TWI426865B - 殺菌組成物 - Google Patents

殺菌組成物 Download PDF

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TWI426865B
TWI426865B TW101121503A TW101121503A TWI426865B TW I426865 B TWI426865 B TW I426865B TW 101121503 A TW101121503 A TW 101121503A TW 101121503 A TW101121503 A TW 101121503A TW I426865 B TWI426865 B TW I426865B
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methyl
benzisothiazolin
ppm
present
microorganisms
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John William Ashmore
Mma Beverly Jean Ela
Beat Heer
Richard Levy
Kiran Pareek
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Rohm & Haas
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    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • A—HUMAN NECESSITIES
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof
    • A—HUMAN NECESSITIES
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    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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Description

殺菌組成物
本發明係關於一種經選擇之殺菌劑的協同組合，其具有之活性比在個別殺菌劑中所觀察到之活性更大。
在某些情況中，即使是在高使用濃度下，由於商用殺菌劑對抗某些類型的微生物(例如，對於某些殺菌劑具有抗性之微生物)之活性弱，或由於侵略性環境條件，而使該等商用殺菌劑無法提供有效的微生物控制。有時候，在特定目的使用環境中使用不同殺菌劑之組合，以提供全面的微生物控制。例如，美國專利申請公開案第2007/0078118號揭示N-甲基-1,2-苯并異噻唑啉-3-酮(MBIT)與其他殺生物劑之協同組合。然而，為提供有效的微生物控制，對於具有抗各種微生物菌株之增強活性的額外殺菌劑組合仍有所需求。再者，為了環境及經濟效益，對於含有較低量個別殺菌劑之組合亦有所需求。本發明係提供此等額外的殺菌劑組合而解決問題。
本發明係有關一種殺菌組成物(下文中有稱為「抗菌組成物」之情形)，其包含：(a)N-甲基-1,2-苯并異噻唑啉-3-酮；及(b)至少一種殺菌劑，其係選自下列各者所組成之群組：月桂醯基精胺酸乙酯鹽酸鹽；椰油醯胺丙基-N-2-羥基乙基胺甲醯基甲基二甲基銨氯化物(cocamidopropyl-N-2-hydroxyethylcarbamoyl methyl dimethyl ammonium chloride)；2-胺基乙醇銅(II)(Cu(II)2-aminoethanolate)與二癸基二甲基銨氯化物；二癸基二甲基銨碳酸鹽與二癸基二甲基銨碳酸氫鹽；2-胺基乙醇銅(II)；單月桂酸甘油酯；單月桂酸丙二醇酯；及辛酸丙二醇酯。
如本文中所使用，除非文中另有明確指示，否則下列術語具有指定的定義。“MBIT”係N-甲基-1,2-苯并異噻唑啉-3-酮。術語“殺菌劑”意指能夠於一位置(locus)殺死微生物、抑制微生物生長或控制微生物生長的化合物；殺菌劑包括殺細菌劑、殺真菌劑及殺藻劑。術語“微生物”包括例如真菌(例如酵母菌及黴菌)、細菌及藻類。術語“位置”意指受到微生物污染之工業系統或產品。下列縮寫係用於說明書全文中：ppm=以重量計之每百萬份之份數(重量/重量)，mL=毫升，ATCC=美國菌種保藏中心(American Type Culture Collection)，MBC=最低殺菌濃度，及MIC=最低抑制濃度。除非另外指明，否則溫度係以攝氏度(℃)計，且百分比(%)之參考基準係以重量計。有機殺菌劑的量係由以ppm(重量/重量)計之活性成分基質呈現。
意外地發現本發明之組成物能在組合的活性成分含量低於個別殺菌劑的活性成分含量之情況下，提供增強的殺菌效力。超出申請專利範圍所列殺菌劑範疇之其他殺菌劑亦可存在於該組成物中。
於本發明的一具體例中，該抗菌組成物包含N-甲基-1,2-苯并異噻唑啉-3-酮及月桂醯基精胺酸乙酯鹽酸鹽。 月桂醯基精胺酸乙酯鹽酸鹽對N-甲基-1,2-苯并異噻唑啉-3-酮之重量比較佳為1：94至1：0.0137。
於本發明的一具體例中，該抗菌組成物包含N-甲基-1,2-苯并異噻唑啉-3-酮及椰油醯胺丙基-N-2-羥基乙基胺甲醯基甲基二甲基銨氯化物。椰油醯胺丙基-N-2-羥基乙基胺甲醯基甲基二甲基銨氯化物對N-甲基-1,2-苯并異噻唑啉-3-酮之重量比較佳為1：188至1：0.0022。
於本發明的一具體例中，該抗菌組成物包含N-甲基-1,2-苯并異噻唑啉-3-酮及2-胺基乙醇銅(II)與二癸基二甲基銨氯化物。2-胺基乙醇銅(II)與二癸基二甲基銨氯化物對N-甲基-1,2-苯并異噻唑啉-3-酮之重量比較佳為1：176至1：0.08。
於本發明的一具體例中，該抗菌組成物包含N-甲基-1,2-苯并異噻唑啉-3-酮及二癸基二甲基銨碳酸鹽與二癸基二甲基銨碳酸氫鹽。二癸基二甲基銨碳酸鹽與二癸基二甲基銨碳酸氫鹽對N-甲基-1,2-苯并異噻唑啉-3-酮之重量比較佳為1：227至1：0.179。
於本發明的一具體例中，該抗菌組成物包含N-甲基-1,2-苯并異噻唑啉-3-酮及2-胺基乙醇銅(II)。2-胺基乙醇銅(II)對N-甲基-1,2-苯并異噻唑啉-3-酮之重量比較佳為1：375至1：0.004。
於本發明的一具體例中，該抗菌組成物包含N-甲基-1,2-苯并異噻唑啉-3-酮及單月桂酸甘油酯。單月桂酸甘油酯對N-甲基-1,2-苯并異噻唑啉-3-酮之重量比較佳為 1：0.143至1：0.0004。
於本發明的一具體例中，該抗菌組成物包含N-甲基-1,2-苯并異噻唑啉-3-酮及單月桂酸丙二醇酯。單月桂酸丙二醇酯對N-甲基-1,2-苯并異噻唑啉-3-酮之重量比較佳為1：0.286至1：0.0286。
於本發明的一具體例中，該抗菌組成物包含N-甲基-1,2-苯并異噻唑啉-3-酮及辛酸丙二醇酯。辛酸丙二醇酯對N-甲基-1,2-苯并異噻唑啉-3-酮之重量比較佳為1：0.442至1：0.0018。
可使用本發明組成物中之殺菌劑“本身”或可先將該殺菌劑與溶劑或固體載劑調製。適當的溶劑包括例如：水；二醇，例如乙二醇、丙二醇、二乙二醇、二丙二醇、聚乙二醇及聚丙二醇；二醇醚；醇，例如甲醇、乙醇、丙醇、苯乙醇及苯氧基丙醇；酮，例如丙酮及甲基乙基酮；酯，例如醋酸乙酯、醋酸丁酯、檸檬酸三乙醯酯及三醋酸甘油酯；碳酸酯，例如碳酸丙二酯及碳酸二甲酯；及其混合物。該溶劑較佳係選自水、二醇、二醇醚、酯及其混合物。適當的固體載劑包括例如：環糊精、氧化矽、矽藻土、蠟、纖維質材料、鹼金屬及鹼土金屬(例如，鈉、鎂、鉀)鹽(例如，氯化物、硝酸鹽、溴化物、硫酸鹽)及木炭。
將殺菌劑組分調製於溶劑中時，該調配物可視需要含有界面活性劑。當此等調配物含有界面活性劑時，其通常呈乳化濃縮物、乳液、微乳化濃縮物、或微乳液形式。乳化濃縮物在添加足量水之後，會形成乳液。微乳化濃縮物 在添加足量水之後，會形成微乳液。此等乳化及微乳化濃縮物於本技術領域中普遍為人所熟知；此等調配物較佳不含界面活性劑。可查閱美國專利第5,444,078號，以進一步獲取製備各種微乳液及微乳化濃縮物之一般及具體細節。
亦可將殺菌劑組分調製成分散液形式。分散液之溶劑組分可為有機溶劑或水，較佳為水。此等分散液可含有佐劑，例如共溶劑、增稠劑、防凍劑、分散劑、填充劑、顏料、界面活性劑、生物分散劑、磺酸基琥珀酸酯、萜烯、呋喃酮、多價陽離子、安定劑、防垢劑及防腐蝕添加劑。
當將兩種殺菌劑各自首先與溶劑調製時，用於第一種殺菌劑之溶劑可與用於調製另一種商用殺菌劑之溶劑相同或不同，但對於大部分工業殺菌應用而言，水為較佳者。該兩種溶劑較佳為可混溶者。
熟悉此項技術者將瞭解，可相繼或同時添加本發明之殺菌劑組分至一位置，或可在添加至該位置之前，先組合該等殺菌劑組分。較佳為同時或相繼添加第一種殺菌劑及第二種殺菌劑組分至一位置。當同時或相繼添加該等殺菌劑時，個別組分可各自含有佐劑，舉例而言，例如溶劑、增稠劑、防凍劑、著色劑、螯合劑(例如乙二胺四醋酸、乙二胺二琥珀酸、亞胺基二琥珀酸及其鹽)、分散劑、界面活性劑、生物分散劑、磺酸基琥珀酸酯、萜烯、呋喃酮、多價陽離子、安定劑、防垢劑及防腐蝕添加劑。
可藉由將殺菌有效量之本發明殺菌組成物引至受微生 物侵襲的位置上、位置內或位置處，而將本發明殺菌組成物用於抑制微生物或較高等水生生物種類(例如原生動物、無脊椎動物、苔蘚蟲類、雙鞭毛藻類、甲殼動物、軟體動物等)的生長。適當的位置包括例如：工業處理水；電塗沉積系統；冷卻塔；空氣清洗器；氣體洗滌器；礦物漿料；廢水處理；裝飾用噴泉；逆滲透過濾；超過濾；壓艙水；蒸發冷凝器；熱交換器；紙漿及紙張加工流體與添加劑；澱粉；塑膠；乳液；分散液；油漆；乳膠；塗料，例如清漆；建築產品，例如膠黏劑(mastics)、填隙劑及密封劑；建築黏著劑，例如陶瓷黏著劑、地毯背襯黏著劑及層合黏著劑；工業或消費性黏著劑；照相化學品；印刷流體；家用產品，例如浴室及廚房清潔劑與清潔濕巾；美容用品；化妝品；洗髮精；肥皀；去汙劑；工業清潔劑；地板光亮劑；洗衣用洗濯水；金屬加工流體；輸送機潤滑劑；液壓流體；皮革及皮革產品；織物；織造產品；木材及木材產品，例如合板、碎木片板、牆板、刨花板、層合樑、定向刨花板、硬板及粒片板；石油加工流體；燃料；油田流體，例如噴射水、裂隙流體及鑽井泥漿；農業佐劑保存；界面活性劑保存；醫學裝置；診斷試劑保存；食物保存，例如塑膠或紙製食品包裝；食品、飲料及工業處理殺菌器；便盆；娛樂用水；水池；以及礦泉。
較佳地，本發明殺菌組成物係用於抑制在選自下列一或多個位置處的微生物之生長：礦物漿料；紙漿及紙張加工流體與添加劑；澱粉；乳液；分散液；油漆；乳膠；塗 料；建築黏著劑，例如陶瓷黏著劑、地毯背襯黏著劑；照相化學品；印刷流體；家用產品，例如浴室及廚房清潔劑與清潔濕巾；美容用品；化妝品；洗髮精；肥皀；去汙劑；工業清潔劑；地板光亮劑；洗衣用洗濯水；金屬加工流體；織造產品；木材及木材產品；農業佐劑保存；界面活性劑保存；診斷試劑保存；食物保存；以及食品、飲料及工業處理殺菌器。
抑制或控制一位置之微生物及較高等水生生物種類的生長所需之本發明組成物的具體量係取決於欲保護之特定位置。典型地，在一位置控制微生物生長的本發明組成物若能於該位置提供0.1至1,000 ppm的該組成物之異噻唑啉酮成分，則其量為足夠。在該位置，該組成物之異噻唑啉酮成分較佳以至少0.5 ppm，更佳以至少4 ppm，最佳以至少10 ppm的量存在。在該位置，該組成物之異噻唑啉酮成分較佳以不超過1000 ppm，更佳以不超過500 ppm，最佳以不超過200 ppm的量存在。
實施例 材料及方法
本發明之組合的協同作用係藉由測試廣泛濃度及比率範圍的該等化合物而予以證實。
協同作用之一種量測法係Kull,F.C.；Eisman,P.C.；Sylwestrowicz,H.D.及Mayer,R.L.在Applied Microbiology 9：538-541(1961)中所述之工業上接受的方法，其係使用下述公式所測定之比率： Qa /QA +Qb /QB =協同指數(“SI”)其中：QA =以ppm計的單獨作用之化合物A(第一種組分)的濃度，其產生一終點(化合物A之MIC)。
Qa =以ppm計的混合物中之化合物A的濃度，其產生一終點。
QB =以ppm計的單獨作用之化合物B(第二種組分)的濃度，其產生一終點(化合物B之MIC)。
Qb =以ppm計的混合物中之化合物B的濃度，其產生一終點。
當Qa /QA 及Qb /QB 之總和大於1時，表示拮抗作用。當該總和等於1時，表示相加性；而當該總和小於1時，則說明為協同作用。SI值愈低，則該特定混合物所展現的協同性愈高。殺菌劑之最低抑制濃度(MIC)為在阻止所添加微生物之生長的一組特別條件下所測得之最低濃度。
使用標準微量滴定盤分析，以設計成使測試微生物達到最佳生長之培養基來進行協同性測試。補充有0.2%葡萄糖及0.1%酵母萃取物的基本鹽類培養基(M9GY培養基)係用於測試細菌；馬鈴薯葡萄糖培養液(PDB培養基)係用於測試酵母菌及黴菌。在此方法中，藉由在各種濃度的MBIT之存在下進行高解析度MIC分析來測試廣範圍的殺菌劑組合。藉由對微量滴定盤的其中一欄添加不同量的殺菌劑，並使用自動液體處理系統進行十倍連續稀釋，以獲得活性成分自2 ppm至10,000 ppm變化的一系列終點，來測定高 解析度MIC。
本發明之組合的協同性係以對抗如下表中所述之數種微生物而予以測定。所使用的細菌之濃度約為每毫升5×106 個細菌，而酶母菌及黴菌之濃度為每毫升5×105 個真菌。此等微生物代表許多消費性及工業性應用中的自然污染物。經過在25℃(酶母菌及黴菌)或30℃(細菌)培養不同時間後，對滴定盤進行微生物生長(混濁度)之視覺評估，以測定MIC。
用於證實本發明之MBIT組合之協同性的測試結果係顯示於下表1至8中。於各測試中，第二組分(B)為MBIT，而第一組分(A)為其他商用殺菌劑。各表係顯示：MBIT與其他組分之特定組合；以各培養時間測試之對抗微生物的結果；藉由單獨的MBIT(QB )、單獨的其他組分(QA )、混合物中的MBIT(Qb )及混合物中的其他組分(Qa )之MIC所量測的以ppm計之終點活性；所計算之SI值；以及所測試之各組合(其他組分/MBIT或A/B)的協同比率範圍。

Claims (1)

  1. 一種協同性殺菌組成物，包含：(a)N-甲基-1,2-苯并異噻唑啉-3-酮；及(b)辛酸丙二醇酯，其中，該辛酸丙二醇酯對N-甲基-1,2-苯并異噻唑啉-3-酮之重量比率為1：0.442至1：0.0018。
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CA2637129C (en) 2011-05-17
TWI418300B (zh) 2013-12-11
JP2011252008A (ja) 2011-12-15
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ATE527879T1 (de) 2011-10-15
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CA2637129A1 (en) 2009-01-18
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BR122015027161B1 (pt) 2016-03-29
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AU2008203010B2 (en) 2014-01-23
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