JP2009096781A - Industrial antimicrobial composition - Google Patents
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Abstract
Description
本発明は、細菌や真菌等の微生物による腐敗からラテックスなどの樹脂エマルジョンや塗料、接着剤等の水系組成物を長期間にわたって保護する工業用抗菌組成物に関するものであり、詳しくは１，２−ベンズイソチアゾリン−３−オンと、一般式（１）
（式中、Ｒ１、Ｒ２はそれぞれ水素原子または炭素数１〜４の低級アルキル基を示す）
で示される１種以上の化合物を含有することを特徴とする工業用抗菌組成物に関するものである。
The present invention relates to an industrial antibacterial composition that protects a water-based composition such as a resin emulsion such as latex, a paint, and an adhesive over a long period of time from spoilage by microorganisms such as bacteria and fungi. Benzisothiazolin-3-one and general formula (1)
(Wherein R 1 and R 2 each represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms)
It is related with the industrial antibacterial composition characterized by containing 1 or more types of compounds shown by these.
１,２−ベンズイソチアゾリン−３−オンは微生物による腐敗に対し水系組成物を保護するための有効な殺菌剤として公知である。しかし、１,２−ベンズイソチアゾリン−３−オンは水に難溶性であり、従来、濃厚な水分散液の形で保存され、使用時に処理すべき水中へ分散して用いられている。しかしながらかかる水分散液は、処理される水系組成物中への添加量を調節するポンプを閉塞する傾向があり、また放置により沈降する傾向があるという欠点があった。それ故１,２−ベンズイソチアゾリン−３−オンの安定性に優れた濃厚溶液、即ち、冬季の屋外のような例えば−１０℃程度の低温下に長時間放置されても、結晶化や凝固を生じず、有効成分が安定に溶解していることが期待出来る濃厚溶液であって、また低温でも容易に注げる充分な流動性を有するものが所望されている。 1,2-Benzisothiazolin-3-one is known as an effective disinfectant for protecting aqueous compositions against spoilage by microorganisms. However, 1,2-benzisothiazolin-3-one is sparingly soluble in water, and is conventionally stored in the form of a concentrated aqueous dispersion and dispersed in water to be treated at the time of use. However, such an aqueous dispersion has a drawback in that it tends to block a pump that adjusts the amount added to the aqueous composition to be treated, and tends to settle upon standing. Therefore, a concentrated solution with excellent stability of 1,2-benzisothiazolin-3-one, that is, crystallization and coagulation even when left at a low temperature of, for example, about −10 ° C. for a long time, such as outdoors in winter. There is a demand for a concentrated solution that does not occur and can be expected to dissolve the active ingredient stably, and that has sufficient fluidity to be poured easily even at low temperatures.
１,２−ベンズイソチアゾリン−３−オンは、アルカリ金属の水酸化物又はアミン類と塩を形成し、これらの塩がそれぞれ水に容易に溶解する事は公知である。例えば、（特許文献１）には、１，２−ベンズイソチアゾリン−３−オンと、ジエタノールアミン、トリエタノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン及びモルホリンよりなるアミン群の内、２種或いはそれ以上のアミンを用いた組成物が記載されている。それまで１０℃程度の低温で固体沈殿物が発生していた事に対し、２種或いはそれ以上のアミンを組み合わせる事により、０℃までの範囲で安定性が向上したことが述べられているが、例えば冬季の屋外等、０℃以下の温度での貯蔵安定性は充分ではない。また、（特許文献２）には、１，２−ベンズイソチアゾリン−３−オンのアルカリ金属塩にプロピレングリコール、ポリプロピレングリコール、低級アルコールを使用した組成物が記載されている。しかしながらこのような工業用抗菌組成物でも、とくに１，２−ベンズイソチアゾリン−３−オンの配合率を高めた場合にはやはり０℃以下の温度での貯蔵安定性は充分ではなく、より低温においても安定であることが実用上求められる。また、（特許文献３）には、１，２−ベンズイソチアゾリン−３−オンとプロパンジアミンを含む組成物が記載されているが、なお低温においての安定性は充分ではなく、かつラテックスなどの樹脂エマルジョン等への相溶性が不充分であるという問題もある。 It is known that 1,2-benzisothiazolin-3-one forms a salt with an alkali metal hydroxide or amine, and each of these salts is readily soluble in water. For example, (Patent Document 1) includes 1,2-benzisothiazolin-3-one and two or more of amine groups consisting of diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine and morpholine. Compositions using amines are described. It was stated that the stability was improved in the range up to 0 ° C by combining two or more amines, whereas solid precipitates were generated at a low temperature of about 10 ° C until then. For example, storage stability at temperatures below 0 ° C., such as outdoors in winter, is not sufficient. (Patent Document 2) describes a composition using propylene glycol, polypropylene glycol, and a lower alcohol as an alkali metal salt of 1,2-benzisothiazolin-3-one. However, even with such an industrial antibacterial composition, especially when the blending ratio of 1,2-benzisothiazolin-3-one is increased, the storage stability at a temperature of 0 ° C. or lower is still insufficient, and at a lower temperature. Is also required for practical use. In addition, (Patent Document 3) describes a composition containing 1,2-benzisothiazolin-3-one and propanediamine, but the stability at low temperature is not sufficient, and a resin such as latex is used. There is also a problem that the compatibility with emulsions and the like is insufficient.
本発明者は、上記のような１，２−ベンズイソチアゾリン−３−オンの低温環境下における安定性を向上させる工業用抗菌組成物を提供することが、本発明の課題である。 It is an object of the present invention to provide an industrial antibacterial composition that improves the stability of 1,2-benzisothiazolin-3-one as described above in a low temperature environment.
本発明者は、このような課題を解決するため、鋭意研究の結果、１，２−ベンズイソチアゾリン−３−オンと特定の化合物を配合することにより低温安定性に優れた組成物が得られることを見出し本発明に至った。すなわち本発明は（１）１，２−ベンズイソチアゾリン−３−オンと、一般式（１）
（式中、Ｒ１、Ｒ２はそれぞれ水素原子または炭素数１〜４の低級アルキル基を示す）
で示される１種以上の化合物を含有することを特徴とする工業用抗菌組成物に関する。また、本発明は、（２）一般式（１）で示される化合物のうち、Ｒ１、Ｒ２がそれぞれ水素またはメチル基であることを特徴とする前記（１）に記載の工業用抗菌組成物に関する。また、本発明は、（３）一般式（１）で示される化合物のうち、Ｒ１、Ｒ２がともに水素であることを特徴とする前記（１）に記載の工業用抗菌組成物に関する。また、本発明は、（４）１，２−ベンズイソチアゾリン−３−オンが２０〜４０重量％の範囲、一般式（１）の化合物と１，２−ベンズイソチアゾリン−３−オンとの比が１：２〜２：１の範囲で含有することを特徴とする前記（１）〜（３）に記載の工業用抗菌組成物に関する。
In order to solve such problems, the present inventor has obtained a composition excellent in low-temperature stability by blending 1,2-benzisothiazolin-3-one and a specific compound as a result of intensive studies. And found the present invention. That is, the present invention relates to (1) 1,2-benzisothiazolin-3-one and general formula (1)
(Wherein R 1 and R 2 each represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms)
It contains the 1 or more types of compound shown by these, The industrial antibacterial composition characterized by the above-mentioned. In addition, the present invention provides the industrial antibacterial composition as described in (1) above, wherein, among the compounds represented by (2) general formula (1), R 1 and R 2 are each hydrogen or methyl group Related to things. The present invention also relates to (3) Among the compounds represented by the general formula (1), for Industrial antimicrobial composition according to (1), wherein R 1, R 2 are both hydrogen. In the present invention, (4) 1,2-benzisothiazolin-3-one is in the range of 20 to 40% by weight, and the ratio of the compound of general formula (1) to 1,2-benzisothiazolin-3-one is It contains in the range of 1: 2-2: 1, It is related with the industrial antimicrobial composition as described in said (1)-(3) characterized by the above-mentioned.
上記の組成物を用いることにより、低温安定性の優れた１，２−ベンズイソチアゾリン−３−オンを含有する組成物を得ることができる。 By using the above composition, a composition containing 1,2-benzisothiazolin-3-one having excellent low-temperature stability can be obtained.
本発明の工業用抗菌組成物は１，２−ベンズイソチアゾリン−３−オンと一般式（１）
（式中、Ｒ１、Ｒ２はそれぞれ水素原子または炭素数１〜４の低級アルキル基を示す）
で示される特定の化合物を含有したものであり、さらに、溶媒として水の他、グリコール系溶剤およびその誘導体等の溶媒、界面活性剤、キレート化剤、消泡剤、防錆剤、１，２−ベンズイソチアゾリン−３−オン以外の抗菌剤などを添加することが可能である。
The industrial antimicrobial composition of the present invention comprises 1,2-benzisothiazolin-3-one and general formula (1)
(Wherein R 1 and R 2 each represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms)
In addition to water as a solvent, solvents such as glycol solvents and derivatives thereof, surfactants, chelating agents, antifoaming agents, rust preventives, 1, 2 -It is possible to add antibacterial agents other than benzisothiazolin-3-one.
本発明の１，２−ベンズイソチアゾリン−３−オンの工業用殺菌組成物における含有率は、とくに限定されるものではないが、好ましくは２０〜４０重量％である。一般式（１）で示される化合物もまたとくに限定されるものではないが、好ましくはＲ１、Ｒ２がそれぞれ水素またはメチル基であり、より好ましくはＲ１、Ｒ２がともに水素である。この一般式（１）で示される化合物と１，２−ベンズイソチアゾリン−３−オンとの比が１：２〜２：１の範囲で含有することが好ましい。 The content of the 1,2-benzisothiazolin-3-one of the present invention in the industrial sterilizing composition is not particularly limited, but is preferably 20 to 40% by weight. The compound represented by the general formula (1) is also not particularly limited, but preferably R 1 and R 2 are each hydrogen or a methyl group, and more preferably R 1 and R 2 are both hydrogen. The ratio of the compound represented by the general formula (1) to 1,2-benzisothiazolin-3-one is preferably in the range of 1: 2 to 2: 1.
本発明の工業用抗菌組成物に配合できるグリコール系溶剤およびその誘導体等の溶媒としては、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ジエチレングリコールモノメチルエーテル等が、その他の溶媒としてはグリセリン、ジグリセリン等のグリセリン系溶剤およびその誘導体等、ジメチルスルホキシド、γ―ブチロラクトン、Ｎ−メチル−ピロリドン、ジメチルアセトアミドなどの極性溶剤を使用することができる。これらの溶剤は、単独で使用しても良く、２種以上を混合して使用することも可能である。 Examples of solvents such as glycol solvents and derivatives thereof that can be incorporated into the industrial antibacterial composition of the present invention include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, and diethylene glycol monomethyl ether. Other solvents include glycerin. Further, polar solvents such as glycerol-based solvents such as diglycerol and derivatives thereof, dimethyl sulfoxide, γ-butyrolactone, N-methyl-pyrrolidone, dimethylacetamide, and the like can be used. These solvents may be used alone or in combination of two or more.
本発明の工業用抗菌組成物は、目的および用途に応じて製剤化すればよいが通常は扱いやすさの観点から液剤として調製することができる。液剤として調製するには、例えば、上記した１，２−ベンズイソチアゾリン−３−オン、一般式（１）で示される化合物、および必要に応じた溶媒を、配合して混合すればよい。このようにして得られる本発明の工業用抗菌組成物は、例えば、−５℃程度の低温環境下においても、１，２−ベンズイソチアゾリン−３−オンの分離、結晶析出や濁りが生じることを防止することができ、しかも、細菌、酵母、かびなどの微生物に対して、１，２−ベンズイソチアゾリン−３−オンが有する優れた効果を発現することができる。そのため、本発明の工業用抗菌組成物は、例えば、切削油などの金属加工用油剤、製紙パルプ工場や冷却水循環工程などの種々の産業用水、ＳＢＲやＮＢＲなどの種々の樹脂エマルジョン、カゼイン、デンプンスラリー、紙用塗工液、サイズ剤、紙力増強剤、水性塗料、インキ、接着剤、コンクリート混和剤などの各種工業製品に対して好適に用いられる。 The industrial antibacterial composition of the present invention may be formulated according to the purpose and application, but can be usually prepared as a liquid from the viewpoint of ease of handling. In order to prepare as a liquid agent, for example, the above-described 1,2-benzisothiazolin-3-one, the compound represented by the general formula (1), and a solvent as necessary may be blended and mixed. The industrial antibacterial composition of the present invention thus obtained is capable of causing separation, crystal precipitation and turbidity of 1,2-benzisothiazolin-3-one even in a low temperature environment of, for example, about −5 ° C. In addition, the excellent effects of 1,2-benzisothiazolin-3-one can be expressed against microorganisms such as bacteria, yeast, and fungi. Therefore, the industrial antibacterial composition of the present invention includes, for example, metal processing oils such as cutting oil, various industrial waters such as paper pulp mills and cooling water circulation processes, various resin emulsions such as SBR and NBR, casein, starch It is suitably used for various industrial products such as slurry, paper coating liquid, sizing agent, paper strength enhancer, water-based paint, ink, adhesive and concrete admixture.
なお、本発明の工業用抗菌組成物は、その適用対象に応じて添加量を適宜決定すればよいが、例えば、５〜１０００ｍｇ（有効成分）／ｋｇ（製品）、好ましくは、２０〜５００ｍｇ（有効成分）／ｋｇ（製品）の濃度として用いられる。 In addition, the industrial antibacterial composition of the present invention may be appropriately determined depending on the application target, and is, for example, 5 to 1000 mg (active ingredient) / kg (product), preferably 20 to 500 mg ( Used as concentration of active ingredient) / kg (product).
本発明を実施例、試験例により更に詳しく説明するが、本発明がこれらによって限定されるものではない。
（工業用抗菌組成物実施例）
下記、表１に従って、各材料を混合し充分攪拌することにより均一な液体として実施例１〜６、比較例１〜３の工業用抗菌組成物を得た。なお、表１に示した配合比率はすべて重量％であり、表中に表記した略号と、商品名、製造元などを下記に示す。
・ＢＩＴ；１，２−ベンズイソチアゾリン−３−オン（アーチ・ケミカルズ（株）製、１，２−ベンズイソチアゾリン−３−オンの含有量８５重量％）
・ＡＥＥ；２−（２−アミノエトキシ）エタノール（和光純薬工業（株）製）
・ＤＭＡＥＥ；２−｛２−（ジメチルアミノ）エトキシ｝エタノール（東京化成工業（株）製）
・ＰＧ；プロピレングリコール（（株）アデカ製）
・ＰＥＧ；ポリエチレングリコール（平均分子量２００、三洋化成工業（株）製）
・ＤＰＧ；ジプロピレングリコール（（株）アデカ製）
・ＰＤＡ；１，２−プロピレンジアミン（広栄化学工業（株）製）
The present invention will be described in more detail with reference to examples and test examples, but the present invention is not limited thereto.
(Examples of industrial antibacterial compositions)
According to Table 1 below, the materials were mixed and sufficiently stirred to obtain industrial antibacterial compositions of Examples 1 to 6 and Comparative Examples 1 to 3 as uniform liquids. In addition, all the mixture ratios shown in Table 1 are% by weight, and abbreviations, trade names, manufacturers, etc. shown in the table are shown below.
BIT: 1,2-benzisothiazolin-3-one (manufactured by Arch Chemicals Co., Ltd., content of 1,2-benzisothiazolin-3-one of 85% by weight)
AEE; 2- (2-aminoethoxy) ethanol (Wako Pure Chemical Industries, Ltd.)
DMAEE; 2- {2- (dimethylamino) ethoxy} ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ PG: Propylene glycol (manufactured by Adeka)
・ PEG: Polyethylene glycol (average molecular weight 200, manufactured by Sanyo Chemical Industries, Ltd.)
・ DPG: Dipropylene glycol (manufactured by Adeka)
PDA: 1,2-propylenediamine (manufactured by Guangei Chemical Industry Co., Ltd.)
（安定性）
実施例１〜６、比較例１〜３の工業用抗菌組成物を室温、０℃、−１０℃に１ヶ月保管し、各試料の安定性を評価した。
○；沈殿物の生成などが認められず安定なもの
×；沈殿物が生成するなど不安定なもの
(Stability)
The antibacterial compositions for industrial use of Examples 1 to 6 and Comparative Examples 1 to 3 were stored at room temperature, 0 ° C., and −10 ° C. for 1 month, and the stability of each sample was evaluated.
○: Stable with no formation of precipitate x: Unstable with formation of precipitate
（相溶性）
実施例１〜６、比較例１〜３の工業用抗菌組成物をＳＢＲラテックス（ＮＳＫ−７２、日本エイアンドエル（株）製）と混合し相溶性を評価した。
○；緩やかな攪拌で相溶するもの
△；強い攪拌で相溶するもの
×；凝集物が生成し相溶性が悪いもの
(Compatibility)
The industrial antibacterial compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were mixed with SBR latex (NSK-72, manufactured by Nippon A & L Co., Ltd.) to evaluate the compatibility.
○: compatible with gentle stirring Δ; compatible with strong stirring ×: agglomerates formed and poor compatibility
１，２−ベンズイソチアゾリン−３−オンと本発明の化合物を含有する実施例１〜６の工業用抗菌組成物は、いずれも安定性、ＳＢＲラテックスに対する相溶性に優れたものであった。しかしながら、本発明の化合物を含有しない比較例１〜３はとくに低温時の安定性が不十分であったり、ＳＢＲラテックスに対する相溶性が不十分であったりして、１，２−ベンズイソチアゾリン−３−オンを高濃度で含有する工業用抗菌組成物としては満足できるものではなかった。 The industrial antibacterial compositions of Examples 1 to 6 containing 1,2-benzisothiazolin-3-one and the compound of the present invention were all excellent in stability and compatibility with SBR latex. However, Comparative Examples 1 to 3 which do not contain the compound of the present invention have insufficient stability at low temperatures or insufficient compatibility with SBR latex, and 1,2-benzisothiazoline-3 -It was not satisfactory as an industrial antibacterial composition containing a high concentration of ON.
本発明により、１，２−ベンズイソチアゾリン−３−オンを高濃度含有し、とくに低温時の安定性に優れ、ＳＢＲラテックスなどの対象物への相溶性に優れた工業用抗菌組成物として好適に用いることができるものである。
According to the present invention, it contains a high concentration of 1,2-benzisothiazolin-3-one, and is particularly suitable as an industrial antibacterial composition having excellent stability at low temperatures and excellent compatibility with objects such as SBR latex. It can be used.
Claims (4)
（式中、Ｒ１、Ｒ２はそれぞれ水素原子または炭素数１〜４の低級アルキル基を示す）
で示される１種以上の化合物を含有することを特徴とする工業用抗菌組成物。 1,2-benzisothiazolin-3-one and general formula (1)
(Wherein R 1 and R 2 each represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms)
1. An industrial antibacterial composition comprising one or more compounds represented by the formula:
The range of 1,2-benzisothiazolin-3-one is 20 to 40% by weight, and the ratio of the compound of general formula (1) to 1,2-benzisothiazolin-3-one is 1: 2 to 2: 1. The industrial antibacterial composition according to any one of claims 1 to 3, wherein
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| JP5907303B1 (en) * | 2015-07-08 | 2016-04-26 | 株式会社メディオクリタス | Remote management system for water-soluble cutting oil |
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|---|---|---|---|---|
| JP2010515731A (en) * | 2007-01-12 | 2010-05-13 | アングス ケミカル カンパニー | Biocidal compositions for amino alcohols and aqueous systems |
| JP2008280334A (en) * | 2007-05-08 | 2008-11-20 | Rohm & Haas Co | Stabilized fluid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5907303B1 (en) * | 2015-07-08 | 2016-04-26 | 株式会社メディオクリタス | Remote management system for water-soluble cutting oil |
| JP2017019024A (en) * | 2015-07-08 | 2017-01-26 | 株式会社メディオクリタス | Remote management system of water-soluble cutting oil |
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