JPH08301708A - Industrial germicidal composition - Google Patents

Industrial germicidal composition

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Publication number
JPH08301708A
JPH08301708A JP10648495A JP10648495A JPH08301708A JP H08301708 A JPH08301708 A JP H08301708A JP 10648495 A JP10648495 A JP 10648495A JP 10648495 A JP10648495 A JP 10648495A JP H08301708 A JPH08301708 A JP H08301708A
Authority
JP
Japan
Prior art keywords
industrial
composition
water
methylenebisthiocyanate
nitrilopropionamide
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.)
Pending
Application number
JP10648495A
Other languages
Japanese (ja)
Inventor
Ryoji Funatsu
亮二 船津
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.)
Somar Corp
Original Assignee
Somar Corp
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 Somar Corp filed Critical Somar Corp
Priority to JP10648495A priority Critical patent/JPH08301708A/en
Publication of JPH08301708A publication Critical patent/JPH08301708A/en
Pending legal-status Critical Current

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Abstract

PURPOSE: To obtain a composition, capable of manifesting excellent exterminating and proliferation suppressing effects on bacteria and molds and good in preservation stability by dissolving a germicide containing cyanoacetamides combined with methylenebisthiocyanate in a specific compound. CONSTITUTION: This industrial germicidal composition is obtained by dissolving an industrial germicidal composition containing (A) a cyanoacetamide compound of the formula (X is a halogen; Y is H or a halogen; R<1> and R<2> are each H or a lower alkyl) and (B) methylenebisthiocyanate in propylene carbonate. The blending weight ratio of the ingredients (A) to (B) is (10:1) to (1:10). 2,2- Dibromo-3-nitrilopropionamide is especially preferred as the ingredient (A) due to its excellence in bactericidal activities. The composition can advantageously be preserved and transported especially under high-temperature conditions. The composition can be used in various water systems especially in the pulp industrial field, e.g. white water in papermaking processes or various water systems such as circulating and cooling water in various industrial fields and further water-based coating materials, coating liquids for paper, latexes, etc., prepared by using industrial water.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は新規な工業用殺菌剤組成
物、さらに詳しくは、優れた細菌及びカビに対する殺滅
効果及び繁殖抑制効果を示す上、良好な保存安定性を有
し、特に紙パルプ工業分野における用水系をはじめ、各
種分野に対して好適に用いられる工業用殺菌剤組成物に
関するものである。
FIELD OF THE INVENTION The present invention relates to a novel industrial fungicide composition, and more particularly, it has excellent bactericidal and fungicidal killing effect and reproduction suppressing effect, and also has good storage stability. The present invention relates to an industrial bactericidal composition suitable for use in various fields including water systems in the pulp and paper industry.

【0002】[0002]

【従来の技術】従来、紙パルプ工業分野における用水
系、例えば抄紙工程の白水や各種産業分野における循環
冷却水などの種々の用水系の他、工業用水を使用して調
製される水性塗料、紙用塗工液、ラテックス、高分子エ
マルション、捺染糊、接着剤、切削油などの金属加工油
剤、皮革、木材などの分野においては、それらに有害な
カビ、バクテリア等の微生物が増繁殖しやすく、これが
生産性や品質の低下の原因となっている。特に紙パルプ
工業分野における用水系では、細菌、糸状菌、酵母類の
増繁殖によりスライムが発生し、パルプスラリーが流れ
る水路、とりわけスラリーが接する壁面の粗い場所やチ
ェスト、フローボックス、輸送パイプ、その他パイプス
ラリーの流速が小さくなって淀むような場所においてス
ライムが付着形成される。
2. Description of the Related Art Conventionally, various water systems in the pulp and paper industry, such as white water in the papermaking process and circulating cooling water in various industries, as well as water-based paints and papers prepared using industrial water. In the fields of coating liquids, latexes, polymer emulsions, printing pastes, adhesives, metalworking oils such as cutting oils, leather and wood, molds harmful to them, microorganisms such as bacteria easily propagate, This causes the deterioration of productivity and quality. Especially in the water system in the pulp and paper industry, slime is generated by the multiplication of bacteria, filamentous fungi, and yeasts, and the channel in which the pulp slurry flows, especially the rough wall surface where the slurry contacts, chests, flow boxes, transport pipes, etc. Slime is deposited and formed in a place where the flow velocity of the pipe slurry becomes small and stagnates.

【0003】このスライムは、しばしば脱離し、紙切れ
や紙パイプ製品の汚染の原因となるほか、微生物の繁殖
による種々の障害をもたらす。
The slime is often detached, which causes paper scraps and contamination of paper pipe products, and causes various obstacles due to the growth of microorganisms.

【0004】このような障害の発生は、特に高速マシン
を使用する際には大きな問題となり、著しい生産性低
下、経済的損失を招来する。
The occurrence of such a trouble becomes a serious problem particularly when a high speed machine is used, which causes a remarkable decrease in productivity and an economic loss.

【0005】また、例えば金属加工油剤などの冷却用循
環用水系における微生物の増繁殖は、冷却性能や乳化性
を阻害したり、また悪臭を発生させ作業環境を悪化させ
るなど公衆衛生上好ましくない現象を引き起こす。
Further, for example, the proliferation of microorganisms in a circulating water system for cooling, such as a metalworking oil, impairs cooling performance and emulsification properties, and also produces a bad odor, which worsens the working environment and is a phenomenon unfavorable to public health. cause.

【0006】さらに、その他、有害微生物の増繁殖によ
る障害は、水性塗料、紙用塗工液、ラテックス、高分子
エマルション、捺染糊、接着剤、切削油などの金属加工
油剤などの工業用製品にもみられる。
In addition, other problems caused by the proliferation of harmful microorganisms are caused in industrial products such as water-based paints, coating liquids for paper, latexes, polymer emulsions, printing pastes, adhesives, and metal working oils such as cutting oils. Also seen.

【0007】ところで、前記用水系又は前記工業用製品
における有害微生物の発生を抑制あるいは防除する薬剤
としては、これまで例えば有機金属化合物類、有機塩素
化合物類、有機硫黄化合物類、第四級アンモニウム塩類
などが使用されてきたが、これらの化合物類は人体に対
し毒性を有し、また悪臭や異臭を発し、さらには発泡な
どの好ましくない現象を生じる。加えて、これらの防除
剤含有水系は、これを一般河川や海などに投流した場合
には、魚介類に対し悪影響を与え環境保全上問題を生じ
る。
By the way, as agents for suppressing or controlling the generation of harmful microorganisms in the water system or the industrial products, for example, organometallic compounds, organochlorine compounds, organosulfur compounds and quaternary ammonium salts have hitherto been used. , Etc. have been used, but these compounds are toxic to the human body, give off a bad odor or an offensive odor, and cause undesirable phenomena such as foaming. In addition, these pesticide-containing water systems, when they are thrown into general rivers or the sea, have an adverse effect on seafood and cause environmental problems.

【0008】このような問題を回避しうるものとして
は、例えばシアノアセトアミド化合物とメチレンビスチ
オシアネートとを、エチレングリコールやポリエチレン
グリコールなどの溶剤に溶解して成る殺菌剤が知られて
いる(特開昭57−114502号公報)。しかしなが
ら、メチレンビスチオシアネートは不純物を含まない純
粋なものを製造するのが極めて困難である上、保存中に
メチレンビスチオシアネートの一部が変質するので、メ
チレンビスチオシアネートには必ず僅かな不純物が含ま
れている。このため、このメチレンビスチオシアネート
をシアノアセトアミド化合物と組み合わせてエチレング
リコールやポリエチレングリコールなどの溶剤に溶解し
た場合、メチレンビスチオシアネートに含まれる不純物
の一部が、シアノアセトアミド化合物の分解を促進する
ために、この殺菌剤は保存安定性が悪く、時間の経過と
ともにシアノアセトアミド化合物の濃度が減少するのを
免れない。したがって、薬剤の長期貯蔵、特に夏期など
の高温条件下で薬剤を貯蔵した場合に、薬剤が変質して
殺菌効果が低下したり、薬剤が変色するなどの欠点があ
った。
As a substance which can avoid such a problem, for example, a bactericidal agent is known in which a cyanoacetamide compound and methylenebisthiocyanate are dissolved in a solvent such as ethylene glycol or polyethylene glycol (Japanese Patent Laid-Open Publication No. Sho. 57-114502). However, it is extremely difficult to produce a pure methylenebisthiocyanate that is free of impurities, and part of the methylenebisthiocyanate is altered during storage, so methylenebisthiocyanate must contain a slight amount of impurities. ing. Therefore, when this methylenebisthiocyanate is dissolved in a solvent such as ethylene glycol or polyethylene glycol in combination with a cyanoacetamide compound, some of the impurities contained in the methylenebisthiocyanate accelerate the decomposition of the cyanoacetamide compound, This bactericide has poor storage stability, and the concentration of the cyanoacetamide compound is unavoidable as time passes. Therefore, when the drug is stored for a long period of time, particularly when the drug is stored under high temperature conditions such as in the summer, there are drawbacks such as deterioration of the drug due to deterioration of the bactericidal effect and discoloration of the drug.

【0009】[0009]

【発明が解決しようとする課題】本発明は、シアノアセ
トアミド化合物とメチレンビスチオシアネートとを組み
合わせた殺菌剤にみられる前記欠点を克服し、シアノア
セトアミド化合物とメチレンビスチオシアネートを含有
し、優れた細菌及びカビに対する殺滅効果及び繁殖抑制
効果を示し、しかも保存安定性の良好な工業用殺菌剤組
成物を提供することを目的としてなされたものである。
DISCLOSURE OF THE INVENTION The present invention overcomes the above-mentioned drawbacks found in bactericides in which a cyanoacetamide compound and methylenebisthiocyanate are combined, and contains a cyanoacetamide compound and methylenebisthiocyanate, and is excellent in bacteria and The purpose of the present invention is to provide an industrial fungicide composition which has a fungicidal killing effect and a growth inhibitory effect and has good storage stability.

【0010】[0010]

【課題を解決するための手段】本発明者は、シアノアセ
トアミド化合物とメチレンビスチオシアネートとを含む
工業用殺菌剤組成物の保存安定性を改良するために鋭意
研究を重ねた結果、シアノアセトアミド化合物とメチレ
ンビスチオシアネートとをプロピレンカーボネートに溶
解することにより、その目的を達成しうることを見出
し、この知見に基づいて本発明を完成するに至った。
Means for Solving the Problems The present inventors have conducted extensive studies to improve the storage stability of an industrial fungicide composition containing a cyanoacetamide compound and methylenebisthiocyanate, and as a result, It was found that the object can be achieved by dissolving methylenebisthiocyanate in propylene carbonate, and the present invention has been completed based on this finding.

【0011】すなわち、本発明は、(A)一般式That is, the present invention provides (A) the general formula

【化2】 (式中のXはハロゲン原子、Yは水素原子又はハロゲン
原子、R1及びR2はそれぞれ水素原子又は低級アルキル
基であり、それらはたがいに同一であってもよいし、異
なっていてもよい)で表わされるシアノアセトアミド化
合物及び(B)メチレンビスチオシアネートをプロピレ
ンカーボネートに溶解してなる工業用殺菌剤組成物を提
供するものである。
Embedded image (In the formula, X is a halogen atom, Y is a hydrogen atom or a halogen atom, and R 1 and R 2 are each a hydrogen atom or a lower alkyl group, and they may be the same or different. And a cyanoacetamide compound represented by the formula (4) and (B) methylenebisthiocyanate are dissolved in propylene carbonate.

【0012】本発明の工業用殺菌剤組成物においては、
(A)成分として、前記一般式(I)で表わされるシア
ノアセトアミド化合物が用いられる。この一般式(I)
において、Xはハロゲン原子、Yは水素原子又はハロゲ
ン原子であり、Xのハロゲン原子及びYのうちのハロゲ
ン原子としては、それぞれ塩素原子及び臭素原子が好ま
しく挙げられる。また、R1及びR2はそれぞれ水素原子
又は低級アルキル基であり、この低級アルキル基として
は、例えばメチル基、エチル基、n‐プロピル基、イソ
プロピル基などが挙げられる。このR1及びR2はたがい
に同一であってもよいし、異なっていてもよい。
In the industrial germicidal composition of the present invention,
As the component (A), the cyanoacetamide compound represented by the general formula (I) is used. This general formula (I)
In the above, X is a halogen atom, Y is a hydrogen atom or a halogen atom, and the halogen atom of X and the halogen atom of Y are preferably a chlorine atom and a bromine atom, respectively. R 1 and R 2 are each a hydrogen atom or a lower alkyl group, and examples of the lower alkyl group include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. R 1 and R 2 may be the same or different.

【0013】この(C)成分のシアノアセトアミド化合
物としては、例えば2‐クロロ‐3‐ニトリロプロピオ
ンアミド、N‐メチル‐2‐クロロ‐3‐ニトリロプロ
ピオンアミド、N,N‐ジメチル‐2‐クロロ‐3‐ニ
トリロプロピオンアミド、2,2‐ジクロロ‐3‐ニト
リロプロピオンアミド、N‐メチル‐2,2‐ジクロロ
‐3‐ニトリロプロピオンアミド、N,N‐ジメチル‐
2,2‐ジクロロ‐3‐ニトリロプロピオンアミド、2
‐ブロモ‐3‐ニトリロプロピオンアミド、N‐メチル
‐2‐ブロモ‐3‐ニトリロプロピオンアミド、N,N
‐ジメチル‐2‐ブロモ‐3‐ニトリロプロピオンアミ
ド、2,2‐ジブロモ‐3‐ニトリロプロピオンアミ
ド、N‐メチル‐2,2‐ジブロモ‐3‐ニトリロプロ
ピオンアミド、N,N‐ジメチル‐2,2‐ジブロモ‐
3‐ニトリロプロピオンアミドなどが挙げられる。これ
らは単独で用いてもよいし、2種以上を組み合わせて用
いてもよいが、中でも、2,2‐ジブロモ‐3‐ニトリ
ロプロピオンアミドが、殺バクテリア性に優れるので特
に好ましい。
Examples of the cyanoacetamide compound as the component (C) include 2-chloro-3-nitrilopropionamide, N-methyl-2-chloro-3-nitrilopropionamide, N, N-dimethyl-2-chloro- 3-Nitrilopropionamide, 2,2-dichloro-3-nitrilopropionamide, N-methyl-2,2-dichloro-3-nitrilopropionamide, N, N-dimethyl-
2,2-dichloro-3-nitrilopropionamide, 2
-Bromo-3-nitrilopropionamide, N-methyl-2-bromo-3-nitrilopropionamide, N, N
-Dimethyl-2-bromo-3-nitrilopropionamide, 2,2-dibromo-3-nitrilopropionamide, N-methyl-2,2-dibromo-3-nitrilopropionamide, N, N-dimethyl-2,2 -Dibromo-
3-Nitrilopropionamide and the like can be mentioned. These may be used singly or in combination of two or more, and among them, 2,2-dibromo-3-nitrilopropionamide is particularly preferable because it has excellent bactericidal properties.

【0014】本発明の殺菌剤組成物においては、(A)
成分と(B)成分との配合割合は、重量比で10:1な
いし1:10、さらに有利には10:1ないし1:5の
範囲とするのが、優れた相乗効果が得られるので好まし
い。(A)成分が少なすぎるとバクテリアに対する殺菌
力が低下する。また(B)成分が少なすぎるとカビに対
する殺菌力が低下し、バクテリアの増殖に対する抑制力
が低下する。
In the fungicide composition of the present invention, (A)
The mixing ratio of the component and the component (B) is preferably 10: 1 to 1:10 by weight, more preferably 10: 1 to 1: 5, because an excellent synergistic effect can be obtained. . When the amount of the component (A) is too small, the bactericidal activity against bacteria decreases. On the other hand, if the amount of component (B) is too small, the bactericidal activity against mold is reduced, and the inhibitory activity against bacterial growth is reduced.

【0015】本発明の殺菌剤組成物は、溶剤としてプロ
ピレンカーボネートを用い、これに、前記(A)成分及
び(B)成分を配合した溶剤溶液型である。プロピレン
カーボネートは、単独で用いるのが好ましく、他の溶剤
と混合すると保存安定性は低下する。
The bactericidal composition of the present invention is of a solvent solution type in which propylene carbonate is used as a solvent and the above-mentioned components (A) and (B) are blended therein. Propylene carbonate is preferably used alone, and when it is mixed with other solvent, the storage stability decreases.

【0016】この殺菌剤組成物の使用に際しての添加量
は、微生物濃度によっても異なるが、一般的に紙パルプ
工業などの分野における用水系の場合は、(A)成分及
び(B)成分の合計量に基づき、1〜100ppm、水
性塗料、糊、皮革などの分野の場合は10〜500pp
mであり、この範囲で良好な殺菌効果が得られる。
The amount of the disinfectant composition to be added at the time of use varies depending on the concentration of microorganisms, but generally in the case of water systems in the fields such as the pulp and paper industry, the total of the components (A) and (B). 1 to 100 ppm based on the amount, 10 to 500 pp in the case of water-based paint, glue, leather, etc.
m, and a good bactericidal effect can be obtained in this range.

【0017】本発明の殺菌剤組成物には、この発明の目
的が損なわれない範囲で、所望により水や界面活性剤な
どを添加することはなんら差し支えない。
If desired, water or a surfactant may be added to the bactericidal composition of the present invention as long as the object of the present invention is not impaired.

【0018】[0018]

【発明の効果】本発明の工業用殺菌剤組成物は、シアノ
アセトアミド化合物とメチレンビスチオシアネートとを
プロピレンカーボネートに配合したものであって、変質
が著しく抑制され、安定性が極めて高い。したがって、
その保存、輸送、特に高温条件下での保存、輸送を有利
に行うことができる。
INDUSTRIAL APPLICABILITY The industrial bactericidal composition of the present invention is a mixture of a cyanoacetamide compound and methylenebisthiocyanate in propylene carbonate, and its deterioration is remarkably suppressed and its stability is extremely high. Therefore,
Its storage and transportation, especially storage and transportation under high temperature conditions, can be advantageously performed.

【0019】本発明の工業用殺菌剤組成物は、殺菌や殺
カビ効果に優れるとともに、細菌やカビの繁殖抑制効果
にも優れ、特に紙パルプ工業分野における用水系、例え
ば抄紙工程の白水や各種産業分野における循環冷却水な
どの種々の用水系の他、工業用水を使用して調製される
水性塗料、紙用塗工液、ラテックス、高分子エマルショ
ン、捺染糊、接着剤、切削油などの金属加工油剤、皮革
などの分野に対して好適に使用される。
The industrial bactericidal composition of the present invention is excellent in sterilization and fungicidal effects as well as in bacterial and fungal growth inhibitory effects, and is particularly useful for water systems in the pulp and paper industry, such as white water and various kinds of paper making processes. In addition to various water systems such as circulating cooling water in the industrial field, water-based paints prepared using industrial water, paper coating liquids, latexes, polymer emulsions, printing pastes, adhesives, metals such as cutting oils. It is preferably used for processing oils, leather and other fields.

【0020】[0020]

【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明は、これらの例によってなんら限定さ
れるものではない。
EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

【0021】実施例1〜6、比較例1〜5 表1〜表2に示す組成の工業用殺菌剤組成物を調製した
のち、各試料を55℃の恒温室に保管し、経日的に試料
の一部を採取し、液体クロマトグラフィーを用いて2,
2‐ジブロモ‐3‐ニトリロプロピオンアミドの残存濃
度を測定した。結果を表3に示す。なお、残存率は次式
で示される。 残存率(%)=(b/a)×100 a:2,2‐ジブロモ‐3‐ニトリロプロピオンアミド
の初期濃度 b:2,2‐ジブロモ‐3‐ニトリロプロピオンアミド
の経日濃度
Examples 1 to 6 and Comparative Examples 1 to 5 After preparing industrial fungicidal compositions having the compositions shown in Tables 1 and 2, each sample was stored in a thermostatic chamber at 55 ° C. Take a portion of the sample and use liquid chromatography to
The residual concentration of 2-dibromo-3-nitrilopropionamide was measured. The results are shown in Table 3. The residual rate is expressed by the following equation. Residual rate (%) = (b / a) × 100 a: initial concentration of 2,2-dibromo-3-nitrilopropionamide b: daily concentration of 2,2-dibromo-3-nitrilopropionamide

【0022】[0022]

【表1】 [Table 1]

【0023】[0023]

【表2】 [Table 2]

【0024】[0024]

【表3】 [Table 3]

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 (A)一般式 【化1】 (式中のXはハロゲン原子、Yは水素原子又はハロゲン
原子、R1及びR2はそれぞれ水素原子又は低級アルキル
基であり、それらはたがいに同一であってもよいし、異
なっていてもよい)で表わされるシアノアセトアミド化
合物及び(B)メチレンビスチオシアネートをプロピレ
ンカーボネート中に溶解してなる工業用殺菌剤組成物。
1. (A) General formula: (In the formula, X is a halogen atom, Y is a hydrogen atom or a halogen atom, and R 1 and R 2 are each a hydrogen atom or a lower alkyl group, and they may be the same or different. ) A bactericidal composition for industrial use, comprising a cyanoacetamide compound represented by the formula (4) and (B) methylenebisthiocyanate dissolved in propylene carbonate.
JP10648495A 1995-04-28 1995-04-28 Industrial germicidal composition Pending JPH08301708A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10648495A JPH08301708A (en) 1995-04-28 1995-04-28 Industrial germicidal composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP10648495A JPH08301708A (en) 1995-04-28 1995-04-28 Industrial germicidal composition

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JPH08301708A true JPH08301708A (en) 1996-11-19

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011059532A1 (en) * 2009-11-10 2011-05-19 Dow Global Technologies Inc. Biocidal compositions and methods of use
WO2012044301A1 (en) * 2010-09-30 2012-04-05 Dow Global Technologies Llc Compositions of dibromomalonamide and their use as biocides

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011059532A1 (en) * 2009-11-10 2011-05-19 Dow Global Technologies Inc. Biocidal compositions and methods of use
WO2012044301A1 (en) * 2010-09-30 2012-04-05 Dow Global Technologies Llc Compositions of dibromomalonamide and their use as biocides
JP2013538850A (en) * 2010-09-30 2013-10-17 ダウ グローバル テクノロジーズ エルエルシー Composition of dibromomalonamide and its use as a biocide
CN107251902A (en) * 2010-09-30 2017-10-17 陶氏环球技术有限公司 The composition of dibromo malonamide and its purposes as biocide

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