201249341 六、發明說明： 【發明所屬之技術領域】 本發明係有關主要在食品工廠等之地板、牆壁、器具、 設備等使用之殺菌或殺菌洗淨之殺菌劑組成物及殺菌洗淨 劑組成物及使用該等組成物之殺菌方法及殺菌洗淨方法。 【先前技術】 在食品工廠、飲食店等之廣房、超市内之加工作業場 所等食品處理現場，從衛生上之觀點而言，地板、牆壁、 器具、設備等必需進行殺菌。以殺菌為目的，從以往使用 酵、氣糸化合物、過氧化物、陽離子界面活性劑、兩性界 面活性劑、雙胍化合物等種種殺菌劑。其中，為陽離子界 面活性劑之第四級銨鹽之氣化二癸基二曱基銨或為雙胍化 合物之聚六亞甲基雙胍鹽酸鹽從殺菌效果及安全性之點而 言’為頻繁被利用之殺菌劑。除此之外，在食品處理現場， 污垢為微生物增殖之原因，所以在作業中或作業後之洗淨 是必需的。因此，廣泛使用除了殺菌效果之外另具有洗淨 效果，洗淨及殺菌可在一步驟實施之殺菌洗淨劑。至今提 案有例如在第四級銨鹽中調配非離子界面活性劑或兩性界 面活性劑之殺菌洗淨劑組成物或在雙胍系殺菌劑中調配非 離子界面活性劑之殺菌洗淨劑組成物。於專利文獻丨揭示 將特定之第四級銨鹽、兩性界面活性劑、非離子界面活性 劑及水以特定之量比含有之殺菌洗淨劑組成物具有高殺菌 效果、洗淨效果及安定性。 惟’近年來重複使用第四級銨鹽或雙胍系殺菌劑，發 324225 4 201249341 生對於該等殺菌劑具有抵抗性之微生物（以下，稱為藥劑抵 抗性菌），導致有殺菌不充分之問題。對於氯化二癸基二曱 基銨或聚六亞甲基雙胍鹽酸鹽之藥劑抵抗性菌已知有例如 非專利文獻1記載之綠腹桿菌（pseud〇monas)屬或沙雷氏 菌（Serratia)屬之菌。對於該等藥劑抵抗性菌，作為預防 其發生之方法，採用定期變更使用藥劑等之對策。惟，相 關之方法在作業性及成本之點負擔大，有敬而遠之之傾向。 又’在確認藥劑抵抗性菌存在時，經由次氯酸鈉等氣系殺 菌劑進行處理。惟，氣系殺菌劑之金屬腐蝕性強，對於設 備或裝置造成很大影響，還有臭味殘留等之問題，有敬而 遠之之傾向。另，氣化二癸基二曱基銨使用後有容易留下 滑溜之傾向，聚六亞曱基雙胍鹽酸鹽在使用後有容易留下 發黏之傾向。 從如上所述之背景’期待除了黴菌等真菌類或一般細 菌之外，對於藥劑抵抗性菌亦具有殺菌效果，即使連續使 用，很難產生藥劑抵抗性菌，可減低使用後滑溜或發黏之 殺菌劑組成物。又，期待具備該等特性且具有高洗淨力之 殺菌洗淨劑組成物。 [先行技術文獻] [專利文獻] [專利文獻1]曰本專利第4468010號公報 [非專利文獻] [非專利文獻1]微生物殺菌實用數據集（2005年8 月Π曰發行’（科學討論會（science forum)(股）公司） 324225 5 201249341 【發明内容】 [發明所欲解決之課題] 本發明目的之一為提供對於真菌類、一般細菌具有殺 菌效果之同時，對於對第四級銨鹽及/或雙胍系殺菌劑具 有抵抗性之微生物亦具有殺菌效果，且對於其本身不易產 生藥劑抵抗性菌之殺菌劑組成物。另，本發明以提供具有 與相關之殺菌劑組成物同樣的特性且具有高洗淨力之殺菌 洗淨劑組成物為目的。 [解決課題之方法] 本發明人等發現含有具有下述式（I)之化合物及三乙 醇胺之組成物及含有下述式（I)之化合物、非離子界面活性 劑及三乙醇胺之組成物可解決上述課題。 亦即，本發明提供含有式（I)之化合物及三乙醇胺之殺 菌劑組成物（以下，稱為「本發明之殺菌劑組成物」）：201249341 VI. Description of the Invention: [Technical Field] The present invention relates to a bactericidal or sterilizing detergent composition and a sterilizing detergent composition mainly used in floors, walls, appliances, equipment, and the like of food factories and the like. And a sterilization method and a sterilization washing method using the components. [Prior Art] Floors, walls, appliances, equipment, etc. must be sterilized from the viewpoint of hygiene in food processing sites such as food factories, restaurants, and other processing sites in supermarkets. For the purpose of sterilization, various fungicides such as yeast, gas compound, peroxide, cationic surfactant, amphoteric surfactant, and biguanide have been used. Among them, the vaporized dimercaptodimethylammonium salt which is the fourth-order ammonium salt of the cationic surfactant or the polyhexamethylene biguanide hydrochloride which is the biguanide compound is frequently used from the point of bactericidal effect and safety. The fungicide used. In addition, at the food processing site, dirt is a cause of microbial growth, so washing during or after work is necessary. Therefore, it is widely used to have a cleaning effect in addition to the sterilizing effect, and the sterilizing detergent which can be carried out in one step by washing and sterilizing. Heretofore, there have been proposed, for example, a sterilizing detergent composition in which a nonionic surfactant or an amphoteric surfactant is formulated in a fourth-stage ammonium salt or a sterilizing detergent composition in which a nonionic surfactant is formulated in a biguanide bactericide. The patent document discloses that the specific fourth-order ammonium salt, amphoteric surfactant, non-ionic surfactant and water have a high bactericidal effect, washing effect and stability in a specific amount of the sterilizing detergent composition. . However, in recent years, the fourth-grade ammonium salt or biguanide fungicide has been repeatedly used, and 324225 4 201249341 microorganisms resistant to these fungicides (hereinafter referred to as drug-resistant bacteria) have been caused, resulting in insufficient sterilization. . For the agent-resistant bacteria of dinonyldimethylammonium chloride or polyhexamethylene biguanide hydrochloride, for example, Pseudomonas sp. (Pseudomonas monas) or Serratia (described in Non-Patent Document 1) are known ( Serratia) is a genus of bacteria. As a method for preventing the occurrence of these drug-resistant bacteria, measures for periodically changing the use of the drug or the like are employed. However, the relevant methods are burdened at the point of workability and cost, and there is a tendency to stay away from it. Further, when the presence of the drug-resistant bacteria is confirmed, the treatment is carried out via a gas-based bactericide such as sodium hypochlorite. However, the metal of the gas germicide is highly corrosive, has a great influence on the equipment or the device, and has problems such as odor residue, and has a tendency to be respected. In addition, the vaporized dimercaptodimethylammonium salt tends to leave a slippery tendency after use, and the polyhexamethylenebisguanidinium hydrochloride has a tendency to leave a sticky tendency after use. From the background as described above, it is expected to have a bactericidal effect on the drug-resistant bacteria in addition to fungi such as mold or general bacteria. Even if it is continuously used, it is difficult to produce a drug-resistant bacteria, which can reduce slipperiness or stickiness after use. Fungicide composition. Further, a sterilizing detergent composition having such characteristics and having high detergency is desired. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent No. 4468010 [Non-Patent Document] [Non-Patent Document 1] Practical Data Collection for Microbial Sterilization (August 2005 issue) (Science Symposium (Science forum) company 324225 5 201249341 [Summary of the Invention] [Problems to be Solved by the Invention] One of the objects of the present invention is to provide a bactericidal effect on fungi and general bacteria, and to a fourth-order ammonium salt. And/or the biocide having resistance to microorganisms also has a bactericidal effect, and is a bactericidal composition which is not easily resistant to the drug-resistant bacteria itself. Further, the present invention provides the same characteristics as the related bactericidal composition. In order to solve the problem, the present inventors have found a composition containing a compound of the following formula (I) and triethanolamine and containing the following formula (I). The compound, the nonionic surfactant, and the composition of triethanolamine can solve the above problems. That is, the present invention provides a compound containing the compound of the formula (I) and triethanolamine. Resist composition (hereinafter referred to as a "biocide composition of the present invention"):
κ2 2Χ [式中，1^表示碳數1至3之飽和直鏈烷基，R2表示碳數8 至12之飽和直鏈烷基，乂_表示鹵素離子，Y表示碳數8至 12之飽和直鏈伸烷基]。 又，本發明亦提供包含將上述殺菌劑組成物與殺菌對 324225 6 201249341 象物接觸之殺菌方法。 另，本發明提供含有式（I)之化合物、非離子界面活性 劑及三乙醇胺之殺菌洗淨劑組成物（以下，稱為「本發明之 殺菌洗淨劑組成物」）：Κ2 2Χ [wherein, 1^ represents a saturated linear alkyl group having 1 to 3 carbon atoms, R2 represents a saturated linear alkyl group having a carbon number of 8 to 12, 乂 represents a halogen ion, and Y represents a saturation of a carbon number of 8 to 12. Linear alkyl group]. Further, the present invention also provides a sterilization method comprising contacting the above-mentioned bactericidal composition with a bactericidal pair of 324225 6 201249341. Further, the present invention provides a sterilizing detergent composition containing a compound of the formula (I), a nonionic surfactant, and triethanolamine (hereinafter referred to as "the sterilizing detergent composition of the present invention"):
[式中，Ri表示碳數1至3之飽和直鏈烷基，R2表示碳數8 至12之飽和直鏈烷基，χ-表示鹵素離子，γ表示碳數8至 12之飽和直鏈伸烷基]。 又’本發明亦提供包含將上述殺菌洗淨劑組成物與殺 菌洗淨對象物接觸之殺菌洗淨方法。 [發明之效果] 本發明之殺菌劑組成物為對於黴菌等真菌類或一般細 菌具有殺菌效果，且對於對第四級銨鹽及/或雙胍系殺菌 劑具有抵抗性之藥劑抵抗性菌亦具有優越殺菌效果之組成 另本發明之殺劑組成物為即使長期連續使用，對 於該組成物本身很難產生藥'劑抵抗性菌，且可降低使用後 滑溜或發黏之組成物。此處，第四級銨鹽之例可列舉氯化 二癸基二甲基銨、氯化苯甲烷銨等。又，雙胍系殺菌劑之 例可列舉聚六亞甲基雙胍鹽酸鹽、葡糖酸雙氯己定 324225 7 201249341 (chlorhexidine gluconate)等。 又’本發明之殺菌洗淨劑組成物為對於黴菌等真菌類 或一般細菌具有殺菌效果，且對於對第四級銨鹽及/或雙 脈系殺菌劑具有抵抗性之藥劑抵抗性菌亦具有優越之殺菌 效果’且’具有高洗淨力之組成物。另，本發明之殺菌洗 淨劑組成物為即使長期連續使用，對於該組成物本身很難 產生藥劑抵抗性菌 【實施方式】 且可降低使用後滑溜或發黏之組成物。 、f發明殺菌劑組成物及殺菌洗淨劑組成物構成成 刀 1之化口物中’ R丨為甲基、乙基或丙基中之任何一 5之二基或乙基更好為甲基。R2較好為碳數8至 °鏈垸基，更好為癸基。X-為齒素離子，較好為 氣離子或溴離子，P4A ^我灯兩 ^ 好為氣離子。γ較好為碳數1〇至12 之餘和直鍵伸轉，更好為伸癸基。 之式纟職物及㈣洗喊物構成成分 2'甲灵“：物之具體例例示二溴化U0-二(3_癸基 碳：广:氣化一严化1,12—二(3_癸基'2、甲基咪唑鏽)十二 二:化1 1ί) 12~二（3~癸基_2_甲基味哇錯）十二碳烧、 一“ ，^一（3—辛基-2_甲基咪唑鑷）癸烧、-氣化 辛終甲基咪蝴十二碳院、二氣化;u 一(3 十，等。該等中，在對於-= 果之點而言，較好為二漠化1，10~二（3-癸基_2_甲 324225 201249341 基味錢）癸燒、二氯化丨，1G_二（3_癸基_2_甲基十坐錯） 癸烷、一 /臭化1，12_二（3_癸基_2_甲基咪唑鑌）十二碳烷、 一氣化1，12-二（3-癸基-2-甲基咪唑鑷）十二碳烷、二溴化 1’12-二（3-辛基-2一甲基咪唑鏽）十二碳烷、二氣化丨，12_ 二（3-辛基-2-甲基咪嗤鏽）十二碳烧’在對於與其他殺菌成 分混合性之點而言，更好為二溴化1，10-二（3-癸美-2-曱 =味嗤⑹魏、二氯化1暑二（3-癸基-2-曱基^峻鑌） 六烷一氯化1’丨2_二（3一癸基_2_曱基咪唑鑌）十二碳烷及 -氣化1’12-二（3_辛基甲基料鏽）十二碳烧，在對於 樂劑抵抗性®之㈣絲及在水巾溶解性之點而言，更好 為氣化1，10 一（3-癸基_2_甲基咪唾鏽）癸烧。 本發明_聽成物及㈣洗淨聽成物巾式⑴化 無特別限制。本發明之殺菌劑組成物及殺菌 比例較:為广物中式⑴化合物之 〇. ^ 重1%，更好為0.005至30重量 ==°15至10咖，…至1〇議‘ _及/ Λ比例未達G.GG1重量％時，對於對第四級敍 ς女/或雙胍系殺_具有抵抗性之藥劑抵抗性菌之抑制 二=:。超過5°重量%時有組成物之黏度 活：==組成物構成成分之非離子界面 324225 聚氧伸乙隸細、聚氧伸乙基 -酉曰、艰氧伸乙基山梨糖醇軒脂肪酸醋、山梨糖醇軒 9 201249341 脂肪酸酯、餘脂肪酸醋、聚氧伸乙基聚氧伸丙基聚合物 ^ 4中，較好為椰子油脂肪酸二乙醇醯胺、聚氧伸烧 、* 土&又，本發明殺菌洗淨劑組成物中之非離子界面 ，性劑較好為HLB值為4至15者，更好為9至Μ者。該 等非離子界面活性劑可併用2種以上。 本發明殺g洗淨劑組成物巾麵子界面活性劑之比例， 對於式（I)之化合物丨4量份較好為Q.丨至2Q重量份，更 為1至10重量伤，最好為2至5重量份。非離子界面活 性劑之比例未達（U重量份時，洗淨力有降低之傾向，超 過20重量伤時，在水溶液形態有會分離或產生白濁，泡沫 消除變差之傾向。 本發明殺菌洗淨劑組成物中之非離子界面活性劑從洗 淨力及貯藏安定性之點而言，較好將椰子油脂肪酸二乙醇 酿胺與聚氧伸烧基院細併用嘴該等併用時之調配比例， 對於椰子油脂肪酸二乙醇醯胺丨重量份，聚氧伸院基烧基 驗較好為0.05至1.〇重量份’更好為〇1至〇·3重量份。 本發明之殺菌劑組成物及殺菌洗淨劑組成物中三乙醇 胺之比例並無特別限制，對於式⑴之化合物丨重量份較好 為0. 0025至24. 5重量份，更好為〇. 〇〇5至5重量份，最 ，為0. 01至1. 5重量份。三乙醇胺之比例未達〇· 〇〇25重 里伤β寺’有I生以下⑴至（lv)問題之慮··⑴殺菌效果變 不充分’（η)將殺菌劑組成物或殺菌洗淨劑組成物作成水 溶液形態時’在低溫條件中之安定性降低，（⑴）調配後遂 之其他殺菌成分或其他添加劑時，水溶液會產生白濁等及 324225 10 201249341 ⑼不能獲得充分之金眉相抑制效果。另— 醇胺之比例超過24. 5重量份時，蔣縣肖一 淨劑袓Am、u f將殺菌劑組成物或殺菌洗 成物作成水溶液形態時，該組成物之邱過度上昇， 有金屬腐截性變高之傾向。 離時m㈣齡祕及殺_淨劑組成物為水溶液 組成物之邱並無特別限制，較好為7至12，更 ，最好為7·7至9,5,又以8至9.4較佳。 本發明之殺菌劑組成物及殺菌洗淨劑組成物中三乙醇 241=’、對於式⑴之化合物1重量份，若在〇. 0025至 • 讀之範圍，則該水溶液形態之該組成物之pH在7 2之範圍。根據所期望，可使用驗劑調整該組成物之 。發明之_劑組成物及殺菌洗淨劑組成物中可含有 =驗劑’只要在該組成物不會引起析出或白濁等變化者即 石關之驗劑可例示例如氫氧化鈉、氫氧化鉀、碳酸納、 齩？鈉、石反酸鉀、碳酸氫鈉、碳酸氫鉀、倍半碳酸鈉、 :=酸=、倍半魏納、正料鈉、正碟酸鈉、焦鱗酸納、 ^聚，酸鋼、四磷酸鈉、六偏填酸鈉等。該等驗劑中，從 一 k、、且成物以水溶液形態保管時該組成物安定性之點而 較好為氫氧化納及氫氧化卸。該等驗劑可併用2種以 上〇 離本發明之殺菌洗淨劑組成物經由將式（丨）之化合物、非 /舌丨生劑及二乙醇胺併用，殺菌力，尤其是對於藥 =抵^菌之殺菌力與單獨使用式⑴之化合物時相比，殺 力提昇，與單獨使用非離子界面活性劑時相比，可發揮 324225 11 201249341 優越之洗淨力。亦即，本發明之㈣洗淨触成物為對於 殺菌力及洗淨力雙方，經由式⑴之化合物、非離子界面活 性劑及三乙賴三成分’可發揮相乘效果之組成物。 本毛月之殺菌劑組成物及殺菌洗淨劑組成物亦可另含 有其他之㈣齡4發明之㈣劑組成物及㈣洗淨劑 組成物可含有之其他殺菌成分例示氣化二癸基二曱基銨、 乳化笨甲紐等第四級録鹽；聚六亞甲基雙胍鹽酸鹽、葡 糖酉文雙氯己疋等雙胍系殺菌劑；填甘胺酸複合體等有機块 系殺菌劑等。該等其他之殺菌成分中，從對於芽胞菌殺菌 效果之點而言，較好為雙胍系殺菌劑，雙胍系殺菌劑中又 以聚六亞甲基雙胍鹽酸鹽較佳。該等其他之殺菌成分可單 獨使用1種，亦可併用2種以上。 本發明之殺菌劑組成物及殺菌洗淨劑組成物中含有其 他之殺菌成分時’該組成物中其他殺菌成分之比例對於式 (I)化合物1重量份，較好為0 5至40重量份，更好為0. 7 至10重量份，最好為1至5重量份。其他殺菌成分之比例 未達0. 5重量份時，有不能充分發揮該其他殺菌成分之殺 菌效果之傾向，超過4〇重量份時，在將級成物以水溶液形 態保管時有產生白濁等之傾向。 本發明之殺菌劑組成物及殺菌洗淨劑組成物根據需要’ 另可含有其他之添加劑。該組成物中可含有之其他添加劑 可列舉例如乙醇、著色料、香料、洗淨助劑等。本發明之 殺菌劑組成物及殺菌洗淨劑組成物中該等其他添加劑之比 例通常在水溶液形態之該組成物之5重量％以下。 324225 201249341 本發明之殺菌劑組成物及殺菌洗淨劑組成物可以錠劑 或粉末等固體形態、糊狀或凝膠狀等半固體形態提供，亦 可以水溶液形態提供。本發明之殺菌劑組成物及殺菌洗淨 劑組成物以固體或半固體形態提供時，通常將該組成物溶 解於水’作成水溶液形態，可適用於殺菌對象物或殺菌洗 淨對象物。本發明之殺菌劑組成物及殺菌洗淨劑組成物以 水溶液形態提供時，該水溶液以原狀或更經稀釋之水溶液， 可適用於殺菌對象物或殺菌洗淨對象物。 本發明殺菌劑組成物及殺菌洗淨劑組成物之調製方法 並無特別限制。例如固體之殺菌劑組成物及殺菌洗淨劑組 成物可由將必要成分根據所期待，與賦形劑等一起只進行 他0而獲得。又，可將必要成分之混合物更供給造粒或打 鍵等通吊之製劑步驟，獲得組成物。半固體之殺菌劑組成 物及殺g洗淨劑組成物例如可由將必要成分及水與黏合劑 ^凝膠化辦混合崎得。水驗耗、之_劑組成物及 殺菌洗淨敝成物可由例如將必要成分均—溶解於水中， 或將經調製之上述固體或半固體組成物溶解於水中而獲得。 調整本發明殺菌劑組成物及殺菌洗淨劑組成物之油 時’進行該PH調整之階段並無特別限制，通常，在經調製 之水溶液形態之㈣劑組成物或㈣洗淨劑組成物中添加 ，劑即可。或可事先決定可將水溶液形態之殺菌劑組成物 或殺菌洗淨劑組成物調整到所期待之邱範圍之驗劑之量， 將該量之驗劑與殺菌劑組成物或殺菌洗淨劑組成物之成分 一同均一溶解於水。可將組成物之PH調整到_待範圍之 324225 13 201249341 事先決定量之驗劑含於半固體之殺菌劑組成物或殺菌洗淨 劑組成物。 以固體或半固體形態提供之本發明殺菌劑組成物之例 可列舉 (a) 為含有式（I)之化合物1至99重量％及三乙醇胺0. 0001 至5重量％之組成物； (b) 為含有式（I)之化合物3至50重量％及三乙醇胺0. 005 至3重量％之組成物； (c) 為含有式（I)之化合物5至15重量％及三乙醇胺0. 001 至1重量％之組成物等。 另含有其他殺菌成分之本發明殺菌劑組成物之例可 列舉 (d) 為含有式（I)之化合物1至98重量％、三乙醇胺〇. 〇〇〇1 至5重量。/。及雙胍系殺菌劑1至98重量％之組成物； (e) 為含有式（！）之化合物3至50重量％、三乙醇胺〇. 〇〇5 至3重量％及雙胍系殺菌劑3至50重量％之組成物； (Ο為含有式（I)之化合物5至15重量％、三乙醇胺〇. 〇〇1 至1重量％及雙胍系殺菌劑5至15重量％之組成物等。 以水溶液形態提供之本發明殺菌劑組成物之例可列 舉 (g) 為含有式（I)之化合物0.001至5〇重量％及三乙醇胺 〇· 075至50重量％之水溶液之組成物； (h) 為含有式（I)之化合物1至20重量％及三乙醇胺〇.〇9 至10重量％之水溶液之組成物； 324225 14 201249341 *- (i)為含有式（I)之化合物3至10重量％及三乙醇胺〇. i至 、 6重量％之水溶液之組成物等。 該等中較好為（h)之組成物，更好為（i)之組成物。 另含有其他殺菌成分之水溶液形態之本發明殺菌劑組 成物之例可列舉 (j) 為含有式（I)之化合物0.001至50重量％、三乙醇胺 〇·〇75至99重量％及雙胍系殺菌劑〇. 0005至3〇重量％之水 溶液之組成物； (k) 為含有式（I)之化合物1至20重量％、三乙醇胺〇.09 至98重量％及雙胍系殺菌劑1至2〇重量％之水溶液之組成 物； (l) 為含有式（I)之化合物3至10重量％、三乙醇胺1至93 重里％及雙胍系殺菌劑3至16重量％之水溶液之組成物等。 該等中較好為（k)之組成物，更好為（1)之組成物，又 以（m)為含有式（I)之化合物3至1〇重量％、三乙醇胺1至 93重量％及聚六亞曱基雙胍鹽酸鹽3至μ重量％之水溶液 之組成物最佳。 為水溶液形態之本發明殺菌劑組成物，根據使用者之 目的，可另加入水作為稀釋劑使用。作為稀釋劑使用時， 較好將式（I)化合物之比例稀釋成〇. 001至5〇重量％。 例如’本發明之殺菌劑組成物可以下述形態使用 (η)為含有式（I)之化合物〇. 〇〇1至〇·25重量％及三乙醇胺 0.0004至0.25重量％之水溶液； (〇)為含有式（I)之化合物〇· 〇〇5至〇· 1重量％及三乙醇胺 324225 15 201249341 〇. 0005至〇. 〇〇15重量％之水溶液； (P) 為含有式（I)之化合物0. 015至〇, 〇45重量％及三乙醇胺 0.0006至o.ooi重量％之水溶液等。 該等中，較好使用（〇)之水溶液形態，更好使用（p)之 水溶液形態。 本發明之殺菌劑組成物另含有其他殺菌成分時，可使 用例如該組成物為下述形態 (Q) 為含有式（I)之化合物0 〇〇1至〇. 25重量％、三乙醇胺 〇. 004至〇· 5重量％及雙胍系殺菌劑〇. 〇〇〇5至〇. 15重量％ 之水溶液； (Ο為含有式（！）之化合物〇· 〇〇5至〇. 1重量％、三乙醇胺 0.0005至0.45重量％及雙胍系殺菌劑0.005至0. 1重量〇/〇 之水溶液； (s)為含有式（I)之化合物〇. 015至〇. 〇45重量％、三乙醇胺 〇. 〇〇5至〇. 4重量％及雙胍系殺菌劑〇. 〇2至〇. 08重量％之 水溶液等。 該等中較好使用（r)之水溶液形態，更好使用（s)之水 溶液形態組成物，又以使用（t)為含有式（丨）之化合物0.015 至0.045重量％、三乙醇胺0.005至〇.4重量。/。及聚六亞曱 基雙胍鹽酸鹽0.02至0.08重量％之水溶液之形態最佳。 以固體或半固體形態提供之本發明殺菌洗淨劑組成物 之例可列舉 (A)為含有式（I)之化合物1至98重量％、非離子界面活性 劑1至98重量％及三乙醇胺〇. 〇〇〇1至5重量％之組成物； 324225 .201249341 (B) 為含有式（i)之化合物3至50重量％、非離子界面活性 劑10至90重量％及三乙醇胺0.0005至3重量％之組成物； (C) 為含有式（I)之化合物5至15重量％、非離子界面活性 劑20至80重量％及三乙醇胺o.ooi至！重量％之組成物等。 另含有其他殺菌成分之本發明殺菌洗淨劑組成物之例 可列舉 (D) 為含有式（I)之化合物1至97重量％、非離子界面活性 劑1至97重量％、三乙醇胺〇·0001至5重量％及雙胍系殺 菌劑1至97重量％之組成物； (Ε)為含有式（I)之化合物3至50重量％、非離子界面活性 劑10至90重量％、三乙醇胺0.0005至3重量％及雙胍系殺 菌劑3至50重量％之組成物； (F) 為含有式（I)之化合物5至15重量％、非離子界面活性 劑20至80重量％、三乙醇胺〇.001至i重量％及雙胍系殺 菌劑5至15重量％之組成物等。 以水溶液形態提供之本發明殺菌洗淨劑組成物之例可 列舉 (G) 為含有式（I)之化合物〇· 〇01至5〇重量％、非離子界面 活性劑0.0001至60重量％及三乙醇胺0.075至50重量％ 之水溶液之組成物； (H) 為含有式（I)之化合物1至2〇重量％、非離子界面活性 劑1至45重量％及三乙醇胺〇. 〇9至1〇重量％之水溶液之組 成物； (J)為含有式（I)之化合物3至10重量％、非離子界面活性 324225 17 201249341 劑6至25重量％及三乙醇胺〇. 1至6重量％之水溶液之組成 物； (K) 為含有式（I)之化合物1至20重量％、椰子油脂肪酸二 乙醇酿胺0. 952至22. 5重量％、聚氧伸烷基烷基醚〇. 〇48 至22. 5重量％及三乙醇胺〇. 〇9至1〇重量％之水溶液之組成 物； (L) 為含有式（I)之化合物3至10重量％、椰子油脂肪酸二 乙醇醢胺5. 45至19. 23重量％、聚氧伸烧基烧基謎〇. 55 至5. 77重量％及三乙醇胺〇. 1至6重量％之水溶液之組成物 等。 該等中較好為（K)之組成物，更好為（L)之組成物。 另含有其他殺菌成分之水溶液形態之本發明殺菌洗淨 劑組成物之例可列舉 (M) 為含有式（I)之化合物o.ooi至50重量％、非離子界面 活性劑〇. 0001至60重量％、三乙醇胺〇. 075至99重量0/〇 及雙胍系殺菌劑0.0005至30重量％之水溶液之組成物； (N) 為含有式（I)之化合物1至20重量％、非離子界面活性 劑1至45重量％、三乙醇胺0.09至97重量％及雙胍系殺菌 劑1至15重量％之水溶液之組成物； (〇)為含有式（I)之化合物3至10重量％、非離子界面活性 劑6至25重量％、三乙醇胺1至89重量％及雙胍系殺菌劑 2至5重量％之水溶液之組成物； (P)為含有式（I)之化合物〇. 〇〇1至50重量％、椰子油脂肪 酸二乙醇醯胺0. 0001至30重量％、聚氧伸烷基烷基醚〇 324225 18 201249341 至30重量％、三乙醇胺0. 075至99重量％及聚六亞甲基雙 胍鹽酸鹽0.0005至30重量％之水溶液之組成物； (Q) 為含有式（I)之化合物1至20重量％、椰子油脂肪酸二 乙醇醯胺0. 952至22· 5重量％、聚氧伸烷基烷基醚〇48 至22.5重量％、三乙醇胺0.09至97重量％及聚六亞曱基雙 胍鹽酸鹽1至15重量％之水溶液之組成物； (R) 為含有式（I)之化合物3至10重量％、椰子油脂肪酸二 乙醇醯胺5.45至19.23重量％、聚氧伸烷基烷基醚〇 55 至5. 77重量％、三乙醇胺1至89重量％及聚六亞甲基雙胍 鹽酸鹽2至5重量％之水溶液之組成物等。 該等中較好為（P)之組成物’更好為（Q)之組成物，最 好為（R)之組成物。 又，為水溶液形態之本發明殺菌洗淨劑組成物根據使 使^目的’另可加人水作為稀釋液使用。在作為稀釋液 量Γ。較好稀釋使式⑴化合物之比例為0. 001至50重 (s)為含有二月之殺菌洗淨劑組成物可以下述形態使用 面活性劑。:_:=3〇.二至及 0.25重量％之水溶液 ·3重及二乙醇胺0.0004至 (Τ)為含有式卩τ) 活性劑〇. 〇〇5至=物〇. 005至〇· 1重量％、非離子界面 重量％之水溶液；·重量％及三乙醇胺0.0005至0.0015 2為含衫⑴丨5iQ屬重務雜子界 19 201249341 面活性劑0. 03至0. 125重量％及三乙醇胺0. 0006至0. 001 重量％之水溶液； (V) 為含有式（I)之化合物0. 005至0. 1重量％、椰子油脂肪 酸二乙醇醯胺0. 00476至0. 1125重量％、聚氧伸烷基烷基 醚0. 00024至0. 1125重量％及三乙醇胺0. 0005至0· 0015 重量％之水溶液； (W) 為含有式（I)之化合物0. 015至0. 045重量％、椰子油脂 肪酸二乙醇醯胺0. 02725至0. 09615重量％、聚氧伸烷基烷 基醚0. 00275至0. 02885重量％及三乙醇胺0. 0006至0· 001 重量％之水溶液等。 該等中較好使用（V)之水溶液形態，更好使用（W)之水 溶液形態。 本發明之殺菌洗淨劑組成物另含有其他殺菌成分時， 例如該組成物可以下述形態使用 (X) 為含有式（I)之化合物0. 001至0. 25重量％、非離子界 面活性劑〇.〇〇〇〇〇〇5至0. 3重量％、三乙醇胺0. 0004至0. 49 重量％及雙胍系殺菌劑0.0005至0. 15重量％之水溶液； (Y) 為含有式（I)之化合物0. 005至0. 1重量％、非離子界面 活性劑0. 005至0. 225重量％、三乙醇胺0. 0005至0. 465 重量％及雙胍系殺菌劑0. 005至0. 1重量％之水溶液； (Z) 為含有式（I)之化合物0. 015至0. 045重量％、非離子界 面活性劑0. 03至0. 125重量％、三乙醇胺0. 005至0. 445 重量％及雙胍系殺菌劑0.01至0.025重量％之水溶液； (AA)為含有式（I)之化合物0. 001至0. 25重量％、椰子油脂 324225 20 201249341 肪酸二乙醇醯胺〇· 0000005至〇. 3重量％、聚氧伸γ其p其 《'三乙物趟錢: 亞曱基雙胍鹽酸鹽0.0005至0.15重量％之水溶液； (AB) 為含有式（I)之化合物〇· 〇〇5至〇·丨重量％、椰子油脂 肪酸二乙醇醯胺〇. 00476至〇. U25重量％、聚氧伸烷基烷 基醚0. 00024至〇· 1125重量％、三乙醇胺〇 〇〇〇5至〇 465 重量％及聚六亞曱基雙胍鹽酸鹽0 005至〇.丨重量％之水溶 液； (AC) 為含有式（I)之化合物〇. 015至〇. 〇45重量％、椰子油 月曰肪酸一乙醇醢胺0. 02725至〇. 09615重量％、聚氧伸烧基 烷基醚0. 00275至0. 02885重量％、三乙醇胺〇. 〇〇5至〇. 445 重量％及聚六亞曱基雙胍鹽酸鹽〇· 01至0. 025重量％之水溶 液等之形態使用。 該等中較好使用（AA)之水溶液形態，更好使用（AB)之 水溶液形態，最好使用（AC)之水溶液形態。 為了使用本發明之殺菌劑組成物或殺菌洗淨劑組成物 將對象物進行殺菌或殺菌洗淨，只要將水溶液形態之該組 成物與該對象物接觸即可。接觸方法並無特別限制，可將 本發明之殺菌劑組成物及殺菌洗淨劑組成物經由散佈、喷 霧、浸潰、擦拭等通常之方法與對象物接觸。另，可將該 殺菌劑組成物或殺菌洗淨劑組成物一同使用刷子或海綿 等’除去殺菌對象物或殺菌洗淨對象物之污垢。 將本發明之殺菌劑組成物或殺菌洗淨劑級成物與殺菌 對象物或殺菌洗淨對象物接觸時之接觸時間並無特別限 324225 21 201249341 制，只要根據有效成分之濃度適當決定即可。例如，將（n) 或（S)之水溶液形態之殺菌劑組成物或殺菌洗淨劑組成物 在常溫與對象物接觸時，通常以30秒至1〇分鐘，較好i 至5分鐘’即可獲得充分之殺菌效果或殺菌洗淨效果。 調製半固體或水溶液形態之本發明殺菌劑組成物及殺 菌洗淨劑組成物中使用之水可為離子交換水、蒸餾水等精 製水；自來水及地下水、河床滲流水等天然水中之任何一 種’從氣或金屬離子之含量少之點而言，較好為精製水。 本發明之殺菌劑組成物及殺菌洗淨劑組成物在食品工 廠、醫院、畜舍、飯店、餐廳、學校、店舖等之地板或牆 壁等’可作為释菌或殺菌洗淨之設備乃用至食品操作設備 用之殺菌劑組成物及破爵洗淨劑組成物使用。又，在食品 工廠等使用之食品製造、加工機器或器具等食品用途之對 象物之殺菌或殺菌洗淨亦有用。食品製造、加工機器可列 舉各種攪拌機、混合機、均化器、自動切割機等。器具可 列舉切菜板、菜刀、食器、食品用容器、抹布等。 本發明之殺菌劑組成物及殺菌洗淨劑組成物為對於黴 菌等真菌類或一般細菌具有殺菌效果，且對於對第四級錢 鹽及/或雙胍系殺菌劑具有抵抗性之微生物，例如對氯化 一癸基一甲基錢（DDAC)及/或聚六亞曱基雙脈鹽酸鹽（ρημβ) 具有抵抗性之微生物亦發揮殺菌力之組成物。因此，本發 明之殺菌劑組成物及殺菌洗淨劑組成物作為對於有對第四 級銨鹽及/或雙胍系殺菌劑具有抵抗性之微生物存在之對 象使用之殺菌劑組成物及殺菌洗淨劑組成物特別有用。 324225 22 201249341 又，本發明之殺菌劑組成物及殺菌洗淨劑組成物與第 四級銨鹽及/或雙胍系殺菌劑比較，即使長時間使用，亦 難產生對於該組成物具有抵抗性之微生物。因此，本發明 之殺菌劑組成物及殺菌洗淨劑組成物在對於經由使用第四 級銨鹽及/或雙胍系殺菌劑會產生對於該藥劑具有抵抗性 之微生物之對象’亦可作為殺菌劑組成物及殺菌洗淨劑組 成物使用。 對於第四級銨鹽及/或雙胍系殺菌劑具有抵抗性之微 生物之例可列舉綠膿桿菌（Pseudomonas)屬之微生物及沙雷 氏菌（Setratia)屬之微生物，例如黏質沙雷氏菌（Serratia marcescens)、液化沙雷氏菌（Serratia liquefaciens)等。 本發明之殺菌劑组成物及殺菌洗淨劑組成物為適合連 續或繼續使用之組成物。具體而言，本發明之殺菌劑組成 物及殺菌洗淨劑組成物為即使長時間連續或繼續使用亦很 難產生對於該組成物具有抵抗性之微生物之組成物。更具 體而言，本發明之殺菌劑組成物及殺菌洗淨劑組成物以將 對於同一對象重複使用時，對於該組成物具有抵抗性微生 物之發生與將第四級銨鹽及/或雙胍系殺菌劑在該對象同 樣操作，重複使用時相比，較少為特徵。此處，「對於同一 對象重複使用」為在同一對象或對象之特定微生物種時對 於同一微生物種，將同一組成物複數次（例如2次、3次、 4次、5次、6次、7次、8次或8次以上）使用。又，「連 續使用」為例如如（組成物A、組成物A、組成物A…）， 相同組成物連續使用2次以上。「繼續使用」為相同之組成 324225 23 201249341 物不連續使用2次以上，在其間使用其他組成物，再繼續 對於同一對象使用。例如，以（組成物A、組成物B、組成 物C、組成物A、組成物D、…）之順序使用時，組成物A 不是連續，而是繼續使用。 [實施例] 以下’根據實施例對本發明作更詳細的說明。於以下 之各試驗，表中之「+」表示確認菌增殖，「一」表示確認 菌未增殖。 試驗例1 將以下表示之供試菌i至“^用生理食鹽水稀釋使成 為 106cfu/mL之菌液 〇. 〇3mL(供試菌 iii 及 viii 為 0. lmL) 與藥劑漠度為1. 25至320ppm之PHMB水溶液3mL(供試菌 ui及viii為i〇mL)混合後於25<t保持5分鐘。敏化作用 時間經過後再次攪拌後從各混合物中取出1白金線圈，接 種於BHI肉湯培養基i〇mL(只有供試菌viii為sCDlp培養 基10mL)，於30°C培養48小時（只有供試菌ii培養120小 時）。以未接種菌之BHI肉湯培養基（只有供試菌viii為未 接種菌之SCDLP培養基）為基準，以目視比較培養基之混 濁’確認PHMB對於各供試菌之殺菌效果。結果表示於表卜 PHMB :聚六亞曱基雙胍鹽酸鹽 BHI .腦心浸出物培養液（Brain Heart Infusion) SCDLP :含卵磷酯及聚山梨糖醇酯8〇之大豆分解蛋白質乾 路素培養液（Soybean-Casein Digest Broth with Lecithin & Polysorbate 80) 324225 24 201249341 . 供試菌 i :綠膿桿菌（Pseudomonas aeruginosa)NBRC 13736 供試菌 ii :黑麴菌（Aspergillus niger)ATCC16404 供試菌 iii :仙人掌桿菌（Bacillus cereus)NBRC15305 供試菌iv :黏質沙雷氏菌（Serratia marcescens)(食品工 廠分離菌1) 供試菌v :液化沙雷氏菌（Serratia liquefaciens)(食品 工廠分離菌2) 供試菌vi :黏質沙雷氏菌（Serratia marcescens)(食品工 廠分離菌3) 供試菌vii :黏質沙雷氏菌（Serratia marcescens)(食品 工廠分離菌4) 供s式菌 viii :枯草桿菌（Baciiius subtilis)IF013719 [表1] PHMB _(ppm) 供試菌 i 供試菌 ii 供婊菌 iii 供試菌 iv 供試菌 V 供試菌 vi 供試菌 vii 供試菌 »«· V111 _ 320 — + — + + + + _ 160 一 + + + + + + 一 _ 80 一 + + + + + + + 〜40 — + + + + + + + 、20 — + + + 十 + + + 10 —~— 一 + + + + + + + 一 + + + + + + + __2, 5 —+ + + + + + + _1.25 + + 試驗例2 使用試驗例1中使用之供試菌i至vi i，將藥劑變更 為DDAC ’以與試驗例1相同之方法確認DDAC對於各供試 菌之殺菌效果。結果表示於表2。 324225 25 201249341 DDAC:氯化二癸基二曱基銨 [表2] PHMB (ppm) 供試菌i 供試菌 ii 供試菌 iii 供試菌 iv 供試菌V 供試菌 vi 供試菌 vii 320 — — — 一 — — — 160 一 + + — — — — 80 — + + + + — — 40 — + + + + + — 20 — + + + + + + 10 — + + + + + + 5 — + + + + + + 2.5 + + + + + + + 1.25 + + + + + + + 試驗例3 調製將式（I)之化合物[二氯化1，10-二（3-癸基-2-曱 基咪唑鏽）癸烷]及PHMB以下述之調配比含有之水溶液，3 小時後確認外觀變化。結果表示於表3。 [表3] 式（I)之化 合物(g) PHMB(g) 水(g) 式（I)之化合 物：PHMB 3小時後之外觀 變化 1.4 7 191.6 1:5 外觀未變化 1.4 35 163.6 1:25 外觀未變化 1.4 42 156.6 1:30 外觀未變化 1.4 56 142.6 1:40 外觀未變化 1.4 70 128.6 1:50 白濁 1.4 84 114.6 1:60 白濁 實施例1至6及比較例1至13 殺菌力試驗1(黴菌） 將以下表示之供試菌之孢子懸濁液用生理食鹽水稀釋 324225 26 201249341 使成為106cfu/mL之菌液〇. 03mL與將表4表示之殺菌劑 組成物稀釋使該組成物濃度為0.1至0.3重量％之水溶液 3mL混合後於25°C保持5分鐘。敏化作用時間經過後再次 攪拌後從各混合物中取出1白金線圈，接種於BHI肉湯培 養基10mL’於3(TC培養120小時。以未接種菌之BHI肉湯 培養基為基準，以目視比較培養基之混濁，判定殺菌劑組 成物之殺菌效果。 供試菌 ii :黑麴菌（Aspergillus niger) ATCC16404 結果表示於表5。本發明之殺菌劑組成物與比較例之 組成物相比，對於黴菌之殺菌力優越。 [表4] 成分 (vtX) 例1 例2 實施 例3 賁施 例4 實施 例5 實施 例6 twa 例1 fcbfe 例2 tbfe 例3 tm 例4 tbfe 例5 例6 味 设菌成 分八※！ 9 0 0 0 4 4 0 0 0 0 0 0 0 设面成 分B规 0 9 0 0 0 0 0 0 0 0 0 0 0 找面成 分(：來3 0 0 9 0 0 0 0 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0 0 分£來5 0 0 0 0 0 0 9 0 0 9 0 0 0 找国成 0 0 0 0 0 0 0 9 0 0 9 0 0 设国成 分(3紹 0 0 0 0 0 0 0 0 9 0 0 9 0 ΡΗΜΒ^δ 0 0 0 8 12 12 0 0 0 0 0 0 9 二乙 榔 0.13 0.13 0.13 1.18 4.4 5 0 0 0 0.13 0.13 0.13 0 她 0 0 0 0 0 0.5 0 0 0 0 0 0 0 水 pH yu. 〇7 9.0 90.87 θΤ" 90.87 J6,82 —9 0 79.6 1.0 78.5 9:0 91 —6了4 91 3.5 91 3.4 90.87 9.0 90.87 9.0 90.87 9.0 91 3.5 ※l殺菌成分A:二氮化1, 10_二（3_癸基_2_甲基咪唑鑌）癸烷（1〇_1〇_1〇_cl) ※之殺菌成分B:二溴化1, ι〇_二（3_癸基_2_甲基咪唑鑌）癸烷（1〇_1〇_1〇_Br) ※苫殺菌成分C :二氱化12_二（3_癸基_2_甲基咪唑鎮）十二碳烷（1〇12_1〇 (：1) ※4殺菌成分D:二氣化】，丨2_二（3_辛基_2_甲基咪唑鏞）十二碳烷（8_i2_8cl) ※亏殺菌成分E:二氯化1，6-二（3_辛基_2_甲基咪唑鍩）己烷（8_6_8_C1) ※6殺菌成分F:二氣化！，丨2 —二（3_己基_2_甲基咪唑鐳）十二碳烷（6_12_6C1) ※了殺菌成分G:二氣化1，1〇_二（3_己基_2_甲基咪唑鏔）癸烷（6_1〇_6_cl) 浓8 PHMB ··聚六亞甲基雙胍鹽後鹽 27 324225 201249341 [表5] (黴菌：黑麴菌（Aspergillus niger) ATCC16404 之增殖） 濃度 (wtX) 實施 例1 實施 例2 實施 例3 實施 例4 實施 例5 實施 例6 比較 例1 比較 例2 比較 例3 比較 例4 比較 例5 比較 例6 比較 例7 0.3 — — — 一 一 — + + + + + + + 0.2 — — — 一 — ~ + + + + + + + 0.1 + + 十 — + + + + + + + + + 殺菌力試驗2(芽胞菌） 將以下表示之供試菌之芽胞懸濁液甩生理食鹽水稀釋 使成為106cfu/mL之菌液〇. lmL與將表4表示之殺菌劑組 成物稀釋使該組成物濃度為0. 1至0. 3重量％之水溶液l〇mL 说合後於25°C保持5分鐘。敏化作用時間經過後再次攪拌 後從各混合物中取出1白金線圈，接種於BHI肉湯培養基 BmL ’於30°C培養48小時。以未接種菌之BHI肉湯培養 基為基準’以目視比較培養基之混濁，判定殺菌劑組成物 對各菌體之殺菌效果。 供試菌 iii :仙人掌桿菌（Bacillus cereus) NBRC15305 、结果表示於表6。本發明之殺菌劑組成物與比較例之 組成物相比，對於芽胞菌之殺菌力優越。 [表6] (芽胞菌：仙人掌桿菌（Bacillus cereus) NBRC15305之增殖） 濃度 η 〇 實施 例1 實施_ 例2 實施 例3 實施 例4 實施 例5 實施 例6 比較 例1 比較 例2 比較 例3 比較 例4 比較 例5 比較 例6 比較 例7 _ ο η ο — — 一 — — — + + + + + + — ν. L Π 1 — 一 — — 一 + 十 + + + + + 1. υ· 1 L±J + + _ -Γ_- —- + L+J + + + UU + 殺菌力試驗3(藥劑抵抗性菌） 324225 28 201249341 將從食品工廠分離之下述供試菌在βΗΙ肉湯培養基， 於30C培養24小時，用生理食鹽水稀釋使成為1〇6cfu// mL之菌液〇.03mL與將實施例1至6之殺菌劑組成物及表7 表不之殺菌劑組成物稀釋使該組成物濃度為〇. 〇25至〇· 1 重篁％之水溶液3mL混合後於25°C保持5分鐘。敏化作用 時間經過後再次攪拌後從各混合物中取出1白金線圈，接 種於冊1肉湯培養基lOmL，於30°C培養48小時。以未接 種菌之BHI肉湯培養基為基準，以目視比較培養基之混濁， 判定殺菌劑組成物對各菌體之殺菌效果。 供》式菌iv ·黏質沙雷氏菌（serratia marcescens)(食品 工廠分離菌1) 結果表示於表8。本發明之殺菌劑組成物與比較例之 組成物相比，對於藥劑抵抗性菌之殺菌力優越。 [表7] 成分(wt%) 比較例8 比較例9 比較例 10 比較例 11 比較例 12 比較例 13 殺菌成分八※l 9 0 0 0 0 0 殺菌成分6※之 0 9 0 0 0 0 殺菌成分(：※苫 0 0 9 0 0 0 殺菌成分0※4 0 1 0 0 9 0 0 PHMB 糾 0 」 0 0 0 16 0 DDAC ※9 0 0 0 0 0 9 水 91 91 91 91 84 91 pH 6.2 — 5,3 3.2 | ' 4.1 3.5 8.7 ※丄殺菌成分A :二氣化ι，ι〇_二（3-癸基-2-甲基咪唑鏘）癸烷（io-10-io—ci) ※之殺菌成分β:二溴化ι，1〇_二（3_癸基_2-曱基咪唑鏘）癸烷（1〇_1〇_1〇_Br) ※3殺菌成分C:二氣化1，12-二(3-癸基-2-甲基咪唑鐯）十二碳烷（10-12-10-C1) ※斗殺菌成分D :二氣化1，12-二（3-辛基-2-甲基咪唑鑌）十二碳烷(8-12-8-C1) ※台PHMB:聚六亞甲基雙胍鹽酸鹽 ※9 DDAC:氣化二癸基二甲基敍 29 324225 201249341 [表8] (藥劑抵抗性菌.黏質沙雷氏菌（serratia marcescens)(食品工廠分離菌 1)之增殖） 濃度 (wt%) 實施 例1 實施 例2 實施 例3 實施 例4 —實施 例5 實施 例6 比較 例8 比較 例9 比較 例10 比較 例11 比較 /χ,ί 1 9 比較 AtA 1Q 0.1 一 — 一 — — + + 一 + + + 0. 05 — — 一 — + + + + + + 0,025 — — — + + + + + + 殺菌力試驗4(藥劑抵抗性菌） 將從食品工廠分離之下述供試菌在BHI肉湯培養基， 於30°C進行前培養24小時，用生理食鹽水稀釋使成為 106cfu/mL之菌液〇. 〇3mL與將實施例！至6之殺菌劑組 成物及表7表示之殺菌劑組成物稀釋使該組成物濃度為 0· 08至1. 33重量％之水溶液3mL混合後於託七保持i分 鐘。敏化作用時間經過後再次攪拌後從各混合物中取出工 白金線圈，接種於BHI肉湯培養基i〇mL，於30¾進行本培 養120小時。以未接種菌之BHI肉湯培養基為基準，以目 視比較培養基之混濁，判定殺菌劑組成物對各菌體之殺菌 效果。 供試菌v .液化沙雷氏菌（Serratia liQuefaciens)(食品 工廠分離菌2) 結果表示於表9。本發明之殺菌劑組成物與比較例之 組成物相比，對於藥劑抵抗性菌之殺菌力優越。 324225 30 201249341 ；[表 9] (藥劑抵抗性菌：液化沙雷氏菌（Serratia liquefaciens)(食品工廠分離 菌2)之增殖） 濃度 (wt%) 實施 例1 實施 例2 實施 例3 實施 例4 實施 例5 實施 例6 比較 例8 比較 例9 比較 例10 比較 例11 比較 例12 比較 例13 1.33 + + — + + 一 0. 66 十 + + + + 一 0.33 + + + + + + 0.16 — + + + + + + 0. 08 + + + — — — + + + + + + 藥劑耐性化抑制試驗 以曰本化學療法學會標準法（微量液體稀釋法）為基準， 連續實施最小發育阻止濃度（MIC)之測定。將實施例1及比 較例13之組成物用滅菌水稀釋，調製組成物濃度為〇. 〇〇7 至1.792重量％之藥液，將調整為指定濃度2倍濃度之營養 肉湯（nutrient broth)培養基（榮研化學（股）公司製造，普 通肉湯培養基‘榮研’ E-MC35)以與藥液同量添加，授拌後 在微型盤（microtype plate)(96孔）中每次少量分注150 "L/孔。接著’將從食品工廠分離之下述供試菌在NB培 養基，於30°C培養20小時之菌液用生理食鹽水稀釋使成 為107cfu/mL後’在注入完上述製作之培養基之微型盤中 每次少量接種7.5yL/孔。將此於30°C之恒溫器内培養 48小時’以目視確認有無菌之生育，測定MIC。另使用在 確認生育之孔中從藥劑濃度最大之孔中採取菌液，用生理 食鹽水稀釋使成為107cfu/mL之菌液，與上述同樣操作， 再次測定MIC。重複該操作，合計進行MIC測定8次，確 324225 31 201249341 認MIC之變化。 供3式菌vi ’黏質沙雷氏菌（serratia marcescens)(食品 工廠分離菌3) 供《式菌vi i .黏質汐雷氏菌（serratia marcescens)(食^ 工廠分離菌4) ^ ° 結果表示於表10及表1卜實施例1之組成物即使在 第8次之試驗，MIC值仍低，為〇 〇56重量％(供試菌 及0.028重量％(供試菌vii)。從相關之結果確認，式（ 之化合物[二氯化1，10-二（3_癸基_2_曱基口米哇鏽）癸 與DDAC比較，難產生藥劑抵抗性菌。 [表 10][wherein, Ri represents a saturated linear alkyl group having 1 to 3 carbon atoms, R 2 represents a saturated linear alkyl group having 8 to 12 carbon atoms, χ- represents a halogen ion, and γ represents a saturated linear chain having a carbon number of 8 to 12. alkyl]. Further, the present invention also provides a sterilizing and washing method comprising contacting the sterilizing detergent composition with a bactericidal cleaning object. [Effects of the Invention] The bactericidal composition of the present invention has a bactericidal effect on fungi or common bacteria such as mold, and is also resistant to a drug resistant bacteria which is resistant to a fourth-order ammonium salt and/or a biguanide bactericide. Composition of superior bactericidal effect Further, the bactericidal composition of the present invention is a composition which is difficult to produce a drug-resistant bacteria for the composition itself even if it is continuously used for a long period of time, and can reduce slipperiness or stickiness after use. Here, examples of the fourth-order ammonium salt include dinonyldimethylammonium chloride and benzylammonium chloride. Further, examples of the biguanide fungicides include polyhexamethylene biguanide hydrochloride, diclofenac gluconate 324225 7 201249341 (chlorhexidine gluconate) and the like. Further, the sterilizing detergent composition of the present invention has a bactericidal effect on fungi or common bacteria such as mold, and is also resistant to a drug resistant bacteria which is resistant to a fourth-order ammonium salt and/or a double-pulver fungicide. Superior bactericidal effect 'and' has a high detergency composition. Further, the sterilizing detergent composition of the present invention is such that it is difficult to produce a drug-resistant bacteria for the composition itself even if it is continuously used for a long period of time. [Embodiment] It is possible to reduce the composition which is slippery or sticky after use. And the composition of the fungicide composition and the sterilizing detergent composition are formed into the mouth of the knife 1. 'R丨 is any one of the methyl group, the ethyl group or the propyl group, or the ethyl group is more preferably A. base. R2 is preferably a carbon number of 8 to ° chain fluorenyl group, more preferably a fluorenyl group. X- is a dentate ion, preferably a gas ion or a bromide ion, and the P4A ^I lamp is preferably a gas ion. Preferably, γ is a carbon number of from 1 〇 to 12 and a direct bond is extended, and more preferably a thiol group. The type of squatting and (4) shampoo composition 2' Jialing": specific examples of the substance of dibrominated U0-two (3_ fluorenyl carbon: wide: gasification a strict 1,12-two (3 _ 癸 ' '2, methyl imidazole rust) 12 two: 1 1 ί) 12 ~ 2 (3 ~ 癸 _2 2 _ methyl miso Wrong) 12 carbon burn, one ", ^ one (3 - xin Base-2_methylimidazolium), smoldering, gasification, singular methyl methacrylate, twelve carbon institutes, two gasification; u one (3, 10, etc. in these, in the point of -= It is better to have two desertifications, 1,10~2 (3-mercapto-2_a 324225 201249341 base money), simmering, bismuth dichloride, 1G_bis(3_mercapto-2-methyl-10- Wrong) decane, one/smelly 1,12_bis(3_mercapto-2-methylimidazolium) dodecane, gasified 1,12-bis(3-mercapto-2-methyl Imidazolium)dodecane, 1'12-bis(3-octyl-2-methylimidazolium) dioxane dibromide, bismuth hydride, 12_bis(3-octyl-2-methyl) Kimi rust) 12 carbon burns 'in the point of mixing with other bactericidal ingredients, it is better to dibrominated 1,10-two (3-癸美-2-曱 = miso (6) Wei, two Chlorination 1 heat 2 (3-mercapto-2-indenyl group) Alkyl monochlorinated 1'丨2_bis(3-indolyl-2-hydrazinyl imidazolium) dodecane and gasified 1'12-bis(3-octylmethyl rust) 12 carbon burned It is better to gasify 1,10-(3-mercapto-2-methylpyrene) smoldering at the point of the resistance of the agent resistance® and the solubility of the water towel. _Listening and (4) Washing and listening to the towel type (1) is not particularly limited. The fungicide composition and the sterilizing ratio of the present invention are: 为. ^1%, more preferably 0.005 to the compound of the formula (1) 30 weight == ° 15 to 10 coffee, ... to 1 ' _ and / Λ 未 未 G G G G G G G G G G G G G 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四 第四Inhibition of Sexual Bacteria 2:: When the content exceeds 5°% by weight, the viscosity of the composition is: == The non-ionic interface of the constituents of the composition is 324225. The polyoxy-extension is fine, the polyoxy-extension is ethyl-anthracene, and the oxygen is difficult. Ethyl sorbitol Xuan fatty acid vinegar, sorbitol Xuan 9 201249341 fatty acid ester, residual fatty acid vinegar, polyoxy-extension ethyl polyoxypropyl propyl polymer ^ 4, preferably coconut oil fatty acid diethanolamine , polyoxygen extension, * Further, the nonionic interface in the sterilizing detergent composition of the present invention preferably has an HLB value of 4 to 15, more preferably 9 to Μ. The nonionic surfactants may be used in combination. The ratio of the surface surfactant of the composition of the g-cleaning agent of the present invention is preferably from Q. 丨 to 2Q parts by weight, more preferably from 1 to 10 parts by weight, of the compound of the formula (I). Preferably, it is 2 to 5 parts by weight. The ratio of the nonionic surfactant is not up to a certain extent (when the U weight is used, the detergency tends to decrease, and when it exceeds 20 weights, the form of the aqueous solution may be separated or white turbid, and the foam is eliminated. Poor tendency. In terms of detergency and storage stability, the nonionic surfactant in the sterilizing detergent composition of the present invention preferably has a coconut oil fatty acid diethanol sulphate and a polyoxygen swellable base. When the ratio of the blending ratio of the coconut oil fatty acid diethanolamine is used, the polyoxyl extension base is preferably 0.05 to 1. The weight fraction is preferably from 1 to 3 parts by weight. 025. The weight of the compound of the formula (1) is preferably from 0. 0025 to 24. 5 parts by weight, more preferably 〇. 5重量份。 。 5 to 5 parts by weight, the most, from 0. 01 to 1. 5 parts by weight. The ratio of triethanolamine is less than 〇· 〇〇25 heavy injury β temple 'has the following I (1) to (lv) problem · (1) bactericidal effect becomes insufficient '(η) bactericide composition or bactericidal detergent When the composition is in the form of an aqueous solution, the stability in the low temperature condition is lowered. ((1)) When the other bactericidal components or other additives of the mash are prepared, the aqueous solution may be white turbid, etc. and 324225 10 201249341 (9) The sufficient effect of suppressing the golden eyebrows cannot be obtained. . In addition, when the ratio of the alcoholamine exceeds 24.5 parts by weight, when the sterilizing agent composition or the sterilizing granule is used as an aqueous solution in the form of the sterilizing agent or the sterilizing granule, the composition of the composition is excessively increased, and there is a metal rot. The tendency to become high. The hourly m (four) age secret and the killing agent composition is not particularly limited, and is preferably from 7 to 12, more preferably from 7. 7 to 9, 5, and further preferably from 8 to 9.4. . In the bactericidal composition of the present invention and the sterilizing detergent composition, triethanol 241 = ', and for the compound of the formula (1), 1 part by weight, if in the range of 025. 0025 to the reading, the composition of the aqueous solution form The pH is in the range of 72. The composition can be adjusted using an assay as desired. In the composition of the invention, the composition of the sterilizing detergent and the composition of the sterilizing detergent may contain a test agent as long as the composition does not cause precipitation or white turbidity, and the like, that is, the agent of Shiguan can be exemplified by sodium hydroxide or potassium hydroxide. , sodium carbonate, 齩? Sodium, potassium citrate, sodium bicarbonate, potassium bicarbonate, sodium sesquicarbonate, :=acid=, sesquitaine, sodium sulphate, sodium succinate, sodium pyrophosphate, poly, acid steel, Sodium tetraphosphate, sodium hexamelate, and the like. Among these assays, it is preferred that sodium hydroxide and hydroxide are removed from the point of stability of the composition when it is stored in the form of an aqueous solution. These test agents can be used in combination with two or more kinds of the sterilizing detergent composition of the present invention by using a compound of the formula (丨), a non-tongue biocide and diethanolamine, and a bactericidal power, especially for a drug = The bactericidal power of the bacteria is improved compared with that of the compound of the formula (1) alone, and the superior detergency of 324225 11 201249341 can be exerted compared with when the nonionic surfactant is used alone. In other words, the (4) cleansing touch product of the present invention is a composition which exhibits a synergistic effect by the compound of the formula (1), the nonionic surfactant, and the triacetate component for both the sterilizing power and the detergency. The composition of the bactericidal agent and the sterilizing detergent composition of the present month may further comprise other (four) age 4 invention (four) agent composition and (4) other bactericidal components which may be contained in the detergent composition, exemplified by gasification of dimercapto a fourth-order salt such as guanyl ammonium, emulsified benzoate, etc.; polyhexamethylene biguanide hydrochloride, glucosinolate diclofenac and other bismuth fungicides; organic glycoside complex and other organic block sterilization Agents, etc. Among these other bactericidal components, a bismuth-based bactericide is preferred from the point of bactericidal effect on the bacterium, and polyhexamethylene biguanide hydrochloride is preferred among the biguanide bactericides. These other sterilizing components may be used singly or in combination of two or more. When the bactericidal composition and the sterilizing detergent composition of the present invention contain other sterilizing components, the ratio of the other bactericidal components in the composition is preferably from 0 to 40 parts by weight per 1 part by weight of the compound of the formula (I). More preferably, it is 0.7 to 10 parts by weight, preferably 1 to 5 parts by weight. When the ratio of the other sterilizing component is less than 0.5 part by weight, the sterilizing effect of the other sterilizing component may not be sufficiently exhibited. When the amount of the sterilized component is more than 4 parts by weight, white turbidity may occur when the graded product is stored as an aqueous solution. tendency. The bactericidal composition and the sterilizing detergent composition of the present invention may further contain other additives as needed. Examples of other additives which may be contained in the composition include ethanol, a coloring matter, a fragrance, a washing aid, and the like. The ratio of the other additives in the bactericidal composition and the sterilizing detergent composition of the present invention is usually 5% by weight or less of the composition in the form of an aqueous solution. 324225 201249341 The bactericidal composition and the sterilizing detergent composition of the present invention may be provided in a solid form such as a tablet or a powder, a solid form such as a paste or a gel, or may be provided in the form of an aqueous solution. When the sterilizing agent composition and the sterilizing detergent composition of the present invention are supplied in a solid or semi-solid form, the composition is usually dissolved in water to form an aqueous solution, and is suitable for use in a sterilizing target or a sterilizing and washing object. When the bactericidal composition and the sterilizing detergent composition of the present invention are provided in the form of an aqueous solution, the aqueous solution can be applied to a sterilizing target or a sterilizing and washing object in an original or more diluted aqueous solution. The method for preparing the bactericidal composition and the sterilizing detergent composition of the present invention is not particularly limited. For example, a solid biocide composition and a sterilizing detergent composition can be obtained by subjecting the essential components to the desired ones together with the excipients and the like. Further, the mixture of the essential components may be further supplied to a preparation step of granulation or keying to obtain a composition. The semi-solid fungicidal composition and the g-killing detergent composition can be obtained, for example, by mixing the essential components and water with a binder. The water consumption, the composition of the agent, and the sterilizing detergent composition can be obtained, for example, by dissolving the essential components in water, or dissolving the prepared solid or semi-solid composition in water. When the oil of the bactericidal composition of the present invention and the sterilizing detergent composition are adjusted, the stage of performing the pH adjustment is not particularly limited, and usually, in the form of the (four) agent or the (four) detergent composition in the form of the prepared aqueous solution. Add, the agent can be. Alternatively, it may be determined in advance that the bactericidal composition or the sterilizing detergent composition in the form of an aqueous solution may be adjusted to the amount of the test agent in the desired range, and the amount of the test agent is combined with the bactericidal composition or the sterilizing detergent. The ingredients of the substance are uniformly dissolved in water. The pH of the composition can be adjusted to the range of 324225. 13 201249341 A predetermined amount of the test agent is contained in a semi-solid fungicide composition or a sterilizing detergent composition. The composition of the bactericidal composition of the present invention which is provided in the form of a solid or a semi-solid is exemplified by (a) a composition containing from 1 to 99% by weight of the compound of the formula (I) and from 0.001 to 5% by weight of the triethanolamine; And a composition of the compound of the formula (I): 5 to 15% by weight of the compound of the formula (I), and 5 to 15% by weight of the compound of the formula (I) and the triethanolamine 0. 001 Up to 1% by weight of the composition and the like. Examples of the bactericidal composition of the present invention which further contains other bactericidal components may be listed as (d) from 1 to 98% by weight of the compound of the formula (I), and triethanolamine hydrazine. 〇〇〇1 to 5 by weight. /. And a composition of the diterpene fungicide of 1 to 98% by weight; (e) 3 to 50% by weight of the compound containing the formula (!), triethanolamine hydrazine, 〇〇5 to 3% by weight, and a biguanide bactericide 3 to 50 % by weight of the composition; (Ο is a composition containing 5 to 15% by weight of the compound of the formula (I), triethanolamine hydrazine. 〇〇1 to 1% by weight, and a composition of the biguanide bactericide 5 to 15% by weight, etc. Examples of the bactericidal composition of the present invention provided by the form include (g) a composition of an aqueous solution containing 0.001 to 5 % by weight of the compound of the formula (I) and 875 to 50% by weight of triethanolamine hydrazine; (h) a composition comprising an aqueous solution of the compound of the formula (I) in an amount of from 1 to 20% by weight and triethanolamine in an amount of from 9 to 10% by weight; 324225 14 201249341 *- (i) 3 to 10% by weight of the compound containing the formula (I) And a composition of an aqueous solution of triethanolamine i.i to 6% by weight, etc., preferably a composition of (h), more preferably a composition of (i), and an aqueous solution form containing other bactericidal components. Examples of the bactericidal composition of the present invention include (j) 0.001 to 50% by weight of the compound containing the formula (I). a composition of an aqueous solution of triethanolamine hydrazine 〇 75 to 99% by weight and a biguanide bactericide . 0005 to 3% by weight; (k) 1 to 20% by weight of a compound containing the formula (I), triethanolamine hydrazine. a composition of an aqueous solution of from 09 to 98% by weight and from 1 to 2% by weight of the biguanide bactericide; (1) 3 to 10% by weight of the compound containing the formula (I), 1 to 93% by weight of the triethanolamine, and bismuth sterilization a composition of an aqueous solution of 3 to 16% by weight, etc., preferably a composition of (k), more preferably a composition of (1), and (m) a compound 3 containing the formula (I) The composition of the aqueous solution of 1% by weight, triethanolamine 1 to 93% by weight, and polyhexamethylene dihydrazide hydrochloride 3 to μ% by weight is optimal. The bactericidal composition of the present invention in the form of an aqueous solution, according to the user For the purpose, water may be additionally added as a diluent. When used as a diluent, the ratio of the compound of the formula (I) is preferably diluted to 0.001 to 5% by weight. For example, the bactericidal composition of the present invention can be used. The form (η) is a compound containing the formula (I) 〇〇. 〇〇1 to 〇·25% by weight and An aqueous solution of ethanolamine 0.0004 to 0.25 wt%; (〇) is an aqueous solution containing the compound of the formula (I) 〇·〇〇5 to 〇·1% by weight and triethanolamine 324225 15 201249341 〇. 0005 to 〇. 〇〇15% by weight (P) is an aqueous solution containing the compound of the formula (I): 015 to 〇, 〇45% by weight, and triethanolamine 0.0006 to o.ooi% by weight, etc. In the above, it is preferred to use an aqueous solution form of (〇), Better use of the aqueous solution form of (p). When the bactericidal composition of the present invention further contains another sterilizing component, for example, the composition may be in the following form (Q) as a compound containing the compound of the formula (I): 〇〇1 to 〇. 25 wt%, triethanolamine hydrazine. 004至〇·5 wt% and biguanide fungicide 〇. 〇〇〇5 to 〇. 15% by weight of an aqueous solution; (Ο is a compound containing formula (!) 〇·〇〇5 to 〇. 1% by weight, three Ethanolamine 0.0005 to 0.45 wt% and a biguanide fungicide 0.005 to 0.1 wt./〇 aqueous solution; (s) is a compound containing the formula (I) . 015 to 〇. 〇45 wt%, triethanolamine 〇. 〇 〇5至〇. 4% by weight and biguanide fungicide 〇. 〇2 to 〇. 08% by weight of aqueous solution, etc. It is better to use (r) aqueous solution form, better use (s) aqueous solution form composition And (t) is an aqueous solution containing 0.015 to 0.045 wt% of the compound of the formula (丨), 0.005 to 4.4 by weight of triethanolamine, and 0.02 to 0.08 wt% of polyhexamethylenebisindole hydrochloride. The form is optimal. Examples of the sterilizing detergent composition of the present invention provided in a solid or semi-solid form (A) is a composition containing 1 to 98% by weight of the compound of the formula (I), 1 to 98% by weight of the nonionic surfactant, and 1 to 5% by weight of the triethanolamine hydrazine; 324225 .201249341 (B) Is a composition containing 3 to 50% by weight of the compound of the formula (i), 10 to 90% by weight of the nonionic surfactant, and 0.0005 to 3% by weight of the triethanolamine; (C) is a compound 5 containing the formula (I) 15% by weight, a nonionic surfactant 20 to 80% by weight, and a composition of triethanolamine o.ooi to % by weight, etc. Examples of the sterilizing detergent composition of the present invention containing another sterilizing component (D) a composition comprising from 1 to 97% by weight of the compound of the formula (I), from 1 to 97% by weight of the nonionic surfactant, from 0001 to 5% by weight of triethanolamine, and from 1 to 97% by weight of the biguanide bactericide; a composition comprising 3 to 50% by weight of the compound of the formula (I), 10 to 90% by weight of the nonionic surfactant, 0.0005 to 3% by weight of the triethanolamine, and 3 to 50% by weight of the biguanide bactericide; (F) 5 to 15% by weight of the compound containing the formula (I), 20 to 80% by weight of the nonionic surfactant, The composition of the ethanolamine 〇.001 to i% by weight and the biguanide bactericide 5 to 15% by weight. Examples of the sterilizing detergent composition of the present invention which are provided in the form of an aqueous solution are (G) containing the formula (I). a composition of an aqueous solution of the compound 〇·〇01 to 5〇% by weight, a nonionic surfactant 0.0001 to 60% by weight, and a triethanolamine 0.075 to 50% by weight; (H) a compound 1 to 2 containing the formula (I) % by weight, nonionic surfactant 1 to 45% by weight and triethanolamine hydrazine. 〇 9 to 1% by weight of the composition of the aqueous solution; (J) 3 to 10% by weight of the compound containing the formula (I), nonionic Interface activity 324225 17 201249341 agent 6 to 25% by weight and triethanolamine hydrazine. 1 to 6% by weight of the composition of the aqueous solution; (K) 1 to 20% by weight of the compound containing the formula (I), coconut oil fatty acid diethanol Alkene 0. 952 to 22.5 wt%, polyoxyalkylene alkyl ether 〇. 〇48 to 22.5 wt% and triethanolamine 〇. 〇 9 to 1 〇 by weight of the composition of the aqueous solution; (L) 5至19. 23。 The compound containing the compound of the formula (I) 3 to 10% by weight, coconut oil fatty acid diethanol decylamine 5. 45 to 19.23 % by weight, polyoxyalkylene-based alkyl radicals. 55 to 5.77 wt% and triethanolamine hydrazine. 1 to 6 wt% of the composition of the aqueous solution, and the like. Among these, it is preferably a composition of (K), more preferably a composition of (L). Further, examples of the sterilizing detergent composition of the present invention in the form of an aqueous solution containing other sterilizing components (M) are compounds containing the formula (I) o.ooi to 50% by weight, nonionic surfactant 〇. 0001 to 60 a composition of an aqueous solution of 5% by weight, triethanolamine 〇. 075 to 99 weight 0/〇 and a biguanide bactericide 0.0005 to 30% by weight; (N) a nonionic interface of 1 to 20% by weight of the compound containing the formula (I) a composition of an aqueous solution of 1 to 45% by weight of active agent, 0.09 to 97% by weight of triethanolamine, and 1 to 15% by weight of a biguanide bactericide; (〇) is a compound containing formula (I) 3 to 10% by weight, nonionic a composition of an aqueous solution of 6 to 25 wt% of a surfactant, 1 to 89 wt% of triethanolamine, and 2 to 5 wt% of a biguanide fungicide; (P) is a compound containing the formula (I). 〇〇1 to 50 % by weight, coconut oil fatty acid diethanol decylamine 0. 0001 to 30% by weight, polyoxyalkylene alkyl ether 〇 324225 18 201249341 to 30% by weight, triethanolamine 0. 075 to 99% by weight and polyhexamethylene a composition of an aqueous solution of acetamidine hydrochloride of 0.0005 to 30% by weight; (Q) is a formula I) a compound of 1 to 20% by weight, coconut oil fatty acid diethanol decylamine 0. 952 to 22.5 wt%, polyoxyalkylene alkyl ether oxime 48 to 22.5 wt%, triethanolamine 0.09 to 97 wt% and a composition of an aqueous solution of 1 to 15% by weight of polyhexamethylene dihydrazide hydrochloride; (R) 3 to 10% by weight of a compound containing the formula (I), 5.45 to 19.23% by weight of a coconut oil fatty acid diethanolamine, A composition of an aqueous solution of polyoxyalkylene alkyl hydrazine 55 to 5.77 wt%, triethanolamine 1 to 89 wt%, and polyhexamethylene biguanide hydrochloride 2 to 5 wt%. Among these, the composition of (P) is more preferably a composition of (Q), and most preferably a composition of (R). Further, the sterilizing detergent composition of the present invention in the form of an aqueous solution is used as a diluent in addition to the addition of human water. Measure as a diluent. Preferably, the ratio of the compound of the formula (1) is from 0.001 to 50 (s) is the composition of the sterilizing detergent containing February. The surfactant can be used in the following form. : _: = 3 〇. 2 to 0.25 wt% of aqueous solution · 3 weights and diethanolamine 0.0004 to (Τ) is containing the formula 卩 )) active agent 〇. 〇〇 5 to = substance 〇. 005 to 〇 · 1 weight %, non-ionic interface weight % of the aqueous solution; ·% by weight and triethanolamine 0.0005 to 0.0015 2 for the shirt (1) 丨 5iQ is a heavy-duty miscellaneous 19 201249341 facial active agent 0. 03 to 0. 125% by weight and triethanolamine 0 00至至1. 1重量重量的聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚015重量0. 045重量。 Oxyalkylene alkyl alkyl ether 0. 00024 to 0. 1125% by weight and triethanolamine 0. 0005 to 0. 0015% by weight of the aqueous solution; (W) is a compound containing formula (I) 0. 015 to 0. 045 weight 0006至0· 001重量%的水溶液的%, 055至0. 001重量重量的水溶液的溶液。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Wait. Among these, it is preferred to use the aqueous solution form of (V), and it is more preferable to use the aqueous solution form of (W). When the sterilizing detergent composition of the present invention further contains other bactericidal components, for example, the composition may be used in the following form (X) is a compound containing the formula (I): 0.001 to 0.25 wt%, nonionic interfacial activity水溶液5至0. 3重量%, triethanolamine 0. 0004 to 0. 49% by weight and a biguanide fungicide 0.0005 to 0.15% by weight of an aqueous solution; (Y) is a formula ( I 005至0. 005至0. 005至0. 5% by weight, non-ionic surfactant 0. 005 to 0. 225% by weight, triethanolamine 0. 0005 to 0. 465% by weight and biguanide fungicides 0. 005 to 0 005至0。 005至0。 005至0. 005至0. 005至0. 005至0. 445 wt% and a biguanide bactericide 0.01 to 0.025% by weight of an aqueous solution; (AA) is a compound containing the formula (I) 0. 001 to 0.25 wt%, coconut fat 324225 20 201249341 fatty acid diethanolamine oxime · 0000005 to 〇. 3 wt%, polyoxygen extension γ, its "the triethyl hydrazine: hydrazide hydrazide hydrochloride 0.0005 to 0.15 wt% aqueous solution; (A B) is a compound containing the formula (I) 〇· 〇〇5 to 〇·丨% by weight, coconut oil fatty acid diethanolamine 〇. 00476 to 〇. U25% by weight, polyoxyalkylene alkyl ether 0. 00024水溶液·1125% by weight, triethanolamine 〇〇〇〇5 to 〇465% by weight, and polyhexamethylene bisphosphonium hydrochloride 0 005 to 〇.丨% by weight of the aqueous solution; (AC) is containing the formula (I) 00至至0. 02885重量%, 00275 to 0. 02885% by weight, 00275 to 0. 02885% by weight, 00275 to 0. 02885% by weight, Triethanolamine 〇. 〇〇5 to 〇. 445% by weight and polyhexamethylene bisphosphonium hydrochloride 〇· 01 to 0. 025% by weight of an aqueous solution or the like. Among these, it is preferred to use the aqueous solution form of (AA), and it is more preferable to use the aqueous solution form of (AB), and it is preferred to use an aqueous solution form of (AC). In order to use the sterilizing agent composition or the sterilizing detergent composition of the present invention, the object may be sterilized or sterilized, and the composition in the form of an aqueous solution may be brought into contact with the object. The contact method is not particularly limited, and the bactericidal composition and the sterilizing detergent composition of the present invention can be brought into contact with an object by a usual method such as spreading, spraying, dipping, or wiping. Further, the sterilizing agent composition or the sterilizing detergent composition may be used together with a brush or a sponge to remove the dirt of the sterilizing object or the sterilizing object. The contact time when the bactericidal composition or the sterilizing detergent composition of the present invention is brought into contact with the sterilizing object or the sterilizing and cleaning object is not particularly limited to 324225 21 201249341, and may be appropriately determined according to the concentration of the active ingredient. . For example, when the bactericidal composition or the sterilizing detergent composition in the form of an aqueous solution of (n) or (S) is brought into contact with an object at a normal temperature, it is usually 30 seconds to 1 minute, preferably i to 5 minutes. A sufficient bactericidal effect or bactericidal cleansing effect can be obtained. The water used in the composition of the sterilizing agent of the present invention and the sterilizing detergent composition in the form of a semi-solid or an aqueous solution may be purified water such as ion-exchanged water or distilled water; any kind of natural water such as tap water, ground water, and river bed seepage water. In the case where the content of gas or metal ions is small, it is preferably purified water. The bactericidal composition and the sterilizing detergent composition of the present invention can be used as a device for releasing bacteria or sterilizing and washing in a floor or a wall of a food factory, a hospital, a barn, a restaurant, a restaurant, a school, a shop, or the like. The bactericidal composition for food handling equipment and the composition of the ruthenium detergent are used. In addition, it is also useful for sterilization or sterilization of objects for food use such as food manufacturing, processing equipment, and appliances used in food factories. Food production and processing machines include various mixers, mixers, homogenizers, and automatic cutting machines. The utensils include a cutting board, a kitchen knife, a food container, a food container, a rag, and the like. The bactericidal composition and the sterilizing detergent composition of the present invention are microorganisms having fungicidal effects on fungi or general bacteria such as molds, and microorganisms resistant to fourth-grade money salts and/or biguanide fungicides, for example, A microorganism which is resistant to microorganisms which also acts as a bactericidal agent, is monomethyl chloroformate (DDAC) and/or polyhexamethylene sulfonate (ρημβ). Therefore, the bactericidal composition and the sterilizing detergent composition of the present invention are used as a bactericidal composition for sterilization of a microorganism having resistance to a fourth-order ammonium salt and/or a biguanide bactericide, and sterilizing and washing. The composition of the agent is particularly useful. 324225 22 201249341 Moreover, the bactericidal composition and the sterilizing detergent composition of the present invention are less resistant to the composition than the quaternary ammonium salt and/or the biguanide bactericide, even when used for a long period of time. microorganism. Therefore, the bactericidal composition and the sterilizing detergent composition of the present invention can also be used as a bactericide for a subject which produces a microorganism resistant to the drug by using a fourth-order ammonium salt and/or a biguanide bactericide. The composition and the sterilizing detergent composition are used. Examples of the microorganism resistant to the fourth-stage ammonium salt and/or the biguanide fungicide include microorganisms of the genus Pseudomonas and microorganisms belonging to the genus Setratia, such as Serratia marcescens. (Serratia marcescens), Serratia liquefaciens, and the like. The bactericidal composition and the sterilizing detergent composition of the present invention are compositions suitable for continuous or continued use. Specifically, the bactericidal composition and the sterilizing detergent composition of the present invention are compositions of microorganisms which are resistant to the composition even if they are continuously or continuously used for a long period of time. More specifically, the bactericidal composition of the present invention and the sterilizing detergent composition are intended to be resistant to the occurrence of microorganisms and to the fourth-order ammonium salt and/or biguanide when the same object is repeatedly used. The bactericide is similarly operated in this object, and is less characteristic than when it is reused. Here, "reuse for the same object" is the same microorganism for the same microorganism species in the same microorganism or the same microorganism species (for example, 2 times, 3 times, 4 times, 5 times, 6 times, 7) Used once, 8 times or more). Further, "continuous use" is, for example, (composition A, composition A, composition A, ...), and the same composition is continuously used twice or more. "Continue to use" is the same composition. 324225 23 201249341 The material is used discontinuously for more than 2 times, and other components are used in between, and then continue to be used for the same object. For example, when used in the order of (composition A, composition B, composition C, composition A, composition D, ...), the composition A is not continuous but continues to be used. [Examples] Hereinafter, the present invention will be described in more detail based on examples. In each of the following tests, "+" in the table indicates that the bacteria were proliferated, and "one" indicates that the bacteria did not proliferate. Test Example 1 The test bacteria i shown below were diluted with physiological saline to obtain a bacterial solution of 106 cfu/mL. 〇 3 mL (test bacteria iii and viii were 0.1 ml) and the drug indifference was 1. 3 mL of PHMB aqueous solution of 25 to 320 ppm (for test bacteria ui and viii is i〇mL), mixed at 25 <t held for 5 minutes. After the sensitization time elapsed, the 1 platinum coil was taken out from each mixture and inoculated into BHI broth medium i〇mL (only the test bacteria viii was sCDlp medium 10 mL), and cultured at 30 ° C for 48 hours (only for testing) Bacteria ii were incubated for 120 hours). The bactericidal effect of PHMB on each of the test bacteria was confirmed by visually comparing the turbidity of the medium with the BHI broth culture medium (the SCDLP medium containing only the test bacteria viii as the uninoculated bacteria). The results are shown in the table PHMB: polyhexamethylene hydrazide hydrochloride BHI. Brain Heart Infusion SCDLP: Soy protein-degrading protein stems containing lecithin and polysorbate 8〇 Culture medium (Soybean-Casein Digest Broth with Lecithin & Polysorbate 80) 324225 24 201249341 . Test bacteria i: Pseudomonas aeruginosa NBRC 13736 Test bacteria ii: Aspergillus niger ATCC16404 Test bacteria iii : Bacillus cereus NBRC15305 test bacteria iv: Serratia marcescens (food factory isolate 1) test bacteria v: Serratia liquefaciens (food factory isolate 2 Test bacteria vi: Serratia marcescens (food factory isolate 3) test bacteria vii: Serratia marcescens (food factory isolate 4) for s-type bacteria viii : Bacillus subtilis IF013719 [Table 1] PHMB _ (ppm) Test bacteria i Test bacteria ii Supply bacteria iii Test bacteria iv Test bacteria V Test bacteria vi Test bacteria vii Test bacteria » « · V111 _ 320 — + — + + + + _ 160 one + + + + + + one _ 80 one + + + + + + + ~40 — + + + + + + + , 20 — + + + ten + + + 10 —~ — one + + + + + + + one + + + + + + + __2, 5 - + + + + + + + _1.25 + + Test Example 2 Using the test bacteria i to vi i used in Test Example 1, the drug was changed to DDAC 'The bactericidal effect of DDAC on each test bacteria was confirmed in the same manner as in Test Example 1. The results are shown in Table 2. 324225 25 201249341 DDAC: Dimercaptodimethylammonium chloride [Table 2] PHMB (ppm) Test bacteria i Test bacteria ii Test bacteria iii Test bacteria iv Test bacteria V Test bacteria vi Test bacteria vii 320 — — — 一 — — — 160 一 + + — — — — 80 — + + + + — — 40 — + + + + + + — 20 — + + + + + + + 10 — + + + + + + + 5 — + + + + + + 2.5 + + + + + + + + 1.25 + + + + + + + Test Example 3 Modification of the compound of formula (I) [1,10-di(3-indolyl-2-chloride dichloride) The mercapto imidazole rust) decane] and the PHMB were mixed in an aqueous solution containing the following ratio, and the appearance change was confirmed after 3 hours. The results are shown in Table 3. [Table 3] Compound of formula (I) (g) PHMB (g) Water (g) Compound of formula (I): appearance change of PHMB after 3 hours 1.4 7 191.6 1:5 Appearance unchanged 1.4 35 163.6 1:25 Appearance unchanged 1.4 42 156.6 1:30 Appearance unchanged 1.4 56 142.6 1:40 Appearance unchanged 1.4 70 128.6 1:50 White turbidity 1.4 84 114.6 1:60 White turbidity Examples 1 to 6 and Comparative Examples 1 to 13 Sterilization test 1 (Mold) The spore suspension of the test bacteria shown below was diluted with physiological saline 324225 26 201249341 to make 106 cfu/mL of bacteria liquid. 03 mL and the fungicide composition shown in Table 4 was diluted to make the composition concentration. 3 mL of an aqueous solution of 0.1 to 0.3% by weight was mixed and kept at 25 ° C for 5 minutes. After the sensitization time elapsed, the 1 white gold coil was taken out from each mixture, and inoculated into BHI broth medium 10 mL' at 3 (TC culture for 120 hours. The medium was visually compared with the BHI broth medium without inoculation bacteria. The turbidity was determined to determine the bactericidal effect of the bactericidal composition. The test bacterium ii: Aspergillus niger ATCC16404 The results are shown in Table 5. The bactericidal composition of the present invention was compared with the composition of the comparative example for mold. [Table 4] Ingredient (vtX) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 twa Example 1 fcbfe Example 2 tbfe Example 3 tm Example 4 tbfe Example 5 Example 6 Flavor component八※! 9 0 0 0 4 4 0 0 0 0 0 0 0 Set the surface component B gauge 0 9 0 0 0 0 0 0 0 0 0 0 0 Find the surface component (: Come 3 0 0 9 0 0 0 0 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0 0 分£来5 0 0 0 0 0 0 9 0 0 9 0 0 0 Looking for Guocheng 0 0 0 0 0 0 0 9 0 0 9 0 0 Set the country's composition (3 Shao 0 0 0 0 0 0 0 9 9 0 0 9 0 ΡΗΜΒ ^ δ 0 0 0 8 12 12 0 0 0 0 0 0 9 2 榔 0.13 0.13 0.13 1.18 4.4 5 0 0 0 0.13 0.13 0.13 0 she 0 0 0 0 0 0.5 0 0 0 0 0 0 0 Water pH yu. 〇7 9.0 90.87 θΤ" 90.87 J6,82 —9 0 79.6 1.0 78.5 9:0 91 —6 4 91 3.5 91 3.4 90.87 9.0 90.87 9.0 90.87 9.0 91 3.5 ※l Sterilization A: 1,10_bis(3_fluorenyl-2-methylimidazolium) decane (1〇_1〇_1〇_cl) ※ bactericidal component B: dibrominated 1, ι〇_二(3_mercapto-2-methylimidazolium) decane (1〇_1〇_1〇_Br) ※苫 bactericidal component C: bismuth 12_2(3_mercapto-2-methylimidazole Town) dodecane (1〇12_1〇(:1) *4 bactericidal component D: two gasification], 丨2_2 (3_octyl-2-methylimidazolium) dodecane (8_i2_8cl) ※ Deficiency of bactericidal component E: 1,6-di(3_octyl-2-methylimidazolium) hexane (8_6_8_C1) *6 Sterilization ingredient F: two gasification! , 丨2 - bis(3_hexyl_2_methylimidazolium) dodecane (6_12_6C1) ※ bactericidal component G: two gasification 1,1 〇 _ two (3_ hexyl_2_methylimidazolium ) decane (6_1〇_6_cl) concentrated 8 PHMB ··polyhexamethylene biguanide salt post salt 27 324225 201249341 [Table 5] (Mold: Aspergillus niger ATCC16404 proliferation) Concentration (wtX) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 0.3 — — — One by one — + + + + + + + + 0.2 — — — 一 — ~ + + + + + + + + + + + + + + + + + + + + + + + bactericidal test 2 (Bacillus) The spore suspension of the test bacteria indicated below The aliquot of the lysate composition of the present invention is diluted with a concentration of 0.1% to 0.3% by weight of the aqueous solution l〇mL after the mixture is diluted with the physiological saline solution to form a bacterial solution of 106 cfu / mL. Hold at 25 ° C for 5 minutes. After the sensitization time was passed, the mixture was stirred again, and 1 platinum coil was taken out from each mixture, and inoculated into BHI broth medium BmL' for 48 hours at 30 °C. The turbidity of the culture medium was visually compared with the BHI broth culture base which was not inoculated, and the bactericidal effect of the bactericidal composition on each bacterial cell was determined. Test bacteria iii: Bacillus cereus NBRC15305, and the results are shown in Table 6. The bactericidal composition of the present invention is superior to the composition of the comparative example in the bactericidal power against the bacterium. [Table 6] (Protease: proliferation of Bacillus cereus NBRC15305) Concentration η 〇 Example 1 Example _ Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparison Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 _ ο η ο — — One — — — + + + + + + — ν. L Π 1 — One — — One + Ten + + + + + 1. υ· 1 L±J + + _ -Γ_- --- + L+J + + + UU + bactericidal test 3 (agent resistant bacteria) 324225 28 201249341 The following test bacteria isolated from the food factory are in the beta broth culture medium, The cells were cultured at 30 C for 24 hours, diluted with physiological saline to obtain 1 〇 6 cfu / / mL of broth 〇 .03 mL, and the bactericidal compositions of Examples 1 to 6 and the bactericidal compositions of Table 7 were diluted. The concentration of the composition was 〇. 25 to 〇·1. The aqueous solution of 3% was mixed and kept at 25 ° C for 5 minutes. Sensitization After the passage of time, the mixture was stirred again, and 1 platinum coil was taken out from each mixture, and seeded in 10 mL of the broth medium of the book 1 and cultured at 30 ° C for 48 hours. Based on the BHI broth culture medium without the inoculum, the turbidity of the medium was visually compared to determine the bactericidal effect of the bactericidal composition on each of the cells. For the bacterium s. serratia marcescens (food factory isolate 1) The results are shown in Table 8. The bactericidal composition of the present invention is superior to the composition of the comparative example in the bactericidal power against the drug-resistant bacteria. [Table 7] Ingredient (wt%) Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Sterilizing ingredient Eight*l 9 0 0 0 0 0 Sterilizing ingredient 6*0 9 0 0 0 0 Sterilization Ingredients (:※苫0 0 9 0 0 0 Sterilization ingredient 0*4 0 1 0 0 9 0 0 PHMB Correction 0) 0 0 0 16 0 DDAC ※9 0 0 0 0 0 9 Water 91 91 91 91 84 91 pH 6.2 — 5,3 3.2 | ' 4.1 3.5 8.7 ※丄Pesticide A: Digastric ι, ι〇_bis(3-mercapto-2-methylimidazolium) decane (io-10-io-ci) ※ Sterilizing ingredient β: dibromo ι, 1 〇 _ bis (3 癸 _2 2 - decyl imidazolium) decane (1 〇 〇 〇 〇 〇 _Br) * 3 bactericidal component C: two gasification 1,12-bis(3-mercapto-2-methylimidazolium) dodecane (10-12-10-C1) ※ Bucketin D: Digasification 1,12-bis (3-octyl) -2-methylimidazolium)dodecane (8-12-8-C1) ※台台PHMB: polyhexamethylene biguanide hydrochloride ※9 DDAC: gasified dimercaptodimethylation 29 324225 201249341 [Table 8] (Proliferation of drug-resistant bacteria. Serratia marcescens (Food Factory isolate 1)) Concentration (wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparison /χ, ί 1 9 Comparison AtA 1Q 0.1 One - One - + + + One + + + 0. 05 — — One — + + + + + + 0,025 — — — + + + + + + bactericidal test 4 (agent-resistant bacteria) The following test bacteria isolated from the food factory were cultured in BHI broth for 24 hours at 30 °C. Dilute with physiological saline to make a bacterial solution of 106 cfu/mL. 〇 3 mL and the bactericidal composition of Examples ～6 and the bactericidal composition shown in Table 7 were diluted so that the concentration of the composition was 0·08 to 1. 3 mL of a 33% by weight aqueous solution was mixed and kept at the top for 7 minutes. After the sensitization time was passed, the working platinum was again stirred, and the platinum coil was taken out from each mixture, and inoculated into the BHI broth medium i〇mL, and the culture was carried out at 303⁄4. The bactericidal effect of the bactericidal composition on each of the cells was determined by visually comparing the turbidity of the medium with the BHI broth culture medium without the inoculation bacteria. Test bacteria v. Serratia liQuefaciens (food Factory isolate 2) Results are shown in Table 9. . The bactericidal composition of the present invention is superior to the composition of the comparative example in the bactericidal power against the drug-resistant bacteria. 324225 30 201249341; [Table 9] (Protein-resistant bacteria: proliferation of Serratia liquefaciens (Food Factory isolate 2)) Concentration (wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 1.33 + + - + + One 0. 66 Ten + + + + One 0.33 + + + + + + 0.16 - + + + + + + 0. 08 + + + — — — + + + + + + The drug resistance inhibition test is based on the standard method of the chemotherapeutic society (micro liquid dilution method), and the minimum developmental inhibition concentration (MIC) is continuously applied. Determination of). The compositions of Example 1 and Comparative Example 13 were diluted with sterilized water to prepare a chemical solution having a composition concentration of 〇. 〇〇7 to 1.792% by weight, and the nutrient broth was adjusted to a concentration twice the concentration. The medium (manufactured by Eiken Chemical Co., Ltd., the common broth medium 'Yongyan' E-MC35) was added in the same amount as the drug solution, and after mixing, it was divided into small portions in a microtype plate (96 holes). Note 150 "L/hole. Then, 'the following test bacteria isolated from the food factory were incubated in NB medium, and the bacterial solution cultured at 30 ° C for 20 hours was diluted with physiological saline to make 107 cfu/mL, and then 'in the microplate filled with the medium prepared above. A small amount of 7.5 μL/well was inoculated each time. This was cultured in a thermostat at 30 ° C for 48 hours to visually confirm the presence of aseptic growth, and the MIC was measured. In the wells where the growth was confirmed, the bacterial solution was taken from the well having the largest concentration of the drug, and diluted with physiological saline to obtain a bacterial solution of 107 cfu/mL, and the MIC was measured again in the same manner as above. This operation was repeated, and the MIC measurement was performed 8 times in total, and it was confirmed that 324225 31 201249341 recognized the change in MIC. For the type 3 bacterium serratia marcescens (food factory isolate 3) for "bacteria vi i. serratia marcescens (food ^ plant isolate 4) ^ ° The results are shown in Table 10 and Table 1. The composition of Example 1 had a low MIC value even at the 8th test, which was 56% by weight (test bacteria and 0.028% by weight (test bacteria vii). As a result of the correlation, it was confirmed that the compound of the formula [1,10-bis(3-fluorenyl-2-hydrazino) is inferior to DDAC, and it is difficult to produce a drug-resistant strain. [Table 10]
實施例I 黏質沙雷氏菌（Serratia marcescens)(食品工廠分離菌3)之增殖 比較例13Example I Proliferation of Serratia marcescens (food factory isolate 3) Comparative Example 13
濃度 (wt%) 0.896 0.448 0.224 0.112 0.056 0.028 0.014 0.007 0.0035 次數 324225 32 201249341 [表 11 ] 黏質沙雷氏菌（Serratia marcescens)(食品工廠分離菌4)之增殖 濃度 (wt«) 實施例1 比較例13 0.896 一 一 一 一 — — — _ + + + + + + + 0.448 一 — — — — — —— 一 + + + + + 4* + 0. 224 ~~ 一 — — — — — — 一 + + + + + + + 0.112 ~~~ 一 一 — — — — — + + + + + + 0. 056 一 — — — — — 一 + + + + + + 十 0. 028 一 一 一 — — — — + + + + + + + 十 0. 014 — — 一 + + + + + + + + + + + 十 0. 007 + + + + + + + + + + + + + + —+ + 0.0035 + + + + + + + + + + + + + + 屮 + 次數 1 2 3 4 5 6 7 8 一 1 2 —3 4 _ 6—一 金屬腐钱性試驗 將實施例1及5及比較例12及13表示之各組成物之 〇. 3%水溶液60inL放入附有蓋子之7〇mL玻璃瓶中’將銅製 小珠子（長50mmx寬30mmx高1mm)浸潰在該玻璃瓶中，在2: 。(:之恒溫器内保存1個月。經由目視觀察保存後銅製小珠 子之外觀，以下述之基準判定腐蝕性。又，使用自來水 代組成物水溶液，將同樣保存之銅製小珠子作為對昭 〇：腐蝕比對照組少△:與對照组同等X:腐4 “、、誕。 組多 $比對丹 結果表示於表12。以實施例1組成物處理之小 持與處理前之小珠子同等之外觀，與對照組相比，，子 抑制腐蝕。以實施例5組成物處理之小珠子只看到^顯 退色，確認無生錄或變色發生。以比較例12組戍物。争 小珠子，小珠子全體變色，比對照組更進行腐麵，义理 例13組成物處理之小珠子明顯的退色，外觀與對辟=比 324225 33 201249341 程度。 [表 12] 實施例1 實施例5 腐钮性判定 〇 〇 列 12 比車ίίΓΤϊΓΐ X 一 一— ~~Δ~ 實施例7至14及比較例14至22 殺菌力試驗5(芽胞菌） 將以下表示之供試菌之芽胞懸濁液用生理食鹽水稀釋 使成為106cfu/mL之菌液〇· lmL與將表13表示之殺菌洗 淨劑組成物稀釋，使該組成物濃度為〇.丨至〇 3重量％之水 溶液胤混合後於饥歸5㈣。敏化作㈣間經過 後再次㈣後從各混合财取出丨白金線圈，接種WCDLp (大豆分解蛋白質乾时）培養基1()mL，於航培養48小 時。以未接種菌之SCDLP培養基為基準，以目視比 基 >之混濁’判枝菌洗淨劑組成物對各菌體之殺菌⑽。 供試菌 viii :括草桿菌（Bacillus subtilis) IF〇13719 結果表示於表14。本發明之殺菌洗淨劑組成物與比較 例之組成物相比，對於芽胞菌之殺菌力優越。 324225 34 201249341 [表 13] 成糾㈣ 實施 例7 實施 例8 例9 雜 例10 實施 例11 實施 例12 嫌 例14 味 例15 味 例16 眯 例17 tm 例18 kbn 例19 丨tbtt 例20 .殺®成分A 4 0 0 0 4 4 0 0 0 0 0 2 4 殺®成分B 0 4 0 0 0 0 0 0 0 0 0 0 0 殺®成分C 0 0 4 0 0 0 0 0 0 0 0 0 0 殺菌成分D 0 0 0 4 0 0 0 0 0 0 0 0 0 —殺菌成分E 0 0 0 0 0 0 4 0 0 0 0 0 0 殺菌成分F 0 0 0 0 0 0 0 4 0 0 0 0 0 段菌成分G 0 0 0 0 0 0 0 0 4 0 0 0 0 非離子界面活 性命JA 3 10 10 10 8 8 10 10 10 8 8 5 8 雜子界面活 性劑B 5 0 0 0 0 0 0 0 0 0 0 0 0 雜子界面活 性谢C 2 10 10 10 1 0 10 10 10 0 I 0 1 PHMB 4 0 0 0 4 4 0 0 0 4 0 2 4 陰離子界面活 性劑 0 0 0 0 0 0 0 0 0 0 0 0.28 0 三乙碎胺 2 5 5 5 2 2 5 5 5 2 2 0 0 水 80 h—?- —71 71 71 81 82 71 71 71 86 8Θ 90,72 83 pH 8. ϋ 9.4 9.4 9.4 8.2 8.3 9.4 9.4 9.4 8.7 10.6 3.7 4.0 殺菌成分A:二氣化1，1〇_二（3_癸基_2_曱基咪唑鏘）癸烷（1〇_1〇_1〇_cl) 殺菌成分B :二漠化l，l〇-二（3-癸基-2-甲基咪唑鑌）癸烷（l〇-i〇-i〇-Br) 殺菌成分C :二氣化ι，12-二（3-癸基-2-甲基咪唑鑌）十二碳烷（10-12-10-C1) 殺菌成分D :二氣化ι，ΐ2-二（3-辛基-2-甲基咪唑鎮）十二碳烷（8-12-8-C1) 殺菌成分E ·二溴化1，6-二（3-辛基-2-甲基咪唑鐳）己烷（8-6-8-C1) 殺菌成分F :二氣化1，12-二（3-己基-2-曱基咪唑鑌）十二碳烷（6-12-6-C1) 殺菌成分G:二氣化1，10_二（3_己基_2_甲基咪唑鑌）癸烷（6_1〇_6_cl) 非離子界面活性劑A :椰子油脂肪酸二乙醇醖胺（HLB值9) 非離子界面活性劑B :椰子油脂肪酸二乙醇醖胺（HLB值12 5) 非離子界面活性劑c:聚氧伸烷基烷基醚（HLB值14) PHMB:聚六亞曱基雙脈鹽酸盤 陰離子界面活性劑：聚氧伸乙基月桂基醚乙酸鈉 [表 14] (芽胞菌·栝草桿菌（Baci 1 lus subti 1 is) IF013719之增殖） 濃度 (wt«) 0 3 實施 例7 貧施 例8 實施 例9 實施 例10 實施 例11 實施 例12 比較 例14 比較 例15 比較 例16 比較 例17 比較 例18 比較 例19 比較 例20 0.2 0.1 ---— + + + + + + + + + + + + + + + + + + + 十」 + + + + 殺菌力試驗6(藥劑抵抗性菌） 將從食品工廠分離之下述供試菌在BHI(腦心浸出物） 324225 35 201249341 培養基，於30°C培養24小時，用生理食鹽水稀釋使成為 106cfu/mL之菌液〇.〇3mL與將表13表示之殺菌洗淨組成 物稀釋’使該組成物濃度為〇. 0125至0. 1重量％之水溶液 3mL混合後於25。(：保持1分鐘。敏化作用時間經過後再次 攪拌後從各混合物中取出1白金線圈，接種於BHI培養基 10mL，於30°C培養48小時。以未接種菌之BHI培養基為 基準’以目視比較培養基之混濁，判定殺菌洗淨劑組成物 對各菌體之殺菌效果。 供試菌iv :黏質沙雷氏菌（Serratia marcescens)(食品 工廠分離菌1) 結果表示於表15。本發明之殺菌洗淨劑組成物與比較 例之組成物相比，對於藥劑抵抗性菌之殺菌力優越。 [表 15] (樂劑抵抗性菌·黏質沙雷氏菌（Serratia marcescens)(食品工礙分離菌 1)之增殖） 濃度 (fftJS) 實施 例7 實施 例8 實施 例9 實施 例10 實施 例11 實施 例12 比較 例14 比較 例15 比較 例16 比較 例Π 比較 例18 比較 Μ 19 比較 例20 0_ 1 一 — — 一 一 + + + 一 十 + + 0. 05 — — — _ 一 一 + + + + + + + 0.025 — — — _ 一 一 + + + + + + + 0.0125 + + + - + + + + + + + + 洗淨力試驗 使用實施例7、8、11及12及表16表示之殺菌洗淨劑 組成物，經由溫度為3〇°C，洗淨時間為3分鐘，洗刷時間 為1分鐘之試驗條件之利納滋法（JIS-K3362)進行洗淨力 試驗。污垢掉落的程度從洗淨前後玻璃片之重量，經由以 下之公式算出洗淨力，進行評估。 324225 36 201249341 [數1] 洗淨力（％)= 寸著玻璃片重量一洗淨後玻璃片重量）xl00 括附著玻璃片重量一裝玻璃片袋子重量） [表 16] 成分(wt%) 饥过Jt、八 A 列 13 實施例14 比較例20 比較例21 比較例22 叔闺成分A 4 4 0 4 非離子界面活性劑A 8 7 8 8 0 非離子界面活性劑C DUHfD " ^!_ 2 1 1 0 γπΜΒ 0 4 4 4 12 二乙醇胺 2 0 2 4.4 水 _π 81 83 85 79.6 pH LID 8.3 4.0 8.3 8.0 殺菌成分A:二氯化丨，10~二（3-癸基-2-甲基咪唑鑌）癸烷（HM0-10-C1) 非離子界面活性劑A :椰子油脂肪酸二乙酵醯胺（⑽值9) 非離子界面活性劑C :聚氧伸烧基烧基it(HLB值14) PHMB :聚六亞甲基雙胍鹽酸鹽 結果表示於表17。本發明之殺菌洗淨劑組成物與比較 例之組成物相比，具有高的洗淨力。 [表 17] —ί施 例7 實施— 例8 例11 實施 例12 一實施_ 例13 ~f^T] 例14 比較 例20 ~ΈήΓ 例21 比較.‘ 例22 洗淨力 (%) 83 85 96 97 96 87 63 61 26 [產業上利用之可能性] 本發明之殺菌劑組成物及殺菌洗淨劑組成物在食品工 廠、醫院、畜舍、飯店、餐廳、學校、店舖等之地板或牆 壁等，可作為殺菌或殺菌洗淨之設備用乃至食品操作設備 用之殺菌劑組成物及殺菌洗淨劑組成物使用。又，在食品 工廠等使用之食品製造、加工機器或器具等食品用途之對 324225 37 201249341 象物之殺菌或殺菌洗淨亦有用。 另，本發明之殺菌劑組成物及殺菌洗淨劑組成物作為 對於存在或會產生對第四級銨鹽及/或雙胍系殺菌劑具有 抵抗性之微生物之對象使用之殺菌劑組成物及殺菌洗淨劑 組成物特別有用。 【圖式簡單說明】 無 【主要元件符號說明】 無 324225 38Concentration (wt%) 0.896 0.448 0.224 0.112 0.056 0.028 0.014 0.007 0.0035 324225 32 201249341 [Table 11] Proliferation concentration of Serratia marcescens (food factory isolate 4) (wt«) Example 1 Comparison Example 13 0.896 One-to-one ——— — _ + + + + + + + 0.448 One — — — — — —— One + + + + + 4* + 0. 224 ~~ One — — — — — — One + + + + + + + 0.112 ~~~ One by one — — — — — + + + + + + 0. 056 One — — — — — One + + + + + + Ten 0. 028 One by one — — — — + + + + + + + ten 0. 014 — — one + + + + + + + + + + + ten 0. 007 + + + + + + + + + + + + + + + + + 0.0035 + + + + + + + + + + + + + + 屮 + number of times 1 2 3 4 5 6 7 8 -1 2 - 3 4 _ 6 - a metal rot yield test will be shown in Examples 1 and 5 and Comparative Examples 12 and 13各 of each composition. 3% aqueous solution 60inL was placed in a 7〇mL glass bottle with a lid. 'The copper beads (length 50mmx width 30mmx height 1mm) were immersed in the glass bottle at 2:. (The temperature was stored in the thermostat for one month. The appearance of the copper beads after storage was visually observed, and the corrosiveness was determined on the basis of the following criteria. Further, using the tap water substitute composition aqueous solution, the same preserved copper beads were used as the pair. : Corrosion is less than control group △: the same as the control group X: rot 4 ", and birthday. The group more than the ratio of dan is shown in Table 12. The small amount of the composition treated with the composition of Example 1 is the same as the beads before the treatment. The appearance was compared with the control group, and the sub-suppressed corrosion. The beads treated with the composition of Example 5 only showed fading, and no occurrence of bio-recording or discoloration was confirmed. Comparative Example 12 group of cockroaches. The small beads were discolored, and the surface of the beads was more rotted than the control group. The beads treated with the composition of the example 13 were obviously faded, and the appearance and the ratio were 324225 33 201249341. [Table 12] Example 1 Example 5 Sex determination column 12 is more than vehicle ίίΓΤϊΓΐ X - one ~ ~ Δ~ Examples 7 to 14 and Comparative Examples 14 to 22 bactericidal force test 5 (Bacillus) The phytosuspension of the test bacteria indicated below is physiologically used Diluted with salt water to make 1 The bacterial liquid 〇·ml of 06 cfu/mL was diluted with the sterilizing detergent composition shown in Table 13, and the concentration of the composition was 〇.丨 to 〇3% by weight of the aqueous solution, and then mixed with hunger 5 (4). (4) After the (four) period, the white gold coil was taken out from each mixed wealth, and 1 () mL of WCDLp (when soybean protein is decomposed) was inoculated, and cultured for 48 hours in the air. Based on the SCDLP medium without inoculation, the visual ratio was used. The turbidity of the base > the mycobacterial detergent composition sterilizes each of the cells (10). The test bacteria viii: Bacillus subtilis IF 〇 13719 The results are shown in Table 14. The sterilizing detergent of the present invention Compared with the composition of the comparative example, the composition has superior bactericidal power against the bacterium. 324225 34 201249341 [Table 13] Cheng Ji (4) Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 14 Example 15 Taste Example 16 Example 17 tm Example 18 kbn Example 19 丨tbtt Example 20. Kill® component A 4 0 0 0 4 4 0 0 0 0 0 2 4 Kill® component B 0 4 0 0 0 0 0 0 0 0 0 0 0 Killing ingredient C 0 0 4 0 0 0 0 0 0 0 0 0 0 Sterilizing ingredient D 0 0 0 4 0 0 0 0 0 0 0 0 0 — Kill Component E 0 0 0 0 0 0 4 0 0 0 0 0 0 Sterilization component F 0 0 0 0 0 0 0 4 0 0 0 0 0 Segment bacteria component G 0 0 0 0 0 0 0 0 4 0 0 0 0 Non-ion Interface activity JA 3 10 10 10 8 8 10 10 10 8 8 5 8 Hetero-surfactant B 5 0 0 0 0 0 0 0 0 0 0 0 0 Heterogeneous interface activity X 2 C 10 10 10 10 0 0 10 10 10 0 I 0 1 PHMB 4 0 0 0 4 4 0 0 0 4 0 2 4 Anionic surfactant 0 0 0 0 0 0 0 0 0 0 0 0.28 0 Triethylamine 2 5 5 5 2 2 5 5 5 2 2 0 0 Water 80 h—?- —71 71 71 81 82 71 71 71 86 8Θ 90,72 83 pH 8. 9.4 9.4 9.4 9.4 8.2 8.3 9.4 9.4 9.4 8.7 10.6 3.7 4.0 Sterilization A: Digasification 1,1 〇_二(3_癸基_2_曱-imidazolium) decane (1〇_1〇_1〇_cl) bactericidal component B: two desertification l, l〇-bis (3-mercapto-2 -methylimidazolium) decane (l〇-i〇-i〇-Br) bactericidal component C: di-gasified iota, 12-bis(3-mercapto-2-methylimidazolium) dodecane ( 10-12-10-C1) bactericidal component D: di-gasification ι, ΐ2-bis(3-octyl-2-methylimidazolium) dodecane (8-12-8-C1) bactericidal component E · 1,6-bis(3-octyl-2-methylimidazolium)hexane (8-6-8-C1) Ingredient F: Dimethylated 1,12-bis(3-hexyl-2-indolyl imidazolium) dodecane (6-12-6-C1) Sterilization ingredient G: two gasification 1,10_2 (3 _Hexyl-2-methylimidazolium) decane (6_1〇_6_cl) Nonionic surfactant A: coconut oil fatty acid diethanol amide (HLB value 9) Nonionic surfactant B: coconut oil fatty acid diethanol hydrazine Amine (HLB value 12 5) Nonionic surfactant c: polyoxyalkylene alkyl ether (HLB value 14) PHMB: polyhexamethylene double pulse hydrochloric acid plate anionic surfactant: polyoxyethylene ethyl lauryl Sodium ether acetate [Table 14] (Proliferation of Baci 1 lus subti 1 is IF013719) Concentration (wt«) 0 3 Example 7 Lean Example 8 Example 9 Example 10 Example 11 Implementation Example 12 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 0.2 0.1 ---— + + + + + + + + + + + + + + + + + + + + Ten + + + + bactericidal test 6 (agent-resistant bacteria) The following test bacteria isolated from the food factory were cultured at 30 ° C for 24 hours in BHI (brain heart extract) 324225 35 201249341 medium, using physiological salt Become so diluted 106cfu / mL of the bacterial suspension 〇.〇3mL Table 13 shows the bactericidal composition was diluted wash 'composition such that the concentration is square. 0125 to 0.1% by weight aqueous solution of 3 mL 25 after mixing. (: 1 minute was kept. After the sensitization time was passed, the platinum coil was again taken out from each mixture after the sensitization time was passed, and 10 mL of BHI medium was inoculated, and cultured at 30 ° C for 48 hours. Based on the BHI medium without inoculation bacteria. The turbidity of the culture medium was compared, and the bactericidal effect of the sterilizing detergent composition on each of the cells was determined. Test bacteria iv: Serratia marcescens (food factory isolate 1) The results are shown in Table 15. The present invention The sterilizing detergent composition is superior to the composition of the comparative example in the bactericidal power against the drug-resistant bacteria. [Table 15] (Serratia marcescens (food worker) Proliferation of isolate 1) Concentration (fftJS) Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example Π Comparative Example 18 Comparative Μ 19 Comparative Example 20 0_ 1 One – One One + + + One Ten + + 0. 05 — — — _ One + One + + + + + + 0.025 — — — _ One + + + + + + + + 0.0125 + + + - + + + + + + + + Detergency test implementation 7,10, 11 and 12 and Table 16 show the sterilizing detergent composition, the temperature is 3 ° C, the washing time is 3 minutes, the washing time is 1 minute of the test conditions of the Lina method (JIS- K3362) The detergency test was carried out. The degree of soil drop was calculated from the weight of the glass piece before and after washing, and the detergency was calculated by the following formula. 324225 36 201249341 [Number 1] Detergency (%) = inch Glass piece weight after washing glass piece weight) xl00 including attached glass piece weight one loaded glass piece bag weight) [Table 16] Composition (wt%) Hungry Jt, 8A column 13 Example 14 Comparative Example 20 Comparative Example 21 Comparative Example 22 Unterminated bismuth component A 4 4 0 4 Nonionic surfactant A 8 7 8 8 0 Nonionic surfactant C DUHfD " ^!_ 2 1 1 0 γπΜΒ 0 4 4 4 12 Diethanolamine 2 0 2 4.4 Water_π 81 83 85 79.6 pH LID 8.3 4.0 8.3 8.0 Sterilization component A: bismuth dichloride, 10~bis(3-mercapto-2-methylimidazolium) decane (HM0-10-C1) Nonionic interface Active agent A: coconut oil fatty acid diacetamide ((10) value 9) Nonionic surfactant C: polyoxyalkylene based base (HLB value 14) PHMB: Hexamethylene biguanide hydrochloride salt The results are shown in Table 17. The sterilizing detergent composition of the present invention has a high detergency compared to the composition of the comparative example. [Table 17] - Example 7 Implementation - Example 8 Example 11 Example 12 One Example _ Example 13 ~ f^T] Example 14 Comparative Example 20 ~ ΈήΓ Example 21 Comparison. 'Example 22 Detergency (%) 83 85 96 97 96 87 63 61 26 [Possibility of industrial use] The bactericide composition and sterilizing detergent composition of the present invention are in the floor or wall of a food factory, a hospital, a barn, a restaurant, a restaurant, a school, a shop, and the like. For example, it can be used as a sterilizing or sterilizing cleaning device, a bactericidal composition for food handling equipment, and a sterilizing detergent composition. In addition, it is also useful for sterilizing or sterilizing the 324225 37 201249341 foods used for food production, processing equipment, and appliances used in food factories. Further, the bactericidal composition and the sterilizing detergent composition of the present invention are used as a bactericidal composition and sterilization for a subject having or capable of producing a microorganism resistant to a fourth-order ammonium salt and/or a biguanide bactericide. Detergent compositions are particularly useful. [Simple diagram description] None [Main component symbol description] None 324225 38