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JP2005089348A - New microbicide composition - Google Patents

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JP2005089348A
JP2005089348A JP2003322894A JP2003322894A JP2005089348A JP 2005089348 A JP2005089348 A JP 2005089348A JP 2003322894 A JP2003322894 A JP 2003322894A JP 2003322894 A JP2003322894 A JP 2003322894A JP 2005089348 A JP2005089348 A JP 2005089348A
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isothiazolin
iodoacetamide
benzisothiazolin
microbicidal
octyl
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Ryoji Funatsu
亮二 船津
Takashi Ono
喬視 大野
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KUREASUTAA KK
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KUREASUTAA KK
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Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new microbicide composition that is negative in Ames and exhibits stable microbicidal effect in an aqueous system for a long period of time. <P>SOLUTION: The microbicide composition is obtained by formulating iodoacetamide with one or more kinds selected from isothiazolin-based compounds of (1) 2-methyl-4-isothiazolin-3-one, (2) 2-n-octyl-4-isothiazolin-3-one, (3) 1,2-benzisothiazolin-3-one, (4) 4,5-dicloro-2-n-octyl-4-isothiazolin-3-one and (5) N-butyl-1,2-benzisothiazolin-3-one. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、諸工業分野において利用されている接着剤、樹脂エマルジョン、インキ、糊剤、塗料、紙、繊維および建材等の水系分散物の微生物汚染を防止し、かつ環境負荷の恐れのない新規な殺微生物組成物に関するものである。   The present invention is a novel material that prevents microbial contamination of aqueous dispersions such as adhesives, resin emulsions, inks, glues, paints, paper, fibers and building materials used in various industrial fields and has no fear of environmental impact. A microbicidal composition.

近年、諸工業分野において利用されている接着剤、樹脂エマルジョン、インキ、糊剤、塗料、紙、繊維および建材等の水系分散物製品およびその製造工程の水系において、その用水や製品に含有されている有機化合物や微量な無機物を栄養源にして、種々の微生物、すなわち細菌、酵母、糸状菌、藻類が増殖して、製品の品質や生産性を著しく低下させるという問題がある。これら問題に対処するため、多種多様な殺菌剤および殺菌組成物が製品等に添加されている。そのような殺菌組成物として、例えば、5―クロロ―2―メチル―4―イソチアゾリン―3−オンと2―メチル―4―イソチアゾリン―3−オンとの混合物(ケミクレア社製9:1混合物商品名:ゾ−ネン−F、ローム&ハ−ス社製3:1混合物商品名:ケ−ソンLX SF25)(特許文献1)またはそれらの金属コンプレックス塩の混合物(ケミクレア社製3:1混合物商品名:ゾ−ネン−C、ローム&ハ−ス社製3:1混合物商品名:ケ−ソンWT)の単独製剤や、それらと、例えば、2−ブロモ−2−ニトロプロパン−1,3−ジオ−ル、2,2−ジブロモ−2−ニトロ−1−エタノ−ル、1,2−ビス(ブロモアセトオキシ)エタン等の有機ブロモ系化合物や更には、メチレンビスチオシアナ−ト、2−(4−チオシアノメチルチオ)ベンゾチアゾ−ル、1,2−ベンズイソチアゾリン−3−オン等との組合せ配合剤が汎用されている(特許文献2および3)。しかしながら、これらはいずれも、エイムズ試験において陽性であり、人体に対して変異原性を示す。更に、2,2−ジブロモ−3−ニトリロプロピオンアミド、2−ブロモ−2−ニトロプロパン−1,3−ジオ−ル、2,2−ジブロモ−2−ニトロ−1−エタノ−ル、1,2−ビス(ブロモアセトオキシ)エタン等の有機ブロモ系化合物や、更には、メチレンビスチオシアナ−ト、2−(4−チオシアノメチルチオ)ベンゾチアゾ−ル等が配合されている組合せ配合剤の場合、いずれも溶剤に希釈されて汎用されているため、水性系分散物の微生物汚染防止のために使用すると、溶剤が揮発性有機化合物(VOC)として大気中に揮散したり、溶剤が水系に流入してCOD(化学酸素要求量)を上昇させ、少なからず環境への負荷を生じさせるという問題があった。
特公昭46−21240号公報 特公昭60−54281号公報 特公昭58−4682号公報
In recent years, in aqueous dispersion products such as adhesives, resin emulsions, inks, glues, paints, paper, fibers, and building materials used in various industrial fields, and in the water systems of their manufacturing processes, they are contained in the water and products used for them. There is a problem in that various microorganisms, that is, bacteria, yeast, filamentous fungi, and algae grow by using organic compounds and trace inorganic substances as nutrients, and the quality and productivity of the product are significantly reduced. In order to address these problems, a wide variety of bactericides and bactericidal compositions have been added to products and the like. As such a bactericidal composition, for example, a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one (9: 1 mixture trade name manufactured by Chemicrea) : Zonen-F, Rohm & Haas 3: 1 mixture trade name: Kaeson LX SF25) (patent document 1) or a mixture of their metal complex salts (Chemclea 3: 1 mixture trade name) : Zonen-C, 3: 1 mixture manufactured by Rohm & Haas Co., Ltd., trade name: Kason WT), and these, for example, 2-bromo-2-nitropropane-1,3-dio -Bromo, 2,2-dibromo-2-nitro-1-ethanol, organic bromo compounds such as 1,2-bis (bromoacetoxy) ethane, and further methylene bis thiocyanate, 2- ( 4-thiocyanomethylthio ) Combination compounding agents such as benzothiazol and 1,2-benzisothiazolin-3-one are widely used (Patent Documents 2 and 3). However, both of these are positive in the Ames test and are mutagenic to the human body. Further, 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitro-1-ethanol, 1,2 -In the case of a combination compounding agent in which an organic bromo compound such as bis (bromoacetoxy) ethane, or methylenebisthiocyanate, 2- (4-thiocyanomethylthio) benzothiazol or the like is compounded, Since both are diluted in solvents and used for general purposes, when used to prevent microbial contamination of aqueous dispersions, the solvents are volatilized into the atmosphere as volatile organic compounds (VOC), or the solvent flows into the aqueous system. As a result, there has been a problem that the COD (chemical oxygen demand) is increased and an environmental load is generated.
Japanese Patent Publication No.46-21240 Japanese Examined Patent Publication No. 60-54281 Japanese Patent Publication No.58-4682

本発明は、上記事情に鑑みてなされたものであり、エイムズ陰性でかつ水性系で長期間に亘り安定した殺微生物効果を発揮できる新規な殺微生物組成物を提供することを目的とするものである。   The present invention has been made in view of the above circumstances, and aims to provide a novel microbicidal composition which is Ames-negative and can exhibit a stable microbicidal effect over a long period of time in an aqueous system. is there.

本発明者らは、新規な殺微生物組成物を開発すべく種々研究を重ねた結果、従来の工業用殺菌剤として用いられていたヨードアセトアミドと、2―メチル―4―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、1,2−ベンズイソチアゾリン−3−オン、4,5−ジクロロ−2−n−オクチル−4−イソチアゾリン−3−オン、およびN−ブチル−1,2−ベンズイソチアゾリン−3−オンよりなる群から選ばれる1種または2種以上とを配合させることによって、エイムズ陰性でありかつ水性系で長期間に亘り安定した殺微生物効果発揮できる殺微生物組成物を作成できることを見出し、この知見に基づいて本発明をなすに至った。すなわち、本発明は、ヨードアセトアミドと、下記の(1)〜(5)のイソチアゾリン系化合物から選ばれる1種または2種以上とを含有する新規な殺微生物組成物を提供するものである
(1)2−メチル−4−イソチアゾリン−3−オン
(2)2−n−オクチル−4−イソチアゾリン−3−オン
(3)1,2−ベンズイソチアゾリン−3−オン
(4)4,5−ジクロロ−2−n−オクチル−4−イソチアゾリン−3−オン
(5)N−ブチル−1,2−ベンズイソチアゾリン−3−オン
好ましくは、ヨードアセトアミドと、前記イソチアゾリン系化合物全体との配合割合は、重量に基づき10:1から1:10である。
As a result of various studies to develop a novel microbicidal composition, the present inventors have found that iodoacetamide and 2-methyl-4-isothiazolin-3-one, which have been used as conventional industrial fungicides, 2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and N-butyl- Microbicidal agent that is Ames-negative and can exhibit a stable microbicidal effect over a long period of time in an aqueous system by incorporating one or more selected from the group consisting of 1,2-benzisothiazolin-3-one The present inventors have found that a composition can be prepared and have come to make the present invention based on this finding. That is, the present invention provides a novel microbicidal composition containing iodoacetamide and one or more selected from the following (1) to (5) isothiazoline compounds (1). ) 2-Methyl-4-isothiazolin-3-one (2) 2-n-octyl-4-isothiazolin-3-one (3) 1,2-benzisothiazolin-3-one (4) 4,5-dichloro- 2-n-octyl-4-isothiazolin-3-one (5) N-butyl-1,2-benzisothiazolin-3-one Preferably, the blending ratio of iodoacetamide and the entire isothiazoline-based compound is Based on 10: 1 to 1:10.

本発明の新規な殺微生物組成物は、ヨードアセトアミドと、上記の(1)〜(5)のイソチアゾリン系化合物から選ばれる1種または2種以上とを含有することによって、エイムズ陰性であり、かつ水性系で長期間に亘り安定な殺微生物効果を発揮できる。従って、本発明は、環境負荷の問題のない、長期間に亘り安定な水性殺微生物製剤の調製を可能にする。   The novel microbicidal composition of the present invention is Ames-negative by containing iodoacetamide and one or more selected from the above (1) to (5) isothiazoline compounds, and A stable microbicidal effect can be exhibited over a long period of time in an aqueous system. Therefore, the present invention enables the preparation of an aqueous microbicidal preparation that is stable over a long period of time without the problem of environmental burden.

本発明において用いられるヨードアセトアミド、および上記(1)〜(5)のイソチアゾリン系化合物は、いずれも工業用殺菌剤として広く使用されており、市販品として容易に入手することができる。上記(1)〜(5)のイソチアゾリン系化合物は、単独で用いても、2種以上を組み合わせて用いてもよい。   The iodoacetamide used in the present invention and the isothiazoline compounds (1) to (5) are widely used as industrial disinfectants and can be easily obtained as commercial products. The isothiazoline-based compounds (1) to (5) may be used alone or in combination of two or more.

ヨードアセトアミドと、上記(1)〜(5)のイソチアゾリン系化合物全体との配合割合は、好ましくは、重量に基づき50:1から1:50であり、より好ましくは10:1から1:10であり、さらに好ましくは5:1から1:5である。係る範囲の配合割合を有する場合に特に長期間に亘り安定した防腐効果を発揮できるが、本願発明の目的を達成できる限り、上記範囲に限定されない。   The blending ratio of iodoacetamide and the whole of the isothiazoline compounds (1) to (5) is preferably 50: 1 to 1:50, more preferably 10: 1 to 1:10, based on weight. More preferably 5: 1 to 1: 5. In the case of having such a blending ratio, a stable antiseptic effect can be exhibited particularly for a long period of time, but it is not limited to the above range as long as the object of the present invention can be achieved.

本発明の1つの実施形態において、本発明の殺微生物組成物は水溶液の形態である。用いられる水は、水道水、イオン交換水、蒸留水、工業用水等のいずれでもよく、特に限定されない。本発明の殺微生物組成物水溶液は、殺菌剤を水に溶解させる任意の公知の方法によって調製することができる。例えば、ヨードアセトアミドと、上記の(1)〜(5)のイソチアゾリン系化合物の1種または2種以上とを、界面活性剤無しにまたは界面活性剤と共に水に添加し、混合することによって、本発明の殺微生物組成物水溶液を調製することができる。界面活性剤としては、例えば、アニオン界面活性剤、ノニオン界面活性剤等、任意の界面活性剤を用いることができる。   In one embodiment of the invention, the microbicidal composition of the invention is in the form of an aqueous solution. The water used may be any of tap water, ion exchange water, distilled water, industrial water and the like, and is not particularly limited. The aqueous microbicidal composition solution of the present invention can be prepared by any known method for dissolving a bactericide in water. For example, iodoacetamide and one or more of the isothiazoline compounds (1) to (5) described above are added to water without a surfactant or together with a surfactant and mixed. An aqueous microbicidal composition solution of the invention can be prepared. As the surfactant, for example, any surfactant such as an anionic surfactant and a nonionic surfactant can be used.

本発明の別の実施形態において、本発明の殺微生物組成物は水系分散液の形態である。用いられる水は、前記の水溶液と同様に特に限定されない。本発明の殺微生物組成物分散液は、殺菌剤を水に分散させる任意の公知の方法によって調製することができる。例えば、ヨードアセトアミドと、上記の(1)〜(5)のイソチアゾリン系化合物の1種または2種以上とを、乳化剤、分散剤、填料、粘度調整剤、電解質、および/または界面補強剤等と共に水に添加し、混合し、さらにコロイドミル、ボ−ルミル、サンドミル、ビ−ズミル等の任意の粉砕機で処理することによって、本発明の殺微生物組成物分散液を調製することができる。乳化剤および分散剤としては、例えば、アニオン界面活性剤、ノニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、高分子界面活性剤などの公知の界面活性剤があげられる。填料としては、例えば、珪酸、ベントナイト、酸性白土、クレ−、カオリン、層状粘土鉱物があげられる。粘度調整剤としては、例えば、カルボキシメチルセルロ−スナトリウム塩、ポリビニルピロリドン、ポリビニルアルコ−ル、グアガム、アルギン酸ナトリウム、アラビアガム等があげられる。電解質としては、例えば、塩化ナトリウム、塩化カリウム等の無機化合物、シュウ酸、酒石酸、マレイン酸等の有機化合物があげられる。界面補強剤としては、例えば、ステアリン酸等の高級脂肪酸類、セタノ−ル等の高級アルコ−ル類、炭化水素類等があげられる。   In another embodiment of the invention, the microbicidal composition of the invention is in the form of an aqueous dispersion. The water used is not particularly limited as in the case of the aqueous solution. The microbicidal composition dispersion of the present invention can be prepared by any known method for dispersing a bactericide in water. For example, iodoacetamide and one or more of the isothiazoline compounds (1) to (5) above are used together with an emulsifier, a dispersant, a filler, a viscosity modifier, an electrolyte, and / or an interfacial reinforcing agent. The microbicidal composition dispersion of the present invention can be prepared by adding to water, mixing, and further treating with an optional pulverizer such as a colloid mill, ball mill, sand mill, or bead mill. Examples of emulsifiers and dispersants include known surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and polymeric surfactants. Examples of the filler include silicic acid, bentonite, acid clay, clay, kaolin, and layered clay mineral. Examples of the viscosity modifier include carboxymethyl cellulose sodium salt, polyvinyl pyrrolidone, polyvinyl alcohol, guar gum, sodium alginate, gum arabic and the like. Examples of the electrolyte include inorganic compounds such as sodium chloride and potassium chloride, and organic compounds such as oxalic acid, tartaric acid, and maleic acid. Examples of the interfacial reinforcing agent include higher fatty acids such as stearic acid, higher alcohols such as cetanol, and hydrocarbons.

本発明の新規殺微生物組成物の使用に際しての添加量は、微生物濃度により異なるが、接着剤、樹脂エマルジョン、インキ、糊剤、塗料、紙、繊維および建材等の諸工業分野において利用されている水系分散物での使用において、20〜500ppm程度であり、この範囲で特に良好な殺微生物効果が得られる。   The amount of addition of the novel microbicidal composition of the present invention varies depending on the microbial concentration, but is used in various industrial fields such as adhesives, resin emulsions, inks, glues, paints, paper, fibers and building materials. When used in an aqueous dispersion, it is about 20 to 500 ppm, and a particularly good microbicidal effect can be obtained in this range.

本発明の殺微生物組成物は、本発明の目的を妨げない限り、必要に応じて、任意の安定剤、緩衝剤等をさらに含有していて差し支えない。   The microbicidal composition of the present invention may further contain an optional stabilizer, buffering agent, etc. as necessary, as long as the object of the present invention is not hindered.

次に本発明を実施例によりさらに詳細に説明するが、本発明はこれら例によってなんら限定されるものではない。   EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.

表1に示す配合組成で、ヨードアセトアミドと、指示されたイソチアゾリン系化合物とを水に溶解または分散させて、表1に示す配合組成の殺微生物組成物を調製した(実施例1〜5、比較例1〜6)

Figure 2005089348
In the formulation shown in Table 1, iodoacetamide and the indicated isothiazoline-based compound were dissolved or dispersed in water to prepare a microbicidal composition having the formulation shown in Table 1 (Examples 1 to 5, comparison) Examples 1-6)
Figure 2005089348

各組成物について、以下に示す試験をおこなった。   Each composition was subjected to the following tests.

(1)紙力増強剤における菌増殖防止試験
紙力増強剤100mlに、濃度が50ppm、100ppm、300ppmになるように各殺微生物組成物を添加し、予め腐敗(1ml当り腐敗菌数10)させておいた紙力増強剤1mlを加え、これを32℃の恒温器に保存した。紙力増強剤中の生菌数を経時的に測定した。その結果を表2に示す:

Figure 2005089348
(1) the bacterial growth prevention test strength agent 100ml in paper strength agent, the concentration is added 50 ppm, 100 ppm, so as to 300ppm each microbicidal compositions, pre rot (1ml per putrefactive bacteria number 108) 1 ml of the paper strength enhancer which had been allowed to be added was added and stored in a thermostat at 32 ° C. The number of viable bacteria in the paper strength enhancer was measured over time. The results are shown in Table 2:
Figure 2005089348

(2)水性塗料における菌増殖防止試験
水性塗料100mlに、濃度が50ppm、100ppm、300ppmになるように各殺微生物組成物を添加し、予め腐敗(1ml当り腐敗菌数10)させておいた水性塗料1mlを加え、これを32℃の恒温器に保存した。水性塗料中の生菌数を経時的に測定した。その結果を表3に示す:

Figure 2005089348
(2) Bacteria growth prevention test in water-based paints Each microbicidal composition was added to 100 ml of water-based paints so that the concentration was 50 ppm, 100 ppm, and 300 ppm, and was previously spoiled (10 8 spoilage bacteria per ml). 1 ml of water-based paint was added and stored in a thermostat at 32 ° C. The number of viable bacteria in the aqueous paint was measured over time. The results are shown in Table 3:
Figure 2005089348

これら結果から明らかであるように、ヨードアセトアミドと、2−メチル−4−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、1,2−ベンズイソチアゾリン−3−オン、4,5−ジクロロ−2−n−オクチル−4−イソチアゾリン−3−オン、およびN−ブチル−1,2−ベンズイソチアゾリン−3−オンよりなる群から選ばれるイソチアゾリン系化合物とを含有する本発明の殺微生物組成物(実施例1から5)は、水性系において、50から300ppmの濃度範囲で、4週間という長期間に亘り高い殺微生物効果を示すことができた。一方、ヨードアセトアミドのみ含有する組成物(比較例1)では、50および100ppmでは2週間目に既に菌の増殖が認められ、300ppmでも4週間後には菌の顕著な増殖が認められた。また、上記のイソチアゾリン系化合物のみを含有する組成物(比較例2から6)では、1週間後に既に菌の増殖が認められ、2週間後にはブランクとほぼ同程度まで菌が増殖し、ほとんど殺微生物効果を示すことができなかった。   As is apparent from these results, iodoacetamide and 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, The present invention contains an isothiazoline compound selected from the group consisting of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and N-butyl-1,2-benzisothiazolin-3-one The microbicidal compositions (Examples 1 to 5) in the aqueous system were able to show a high microbicidal effect over a long period of 4 weeks in a concentration range of 50 to 300 ppm in an aqueous system. On the other hand, in the composition containing only iodoacetamide (Comparative Example 1), the growth of bacteria was already observed at 2 weeks at 50 and 100 ppm, and the remarkable growth of bacteria was observed after 4 weeks even at 300 ppm. In addition, in the composition containing only the above isothiazoline-based compound (Comparative Examples 2 to 6), the growth of bacteria was already observed after 1 week, and after 2 weeks, the bacteria grew to almost the same level as the blank, and almost killed. The microbial effect could not be shown.

Claims (2)

ヨードアセトアミドと、下記の(1)〜(5)のイソチアゾリン系化合物から選ばれる1種または2種以上とを含有する殺微生物組成物
(1)2−メチル−4−イソチアゾリン−3−オン
(2)2−n−オクチル−4−イソチアゾリン−3−オン
(3)1,2−ベンズイソチアゾリン−3−オン
(4)4,5−ジクロロ−2−n−オクチル−4−イソチアゾリン−3−オン
(5)N−ブチル−1,2−ベンズイソチアゾリン−3−オン。
Microbicidal composition comprising iodoacetamide and one or more selected from the following (1) to (5) isothiazoline compounds (1) 2-methyl-4-isothiazolin-3-one (2 ) 2-n-octyl-4-isothiazolin-3-one (3) 1,2-benzisothiazolin-3-one (4) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one ( 5) N-butyl-1,2-benzisothiazolin-3-one.
前記ヨードアセトアミドと、前記イソチアゾリン系化合物全体との配合割合が、重量に基づき10:1から1:10であることを特徴とする請求項1記載の殺微生物組成物。   The microbicidal composition according to claim 1, wherein the blending ratio of the iodoacetamide and the whole isothiazoline-based compound is 10: 1 to 1:10 based on weight.
JP2003322894A 2003-09-16 2003-09-16 New microbicide composition Pending JP2005089348A (en)

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