JP3176676B2 - Sterilizing composition - Google Patents
Sterilizing compositionInfo
- Publication number
- JP3176676B2 JP3176676B2 JP35639691A JP35639691A JP3176676B2 JP 3176676 B2 JP3176676 B2 JP 3176676B2 JP 35639691 A JP35639691 A JP 35639691A JP 35639691 A JP35639691 A JP 35639691A JP 3176676 B2 JP3176676 B2 JP 3176676B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- isothiazolone
- present
- stability
- germicidal
- 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
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は水系分散物が微生物汚染
を受けることを防止するための殺菌組成物に関するもの
であり、特に安定性を改良した殺菌組成物に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bactericidal composition for preventing an aqueous dispersion from being contaminated with microorganisms, and more particularly to a bactericidal composition having improved stability.
【０００２】[0002]
【従来の技術および発明が解決しようとする課題】従
来、工業用殺菌剤として多くの化合物が使用されてい
る。これらのうち、コスト当りの効果の優れているもの
の一つとして一般式（Ｉ）で示されるイソチアゾロン系
化合物があげられる。イソチアゾロン系化合物は、接着
剤、塗料、紙、繊維および建材等の諸工業分野において
利用されている天然ゴムラテックス、合成ゴムラテック
ス、アクリル系エマルジョン、酢酸ビニル系エマルジョ
ンおよびこれらの混合物等の合成高分子水系分散物の腐
敗、着色等の微生物汚染を防止するために添加されるこ
とが多い。しかし、このイソチアゾロン系化合物は安定
性が悪く、これを向上させるため、マグネシウム、カル
シウム等の各種金属塩を添加した殺菌組成物として使用
されているが、上記の合成高分子水系分散物に添加した
とき、殺菌組成物中に含まれる金属塩が原因となって合
成高分子水系分散物が凝集するという致命的な問題を生
じる。この問題を避けるために特開昭６０−９６６５２
号には、上記殺菌組成物にアニオン性界面活性剤を添加
する方法が提案されているが、この方法では殺菌組成物
を水で希釈し添加する必要があり、煩雑さを伴い、また
添加量が制限されたり、希釈液の安定性が著しく低下す
る等の問題が起こるため実用的ではない。また、イソチ
アゾロン系化合物の殺菌組成物から金属塩を除去したも
のはこのような凝集物の発生は認められないが、殺菌組
成物としての安定性は著しく低下するため実用に到底耐
えられない欠点を有する。特開平１−１７５９０５には
金属塩を含まないイソチアゾロン系化合物にアニオンお
よびノニオン界面活性剤を添加することによって安定化
する方法が提案されているが、製品安定性は十分ではな
い。BACKGROUND OF THE INVENTION Conventionally, many compounds have been used as industrial fungicides. Among them, an isothiazolone-based compound represented by the general formula (I) is one of those having excellent effects per cost. Isothiazolone compounds are synthetic polymers such as natural rubber latex, synthetic rubber latex, acrylic emulsion, vinyl acetate emulsion and mixtures thereof used in various industrial fields such as adhesives, paints, papers, fibers and building materials. It is often added to prevent microbial contamination such as spoilage and coloring of the aqueous dispersion. However, this isothiazolone-based compound has poor stability and is used as a bactericidal composition to which various metal salts such as magnesium and calcium are added to improve the stability. At this time, a fatal problem arises in that the synthetic polymer aqueous dispersion aggregates due to the metal salt contained in the sterilizing composition. To avoid this problem, Japanese Patent Application Laid-Open No. 60-96652
No., a method of adding an anionic surfactant to the germicidal composition is proposed, but in this method, it is necessary to add the bactericidal composition diluted with water, which is cumbersome, and requires an additional amount. And the stability of the diluent is significantly reduced, which is not practical. In addition, the generation of such aggregates is not recognized in the case where the metal salt is removed from the bactericidal composition of the isothiazolone-based compound. Have. JP-A-1-175905 proposes a method for stabilizing an isothiazolone-based compound containing no metal salt by adding an anionic or nonionic surfactant, but the product stability is not sufficient.
【０００３】このように従来のイソチアゾロン系化合物
の金属塩安定剤含有殺菌組成物を水で希釈することなし
に合成高分子水系分散物に添加すると凝集物が発生し、
合成高分子水系分散物の品質上重大な問題となってい
た。一方、凝集物の発生が起こらないように金属塩を含
有していないイソチアゾロン系化合物を用いた殺菌組成
物は安定性が低く、実用上問題となっていた。[0003] When a conventional sterilizing composition containing a metal salt stabilizer of an isothiazolone compound is added to a synthetic polymer aqueous dispersion without diluting with water, aggregates are generated,
This has been a serious problem in the quality of the synthetic polymer aqueous dispersion. On the other hand, a germicidal composition using an isothiazolone-based compound containing no metal salt so as not to generate aggregates has low stability and has been a practical problem.
【０００４】[0004]
【課題を解決するための手段】本発明者は前記欠点を改
良すべく鋭意研究の結果、前記の欠点が改良されること
を見いだし、本発明を完成した。発明は、一般式（Ｉ） （式中ＸおよびＹは同じかまたは異なり水素またはハロ
ゲンを示す）で表される化合物の少なくとも一種を有効
成分とし、臭素酸、よう素酸、過よう素酸またはこれら
の塩から選ばれる１種以上を安定剤として含有する殺菌
組成物である。以下本発明について詳細に説明する。Means for Solving the Problems The present inventor has made intensive studies to improve the above-mentioned drawbacks, and as a result, found that the above-mentioned drawbacks were improved, and completed the present invention. The invention relates to a compound of the general formula (I) (Wherein X and Y are the same or different and represent hydrogen or halogen), and at least one compound selected from the group consisting of bromate, iodate, periodate and salts thereof as an active ingredient A bactericidal composition containing the above as a stabilizer. Hereinafter, the present invention will be described in detail.
【０００５】本発明で使用するイソチアゾロン系化合物
は殺菌、殺カビ物質で前記一般式（Ｉ）中のＸおよびＹ
は同じかまたは異なり水素またはハロゲン元素を示す。
ハロゲン元素としては塩素、臭素およびヨウ素元素が挙
げられるが、殺菌力および殺カビ力から塩素元素が最も
良い。その代表的なものとしては２−メチルイソチアゾ
リン−３−オン、２−メチル−４−クロロイソチアゾリ
ン−３−オン、２−メチル−５−クロロイソチアゾリン
−３−オン、および２−メチル−４，５−ジクロロイソ
チアゾリン−３−オン等が挙げられ、殺菌組成物中でこ
れらの一種あるいは二種以上の混合物を用いることがで
きる。本発明の殺菌組成物中で使用する安定剤は、臭素
酸、よう素酸および過よう素酸またはそれらの塩である
が、臭素酸、臭素酸ナトリウム、よう素酸、よう素酸カ
リウム、過よう素酸、過よう素酸カリウム等を用いるこ
とができる。これらの安定剤は一種を単独で用いても二
種以上を併用しても良い。本発明の殺菌組成物における
上記一般式（Ｉ）で示されるイソチアゾロン系化合物
は、殺菌組成物の安定性およびこれを加える合成高分子
水系分散物への添加時の凝集防止の点から、殺菌組成物
中０．５〜２０重量％となるように含有させるのが良
く、好ましくは２〜１０重量％とするのが良い。また、
本発明で使用する安定剤は殺菌組成物中０．００１〜１
０重量％となるように含有させるのが良く、好ましくは
０．１〜２重量％とするのが良い。The isothiazolone compounds used in the present invention are fungicidal and fungicidal substances, X and Y in the aforementioned general formula (I).
Represents the same or different hydrogen or halogen elements.
Examples of the halogen element include chlorine, bromine and iodine elements, and the chlorine element is the best in terms of bactericidal activity and fungicidal activity. Representative examples are 2-methylisothiazolin-3-one, 2-methyl-4-chloroisothiazolin-3-one, 2-methyl-5-chloroisothiazolin-3-one, and 2-methyl-4,5. -Dichloroisothiazolin-3-one and the like, and one or a mixture of two or more of these can be used in the sterilizing composition. Stabilizers used in the germicidal compositions of the present invention are bromate, iodate and periodate or salts thereof, but may be bromate, sodium bromate, iodate, potassium iodate, peroxide Iodine acid, potassium periodate or the like can be used. These stabilizers may be used alone or in combination of two or more. The isothiazolone-based compound represented by the above general formula (I) in the germicidal composition of the present invention has a germicidal composition in view of the stability of the germicidal composition and the prevention of aggregation when added to an aqueous synthetic polymer dispersion to which the germicidal composition is added. The content is preferably 0.5 to 20% by weight, and more preferably 2 to 10% by weight. Also,
The stabilizer used in the present invention is 0.001 to 1 in the germicidal composition.
The content is preferably 0% by weight, more preferably 0.1 to 2% by weight.
【０００６】[0006]
【実施例】次に本発明の実施例および比較例をあげて説
明するが、本発明はこれらに限定されるものではない。
以下に示した配合比率はすべて重量％である。また、各
実施例の殺菌組成物は各実施例に示す各成分をそれぞれ
示す割合で常温において通常の攪拌によって調製した。
また、使用したイソチアゾロン系化合物は下記のように
略記した。 ＣＭＴ ：２−メチル−５−クロロイソチアゾリン−３
−オン ＭＴ ：２−メチルイソチアゾリン−３−オン ＤＣＭＴ：２−メチル−４，５−ジクロロイソチアゾリ
ン−３−オンEXAMPLES Next, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
All the compounding ratios shown below are% by weight. In addition, the germicidal composition of each example was prepared by ordinary stirring at room temperature at a ratio indicated for each component shown in each example.
The isothiazolone compounds used were abbreviated as follows. CMT: 2-methyl-5-chloroisothiazoline-3
-One MT: 2-methylisothiazolin-3-one DCMT: 2-methyl-4,5-dichloroisothiazolin-3-one
【０００７】実施例１〜９、比較例１〜６ イソチアゾロン系化合物を表１および表２に示す配合で
製剤し、殺菌組成物を得た。これらの殺菌組成物につい
ての安定性試験、合成高分子水系分散物に添加し、凝固
物発生試験を行った。Examples 1 to 9 and Comparative Examples 1 to 6 Isothiazolone compounds were formulated in the formulations shown in Tables 1 and 2 to obtain germicidal compositions. Stability tests on these sterilizing compositions and addition to a synthetic polymer aqueous dispersion and a coagulation test were conducted.
【０００８】[0008]
【表１】 [Table 1]
【０００９】[0009]
【表２】 [Table 2]
【００１０】（１）安定性試験 殺菌組成物を４５℃の恒温器中に放置し、一定期間毎に
イソチアゾロン系化合物の含有量（％）を高速液体クロ
マトグラフィーを用いて分析した。結果を表３に示す。
表３から明らかなように、本発明の殺菌組成物は水溶液
中においても非常に安定化されていることがわかる。(1) Stability test The bactericidal composition was left in a thermostat at 45 ° C., and the content (%) of the isothiazolone compound was analyzed at regular intervals by high performance liquid chromatography. Table 3 shows the results.
As is clear from Table 3, it can be seen that the germicidal composition of the present invention is extremely stabilized even in an aqueous solution.
【００１１】[0011]
【表３】 [Table 3]
【００１２】（２）凝固物発生試験 合成高分子水系分散物スチレン−ブタジエン共重合体ラ
テックス（固形分７０％）およびアクリルエマルジョン
（固形分５０％）１００ｇに殺菌組成物を１ｍｌ添加
し、マグネチックスターラーで５分間攪拌する。これを
１２０メッシュ金網でろ過し、１００℃で２時間乾燥
後、金網上に捕集された凝固物の重量を測定した。結果
を表４に示す。表４から明らかなように本発明の殺菌組
成物はマグネシウム塩を含有している比較例４よりも凝
固物の発生量ははるかに少なかった。(2) Coagulation product generation test 1 ml of a sterilizing composition was added to 100 g of a styrene-butadiene copolymer latex (solid content: 70%) and an acrylic emulsion (solid content: 50%) of a synthetic polymer aqueous dispersion. Stir for 5 minutes with stirrer. This was filtered through a 120-mesh wire net, dried at 100 ° C. for 2 hours, and the weight of the coagulated material collected on the wire net was measured. Table 4 shows the results. As is clear from Table 4, the germicidal composition of the present invention produced much less coagulated product than Comparative Example 4 containing a magnesium salt.
【００１３】[0013]
【表４】 [Table 4]
【００１４】[0014]
【発明の効果】本発明の殺菌組成物は製剤安定性に優れ
ているため、確実な防腐効果が得られ、また、低温倉庫
等に保管する必要がないためコスト的なメリットも得ら
れる。安定剤として２価以上の金属塩を含んでいないた
め、合成高分子水系分散物に悪影響を与えることなく使
用でき、安定な防腐効果を得ることができる。The germicidal composition of the present invention is excellent in the stability of the preparation, so that a reliable preservative effect can be obtained. In addition, since it is not necessary to store it in a low-temperature warehouse or the like, the merit of cost can be obtained. Since it does not contain a divalent or higher metal salt as a stabilizer, it can be used without adversely affecting the synthetic polymer aqueous dispersion, and a stable preservative effect can be obtained.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−221813（ＪＰ，Ａ) 特開 平６−65221（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) A01N 43/80 102 A01N 25/22 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-221813 (JP, A) JP-A-6-65221 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) A01N 43/80 102 A01N 25/22
Claims (1)
ゲンを示す）で表される化合物の少なくとも一種を有効
成分とし、よう素酸、過よう素酸、よう素酸塩、および
過よう素酸塩からなる群から選択される１種以上を安定
剤として含有することを特徴とする殺菌組成物。1. A compound of the general formula (I) (Wherein X and Y are the same or different and represent hydrogen or halogen), and at least one of the compounds represented by the following formulas is used as an active ingredient: iodic acid, periodate, iodate and periodate A germicidal composition comprising, as a stabilizer, at least one selected from the group consisting of:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35639691A JP3176676B2 (en) | 1991-12-24 | 1991-12-24 | Sterilizing composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35639691A JP3176676B2 (en) | 1991-12-24 | 1991-12-24 | Sterilizing composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05170608A JPH05170608A (en) | 1993-07-09 |
| JP3176676B2 true JP3176676B2 (en) | 2001-06-18 |
Family
ID=18448812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35639691A Expired - Lifetime JP3176676B2 (en) | 1991-12-24 | 1991-12-24 | Sterilizing composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3176676B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756005A (en) * | 1995-11-01 | 1998-05-26 | Rohm And Haas Company | Stabilization of non-halogenated 3-isothiazolones in aggressive systems |
| US6008238A (en) * | 1997-10-28 | 1999-12-28 | Rohm And Haas Company | Stabilization of 3-isothiazolone solutions |
| US5910503A (en) * | 1997-10-28 | 1999-06-08 | Rohm And Haas Company | Stable microbicide formulation |
| KR100369843B1 (en) * | 1999-07-08 | 2003-01-29 | 에스케이케미칼주식회사 | 3-Isothiazolone solution |
| KR100385714B1 (en) * | 1999-12-31 | 2003-05-27 | 에스케이케미칼주식회사 | A stabilized isothiazolone composition and method of stabilization of isothiazolone |
| WO2003099799A1 (en) * | 2002-05-29 | 2003-12-04 | Sk Chemicals Co., Ltd. | Isothiazolone composition and method for stabilizing isothiazolone |
| JP5194205B2 (en) * | 2004-02-19 | 2013-05-08 | 住化エンビロサイエンス株式会社 | Industrial antibacterial composition |
| JP4903745B2 (en) * | 2007-05-08 | 2012-03-28 | ローム アンド ハース カンパニー | Stabilized fluid |
-
1991
- 1991-12-24 JP JP35639691A patent/JP3176676B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05170608A (en) | 1993-07-09 |
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