JPH0232247B2 - YOSUIKEINOKOKINZAI - Google Patents

YOSUIKEINOKOKINZAI

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Publication number
JPH0232247B2
JPH0232247B2 JP1521783A JP1521783A JPH0232247B2 JP H0232247 B2 JPH0232247 B2 JP H0232247B2 JP 1521783 A JP1521783 A JP 1521783A JP 1521783 A JP1521783 A JP 1521783A JP H0232247 B2 JPH0232247 B2 JP H0232247B2
Authority
JP
Japan
Prior art keywords
water
slime
antibacterial agent
bromoacetoxy
propanediol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP1521783A
Other languages
Japanese (ja)
Other versions
JPS59141501A (en
Inventor
Hirohisa Tashiro
Masaaki Fuha
Koji Kiuchi
Takao Numakura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kurita Water Industries Ltd
Original Assignee
Kurita Water Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kurita Water Industries Ltd filed Critical Kurita Water Industries Ltd
Priority to JP1521783A priority Critical patent/JPH0232247B2/en
Publication of JPS59141501A publication Critical patent/JPS59141501A/en
Publication of JPH0232247B2 publication Critical patent/JPH0232247B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Description

【発明の詳細な説明】[Detailed description of the invention]

この発明は用水系の微生物の殺菌または抑制を
行うための抗菌剤に関するものである。 化学工業、製紙工業などの製造工業では、冷却
水、プロセス水等の用水として多量の水が使用さ
れているが、工業用水の絶対量の不足を補うため
に、水の循環率を上げたり、廃水の再利用が行わ
れ、用水系は微生物の生息、増殖に適した環境と
なつている。このため、これらの用水系では微生
物の増殖によるスライムが発生し、例えば冷却水
系では熱交換器の伝熱効率の低下や流路の閉塞な
どのスライム障害が発生している。また製紙工業
では古紙の再利用が行われているため、さらにス
ライムが発生しやすくなつており、抄紙系におけ
る紙切れやいわゆる目玉といわれる斑点の発生な
どのスライム障害が発生している。 このような用水系におけるスライム障害を除去
するために種々の抗菌剤が使用されているが、こ
れらの抗菌剤は処理コストに占める比率が高いこ
と、ならびに多かれ少なかれ毒性を有することか
ら、少ない量で高い抗菌活性を示すことが望まれ
る。2−ブロモ−2−ニトロ−1,3−プロパン
ジオールおよび1,4−ビス(ブロモアセトキ
シ)−2−ブテンは、それぞれ単独では抗菌剤と
して公知であるが、上記の観点からみて、必ずし
も優れた効果を示すものとはいえなかつた。 この発明は従来の抗菌剤の抗菌活性を改善する
ためのもので、2−ブロモ−2−ニトロ−1,3
−プロパンジオールおよび1,4−ビス(ブロモ
アセトキシ)−2−ブテンを有効成分として併用
することにより、相乗効果による優れた抗菌活性
を示す用水系の抗菌剤を提供することを目的とし
ている。 2−ブロモ−2−ニトロ−1,3−プロパンジ
オールは次の〔〕式で示される。 1,4−ビス(ブロモアセトキシ)−2−ブテ
ンは次の〔〕式で示される。 2−ブロモ−2−ニトロ−1,3−プロパンジ
オールおよび1,4−ビス(ブロモアセトキシ)
−2−ブテンは抗菌剤として使用される状態で用
水系に有効成分として共存していればよいから、
両成分を混合状態で水に添加してもよく、同時ま
たは別々に水に添加してもよい。添加方法は均一
に分散できるような方法で行えばよく、特に制限
はないが、一般的にはジメチルフオルムアミドな
どの水との混和性のよい溶媒で溶解するのが望ま
しい。このとき必要により分散剤を使用すること
ができる。 2−ブロモ−2−ニトロ−1,3−プロパンジ
オールと1,4−ビス(ブロモアセトキシ)−2
−ブテンの配合比は相乗効果を示す範囲であれば
特に制限はないが、一般的には1:19ないし19:
1が好ましく、特に9:1ないし2:3がさらに
好ましく、4:1ないし1:1が最も好ましい。 本発明の抗菌剤はこれらの2種の有効成分だけ
を含むものでもよいが、必要により他の抗菌剤と
併用してもよく、また界面活性剤等の促進剤、あ
るいは過酸化水素等の剥離剤など、他の添加剤を
さらに含んでいてもよい。 対象となる用水系はスライム障害等の微生物障
害の発生する可能性のある系であつて、例えば冷
却水系、抄紙系などが例示できるが、特別の制限
はない。また抗菌の対象となる微生物も制限はな
く、一般にスライムの原因とされるシユードモナ
スその他の細菌、糸状菌等が対象となり、抄紙系
では一般のスライムの他のピンクスライムの原因
となるピンク細菌も含まれる。 これらの微生物は本発明の抗菌剤の添加により
殺菌され、あるいは抑制される。スライム障害を
防除するためには、完全に殺菌してもよいが、増
殖を抑制するだけでもよく、本発明における抗菌
はこのような作用を意味する。 したがつて本発明の抗菌剤の添加濃度も、殺菌
を目的とするときは殺菌濃度、抑制を目的とする
ときは抑制濃度となる。具体的な添加濃度は対象
となる用水系によつて異なるので、それぞれの水
系ごとに実験的に確認することができるが、一般
的には2成分の純分の合計量で0.1〜200mg/程
度である。このような殺菌濃度あるいは抑制濃度
を常に維持するように、抗菌剤を連続的に添加し
てもよいが、一度殺菌濃度あるいは抑制濃度に達
すると、微生物の増殖傾向が回復するまでに相当
の時間を要するので、間欠的に添加する方が効率
的である。 本発明の抗菌剤は、含まれる2成分が相乗作用
を示し、それぞれ単独で使用する場合よりもはる
かに優れた抗菌活性が得られ、用水系における微
生物を殺菌または抑制することができる。このた
め冷却水系における熱交換器の熱交換効率の低下
や流路の閉塞、あるいは抄紙系における紙切れや
斑点の発生などのスライム障害を防除することが
できる。 次にこの発明の実施例について説明する。実施
例中、2−ブロモ−2−ニトロ−1,3−プロパ
ンジオールを化合物A,1,4−ビス(ブロモア
セトキシ)−2−ブテンを化合物Bとする。 実施例 1 用水中で繁殖する代表的な細菌であるシユード
モナス・アエルギノーサをブイヨン培地で24時間
振とう培養した後、新しいブイヨン培地(PH7)
中に5×106cell/mlとなるように加え、これに
配合比を変えて化合物AおよびBを添加し、24時
間後に菌の増殖の有無を判定して、24時間後の最
少抑制濃度(純分換算…以下同じ)を求めた。結
果を表−1に示す。 表−1から明らかなように、化合物AおよびB
併用のものは配合比1:19ないし19:1の広い範
囲にわたつて相乗効果が認められ、その効果は
9:1ないし2:3でさらに大きく、4:1ない
し1:1で最も大きい。
This invention relates to an antibacterial agent for killing or suppressing microorganisms in water systems. In manufacturing industries such as the chemical industry and paper manufacturing industry, large amounts of water are used for cooling water, process water, etc., but in order to compensate for the lack of absolute amount of industrial water, it is necessary to increase the water circulation rate, Wastewater is reused, and the water system has become an environment suitable for the inhabitation and proliferation of microorganisms. For this reason, in these water systems, slime is generated due to the proliferation of microorganisms, and for example, in cooling water systems, slime failures such as a decrease in heat transfer efficiency of heat exchangers and blockage of flow paths occur. In addition, as waste paper is reused in the paper industry, slime is more likely to be generated, and slime problems such as paper breakage and so-called spots in the papermaking system are occurring. Various antibacterial agents are used to remove such slime problems in water systems, but these antibacterial agents account for a high proportion of the treatment cost and are more or less toxic, so they can only be used in small amounts. It is desired that they exhibit high antibacterial activity. 2-Bromo-2-nitro-1,3-propanediol and 1,4-bis(bromoacetoxy)-2-butene are known as antibacterial agents when used alone, but from the above point of view, they are not necessarily superior. It could not be said that it was effective. This invention is aimed at improving the antibacterial activity of conventional antibacterial agents.
The object of the present invention is to provide a water-based antibacterial agent that exhibits excellent antibacterial activity due to a synergistic effect by using propanediol and 1,4-bis(bromoacetoxy)-2-butene together as active ingredients. 2-bromo-2-nitro-1,3-propanediol is represented by the following formula. 1,4-bis(bromoacetoxy)-2-butene is represented by the following formula. 2-bromo-2-nitro-1,3-propanediol and 1,4-bis(bromoacetoxy)
-2-Butene only needs to coexist as an active ingredient in the water system when used as an antibacterial agent.
Both components may be added to the water in a mixed state, or may be added to the water simultaneously or separately. The addition method is not particularly limited as long as it can be uniformly dispersed, but it is generally desirable to dissolve it in a solvent that is highly miscible with water, such as dimethyl formamide. At this time, a dispersant can be used if necessary. 2-bromo-2-nitro-1,3-propanediol and 1,4-bis(bromoacetoxy)-2
- The blending ratio of butene is not particularly limited as long as it shows a synergistic effect, but generally it is 1:19 to 19:1.
1 is preferred, particularly 9:1 to 2:3 is more preferred, and 4:1 to 1:1 is most preferred. The antibacterial agent of the present invention may contain only these two types of active ingredients, but if necessary, it may be used in combination with other antibacterial agents. The composition may further contain other additives such as additives. The target water system is a system in which microbial damage such as slime damage may occur, such as a cooling water system or a papermaking system, but there are no particular limitations. There are also no restrictions on the microorganisms that can be targeted for antibacterial treatment, such as Pseudomonas, other bacteria, and filamentous fungi that are generally the cause of slime. It will be done. These microorganisms are sterilized or inhibited by the addition of the antibacterial agent of the present invention. In order to control slime damage, complete sterilization may be used, but it is also sufficient to simply suppress proliferation, and the term "antibacterial" in the present invention refers to such action. Therefore, the added concentration of the antibacterial agent of the present invention is also a bactericidal concentration when the purpose is sterilization, and an inhibitory concentration when the purpose is inhibition. The specific additive concentration varies depending on the target water system, so it can be confirmed experimentally for each water system, but in general, the total amount of the pure components of the two components is about 0.1 to 200 mg/concentration. It is. The antibacterial agent may be added continuously to maintain such a bactericidal or inhibitory concentration, but once the bactericidal or inhibitory concentration is reached, it may take a considerable period of time for the propagation tendency of microorganisms to recover. Therefore, it is more efficient to add intermittently. The two components contained in the antibacterial agent of the present invention exhibit a synergistic effect, resulting in far superior antibacterial activity than when each is used alone, and can sterilize or suppress microorganisms in a water system. Therefore, it is possible to prevent slime failures such as a decrease in heat exchange efficiency of a heat exchanger in a cooling water system, blockage of a flow path, or occurrence of paper breaks and spots in a papermaking system. Next, embodiments of this invention will be described. In the examples, 2-bromo-2-nitro-1,3-propanediol is designated as Compound A, and 1,4-bis(bromoacetoxy)-2-butene is designated as Compound B. Example 1 Pseudomonas aeruginosa, a typical bacterium that grows in industrial water, was cultured with shaking in a broth medium for 24 hours, and then a new broth medium (PH7) was cultured.
Compounds A and B were added to the solution at a concentration of 5 x 10 6 cells/ml, and the mixing ratio was changed. After 24 hours, the presence or absence of bacterial growth was determined, and the minimum inhibitory concentration after 24 hours was determined. (purity conversion...the same applies below) was calculated. The results are shown in Table-1. As is clear from Table 1, compounds A and B
When used in combination, a synergistic effect was observed over a wide range of blending ratios of 1:19 to 19:1, the effect was even greater at 9:1 to 2:3, and the greatest at 4:1 to 1:1.

【表】 実施例 2 製紙工場の抄紙系の白水9部にブイヨン培地1
部を加えた後、化合物A,B混合液(化合物Aお
よびB各5部をN−ジメチルフオルムアミド90部
に溶解したもの)を加え、24時間後に菌数の増殖
の有無を判定して、24時間後の最少抑制濃度を求
めた。比較のために、化合物A,Bそれぞれ単独
添加の場合について同様の試験をした。結果を表
−2に示す。 表−2から明らかなように、化合物A,B混合
液には相乗効果が認められる。
[Table] Example 2 1 part of bouillon culture medium to 9 parts of papermaking white water at a paper mill
After adding 1 part, a mixed solution of compounds A and B (5 parts each of compounds A and B dissolved in 90 parts of N-dimethylformamide) was added, and after 24 hours, the presence or absence of growth in the number of bacteria was determined. The minimum inhibitory concentration after 24 hours was determined. For comparison, a similar test was conducted in which Compounds A and B were added alone. The results are shown in Table-2. As is clear from Table 2, the mixed solution of compounds A and B has a synergistic effect.

【表】 実施例 3 スライム障害が発生している製紙工場の抄紙系
において、白水に1日3回の割合で、実施例2で
使用した化合物A,B混合液を2mg/(純分換
算)となるように4時間づつ注入したところ、そ
れまでスライムによる目玉発生回数が1日あたり
3回であつたのが、1日あたり0.5回に減少した。 実施例 4 化学工場の循環式冷却水系に、実施例2で使用
した化合物A,B混合液を、保有水量に対し20
mg/(純分換算)となるように、2日に1回の
割合で注入したところ、冷却塔下部水曹内に30日
間浸漬したスライムボード(10cm×10cm)のスラ
イム付着量は、従来の35gから3gに減少した。 以上の結果より、本発明の抗菌剤は相乗効果に
より、優れた抗菌活性を示すことがわかる。
[Table] Example 3 In the papermaking system of a paper mill where slime damage has occurred, the mixed solution of compounds A and B used in Example 2 was added to white water at a rate of 2 mg/(purity equivalent) three times a day. When the slime was injected for 4 hours at a time, the number of eyeballs caused by slime decreased from 3 times per day to 0.5 times per day. Example 4 The mixed solution of compounds A and B used in Example 2 was added to the circulating cooling water system of a chemical factory at a rate of 20% of the amount of water held.
mg/(converted to pure content) once every two days, the amount of slime attached to a slime board (10 cm x 10 cm) immersed in the water soda at the bottom of the cooling tower for 30 days was lower than that of the conventional method. Reduced from 35g to 3g. The above results show that the antibacterial agent of the present invention exhibits excellent antibacterial activity due to the synergistic effect.

Claims (1)

【特許請求の範囲】 1 2−ブロモ−2−ニトロ−1,3−プロパン
ジオールおよび1,4−ビス(ブロモアセトキ
シ)−2−ブテンを有効成分とする用水系の抗菌
剤。 2 2−ブロモ−2−ニトロ−1,3−プロパン
ジオールおよび1,4−ビス(ブロモアセトキ
シ)−2−ブテンの配合比が1:19ないし19:1
である特許請求の範囲第1項記載の用水系の抗菌
剤。 3 2−ブロモ−2−ニトロ−1,3−プロパン
ジオールおよび1,4−ビス(ブロモアセトキ
シ)−2−ブテンの配合比が4:1ないし1:1
である特許請求の範囲第1項記載の用水系の抗菌
剤。 4 用水系が冷却水系または抄紙系である特許請
求の範囲第1項ないし第3項のいずれかに記載の
用水系の抗菌剤。
[Scope of Claims] 1. A water-based antibacterial agent containing 2-bromo-2-nitro-1,3-propanediol and 1,4-bis(bromoacetoxy)-2-butene as active ingredients. 2 The blending ratio of 2-bromo-2-nitro-1,3-propanediol and 1,4-bis(bromoacetoxy)-2-butene is 1:19 to 19:1
A water-based antibacterial agent according to claim 1. 3 The blending ratio of 2-bromo-2-nitro-1,3-propanediol and 1,4-bis(bromoacetoxy)-2-butene is 4:1 to 1:1
A water-based antibacterial agent according to claim 1. 4. The antibacterial agent for a water system according to any one of claims 1 to 3, wherein the water system is a cooling water system or a papermaking system.
JP1521783A 1983-01-31 1983-01-31 YOSUIKEINOKOKINZAI Expired - Lifetime JPH0232247B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1521783A JPH0232247B2 (en) 1983-01-31 1983-01-31 YOSUIKEINOKOKINZAI

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1521783A JPH0232247B2 (en) 1983-01-31 1983-01-31 YOSUIKEINOKOKINZAI

Publications (2)

Publication Number Publication Date
JPS59141501A JPS59141501A (en) 1984-08-14
JPH0232247B2 true JPH0232247B2 (en) 1990-07-19

Family

ID=11882702

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1521783A Expired - Lifetime JPH0232247B2 (en) 1983-01-31 1983-01-31 YOSUIKEINOKOKINZAI

Country Status (1)

Country Link
JP (1) JPH0232247B2 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5013755A (en) * 1988-10-27 1991-05-07 Somar Corporation Germicidal composition
JP4552165B2 (en) * 2000-03-17 2010-09-29 栗田工業株式会社 Industrial antibacterial agent composition and industrial antibacterial method

Also Published As

Publication number Publication date
JPS59141501A (en) 1984-08-14

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