TW202348565A - Method for suppressing decomposition of isothiazoline compound in aqueous system - Google Patents
Method for suppressing decomposition of isothiazoline compound in aqueous system Download PDFInfo
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- TW202348565A TW202348565A TW112114108A TW112114108A TW202348565A TW 202348565 A TW202348565 A TW 202348565A TW 112114108 A TW112114108 A TW 112114108A TW 112114108 A TW112114108 A TW 112114108A TW 202348565 A TW202348565 A TW 202348565A
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- -1 isothiazoline compound Chemical class 0.000 title claims abstract description 46
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 230000002401 inhibitory effect Effects 0.000 claims description 16
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 14
- 229940005654 nitrite ion Drugs 0.000 claims description 14
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- 239000000498 cooling water Substances 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical class ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 4
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 claims description 4
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 claims description 2
- 229940044120 2-n-octyl-4-isothiazolin-3-one Drugs 0.000 claims description 2
- JRQLZCFSWYQHPI-UHFFFAOYSA-N 4,5-dichloro-2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1CCCCC1 JRQLZCFSWYQHPI-UHFFFAOYSA-N 0.000 claims description 2
- NKEKPBPHPFSSIT-UHFFFAOYSA-N 5-chloro-2-(2,4,4-trimethylpentan-2-yl)-1,2-thiazol-3-one Chemical compound CC(C)(C)CC(C)(C)N1SC(Cl)=CC1=O NKEKPBPHPFSSIT-UHFFFAOYSA-N 0.000 claims description 2
- MMONDPHQMXRZDG-UHFFFAOYSA-N 5-chloro-2-ethyl-1,2-thiazol-3-one Chemical compound CCN1SC(Cl)=CC1=O MMONDPHQMXRZDG-UHFFFAOYSA-N 0.000 claims description 2
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 2
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 claims description 2
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 claims description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 claims description 2
- 235000010289 potassium nitrite Nutrition 0.000 claims description 2
- 239000004304 potassium nitrite Substances 0.000 claims description 2
- UEFCKYIRXORTFI-UHFFFAOYSA-N 1,2-thiazolidin-3-one Chemical compound O=C1CCSN1 UEFCKYIRXORTFI-UHFFFAOYSA-N 0.000 claims 1
- ASKFWACWQQZSSS-UHFFFAOYSA-N 2-ethyl-1,2-thiazol-3-one Chemical compound CCN1SC=CC1=O ASKFWACWQQZSSS-UHFFFAOYSA-N 0.000 claims 1
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical class C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- 239000003242 anti bacterial agent Substances 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- LTMQZVLXCLQPCT-UHFFFAOYSA-N 1,1,6-trimethyltetralin Chemical compound C1CCC(C)(C)C=2C1=CC(C)=CC=2 LTMQZVLXCLQPCT-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000589651 Zoogloea Species 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Mycology (AREA)
- Microbiology (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Removal Of Specific Substances (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
本發明是有關於一種水系統中的異噻唑啉系化合物的分解抑制方法，其中於添加有異噻唑啉系化合物作為抗菌劑的水系統中，對異噻唑啉系化合物的分解進行抑制，從而穩定地維持水中的異噻唑啉系化合物濃度。The present invention relates to a method for inhibiting the decomposition of an isothiazoline compound in a water system, in which the decomposition of the isothiazoline compound is inhibited in a water system in which an isothiazoline compound is added as an antibacterial agent, thereby stabilizing Maintain the concentration of isothiazoline compounds in water.
為了抑制冷卻水系統等中的由菌膠團（zoogloea）狀細菌、藻類、絲狀菌等引起的黏泥（slime）障礙，進行添加抗菌劑的操作。作為抗菌劑，異噻唑啉系化合物的抗菌力高，被廣泛使用。 然而，異噻唑啉系化合物於水系統中的分解速度比較快，難以維持濃度。 Antibacterial agents are added to suppress slime obstruction caused by zoogloea bacteria, algae, filamentous bacteria, etc. in cooling water systems. As antibacterial agents, isothiazoline compounds have high antibacterial power and are widely used. However, isothiazoline compounds decompose relatively quickly in water systems, making it difficult to maintain their concentration.
先前，作為抑制水系統中的異噻唑啉系化合物的分解的方法，提出有：併用添加磷酸或紫羅烯聚合物（ionene polymer）等的方法、或將異噻唑啉系化合物與其他藥劑組合而用作抗菌劑組成物的方法（例如，專利文獻1～專利文獻3）。 [現有技術文獻] [專利文獻] Previously, as a method of suppressing the decomposition of isothiazoline compounds in a water system, a method of adding phosphoric acid or an ionene polymer in combination, or a combination of an isothiazoline compound and other chemicals have been proposed. A method of using it as an antibacterial agent composition (for example, Patent Document 1 to Patent Document 3). [Prior art documents] [Patent Document]
專利文獻1：日本專利特開2011-212522號公報 專利文獻2：日本專利特開平11-158014號公報 專利文獻3：日本專利特開2000-327506號公報 Patent Document 1: Japanese Patent Application Publication No. 2011-212522 Patent Document 2: Japanese Patent Application Publication No. 11-158014 Patent Document 3: Japanese Patent Application Laid-Open No. 2000-327506
[發明所欲解決之課題] 然而，於現有方法中，存在如下問題等問題：需要以高濃度添加用於抑制異噻唑啉系化合物的分解的藥劑；無法充分抑制異噻唑啉系化合物的分解；於對環境的影響、安全性的方面存在擔憂。 [Problem to be solved by the invention] However, existing methods have problems such as the following: it is necessary to add agents for inhibiting the decomposition of isothiazoline compounds at high concentrations; the decomposition of isothiazoline compounds cannot be sufficiently inhibited; and the impact on the environment and safety There are concerns about.
例如，於使用磷酸的方法中，需要以高濃度添加磷酸，存在處理成本高的問題。For example, in a method using phosphoric acid, phosphoric acid needs to be added at a high concentration, resulting in high processing costs.
於使用紫羅烯聚合物的方法中，化合物的成本高，另外穩定性不充分。進而亦具有安全性或環境方面的問題。In the method using an ionene polymer, the cost of the compound is high and the stability is insufficient. There may also be safety or environmental issues.
另外，於使用多種藥劑製成抗菌劑組成物時，藥劑成本高漲。In addition, when multiple chemicals are used to prepare an antibacterial agent composition, the cost of the chemicals increases.
本發明的課題在於提供一種使用安全性或環境方面的問題小的化合物、以低成本抑制水系統中的異噻唑啉系化合物的分解的方法。 [解決課題之手段] An object of the present invention is to provide a method for suppressing the decomposition of an isothiazoline compound in a water system at low cost using a compound with little safety or environmental problems. [Means to solve the problem]
本發明者為了解決所述課題而反覆研究，結果發現，藉由以低濃度添加安全性高的亞硝酸化合物，可以低成本有效地抑制異噻唑啉系化合物的分解。The present inventors conducted repeated studies to solve the above-mentioned problems, and found that decomposition of the isothiazoline compound can be effectively suppressed at low cost by adding a highly safe nitrous acid compound at a low concentration.
本發明以如下內容為主旨。The present invention is based on the following contents.
[1] 一種水系統中的異噻唑啉系化合物的分解抑制方法，為抑制水系統中的異噻唑啉系化合物的分解的方法，其特徵在於：以亞硝酸根離子濃度成為5 mg/L以上的方式於該水系統中添加亞硝酸化合物。[1] A method for inhibiting the decomposition of isothiazoline compounds in a water system, which is a method for inhibiting the decomposition of isothiazoline compounds in a water system, characterized in that the nitrite ion concentration is 5 mg/L or more way to add nitrous acid compounds to the water system.
[2] 如[1]所述的水系統中的異噻唑啉系化合物的分解抑制方法，其中所述水系統為冷卻水系統、紙漿製造水系統、或洗滌器水系統。 [發明的效果] [2] The method for inhibiting the decomposition of an isothiazoline compound in a water system as described in [1], wherein the water system is a cooling water system, a pulp manufacturing water system, or a scrubber water system. [Effects of the invention]
根據本發明，藉由以低濃度添加安全性高的亞硝酸化合物，可以低成本有效地抑制異噻唑啉系化合物的分解。According to the present invention, by adding a highly safe nitrous acid compound at a low concentration, the decomposition of the isothiazoline compound can be effectively suppressed at low cost.
以下，對本發明的實施形態進行詳細說明。Hereinafter, embodiments of the present invention will be described in detail.
於本發明中，藉由在添加有異噻唑啉系化合物的水系統中以亞硝酸根離子濃度成為5 mg/L以上的方式添加亞硝酸化合物，來抑制異噻唑啉系化合物的分解。In the present invention, the decomposition of the isothiazoline compound is suppressed by adding a nitrous acid compound to the water system to which the isothiazoline compound is added so that the nitrite ion concentration becomes 5 mg/L or more.
關於藉由亞硝酸根離子的存在而抑制異噻唑啉系化合物的分解的作用機制，尚不清楚，但若亞硝酸根離子濃度為5 mg/L以上，則如以後揭示的實驗例1所示，可抑制異噻唑啉系化合物的分解，可長期穩定地維持水系統中的異噻唑啉系化合物濃度。The mechanism of action that inhibits the decomposition of isothiazoline compounds by the presence of nitrite ions is not yet clear, but if the nitrite ion concentration is 5 mg/L or more, as shown in Experimental Example 1 to be disclosed later , can inhibit the decomposition of isothiazoline compounds and can stably maintain the concentration of isothiazoline compounds in the water system for a long time.
於本發明中，水系統的亞硝酸根離子濃度只要為5 mg/L以上即可，由於存在亞硝酸根離子濃度越高、異噻唑啉系化合物的分解抑制效果越高的傾向，因此較佳為10 mg/L以上，更佳為200 mg/L以上。其中，若使亞硝酸根離子濃度過高，則於經濟方面不利，或者電導率變高並加劇腐蝕，或者排水時的環境影響變高，因此亞硝酸根離子濃度的上限通常為3,000 mg/L左右。In the present invention, the nitrite ion concentration of the water system only needs to be 5 mg/L or more. Since there is a tendency that the higher the nitrite ion concentration is, the higher the decomposition inhibitory effect of the isothiazoline compound is, so it is preferable. It is 10 mg/L or more, and more preferably, it is 200 mg/L or more. Among them, if the nitrite ion concentration is too high, it will be economically disadvantageous, the electrical conductivity will increase and corrosion will be aggravated, or the environmental impact during drainage will increase. Therefore, the upper limit of the nitrite ion concentration is usually 3,000 mg/L. about.
作為亞硝酸化合物，可使用亞硝酸鈉、亞硝酸鉀、及亞硝酸銨等亞硝酸鹽的一種或兩種以上。As the nitrite compound, one or more types of nitrites such as sodium nitrite, potassium nitrite, and ammonium nitrite can be used.
所謂應用本發明的水系統，是指進行了利用異噻唑啉系化合物的抗菌處理的水系統，可列舉：冷卻水系統、紙漿製造水系統、洗滌器水系統等。The water system to which the present invention is applied refers to a water system that has been subjected to antibacterial treatment using an isothiazoline compound, and examples include a cooling water system, a pulp production water system, a scrubber water system, and the like.
作為於該些水系統中作為抗菌劑而添加的異噻唑啉系化合物，例如可列舉：2-甲基-4-異噻唑啉-3-酮、2-乙基-4-異噻唑啉-3-酮、2-正辛基-4-異噻唑啉-3-酮、5-氯-2-甲基-4-異噻唑啉-3-酮、5-氯-2-乙基-4-異噻唑啉-3-酮、5-氯-2-第三辛基-4-異噻唑啉-3-酮、4,5-二氯-2-正辛基-4-異噻唑啉-3-酮、及4,5-二氯-2-環己基-4-異噻唑啉-3-酮等。該些異噻唑啉系化合物可單獨使用一種，或者亦可組合使用兩種以上。另外，作為異噻唑啉系化合物，亦可使用所述異噻唑啉系化合物與氯化鎂、硝酸鎂、氯化銅、硝酸銅、氯化鈣等的錯合化合物。Examples of isothiazoline compounds added as antibacterial agents in these water systems include: 2-methyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3 -Ketone, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-iso Thiazolin-3-one, 5-chloro-2-tertiary octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one , and 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one, etc. These isothiazoline compounds may be used individually by 1 type, or may be used in combination of 2 or more types. In addition, as the isothiazoline-based compound, a complex compound of the isothiazoline-based compound and magnesium chloride, magnesium nitrate, copper chloride, copper nitrate, calcium chloride, etc. can also be used.
異噻唑啉系化合物與亞硝酸化合物可在水系統的同一部位添加，亦可在不同的部位添加。於在同一部位添加的情況下，異噻唑啉系化合物與亞硝酸化合物可製成一劑來添加，亦可各自分別添加。於在水系統的不同部位添加異噻唑啉系化合物與亞硝酸化合物的情況下，若異噻唑啉系化合物與亞硝酸化合物的添加部位過於分離，則有時無法充分獲得由亞硝酸化合物帶來的異噻唑啉系化合物的分解抑制效果，因此亞硝酸化合物較佳為在相對於異噻唑啉系化合物的添加部位而言可均勻混合的部位、例如具有流速的部位添加。The isothiazoline compound and the nitrous acid compound can be added at the same part of the water system, or they can be added at different parts. When they are added at the same site, the isothiazoline compound and the nitrous acid compound may be added as one dose, or they may be added separately. When an isothiazoline compound and a nitrous acid compound are added to different parts of the water system, if the adding parts of the isothiazoline compound and the nitrous acid compound are too separated, the benefits brought by the nitrous acid compound may not be fully obtained. Because of the decomposition inhibitory effect of the isothiazoline-based compound, the nitrous acid compound is preferably added at a location where the isothiazoline-based compound can be uniformly mixed with respect to the location where the isothiazoline-based compound is added, for example, a location with a flow rate.
根據本發明，於進行了利用異噻唑啉系化合物的抗菌處理的冷卻水系統等各種水系統中，僅藉由使亞硝酸根離子以規定濃度以上存在，便能夠抑制異噻唑啉系化合物的分解，並長期維持由異噻唑啉系化合物帶來的抗菌效果。 [實施例] According to the present invention, in various water systems such as cooling water systems that have undergone antibacterial treatment using isothiazoline compounds, it is possible to suppress the decomposition of isothiazoline compounds simply by allowing nitrite ions to exist at a predetermined concentration or above. , and maintain the antibacterial effect brought by isothiazoline compounds for a long time. [Example]
以下，列舉代替實施例的實驗例，更具體地示出本發明的效果。Hereinafter, experimental examples in place of the Examples will be given to demonstrate the effects of the present invention more specifically.
[實驗例1] 按照以下的（1）～（4）的順序，進行對由亞硝酸根離子帶來的異噻唑啉系化合物的分解抑制效果進行調查的實驗。 作為異噻唑啉系化合物，使用下述結構式所表示的5-氯-2-甲基-4-異噻唑啉-3-酮（5-chloro-2-methyl-4-isothiazoline-3-one，CL-MIT）。 [Experimental example 1] An experiment was conducted to investigate the effect of inhibiting the decomposition of an isothiazoline-based compound by nitrite ions in accordance with the following procedures (1) to (4). As the isothiazoline compound, 5-chloro-2-methyl-4-isothiazoline-3-one represented by the following structural formula is used. CL-MIT).
[化1] [Chemical 1]
再者，為了於實際設備中在配管內的循環水中添加抗菌劑，設想與實際設備接近的環境來進行。Furthermore, in order to add an antibacterial agent to the circulating water in the pipe in an actual facility, an environment close to that of the actual facility is assumed.
（1） 於100 mL燒杯中放入自來水脫氯水100 mL，浸漬SPCC試驗片（30 mm×50 mm×1 mm）。(1) Put 100 mL of dechlorinated tap water into a 100 mL beaker, and immerse the SPCC test piece (30 mm × 50 mm × 1 mm).
（2） 向其中添加10重量%CL-MIT水溶液與0.1重量%亞硝酸鈉水溶液（其中，空白中不添加）。(2) Add 10% by weight CL-MIT aqueous solution and 0.1% by weight sodium nitrite aqueous solution (no addition is made to the blank).
（3） 開始利用磁攪拌器（magnetic stirrer）的攪拌，測定開始時與4天後的CL-MIT濃度，根據下述式子算出CL-MIT的殘存率。 CL-MIT殘存率（%） =試驗後的CL-MIT濃度（mg/L）÷試驗前的CL-MIT（mg/L）×100 (3) Start stirring with a magnetic stirrer, measure the CL-MIT concentration at the beginning and 4 days later, and calculate the residual rate of CL-MIT according to the following formula. CL-MIT survival rate (%) = CL-MIT concentration after the test (mg/L) ÷ CL-MIT before the test (mg/L) × 100
（4） 試驗是改變亞硝酸鈉水溶液的添加量而進行，改變水中的亞硝酸根離子濃度，對亞硝酸根離子濃度與CL-MIT殘存率的關係進行調查，將結果示於表1及圖1中。(4) The test was conducted by changing the amount of sodium nitrite aqueous solution added, changing the nitrite ion concentration in the water, and investigating the relationship between the nitrite ion concentration and the CL-MIT residual rate. The results are shown in Table 1 and the figure. 1 in.
[比較實驗例1] 使用0.1重量%磷酸水溶液來代替亞硝酸鈉水溶液，並與實驗例1同樣地進行實驗。將結果示於表2及圖1中。 [Comparative Experiment Example 1] An experiment was performed in the same manner as Experimental Example 1 using a 0.1% by weight phosphoric acid aqueous solution instead of the sodium nitrite aqueous solution. The results are shown in Table 2 and Figure 1.
[表1]
[表2]
如根據表1、表2及圖1而明瞭般，得知，於磷酸中，即便以高濃度添加而高達50 mg/L，亦只是略微確認到CL-MIT的分解抑制效果，但若為亞硝酸根離子，則可藉由5 mg/L的低濃度添加來抑制CL-MIT的分解，藉由進一步提高添加量，可更高程度地抑制CL-MIT的分解。As is clear from Table 1, Table 2 and Figure 1, even if it is added at a high concentration of 50 mg/L in phosphoric acid, the decomposition inhibitory effect of CL-MIT is only slightly confirmed, but if it is sub- For nitrate ions, the decomposition of CL-MIT can be inhibited by adding a low concentration of 5 mg/L. By further increasing the addition amount, the decomposition of CL-MIT can be inhibited to a higher degree.
於實驗例1中，認為亞硝酸根離子濃度為100 mg/L時CL-MIT殘存率成為111%是於高濃度的亞硝酸的存在下產生的分析誤差。In Experimental Example 1, it is believed that the CL-MIT residual rate being 111% when the nitrite ion concentration is 100 mg/L is an analytical error caused by the presence of high-concentration nitrous acid.
使用特定的態樣詳細說明了本發明，但所屬技術領域具有通常知識者明瞭：能夠於不脫離本發明的意圖與範圍的情況下進行各種變更。 本申請案基於2022年6月3日提出申請的日本專利申請案2022-090989，並藉由引用而援引其全文。 Although the present invention has been described in detail using specific aspects, it will be apparent to those skilled in the art that various changes can be made without departing from the intention and scope of the present invention. This application is based on Japanese Patent Application 2022-090989 filed on June 3, 2022, and the entire text thereof is incorporated by reference.
無without
圖1是表示實驗例1及比較實驗例1的結果的圖表。FIG. 1 is a graph showing the results of Experimental Example 1 and Comparative Experimental Example 1.
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| DE4339248A1 (en) * | 1993-11-18 | 1995-05-24 | Riedel De Haen Ag | Storage-stable aqueous solutions of isothiazolin-3-ones |
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