的にスライムの発生を抑制する。
【００３９】
【試験例２】
（相乗効果の確認）
パルプ０．０１％、ＰＡＭ０．０１％を添加したｐＨ７のリン酸クエン酸緩衝液に細菌（Pseudomonas aeruginosa）、或いは糸状菌（Geotrichum candidum）を接種し、１０4〜１０6ＣＦＵ／ｍｌの菌体懸濁液を調製した。これら菌体懸濁液についてＤＢＮＰＡとＣＦＰＮから構成されるＡ成分、ＤＢＮＰＡとＢＢＡＥ或いはＢＢＡＢから構成されるＢ成分のそれぞれを所定量添加し、３０℃で３０分間の振盪培養を行った。３０分後、寒天平板混釈法により菌体懸濁液中の生菌数を計測した。
【００４０】
表６、表７中の各マス目における生菌数と組成比は、縦軸のＡ成分（ＤＢＮＰＡとＣＦＰＮ）とＢ成分（ＤＢＮＰＡとＢＢＡＥ或いはＢＢＡＢ）を合計した成分の存在下における残存生菌数とその時の各成分の組成比を示す。
【００４１】
【表６】
【表７】
表６、表７からＤＢＮＰＡ、ＣＦＰＮ、ＢＢＡＥ或いはＢＢＡＢからなる組成物は一定範囲の配合比において強力な相乗的殺菌効果を示している。これは２成分から成る組成物以上の殺菌効果であり、また細菌のみならず糸状菌においてもこの相乗的殺菌効果は認められる。この様な特性は種々の微生物により汚染されている循環用水系、特に製紙白水、切削油、工業用冷却水の殺菌やスライム防除の用途に好適であり、また各種の水性工業製品の殺菌防腐の用途にも好適である。[0001]
[Industrial application fields]
The present invention relates to a sterilizing composition for industrial use and a sterilizing method, which are used mainly for prevention of microbial damage that occurs mainly in the field of industrial water use and for sterilization of industrial products.
[0002]
[Prior art]
In the papermaking process of papermaking, metal processing cutting oil, and general water systems for circulation such as industrial cooling water, various microorganisms such as bacteria, yeasts, and filamentous fungi grow using organic substances mixed in the water as nutrients. If microbial management is not sufficient, fine fibers and suspended matter in the system are taken into the viscous material secreted by these microorganisms, and a slime layer is gradually formed where the flow velocity becomes slow.
[0003]
Once the slime layer is formed, the penetration of the sterilizing substance becomes very slow, resulting in insufficient sterilization of the microorganisms present therein, resulting in the emergence of resistant bacteria and, further, the slime layer as a source of contamination. The entire system will be severely contaminated.
[0004]
The direct damage caused by the formation of the slime layer is clogging of the piping. Cooling water reduces cooling efficiency, and further, peeling of the slime layer-mixing into the circulating water system causes product quality degradation and shutdown. It is. Depending on the water system, troubles such as indirect deterioration of the working environment may occur due to the generation of unpleasant odors.
[0005]
In addition, starch slurries, gelatinized liquids, and latex used as processing raw materials for various aqueous industrial products and paper mills are easily contaminated by various microorganisms. Not only the product but also the quality of the final product is greatly reduced. In order to minimize such damage, it is necessary to control living bacteria such as bacteria, yeast, and filamentous fungi that inhabit circulating water systems and sterilized antiseptic objects at a certain level or less. For such applications, it is desirable to use a bactericidal and antiseptic component having a broad bactericidal spectrum.
[0006]
Conventionally, various organic sterilizing components have been used for such applications. The 2,2-dibromo-3-nitrilopropionamide, tetrahalogenated isophthalonitrile compound, and halogenated acetic acid ester compound used in the industrial sterilizing composition of the present invention are disclosed in Japanese Patent Publication Nos. 42-10386 and 41-11358. Is already known as an antimicrobial substance as a single agent.
[0007]
Any of these antimicrobial substances can be used alone, but in recent years, preparations and sterilization methods intended for broadening the sterilization spectrum and synergistic effects by mixing / adding two agents simultaneously There is. For example, JP-B-5-3841 and JP-B-6-682 have a mixed preparation of 2,2-dibromo-3-nitrilopropionamide and a tetrahalogenated isophthalonitrile compound, and JP-B-52-46285 has 2 , 2-dibromo-3-nitrilopropionamide and a halogenated acetate compound are disclosed.
[0008]
Specifically, the biological properties of 2,2-dibromo-3-nitrilopropionamide mainly include an excellent fast-acting bactericidal power against bacteria. Biological properties of tetrahalogenated isophthalonitrile compounds and halogenated acetate compounds As an excellent bactericidal effect against filamentous fungi. The above-mentioned Japanese Patent Publication No. 5-3841, No. 6-682 and Japanese Examined Publication No. Sho 52-46285 can be expected to have a wide sterilization spectrum from bacteria to filamentous fungi and a fast-acting effect. It is a combination suitable for suppression.
[0009]
On the other hand, the combination of a tetrahalogenated isophthalonitrile compound and a halogenated acetic ester compound disclosed in Japanese Patent No. 2631119 can be expected to have a bactericidal effect on filamentous fungi from the biological properties of each drug, but has a rapid bactericidal effect on bacteria. Cannot be expected at all. In other words, the irrigation system in which bacteria and filamentous fungi are mixed is insufficient in effectiveness, and cannot be said to be a combination suitable for slime suppression in such an irrigation system.
[0010]
[Problems to be solved by the invention]
Increased water temperature due to the recent closure of water, enrichment with various additives used to make products have high functionality, high concentration of reducing substances and neutral papermaking in the case of papermaking white water The transition to has facilitated the growth of various microorganisms such as bacteria, yeast, and filamentous fungi in the irrigation system, and can be said to be a situation where slime is very likely to occur.
[0011]
The broadening of the sterilization spectrum and the synergistic effect of the intended combination of each of the above-mentioned mixed preparations, although an improvement in performance is recognized compared to the single agent, the reduction of the environmental burden required by the users today, It is difficult to say that it is sufficient to reduce costs, that is, to reduce the amount of medicine used.
[Means for Solving the Problems]
[0012]
As a result of diligent research in view of the above problems, the present inventors have determined that three types of bactericidal components, 2,2-dibromo-3-nitrilopropionamide, a tetrahalogenated isophthalonitrile compound, and a halogenated acetic acid ester compound, are blended in a predetermined manner. The sterilizing composition and the sterilizing method used in combination in a ratio show not only the efficacy of each sterilizing component alone, but also show a very powerful synergistic sterilizing effect that cannot be achieved with the above-mentioned two-component mixture, Based on this finding, the present invention has been accomplished.
[0013]
That is, the present invention
(1) Industrial bactericidal composition comprising 2,2-dibromo-3-nitrilopropionamide, one or more tetrahalogenated isophthalonitrile compounds and one or more halogenated acetic acid ester compounds as active ingredients. .
[0014]
(2) One type selected from 2,2-dibromo-3-nitrilopropionamide, 5-chloro-2,4,6-trifluoroisophthalonitrile and 2,4,5,6-tetrafluoroisophthalonitrile Effective use of the above tetrahalogenated isophthalonitrile compounds and one or more halogenated acetate compounds selected from 1,4-bis (bromoacetoxy) -2-butene and 1,2-bis (bromoacetoxy) ethane Industrial sterilization composition comprising as an ingredient.
[0015]
(3) Effectively 0.02 to 20 parts by weight of a tetrahalogenated isophthalonitrile compound and 0.05 to 40 parts by weight of a halogenated acetate compound with respect to 1 part by weight of 2,2-dibromo-3-nitrilopropionamide Industrial sterilization composition comprising as an ingredient.
[0016]
(4) 0.1 to 10 parts by weight of 5-chloro-2,4,6-trifluoroisophthalonitrile, 1, 4-bis (1 part by weight of 2,2-dibromo-3-nitrilopropionamide An industrial bactericidal composition comprising 0.1 to 10 parts by weight of bromoacetoxy) -2-butene or 1,2-bis (bromoacetoxy) ethane as an active ingredient.
[0017]
(5) 0.02 to 20 parts by weight of a tetrahalogenated isophthalonitrile compound and 0.05 to 20 parts by weight of a halogenated acetic ester compound with respect to 1 part by weight of 2,2-dibromo-3-nitrilopropionamide A method of sterilizing and preserving the target system by adding 40 parts by weight at the same time and / or separately.
[0018]
(6) 0.1-10 parts by weight of 5-chloro-2,4,6-trifluoroisophthalonitrile with respect to 1 part by weight of 2,2-dibromo-3-nitrilopropionamide as a target for sterilization and preservation; , 4-bis (bromoacetoxy) -2-butene, or 1,2-bis (bromoacetoxy) ethane 0.1 to 10 parts by weight simultaneously and / or separately to sterilize and preserve the target system Is the method.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a composition comprising 2,2-dibromo-3-nitrilopropionamide, one or more tetrahalogenated isophthalonitrile compounds and one or more halogenated acetic acid ester compounds, or an active ingredient thereof. It is a method of sterilizing and preserving the target system by adding simultaneously and / or separately.
[0020]
Specifically, the composition is composed of 0.02 to 20 parts by weight of a tetrahalogenated isophthalonitrile compound and 0.05 to 40 parts by weight of a halogenated acetate compound with respect to 1 part by weight of 2,2-dibromo-3-nitrilopropionamide. Preferably, 0.1 part by weight of tetrahalogenated isophthalonitrile compound, 0.1-10 parts by weight of halogenated acetate compound, and 1 part by weight of 2,2-dibromo-3-nitrilopropionamide, A tetrahalogenated isophthalonitrile compound 0.2 to 5 parts by weight and a halogenated acetate compound 0.2 to 5 parts by weight are more preferable for 1 part by weight of 2,2-dibromo-3-nitrilopropionamide. .
[0021]
The tetrahalogenated isophthalonitrile compound to be blended is 5-chloro-2,4,6-trifluoroisophthalonitrile, 2,4,5,6-tetrafluoroisophthalonitrile, 2,4,5,6-tetra. One or more types selected from chloroisophthalonitrile can be mentioned, especially when application of 5-chloro-2,4,6-trifluoroisophthalonitrile is effective and formulation stability, and further to the environment From the point of consideration of
[0022]
The halogenated acetate compound to be blended is selected from 1,4-bis (bromoacetoxy) -2-butene, 1,2-bis (bromoacetoxy) ethane, and 1,2-bis (bromoacetoxy) propane. More than one type can be mentioned, and application of 1,2-bis (bromoacetoxy) ethane is particularly preferable in terms of efficacy and formulation stability when it is used as one solution.
[0023]
In the present invention, in addition to the active ingredient, a solvent, water, surfactant, thickener, rust inhibitor, and other auxiliary agents are added to form a water-soluble liquid agent, an emulsifiable liquid agent, a flowable agent, a granule, a wettable powder, I can do it. In the case of formulation as a water-soluble liquid agent, the dispersibility in water can be improved by selecting a solvent capable of sufficiently dissolving each active ingredient and blending a surfactant as necessary.
[0024]
Suitable solvents include, for example, polyhydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol 200, propylene glycol, dipropylene glycol, carbitols, cellosolves and derivatives thereof, N, N-dimethylacetamide, N, N-dimethyl. Examples include aprotic solvents such as formamide, N-methyl-2-pyrrolidinone, propylene carbonate, γ-butyrolactone, dimethyl phthalate, and dimethyl maleate. Further, two or more kinds of solvents can be mixed and used for the purpose of improving cold resistance and adjusting the viscosity. As the surfactant, an anionic surfactant, a nonionic surfactant, or a combination thereof can be used, and the surfactant is selectively applied depending on the solvent to be used.
[0025]
In the case of preparation as an emulsifying liquid, an anionic surfactant or a nonionic surfactant is blended using a solvent of an aromatic hydrocarbon such as toluene or xylene or a halogenated hydrocarbon such as chlorobenzene. When formulating as a flowable agent, a granule, or a wettable powder, a solid extender such as clay, calcium carbonate, and white carbon and a surfactant are blended and then finely pulverized to prepare each dosage form.
[0026]
The bactericidal composition of the present invention is the simplest to use as a one-component type mixture, but there are cases where it is better to formulate the active ingredients individually in terms of the location of addition and long-term storage stability. . Thus, even when it is not a one-component type, if each active ingredient is added at a predetermined ratio in the system to be sterilized at the time of use, an effect that is not different from that of a one-component type mixture can be obtained.
[0027]
【The invention's effect】
The industrial sterilization composition and sterilization method of the present invention are composed of a compound selected from 2,2-dibromo-3-nitrilopropionamide, a tetrahalogenated isophthalonitrile compound, and a compound selected from a halogenated acetate compound. By using the active ingredients in combination at a predetermined ratio, it is possible to achieve an extremely powerful synergistic bactericidal effect that cannot be achieved with a single agent or a combination of two agents, and a wide range from bacteria to yeasts and filamentous fungi Can have a sterilization spectrum.
This excellent sterilizing effect is suitable for the purpose of controlling the slime of circulating water and preserving water-based industrial products, particularly for the purpose of controlling the slime of papermaking white water, cutting oil and industrial cooling water.
[0028]
【Example】
The present invention will be described in more detail based on examples. The bactericidal composition of the present invention was obtained by the following formulation (% by weight). The active ingredient used is 2,2-dibromo-3-nitrilopropionamide is DBNPA, 5-chloro-2,4,6-trifluoroisophthalonitrile is CFPN, 2,4,5,6-tetrafluoroisophthalo. Nitrile is represented by using TFPN, 1,4-bis (bromoacetoxy) -2-butene by BBAB, and 1,2-bis (bromoacetoxy) ethane by BBAE.
[0029]
DBNPA, CFPN, BBAB, and BBAE used in Examples 1 to 8, Comparative Examples 1 to 7, Test Example 1 and Test Example 2 are easily available industrial grades (purity 90 to 98%). A standard product having a purity of 99.5% or higher was further used at Aikasei Co., Ltd. through a purification process. In addition, TFPN was subjected to indoor synthesis and purification at KAI Kasei Co., Ltd., and a preparation with a purity of 99.0% or higher was used in each of the above-described tests.
[0030]
[Table 1]
[Table 2]
[Test Example 1]
(Slime suppression test)
A slime suppression test was performed using a five-unit water circulation device composed of a plastic cage (L100cm x H4cm x W5cm) fixed at an inclination of 5 to 10 °, a circulation pump, a precision metering pump for adding chemicals, and a reservoir. . Four resistance plates that suppress the flow rate were attached to the ridge, and the slime suppression effect was determined based on the amount of slime wet weight attached to the ridge.
[0033]
The water to be circulated was artificial white water adjusted to 30 ° C. (containing 50 ppm pulp, 200 ppm calcium carbonate, 100 ppm PAM, 500 ppm peptone, and adjusted to pH 6-7), and two bacterial strains isolated from white paper mill paper ( Unidentified), two yeast strains (unidentified), and one filamentous fungus strain (unidentified) were inoculated and the test was started. Each of the five circulation pumps was operated at about 10 L / hour, the overflow was set at about 2 L / hour, and the addition of the chemical solution was set at 0.5 ml every 8 hours (the concentration in the system was about 25 ppm).
[0034]
Seven days after the start of the test, all the slime adhering to the cocoon was scraped off, spread on a 12-mesh screen and left in a constant temperature and humidity chamber for 1 hour to measure the wet weight, which was taken as the amount of adhering slime. The slime suppression effect of an Example is shown in Table 3-Table 5.
[0035]
[Table 3]
[Table 4]
[Table 5]
From the results of the slime suppression test in an aqueous system contaminated with bacteria, yeast and filamentous fungi, it is shown that the examples of the present invention have a better slime suppression effect than the comparative examples. In other words, in addition to the synergistic sterilization effect of the two components shown in the comparative example, the powerful synergistic sterilization effect of the example in which the three components are blended, the circulatory water system complexly contaminated with such various microorganisms. In contrast, it effectively suppresses slime generation.
[0039]
[Test Example 2]
(Confirm synergy effect)
Bacteria (Pseudomonas aeruginosa) or filamentous fungus (Geotrichum candidum) is inoculated in a phosphate citrate buffer solution of pH 7 supplemented with 0.01% pulp and 0.01% PAM, and 10 4 to 10 6 CFU / ml cells A suspension was prepared. Predetermined amounts of each of the A component composed of DBNPA and CFPN and the B component composed of DBNPA and BBAE or BBAB were added to these cell suspensions, followed by shaking culture at 30 ° C. for 30 minutes. After 30 minutes, the number of viable bacteria in the cell suspension was measured by the agar plate pour method.
[0040]
The number of viable bacteria and the composition ratio in each square in Table 6 and Table 7 are the remaining viable bacteria in the presence of the sum of the A component (DBNPA and CFPN) and the B component (DBNPA and BBAE or BBAB) on the vertical axis. The number and the composition ratio of each component at that time are shown.
[0041]
[Table 6]
[Table 7]
From Tables 6 and 7, the composition comprising DBNPA, CFPN, BBAE or BBAB shows a strong synergistic bactericidal effect at a certain range of compounding ratio. This is a bactericidal effect more than a composition composed of two components, and this synergistic bactericidal effect is recognized not only in bacteria but also in filamentous fungi. Such characteristics are suitable for circulatory water systems contaminated by various microorganisms, especially paper white water, cutting oil, industrial cooling water for sterilization and slime control, and for sterilizing and preserving various aqueous industrial products. It is also suitable for applications.
Claims (6)
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| JP29537599A JP4279956B2 (en) | 1999-10-18 | 1999-10-18 | Industrial sterilization composition and sterilization method |
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| CN105104420A (en) * | 2015-08-04 | 2015-12-02 | 威海翔宇环保科技股份有限公司 | Fungicide for compound oilfield reinjection water, and preparation method therefor |
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| JP2003251355A (en) | 2001-12-28 | 2003-09-09 | Omega:Kk | Method for cleaning and sterilizing service water or the like and device therefor |
| JP2006232748A (en) * | 2005-02-25 | 2006-09-07 | Shinto Fine Co Ltd | Antimicrobial composition for industrial use |
| JP2007145720A (en) * | 2005-11-24 | 2007-06-14 | K I Chemical Industry Co Ltd | Industrial antimicrobial composition |
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| CN105104420A (en) * | 2015-08-04 | 2015-12-02 | 威海翔宇环保科技股份有限公司 | Fungicide for compound oilfield reinjection water, and preparation method therefor |
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