WO2000038520A1 - Antimicrobial compositions - Google Patents

Antimicrobial compositions Download PDF

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Publication number
WO2000038520A1
WO2000038520A1 PCT/JP1999/007384 JP9907384W WO0038520A1 WO 2000038520 A1 WO2000038520 A1 WO 2000038520A1 JP 9907384 W JP9907384 W JP 9907384W WO 0038520 A1 WO0038520 A1 WO 0038520A1
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Prior art keywords
antimicrobial
antimicrobial composition
pyridinethiol
composition
octyl
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PCT/JP1999/007384
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French (fr)
Japanese (ja)
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WO2000038520A9 (en
Inventor
Toshimasa Ohnishi
Ikuya Tanaka
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Nagase Chemicals Ltd.
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Publication of WO2000038520A1 publication Critical patent/WO2000038520A1/en
Publication of WO2000038520A9 publication Critical patent/WO2000038520A9/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the present invention relates to an antimicrobial composition useful for industrial use. More specifically, by combining 2-pyridinepyridinethiol-1-oxide zinc salt with 2-n-octyl-4-isothiazoline-13-one, an antimicrobial agent composition having a synergistic effect of these compounds is obtained. About things. Background art
  • heavy metal compounds such as mercury, tin, and copper
  • these heavy metal compounds are highly toxic and may cause harm to human health.
  • the use of heavy metal compounds as antimicrobial agents is not appropriate because they can lead to environmental damage.
  • non-metallic antimicrobial agents eg, organic iodine compounds, nitrile compounds, isothiazolone compounds, benzimidazole compounds, pyrithione compounds
  • these non-metallic antimicrobial agents have no effect.
  • An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide an antimicrobial composition having high safety, high efficacy, and a broad antibacterial spectrum. Disclosure of the invention
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, the present inventors have found that a combination of 2-pyridinethiol-11-year-old zinc oxide salt and 2-n-octyl-4-isothiazoline-3-one is expected. It has been found that a synergistic effect can be obtained. In other words, they have found that the combination of the above two compounds enhances the potency as compared with the case where each compound is used alone, and that an antimicrobial composition having a broader antibacterial spectrum can be obtained. I came to.
  • an antimicrobial composition comprising 2-pyridinethiol-1-one-year-old zinc oxide salt and 2-n-octyl-4-isothiazolin-3-one.
  • the antimicrobial composition of the present invention is a composition that inhibits the growth of, or kills, bacteria, yeast, or algae. In a preferred embodiment, the antimicrobial composition of the present invention is a composition that inhibits the growth of bacteria or algae or kills these microorganisms.
  • the antimicrobial composition of the present invention is a composition that inhibits bacterial growth or kills bacteria.
  • the antimicrobial composition of the present invention is a composition that inhibits the growth of or kills algae.
  • the weight ratio of the 2-pyridinethiol-11-year-old zinc oxide salt to the 2-n-octyl-4-isothiazolin-3-one is in the range of 20: 1 to 1:20. More preferably, the weight ratio of the above 2-pyridinethiol-11-year-old zinc oxide salt to the 2-n-year-old octyl-4-isothiazolin-3-one is: Five : :! ⁇ 1: The range is 5.
  • antimicrobial composition refers to a composition that has the effect of inhibiting the growth of bacteria, yeast, or algae, or killing these microorganisms.
  • composition of antimicrobial composition A. Composition of antimicrobial composition
  • the antimicrobial composition of the present invention contains zinc 2-pyridinethiol-111-oxide and 2-n-octyl-4-isothiazolin-3-one as active ingredients.
  • Zinc 2-pyridinethiol-1-oxide can be synthesized by the method described in US Pat. No. 3,583,999.
  • the proportions of 2-pyridinethiol-1-oxide zinc salt and 2-n_octyl-4-isothiazolin-3-one in the antimicrobial composition depend on the type of the target microorganism and the above composition as an antimicrobial agent. It can be selected appropriately depending on the conditions used. Normally, the ratio of 2-pyridinethiol-1-oxide zinc salt to 2-n-octyl-4-isothiazolin-3-one is 20: 1-1: 1: 20, preferably 5 ::, by weight. ! To 1: 5, particularly preferably in the range of 3: 1 to 1: 3.
  • the antimicrobial composition of the present invention can be used in a form depending on the purpose of use.
  • the antimicrobial composition of the present invention may be simply a mixture of 2-pyridinethiol-l-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one, but is preferably In addition to 2-pyridinethiol-1 zinc oxide and 2-n-octyl-4-isothiazolin-3-one, it may contain suitable solvents and dispersants or carriers or other components.
  • the total content of 2-pyridinethiol-11-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one in the composition of the present invention depends on the dosage form and the purpose of use. Although it depends on the target, etc., it is usually 0.
  • % To 95% by weight preferably 0.2% to 60% by weight.
  • the amount of the antimicrobial agent composition of the present invention varies depending on the composition and the type and concentration of the target microorganism, but in general, when used in fibers, paints, adhesives, etc. A good effect can be obtained at about 1 to 100 Om gZ kg.
  • the target system is various industrial water systems
  • Solvents that can be used in the antimicrobial composition of the present invention include any solvent that does not adversely affect the active ingredient, for example, water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol, diethylene glycol) , Glycerin, etc.), ketones (eg, acetone, methylethyl ketone, etc.), ethers (eg, dioxane, tetrahydrofuran, cellosolve, diethylene glycol dimethyl ether, etc.), aliphatic hydrocarbons (eg, hexane, kerosene, etc.), aromatics Group hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, methyl naphthylene, etc.), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), acid amides (eg, Etc.
  • alcohols eg
  • Mechiruhorumua bromide esters (e.g., methyl acetate, acetic Echiruesuteru, butyl acetate ester, fatty acid glycerin ester, etc.), and nitriles such (for example, such as Asetonitoriru) and the like.
  • esters e.g., methyl acetate, acetic Echiruesuteru, butyl acetate ester, fatty acid glycerin ester, etc.
  • nitriles such as Asetonitoriru
  • solvents can be used alone or in combination of two or more.
  • Examples of the dispersant that can be used in the antimicrobial composition of the present invention include any dispersant that does not adversely affect the active ingredient, for example, a surfactant.
  • a surfactant examples include soaps, sulfates of higher alcohols, alkylsulfonic acids, alkylarylsulfonic acids, quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxide compounds, Anhydrosorbitol-based compounds and the like can be mentioned.
  • These dispersants can be used alone or in combination of two or more. Usually, it is 0.1% to 95% by weight, preferably 0.2% to 60% by weight of the whole antimicrobial composition obtained, although it depends on the target.
  • the amount of the antimicrobial agent composition of the present invention varies depending on the composition and the type and concentration of the target microorganism, but in general, when used in fibers, paints, adhesives, etc. A good effect can be obtained with about 1 to 100 Omg Z kg.
  • the target system is various industrial water systems
  • Solvents that can be used in the antimicrobial composition of the present invention include any solvent that does not adversely affect the active ingredient, for example, water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol, diethylene glycol) , Glycerin, etc.), ketones (eg, acetone, methylethyl ketone, etc.), ethers (eg, dioxane, tetrahydrofuran, cellosolve, diethylene glycol dimethyl ether, etc.), aliphatic hydrocarbons (eg, hexane, kerosene, etc.), aromatics Group hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, methyl naphthylene, etc.), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), acid amides (eg, Etc.
  • alcohols eg
  • Mechiruhorumua bromide esters (e.g., methyl acetate, acetic Echiruesuteru, butyl acetate ester, fatty acid glycerin ester, etc.), and nitriles such (for example, such as Asetonitoriru) and the like.
  • esters e.g., methyl acetate, acetic Echiruesuteru, butyl acetate ester, fatty acid glycerin ester, etc.
  • nitriles such as Asetonitoriru
  • solvents can be used alone or in combination of two or more.
  • Examples of the dispersant that can be used in the antimicrobial composition of the present invention include any dispersant that does not adversely affect the active ingredient, for example, a surfactant.
  • a surfactant examples include soaps, sulfates of higher alcohols, alkylsulfonic acids, alkylarylsulfonates, quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxide compounds, Anhydrosorbitol-based compounds and the like can be mentioned. These dispersants can be used alone or in combination of two or more.
  • Fungi such as Agenus, Penici 11 1 i enm, Trich od erma, yeasts such as C and ida, Rh od otorula, Ch 1 ore
  • Algae such as the genus 1 la, the genus Trente pohllia, the genus Nostoc, and the genus Phormidium are included.
  • the antimicrobial composition of the present invention can be applied to various industrial products or industrial raw materials.
  • various industrial products or industrial raw materials include fibers, paints, adhesives, wood, leather, processed paper products, electronic components, wall coverings, and resin molded products.
  • MIC refers to the minimum inhibitory concentration (ppm) of the active ingredient in the antimicrobial composition. More specifically, in an antimicrobial agent composition capable of inhibiting the growth of bacteria, fungi or algae, 2-pyridinethiol-1-oxoxide zinc salt, 2-n-octyl-4-isothiazoline-3- refers to the minimum concentration of the mixture with ON.
  • the bacterial solution for inoculation used in Example 1 was prepared as follows. Five separate bacteria (Bacillus subtilis IF 03134, Staphylococcus aureus I F012732> Enterobacteraer ogenes IF 01 3534, Escherichiacoli IF 03972, and P. seud omo nasaer uginosa IF 013275) was inoculated, and cultured with shaking at 30 ° C for 4 to 6 hours to prepare five kinds of bacterial liquids for inoculation.
  • Five separate bacteria Bacillus subtilis IF 03134, Staphylococcus aureus I F012732> Enterobacteraer ogenes IF 01 3534, Escherichiacoli IF 03972, and P. seud omo nasaer uginosa IF 013275
  • Example 2 The spore suspension for inoculation used in Example 2 was prepared as follows. Each fungus
  • the algal suspension for inoculation used in Example 3 was prepared as follows.
  • BB liquid medium 50 ml was inoculated with ChlorelnapyrenoidosaNiS 226, and cultured with shaking at 25 ° C for 14 days to prepare an algal suspension for inoculation.
  • 2-Pyridinethiol 11-year-old zinc oxide salt and 2-n—year-old tertellate—4-isothiazolin-3-one were added to dimethyl sulfoxide at the respective weight ratios shown in Table 1 below.
  • Three antimicrobial compositions were prepared. Next, a serially diluted aqueous solution (0.2 ml) of the antimicrobial agent composition was added to a normal broth liquid medium (10 ml) to prepare each test medium. Each test medium is inoculated with the above inoculum (0.1 ml), cultured at 30 ° C for 24 hours, and visually inspected for turbidity of the medium to determine the presence or absence of bacterial growth. Were determined.
  • the minimum concentration of the mixture of 2-pyridinethiol-1-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one that could inhibit bacterial growth in the medium was defined as MIC.
  • Table 1 shows the MIC for each bacterium of the antimicrobial composition at each weight ratio.
  • the minimum concentration of a mixture of 2-pyridinethiol-111-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one that could inhibit fungal growth on the medium was defined as MIC.
  • Table 2 shows the MIC for each fungus of the antimicrobial composition at each weight ratio.
  • 2-Pyridinethiol 1-year-old zinc oxide salt and 2-n-year-old octyl-4-isothiazolin-3-one were added to dimethyl sulfoxide at the respective weight ratios shown in Table 3 below.
  • An antimicrobial composition was prepared. Next, this antimicrobial group A serially diluted aqueous solution (0.1 ml) of the product was added to BB agar medium (15 ml) to prepare each test medium. Each test medium is inoculated with the above algal suspension for inoculation (1 ml), cultured at 25 ° C and 1500 lux for 14 days, and then visually inspected for algal growth on the medium. The presence or absence of growth of each was determined.
  • the MIC was defined as the minimum concentration of a mixture of 2-pyridinethiol-11-oxide zinc salt and 2-n-octyl-14-isothiazolin-3-one that could inhibit the growth of algae on the medium.
  • Table 3 shows the MIC for the algae of the antimicrobial composition at each weight ratio.
  • Drug B 2 n-one-year-old tylyl 4-isothiazolin-3-one
  • the antimicrobial composition of the present invention is compared with the conventional antimicrobial composition due to the synergistic effect of the active ingredient. It shows high efficacy and wide antibacterial spectrum. Furthermore, it is shown that the concentration of the antimicrobial composition used to inhibit the growth of the same amount of bacteria, fungi or algae can be kept very low compared to when the active ingredient is used alone. Industrial applicability
  • an antimicrobial composition comprising 2-pyridinethiol-11-year-old zinc oxide salt and 2-n-octyl-4-isothiazolin-3-one as active ingredients.
  • An antimicrobial composition having a synergistic effect of components, high safety, high efficacy, and a broad antibacterial spectrum is provided.
  • concentration of the active ingredient contained in the antimicrobial composition of the present invention can be kept low, it can be prepared at extremely low cost and has little effect on the environment.
  • the antimicrobial composition of the present invention is effective for the preservative and fungal control of various industrial products and industrial raw materials.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Antimicrobial compositions containing 2-pyridinethiol-1-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one which have a high safety, a potent efficacy and a broad antimicrobial spectrum.

Description

明 細 書 抗微生物剤組成物 技術分野  Description Antimicrobial composition Technical field
本発明は、 工業用途に有用な抗微生物剤組成物に関する。 より詳細には、 2 - ピリジンチオール一 1—ォキシド亜鉛塩と、 2— n—ォクチルー 4一イソチアゾ リン一 3—オンとを組み合わせることにより、 これらの化合物の相乗効果を有す る抗微生物剤組成物に関する。 背景技術  The present invention relates to an antimicrobial composition useful for industrial use. More specifically, by combining 2-pyridinepyridinethiol-1-oxide zinc salt with 2-n-octyl-4-isothiazoline-13-one, an antimicrobial agent composition having a synergistic effect of these compounds is obtained. About things. Background art
従来から、 工業製品または工業用原材料の抗微生物剤として、 主として水銀、 錫、 銅などの重金属を含有する無機化合物または有機化合物 （以下、 「重金属化 合物」 という） が広く用いられている。 しかし、 これらの重金属化合物は毒性が 強いため、 人体に悪影響を及ぼす危険性がある。 さらに、 重金属化合物は環境破 壊につながる恐れを有するため、 重金属化合物を抗微生物剤として使用すること は適切ではない。  Conventionally, inorganic or organic compounds containing heavy metals such as mercury, tin, and copper (hereinafter referred to as “heavy metal compounds”) have been widely used as antimicrobial agents for industrial products or industrial raw materials. However, these heavy metal compounds are highly toxic and may cause harm to human health. Furthermore, the use of heavy metal compounds as antimicrobial agents is not appropriate because they can lead to environmental damage.
このような重金属化合物の問題点を解決するために開発された多くの非金属系 抗微生物剤 （例えば、 有機ヨウ素系化合物、 二トリル系化合物、 イソチアゾロン 系化合物、 ベンズイミダゾール系化合物、 ピリチオン系化合物） については、 そ の抗菌スペクトルに選択性がある。 このため、 これらの非金属系抗微生物剤を、 工業製品または工業用原材料、 特に有機材料 （例えば、 繊維、 塗料、 糊剤など） に適用しても、 これら抗微生物剤が効力を奏しない、 あるいは奏しにくい微生物 が発育、 繁殖するため、 工業製品などの汚染、 あるいは工業用原材料の変質 （例 えば、 劣化） が生じる。 従って、 従来の抗微生物剤組成物によっては、 満足すベ き殺菌効果が得られない。  Many non-metallic antimicrobial agents (eg, organic iodine compounds, nitrile compounds, isothiazolone compounds, benzimidazole compounds, pyrithione compounds) developed to solve such problems of heavy metal compounds Is selective in its antimicrobial spectrum. Therefore, even if these non-metallic antimicrobial agents are applied to industrial products or industrial raw materials, especially organic materials (eg, fibers, paints, sizing agents, etc.), these antimicrobial agents have no effect. Alternatively, microorganisms that are difficult to play grow and proliferate, causing contamination of industrial products and the like, and deterioration (for example, deterioration) of industrial raw materials. Therefore, satisfactory antibacterial effects cannot be obtained with conventional antimicrobial compositions.
このため、 2種類以上の抗微生物剤を組み合わせることにより、 抗菌スぺクト ルを広げること、 抗微生物作用を増大させることなどが試みられている。 しかし、 通常は 1種類のみの抗微生物剤の効果の発現に留まるか、 あるいは相加平均的な 効果しか得られない。 For this reason, attempts have been made to combine two or more antimicrobial agents to broaden the antimicrobial spectrum and increase the antimicrobial activity. However, usually only one type of antimicrobial is effective, or an arithmetic average Only effects can be obtained.
(発明が解決しょうとする課題）  (Problems to be solved by the invention)
本発明は上記課題を解決するものであり、 その目的とするところは、 安全性が 高く、 効力が高く、 さらに広い抗菌スペクトルを有する抗微生物剤組成物を提供 することである。 発明の開示  An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide an antimicrobial composition having high safety, high efficacy, and a broad antibacterial spectrum. Disclosure of the invention
(課題を解決するための手段）  (Means for solving the problem)
本発明者らは、 上記課題を解決するため、 鋭意検討した結果、 2—ピリジンチ オール一 1一才キシド亜鉛塩と、 2— n—ォクチル—4一イソチアゾリンー 3— オンとの組み合わせにより、 予期せぬ相乗効果が得られることを見出した。 つま り、 上記 2種の化合物の組み合わせにより、 各化合物を単独で用いた場合よりも 効力が増強され、 さらに抗菌スぺクトルが広い抗微生物剤組成物が得られること を見出し、 本発明を完成するに至った。  The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, the present inventors have found that a combination of 2-pyridinethiol-11-year-old zinc oxide salt and 2-n-octyl-4-isothiazoline-3-one is expected. It has been found that a synergistic effect can be obtained. In other words, they have found that the combination of the above two compounds enhances the potency as compared with the case where each compound is used alone, and that an antimicrobial composition having a broader antibacterial spectrum can be obtained. I came to.
本発明によれば、 2—ピリジンチオール— 1一才キシド亜鉛塩と、 2 _ n—ォ クチルー 4一イソチアゾリンー 3—オンとを含有する抗微生物剤組成物が提供さ れる。  According to the present invention, there is provided an antimicrobial composition comprising 2-pyridinethiol-1-one-year-old zinc oxide salt and 2-n-octyl-4-isothiazolin-3-one.
一つの実施態様において、 本発明の抗微生物剤組成物は、 細菌、 酵母、 もしく は藻類の増殖を抑制するか、 またはこれらの微生物を死滅させる組成物である。 好ましい実施態様において、 本発明の抗微生物剤組成物は、 細菌もしくは藻類 の増殖を抑制するか、 またはこれらの微生物を死滅させる組成物である。  In one embodiment, the antimicrobial composition of the present invention is a composition that inhibits the growth of, or kills, bacteria, yeast, or algae. In a preferred embodiment, the antimicrobial composition of the present invention is a composition that inhibits the growth of bacteria or algae or kills these microorganisms.
特に好ましい実施態様において、 本発明の抗微生物剤組成物は、 細菌の増殖を 抑制するか、 または細菌を死滅させる組成物である。  In a particularly preferred embodiment, the antimicrobial composition of the present invention is a composition that inhibits bacterial growth or kills bacteria.
また別の特に好ましい実施態様において、 本発明の抗微生物剤組成物は、 藻類 の増殖を抑制するか、 または藻類を死滅させる組成物である。  In another particularly preferred embodiment, the antimicrobial composition of the present invention is a composition that inhibits the growth of or kills algae.
好ましくは、 上記 2 _ピリジンチオール一 1一才キシド亜鉛塩と、 上記 2— n —ォクチルー 4一イソチアゾリン— 3—オンとの重量比は、 2 0 ： 1〜1 ： 2 0 の範囲である。 さらに好ましくは、 上記 2—ピリジンチオール— 1一才キシド亜 鉛塩と、 上記 2— n—才クチルー 4一イソチアゾリンー 3—オンとの重量比は、 5 ： ：！〜 1 ： 5の範囲である。 発明を実施するための最良の形態 Preferably, the weight ratio of the 2-pyridinethiol-11-year-old zinc oxide salt to the 2-n-octyl-4-isothiazolin-3-one is in the range of 20: 1 to 1:20. More preferably, the weight ratio of the above 2-pyridinethiol-11-year-old zinc oxide salt to the 2-n-year-old octyl-4-isothiazolin-3-one is: Five : :! ~ 1: The range is 5. BEST MODE FOR CARRYING OUT THE INVENTION
本明細書において用いられる用語 「抗微生物剤組成物」 とは、 細菌、 酵母、 も しくは藻類の増殖を抑制するか、 またはこれらの微生物を死滅させる効果を有す る組成物を意味する。  As used herein, the term "antimicrobial composition" refers to a composition that has the effect of inhibiting the growth of bacteria, yeast, or algae, or killing these microorganisms.
A. 抗微生物剤組成物の構成  A. Composition of antimicrobial composition
A. 1 . 有効成分  A. 1. Active ingredient
本発明の抗微生物剤組成物は、 2—ピリジンチオール一 1 一ォキシド亜鉛塩と 2— n—ォクチルー 4ーィソチアゾリン— 3—オンとを有効成分として含有する。  The antimicrobial composition of the present invention contains zinc 2-pyridinethiol-111-oxide and 2-n-octyl-4-isothiazolin-3-one as active ingredients.
2—ピリジンチオール— 1ーォキシド亜鉛塩は、 米国特許 3， 5 8 3 , 9 9 9 号に記載の方法により合成され得る。  Zinc 2-pyridinethiol-1-oxide can be synthesized by the method described in US Pat. No. 3,583,999.
2— n—ォクチル一 4一^ Γソチアゾリン— 3—オンもまた、 J . H e t e r o c y c l . C h e m. ( 1 9 7 1 ) , 8 ( 4 ) , 5 7 1— 5 8 0に記載の方法に より合成され得る。  2-n-octyl-1-41-sothiazoline-3-one is also described in J. Heterocycl. Chem. (1971), 8 (4), 571-580. Can be synthesized by
抗微生物剤組成物中の 2—ピリジンチオール— 1—ォキシド亜鉛塩と 2— n _ ォクチルー 4—イソチアゾリンー 3—オンとの割合は、 対象となる微生物の種類 ならびに上記組成物を抗微生物剤として使用する条件などに依存して適切に選択 され得る。 通常、 2—ピリジンチオール— 1—ォキシド亜鉛塩と 2— n—才クチ ルー 4—イソチアゾリンー 3—オンとの割合は、 重量比で 2 0 ： 1〜1 ： 2 0、 好ましくは 5 ： ：！〜 1 ： 5、 特に好ましくは 3 ： 1〜1 ： 3の範囲である。  The proportions of 2-pyridinethiol-1-oxide zinc salt and 2-n_octyl-4-isothiazolin-3-one in the antimicrobial composition depend on the type of the target microorganism and the above composition as an antimicrobial agent. It can be selected appropriately depending on the conditions used. Normally, the ratio of 2-pyridinethiol-1-oxide zinc salt to 2-n-octyl-4-isothiazolin-3-one is 20: 1-1: 1: 20, preferably 5 ::, by weight. ! To 1: 5, particularly preferably in the range of 3: 1 to 1: 3.
本発明の抗微生物剤組成物は、 使用目的に応じた形態で使用され得る。 例えば、 本発明の抗微生物剤組成物は、 単に 2—ピリジンチオール— 1 一ォキシド亜鉛塩 と 2— n—ォクチル— 4—イソチアゾリン— 3—オンを混合したものであっても よいが、 好ましくは 2—ピリジンチオール— 1一才キシド亜鉛塩および 2— n— ォクチルー 4—ィソチアゾリン— 3—オンの他に適切な溶媒および分散剤または 担体またはその他の成分を含有し得る。  The antimicrobial composition of the present invention can be used in a form depending on the purpose of use. For example, the antimicrobial composition of the present invention may be simply a mixture of 2-pyridinethiol-l-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one, but is preferably In addition to 2-pyridinethiol-1 zinc oxide and 2-n-octyl-4-isothiazolin-3-one, it may contain suitable solvents and dispersants or carriers or other components.
本発明の組成物中の 2—ピリジンチオール一 1—ォキシド亜鉛塩と 2— n—ォ クチルー 4ーィソチアゾリンー 3—オンとの総含有量は、 その剤型および使用目 的などによっても異なるが、 通常、 得られる抗微生物剤組成物全体の 0 . The total content of 2-pyridinethiol-11-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one in the composition of the present invention depends on the dosage form and the purpose of use. Although it depends on the target, etc., it is usually 0.
%〜9 5重量％であり、 好ましくは 0 . 2重量％〜6 0重量％である。 % To 95% by weight, preferably 0.2% to 60% by weight.
また、 本発明の抗微生物剤組成物の使用量は、 組成物および対象となる微生物 の種類やその濃度によっても異なるが、 一般的に、 繊維、 塗料、 接着剤などに使 用する場合は、 1〜1 0 0 0 O m gZ k g程度で良好な効果が得られる。  The amount of the antimicrobial agent composition of the present invention varies depending on the composition and the type and concentration of the target microorganism, but in general, when used in fibers, paints, adhesives, etc. A good effect can be obtained at about 1 to 100 Om gZ kg.
A. 2 . 溶媒および分散剤  A. 2. Solvents and dispersants
対象となる系が各種工業用水系の場合には、 有効成分の溶解、 分散性などを考 慮して、 後述するように、 溶媒および分散剤を含有する液剤を調製することが好 ましい。  When the target system is various industrial water systems, it is preferable to prepare a solution containing a solvent and a dispersant, as described later, in consideration of the dissolution and dispersibility of the active ingredient.
本発明の抗微生物剤組成物に用いられ得る溶媒としては、 有効成分に悪影響を 与えない任意の溶媒、 例えば、 水、 アルコール類 （例えば、 メチルアルコール、 エチルアルコール、 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、 グリセリンなど） 、 ケトン類 （例えば、 アセトン、 メチルェチルケ卜 ンなど） 、 エーテル類 （例えば、 ジォキサン、 テトラヒドロフラン、 セロソルブ、 ジエチレングリコールジメチルエーテルなど） 、 脂肪族炭化水素類 （例えば、 へ キサン、 灯油など） 、 芳香族炭化水素類 （例えば、 ベンゼン、 トルエン、 キシレ ン、 ソルベントナフサ、 メチルナフ夕レンなど） 、 ハロゲン化炭化水素類 （例え ば、 クロ口ホルム、 四塩化炭素など） 、 酸アミド類 （例えば、 ジメチルホルムァ ミドなど） 、 エステル類 （例えば、 酢酸メチルエステル、 酢酸ェチルエステル、 酢酸ブチルエステル、 脂肪酸グリセリンエステルなど） および二トリル類 （例え ば、 ァセトニトリルなど） などが挙げられる。 これらの溶媒は、 単独であるいは 2種類以上を組み合わせて用いられ得る。  Solvents that can be used in the antimicrobial composition of the present invention include any solvent that does not adversely affect the active ingredient, for example, water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol, diethylene glycol) , Glycerin, etc.), ketones (eg, acetone, methylethyl ketone, etc.), ethers (eg, dioxane, tetrahydrofuran, cellosolve, diethylene glycol dimethyl ether, etc.), aliphatic hydrocarbons (eg, hexane, kerosene, etc.), aromatics Group hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, methyl naphthylene, etc.), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), acid amides (eg, Etc. Mechiruhorumua bromide), esters (e.g., methyl acetate, acetic Echiruesuteru, butyl acetate ester, fatty acid glycerin ester, etc.), and nitriles such (for example, such as Asetonitoriru) and the like. These solvents can be used alone or in combination of two or more.
本発明の抗微生物剤組成物に用いられ得る分散剤としては、 有効成分に悪影響 を与えない任意の分散剤、 例えば、 界面活性剤が挙げられる。 このような界面活 性剤としては、 石けん類、 高級アルコールの硫酸エステル、 アルキルスルホン酸、 アルキルァリールスルホン酸、 第 4級アンモニゥム塩、 ォキシアルキルァミン、 脂肪酸エステル、 ポリアルキレンオキサイド系化合物、 アンヒドロソルビトール 系化合物などが挙げられる。 これらの分散剤は、 単独であるいは 2種類以上を組 み合わせて用いられ得る。 的などによっても異なるが、 通常、 得られる抗微生物剤組成物全体の 0 . 1重量 %〜9 5重量％であり、 好ましくは 0 . 2重量％〜6 0重量％である。 Examples of the dispersant that can be used in the antimicrobial composition of the present invention include any dispersant that does not adversely affect the active ingredient, for example, a surfactant. Examples of such surfactants include soaps, sulfates of higher alcohols, alkylsulfonic acids, alkylarylsulfonic acids, quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxide compounds, Anhydrosorbitol-based compounds and the like can be mentioned. These dispersants can be used alone or in combination of two or more. Usually, it is 0.1% to 95% by weight, preferably 0.2% to 60% by weight of the whole antimicrobial composition obtained, although it depends on the target.
また、 本発明の抗微生物剤組成物の使用量は、 組成物および対象となる微生物 の種類やその濃度によっても異なるが、 一般的に、 繊維、 塗料、 接着剤などに使 用する場合は、 1〜1 0 0 0 O m g Z k g程度で良好な効果が得られる。  The amount of the antimicrobial agent composition of the present invention varies depending on the composition and the type and concentration of the target microorganism, but in general, when used in fibers, paints, adhesives, etc. A good effect can be obtained with about 1 to 100 Omg Z kg.
A. 2 . 溶媒および分散剤  A. 2. Solvents and dispersants
対象となる系が各種工業用水系の場合には、 有効成分の溶解、 分散性などを考 慮して、 後述するように、 溶媒および分散剤を含有する液剤を調製することが好 ましい。  When the target system is various industrial water systems, it is preferable to prepare a solution containing a solvent and a dispersant, as described later, in consideration of the dissolution and dispersibility of the active ingredient.
本発明の抗微生物剤組成物に用いられ得る溶媒としては、 有効成分に悪影響を 与えない任意の溶媒、 例えば、 水、 アルコール類 （例えば、 メチルアルコール、 エチルアルコール、 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、 グリセリンなど） 、 ケトン類 （例えば、 アセトン、 メチルェチルケ卜 ンなど） 、 エーテル類 （例えば、 ジォキサン、 テトラヒドロフラン、 セロソルブ、 ジエチレングリコールジメチルエーテルなど） 、 脂肪族炭化水素類 （例えば、 へ キサン、 灯油など） 、 芳香族炭化水素類 （例えば、 ベンゼン、 トルエン、 キシレ ン、 ソルベントナフサ、 メチルナフ夕レンなど） 、 ハロゲン化炭化水素類 （例え ば、 クロ口ホルム、 四塩化炭素など） 、 酸アミド類 （例えば、 ジメチルホルムァ ミドなど） 、 エステル類 （例えば、 酢酸メチルエステル、 酢酸ェチルエステル、 酢酸ブチルエステル、 脂肪酸グリセリンエステルなど） および二トリル類 （例え ば、 ァセトニトリルなど） などが挙げられる。 これらの溶媒は、 単独であるいは 2種類以上を組み合わせて用いられ得る。  Solvents that can be used in the antimicrobial composition of the present invention include any solvent that does not adversely affect the active ingredient, for example, water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol, diethylene glycol) , Glycerin, etc.), ketones (eg, acetone, methylethyl ketone, etc.), ethers (eg, dioxane, tetrahydrofuran, cellosolve, diethylene glycol dimethyl ether, etc.), aliphatic hydrocarbons (eg, hexane, kerosene, etc.), aromatics Group hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, methyl naphthylene, etc.), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), acid amides (eg, Etc. Mechiruhorumua bromide), esters (e.g., methyl acetate, acetic Echiruesuteru, butyl acetate ester, fatty acid glycerin ester, etc.), and nitriles such (for example, such as Asetonitoriru) and the like. These solvents can be used alone or in combination of two or more.
本発明の抗微生物剤組成物に用いられ得る分散剤としては、 有効成分に悪影響 を与えない任意の分散剤、 例えば、 界面活性剤が挙げられる。 このような界面活 性剤としては、 石けん類、 高級アルコールの硫酸エステル、 アルキルスルホン酸、 アルキルァリールスルホン酸、 第 4級アンモニゥム塩、 ォキシアルキルァミン、 脂肪酸エステル、 ポリアルキレンオキサイド系化合物、 アンヒドロソルビトール 系化合物などが挙げられる。 これらの分散剤は、 単独であるいは 2種類以上を組 み合わせて用いられ得る。  Examples of the dispersant that can be used in the antimicrobial composition of the present invention include any dispersant that does not adversely affect the active ingredient, for example, a surfactant. Examples of such surfactants include soaps, sulfates of higher alcohols, alkylsulfonic acids, alkylarylsulfonates, quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxide compounds, Anhydrosorbitol-based compounds and the like can be mentioned. These dispersants can be used alone or in combination of two or more.
4 1 a d i u m属、 P e n i c i 1 1 i υ m属、 Tr i c h od e rma属などの 真菌、 C and i d a属、 Rh od o t o r u l a属などの酵母、 C h 1 o r eFour 1 Fungi such as Agenus, Penici 11 1 i enm, Trich od erma, yeasts such as C and ida, Rh od otorula, Ch 1 ore
1 l a属、 Tr e n t e poh l i a属、 No s t o c属、 P h o r m i d i u m属などの藻類などが挙げられる。 Algae such as the genus 1 la, the genus Trente pohllia, the genus Nostoc, and the genus Phormidium are included.
本発明の抗微生物剤組成物は、 各種の工業製品または工業用原材料に適用され 得る。 このような種々の工業製品または工業用原材料としては、 繊維、 塗料、 接 着剤、 木材、 皮革、 紙加工品、 電子部品、 壁装材、 樹脂成形物などが挙げられる。  The antimicrobial composition of the present invention can be applied to various industrial products or industrial raw materials. Examples of such various industrial products or industrial raw materials include fibers, paints, adhesives, wood, leather, processed paper products, electronic components, wall coverings, and resin molded products.
(実施例） (Example)
以下の実施例により、 本発明による抗微生物剤組成物の抗微生物効力をさらに 詳しく説明する。 本実施例において用いられる用語 「MI C」 とは、 抗微生物剤 組成物中の有効成分の最小発育阻止濃度 （p pm) を指す。 より具体的には、 細 菌、 真菌または藻類の発育を阻止し得る抗微生物剤組成物中の、 2—ピリジンチ オール— 1—ォキシド亜鉛塩と、 2— n—ォクチル— 4—イソチアゾリン— 3— オンとの混合物の最小濃度を指す。  The following examples further illustrate the antimicrobial efficacy of the antimicrobial composition of the present invention. The term “MIC” used in this example refers to the minimum inhibitory concentration (ppm) of the active ingredient in the antimicrobial composition. More specifically, in an antimicrobial agent composition capable of inhibiting the growth of bacteria, fungi or algae, 2-pyridinethiol-1-oxoxide zinc salt, 2-n-octyl-4-isothiazoline-3- Refers to the minimum concentration of the mixture with ON.
(接種用菌液の調製）  (Preparation of bacterial solution for inoculation)
実施例 1で用いられる接種用菌液を以下のようにして調製した。 5つの別個の 普通ブイョン液体培地 （10m l ) に、 各細菌 5種 （Ba c i l l u s s u b t i l i s I F 03134, S t a phy l o c o c c u s au r eu s I F012732> En t e r o b a c t e r a e r oge n e s I F 01 3534、 E s c h e r i c h i a c o l i I F 03972, および P s e u d omo n a s a e r ug i no s a I F 013275) をそれぞれ接種 し、 30°Cで 4〜6時間振盪培養して 5種の接種用菌液を調製した。  The bacterial solution for inoculation used in Example 1 was prepared as follows. Five separate bacteria (Bacillus subtilis IF 03134, Staphylococcus aureus I F012732> Enterobacteraer ogenes IF 01 3534, Escherichiacoli IF 03972, and P. seud omo nasaer uginosa IF 013275) was inoculated, and cultured with shaking at 30 ° C for 4 to 6 hours to prepare five kinds of bacterial liquids for inoculation.
(接種用胞子懸濁液の調製）  (Preparation of spore suspension for inoculation)
実施例 2で用いられる接種用胞子懸濁液を以下のようにして調製した。 各真菌 The spore suspension for inoculation used in Example 2 was prepared as follows. Each fungus
4種 （As p e r g i l l u s n i ge r I F0634 G l i o c l a d i um v i r e n s I F 06355, Pe n i c i 1 1 i um f u n i c u l o s um I F06345、 および T r i c hod e rma v i r i d e I F 05720) を、 薬剤を含有しない 4つのポテトデキストロース寒天培 地上で培養し、 胞子を形成させた。 次いで、 潤滑剤を 0. 005 %添加した滅菌 水に上記真菌胞子を分散し、 4種の接種用胞子懸濁液を調製した。 Four species (As pergillusni ger I F0634 G liocladi um virens IF 06355, Penici 11 i um funiculos um I F06345, and Tric hod e rma viride IF 05720) were added to four potato dextrose agar plates containing no drug. Cultured on the ground to form spores. Next, the fungal spores were dispersed in sterile water to which 0.005% of a lubricant was added to prepare four kinds of spore suspensions for inoculation.
(接種用藻懸濁液の調製）  (Preparation of algae suspension for inoculation)
実施例 3で用いられる接種用藻懸濁液を以下のようにして調製した。 B B液体 培地 （50ml) に、 Ch l o r e l l a py r e n o i d o s a N I E S 226を接種し、 25°Cで 14日間振盪培養して接種用藻懸濁液を調製した。  The algal suspension for inoculation used in Example 3 was prepared as follows. BB liquid medium (50 ml) was inoculated with ChlorelnapyrenoidosaNiS 226, and cultured with shaking at 25 ° C for 14 days to prepare an algal suspension for inoculation.
(実施例 1 )  (Example 1)
2—ピリジンチオール— 1一才キシド亜鉛塩と、 2— n—才クテル—4一イソ チアゾリンー 3—オンとを、 以下の表 1に示される各重量比でジメチルスルホキ シドに添加し、 5つの抗微生物剤組成物を調製した。 次いで、 普通ブイヨン液体 培地 （10m l ) に、 抗微生物剤組成物の段階希釈水溶液 （0. 2ml) をそれ ぞれ添加して、 各試験培地を調製した。 この各試験培地に、 上記の接種用菌液 （ 0. lm l ) を接種し、 30°Cで 24時間培養した後、 培地の濁度を目視検査す ることによって細菌の発育の有無をそれぞれ決定した。 培地中での細菌の発育を 阻止し得る、 2—ピリジンチォ一ルー 1—ォキシド亜鉛塩と 2— n—才クチルー 4一イソチアゾリン— 3—オンとの混合物の最小濃度を M I Cとした。 各重量比 の抗微生物剤組成物の、 各細菌についての M I Cを表 1に示す。  2-Pyridinethiol—11-year-old zinc oxide salt and 2-n—year-old tertellate—4-isothiazolin-3-one were added to dimethyl sulfoxide at the respective weight ratios shown in Table 1 below. Three antimicrobial compositions were prepared. Next, a serially diluted aqueous solution (0.2 ml) of the antimicrobial agent composition was added to a normal broth liquid medium (10 ml) to prepare each test medium. Each test medium is inoculated with the above inoculum (0.1 ml), cultured at 30 ° C for 24 hours, and visually inspected for turbidity of the medium to determine the presence or absence of bacterial growth. Were determined. The minimum concentration of the mixture of 2-pyridinethiol-1-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one that could inhibit bacterial growth in the medium was defined as MIC. Table 1 shows the MIC for each bacterium of the antimicrobial composition at each weight ratio.
Figure imgf000009_0001
Figure imgf000009_0001
1 ) 薬剤 A： 2—ピリジンチオール- - 1—ォキシド亜鉛塩  1) Drug A: 2-pyridinethiol--1-oxide zinc salt
2) 薬剤 B ： 2— n—ォクチル— 4- イソチアゾリン— 3—オン (実施例 2 ) 2) Drug B: 2—n-octyl—4-isothiazoline—3—one (Example 2)
2 —ピリジンチオール— 1—ォキシド亜鉛塩と、 2 — n—ォクチルー 4—イソチ ァゾリン- 3 —オンとを、 以下の表 2に示される各重量比でジメチルスルホキシ ドに添加し、 5つの抗微生物剤組成物を調製した。 次いで、 この抗微生物剤組成 物の段階希釈水溶液 （0 . 3 m l ) を、 ポテトデキストロース寒天培地 （1 5 m 1 ) に添加し、 各試験培地を調製した。 この各試験培地に、 上記の接種用胞子懸 濁液 （1 m l ) を接種し、 2 8 °Cで 7日間培養した後、 培地上の真菌の発育を目 視検査することにより真菌の発育の有無をそれぞれ決定した。 培地上での真菌の 発育を阻止し得る、 2—ピリジンチオール一 1 一ォキシド亜鉛塩と 2— n—ォク チルー 4一イソチアゾリンー 3—オンとの混合物の最小濃度を M I Cとした。 各 重量比の抗微生物剤組成物の、 各真菌についての M I Cを表 2に示す。 表 2  2—Pyridinethiol—1-oxide zinc salt and 2—n-octyl-4-isothiazolin-3-one were added to dimethyl sulfoxide at the weight ratios shown in Table 2 below to give 5 A microbial agent composition was prepared. Next, a serially diluted aqueous solution (0.3 ml) of the antimicrobial composition was added to a potato dextrose agar medium (15 ml) to prepare each test medium. Each test medium was inoculated with the above spore suspension (1 ml) for inoculation, cultured at 28 ° C for 7 days, and then visually inspected for fungal growth on the medium. The presence or absence was determined respectively. The minimum concentration of a mixture of 2-pyridinethiol-111-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one that could inhibit fungal growth on the medium was defined as MIC. Table 2 shows the MIC for each fungus of the antimicrobial composition at each weight ratio. Table 2
Figure imgf000010_0001
Figure imgf000010_0001
1 ) 薬剤 A : 2—ピリジンチオール— 1 —ォキシド亜鉛塩  1) Drug A: 2-pyridinethiol-1-zinc oxide salt
2 ) 薬剤 B： 2— n—才クチル— 4 _イソチアゾリンー 3—オン  2) Drug B: 2—n—Cutyl—4_isothiazoline-3-one
(実施例 3 ) (Example 3)
2—ピリジンチォ一ルー 1一才キシド亜鉛塩と、 2— n—才クチルー 4—イソ チアゾリンー 3 —オンとを、 以下の表 3に示される各重量比でジメチルスルホキ シドに添加し、 5つの抗微生物剤組成物を調製した。 次いで、 この抗微生物剤組 成物の段階希釈水溶液 （0. 1ml ) を、 BB寒天培地 （15ml) に添加し、 各試験培地を調製した。 この各試験培地に、 上記の接種用藻懸濁液 （1m l ) を 接種し、 25°C、 1500 1 uxで 14日間培養した後、 培地上の藻の発育を目 視検査することにより藻の発育の有無をそれぞれ決定した。 培地上での藻の発育 を阻止し得る、 2—ピリジンチオール— 1一ォキシド亜鉛塩と 2— n—才クチル 一 4—イソチアゾリン— 3—オンとの混合物の最小濃度を M I Cとした。 各重量 比の抗微生物剤組成物の、 藻についての M I Cを表 3に示す。 表 3 2-Pyridinethiol 1-year-old zinc oxide salt and 2-n-year-old octyl-4-isothiazolin-3-one were added to dimethyl sulfoxide at the respective weight ratios shown in Table 3 below. An antimicrobial composition was prepared. Next, this antimicrobial group A serially diluted aqueous solution (0.1 ml) of the product was added to BB agar medium (15 ml) to prepare each test medium. Each test medium is inoculated with the above algal suspension for inoculation (1 ml), cultured at 25 ° C and 1500 lux for 14 days, and then visually inspected for algal growth on the medium. The presence or absence of growth of each was determined. The MIC was defined as the minimum concentration of a mixture of 2-pyridinethiol-11-oxide zinc salt and 2-n-octyl-14-isothiazolin-3-one that could inhibit the growth of algae on the medium. Table 3 shows the MIC for the algae of the antimicrobial composition at each weight ratio. Table 3
Figure imgf000011_0001
Figure imgf000011_0001
1) 薬剤 A： 2 ピリジンチオール一 1一ォキシド亜鉛塩  1) Drug A: 2 Pyridine thiol 1-1 Oxide zinc salt
2) 薬剤 B： 2 n一才クチルー 4—ィソチアゾリンー 3—オン 表 1、 2および 3から、 本発明の抗微生物剤組成物は、 有効成分の相乗効果に より従来の抗微生物剤組成物と比較して効力が高く、 かつ広い抗菌スぺクトルを 示すことが示される。 さらに、 単独で有効成分を用いた場合と比較して、 同一量 の細菌、 真菌または藻類の発育を阻止するために用いられる抗微生物剤組成物の 濃度は、 極めて低く抑えられることが示される。 産業上の利用可能性 2) Drug B: 2 n-one-year-old tylyl 4-isothiazolin-3-one From Tables 1, 2 and 3, the antimicrobial composition of the present invention is compared with the conventional antimicrobial composition due to the synergistic effect of the active ingredient. It shows high efficacy and wide antibacterial spectrum. Furthermore, it is shown that the concentration of the antimicrobial composition used to inhibit the growth of the same amount of bacteria, fungi or algae can be kept very low compared to when the active ingredient is used alone. Industrial applicability
本発明によれば、 2—ピリジンチオール一 1一才キシド亜鉛塩および 2— n— ォクチル— 4ーィソチアゾリン— 3—オンを有効成分として含有する抗微生物剤 組成物が得られる。 これら 2種の有効成分を組み合わせることにより、 これらの 成分の相乗作用が得られ、 安全性が高く、 効力が高く、 さらに広い抗菌スぺク卜 ルを有する抗微生物剤組成物が提供される。 さらに、 本発明の抗微生物剤組成物 に含有される有効成分の濃度は低く抑えられるので、 極めて安価に調製され得、 さらに環境に与える影響は少ない。 本発明の抗微生物剤組成物は、 種々の工業製 品および工業用原材料の防腐防かび防藻に有効である。 According to the present invention, there is obtained an antimicrobial composition comprising 2-pyridinethiol-11-year-old zinc oxide salt and 2-n-octyl-4-isothiazolin-3-one as active ingredients. By combining these two active ingredients, An antimicrobial composition having a synergistic effect of components, high safety, high efficacy, and a broad antibacterial spectrum is provided. Furthermore, since the concentration of the active ingredient contained in the antimicrobial composition of the present invention can be kept low, it can be prepared at extremely low cost and has little effect on the environment. INDUSTRIAL APPLICABILITY The antimicrobial composition of the present invention is effective for the preservative and fungal control of various industrial products and industrial raw materials.

Claims

請求の範囲 The scope of the claims
1 . 2—ピリジンチオール一 1—ォキシド亜鉛塩と、 2— n—ォクチルー 4— ィソチアゾリンー 3—オンとを含有する抗微生物剤組成物。 An antimicrobial composition comprising 1.2-pyridinethiol-1-oxoxide zinc salt and 2-n-octyl-4-isothiazolin-3-one.
2 . 前記 2—ピリジンチォ一ルー 1—ォキシド亜鉛塩と、 前記 2— n—才クチ ルー 4一イソチアゾリン— 3—オンとの重量比が、 2 0 ： 1〜 1 ： 2 0の範囲で ある、 請求項 1に記載の抗微生物剤組成物。 2. The weight ratio of the zinc salt of 2-pyridinethiol 1-oxide to the salt of 2-n-cyclohexyl 4-isothiazolin-3-one is in the range of 20: 1 to 1:20. The antimicrobial composition according to claim 1.
3 . 前記 2 —ピリジンチォ一ルー 1—ォキシド亜鉛塩と、 前記 2— n—才クチ ル—4—イソチアゾリンー 3 —オンとの重量比が、 5 ： 1〜1 ： 5の範囲である、 請求項 1に記載の抗微生物剤組成物。 3. The weight ratio of the 2-pyridinepyridine 1-oxide zinc salt to the 2-n-octyl-4-isothiazolin-3-one is in the range of 5: 1 to 1: 5. Item 4. The antimicrobial composition according to Item 1.
PCT/JP1999/007384 1998-12-28 1999-12-28 Antimicrobial compositions WO2000038520A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012130822A1 (en) * 2011-03-28 2012-10-04 Arch Chemicals Inc. Wet state preservation of mineral slurries
US9717250B2 (en) 2006-05-26 2017-08-01 Arch Chemicals, Inc. Isothiazolinone biocides enhanced by zinc ions

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10040814A1 (en) * 2000-08-21 2002-03-07 Thor Gmbh Synergistic biocide composition
JP2002265310A (en) * 2001-03-06 2002-09-18 Nagase Chemtex Corp Antimicrobial agent composition
JP4766641B2 (en) * 2001-08-29 2011-09-07 住化エンビロサイエンス株式会社 Industrial antibacterial composition and antibacterial method
EP1772055A1 (en) 2005-10-04 2007-04-11 Rohm and Haas France SAS Synergistic microbicidal compositions comprising a N-alkyl-1,2-benzoisothiazolin-3-one
KR101230109B1 (en) * 2006-01-25 2013-02-05 쓰리엠 이노베이티브 프로퍼티즈 캄파니 Air filter having antimicrobial property
JP6125400B2 (en) * 2013-10-21 2017-05-10 株式会社ピュアソン Antibacterial treatment method and antibacterial agent

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57156405A (en) * 1981-03-24 1982-09-27 Yoshitomi Pharmaceut Ind Ltd Fungicide for industrial purpose
EP0492811A1 (en) * 1990-12-20 1992-07-01 Zeneca Limited Antimicrobial composition and use
JPH06227912A (en) * 1993-01-28 1994-08-16 Sekisui Chem Co Ltd Mildew-proofing sealing material composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57156405A (en) * 1981-03-24 1982-09-27 Yoshitomi Pharmaceut Ind Ltd Fungicide for industrial purpose
EP0492811A1 (en) * 1990-12-20 1992-07-01 Zeneca Limited Antimicrobial composition and use
JPH06227912A (en) * 1993-01-28 1994-08-16 Sekisui Chem Co Ltd Mildew-proofing sealing material composition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9717250B2 (en) 2006-05-26 2017-08-01 Arch Chemicals, Inc. Isothiazolinone biocides enhanced by zinc ions
US9723842B2 (en) 2006-05-26 2017-08-08 Arch Chemicals, Inc. Isothiazolinone biocides enhanced by zinc ions
WO2012130822A1 (en) * 2011-03-28 2012-10-04 Arch Chemicals Inc. Wet state preservation of mineral slurries
US8317912B2 (en) 2011-03-28 2012-11-27 Arch Chemicals, Inc. Wet state preservation of mineral slurries
AU2012234326B2 (en) * 2011-03-28 2015-08-27 Arch Chemicals Inc. Wet state preservation of mineral slurries

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