以下，對本發明進行詳細說明。 (a)月桂基二甲基胺基乙酸甜菜鹼 本發明中所使用之月桂基二甲基胺基乙酸甜菜鹼(亦記載為N-月桂基二甲基胺基乙酸甜菜鹼)係具有下述式(1)所表示之結構之化合物。 C12
H25
-N+
(CH3
)2
-CH2
COO-
(1) 本發明之清潔劑組合物中之月桂基二甲基胺基乙酸甜菜鹼之調配量係以下述高級脂肪酸皂之調配量為基準而決定，通常為2～20質量%，較佳為2.5～18質量%，更佳為3～15質量%，但並不限定於該等，亦可設為上述範圍中所包含之範圍、例如2～9質量%、3～8質量%、或4～7質量%等範圍。 (b)高級脂肪酸皂 本發明之清潔劑組合物含有高級脂肪酸皂作為清潔成分。本發明之高級脂肪酸皂係由碳數5～25之脂肪酸陰離子與抗衡陽離子之鹽所形成。碳數5～25之脂肪酸係直鏈狀或支鏈狀之飽和或不飽和之一價烴基、例如具有於烷基、伸烷基等上鍵結有羧基之結構的羧酸，上述烴基亦可任意地經羥基等取代。 作為碳數5～25之脂肪酸之例，可列舉：己酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、月桂酸、癸烯酸、十一碳烯酸、月桂烯酸、2-乙基丁酸、異戊酸、2-乙基戊酸、2-乙基己酸、異壬酸、3,5,5-三甲基己酸、十三烷酸、四甲基壬酸、肉豆蔻酸、十五烷酸、棕櫚酸、硬脂酸、花生酸、山萮酸、木蠟酸、蠟酸、肉豆蔻油酸、棕櫚油酸、油酸、反油酸、巨頭鯨魚酸、芥酸、鯊魚酸、亞麻油酸、反亞麻油酸、次亞麻油酸、花生四烯酸、2-己基癸酸、異硬脂酸、12-羥基硬脂酸、椰子油脂肪酸、氫化椰子油脂肪酸、棕櫚油脂肪酸、氫化棕櫚油脂肪酸、棕櫚仁油脂肪酸、氫化棕櫚仁油脂肪酸、牛脂脂肪酸、氫化牛脂脂肪酸等。 於本發明中，於碳數5～25之脂肪酸中，較佳為使用由碳數8～20、或者碳數12～18之直鏈狀飽和脂肪酸所形成之高級脂肪酸。即，本發明中所使用之脂肪酸皂包括不包含由支鏈狀脂肪酸或不飽和脂肪酸所形成之脂肪酸皂之態樣。 本發明之清潔劑組合物含有由包含(b-1)月桂酸及(b-2)肉豆蔻酸及(b-3)選自棕櫚酸及硬脂酸中之至少1種的直鏈狀飽和脂肪酸所形成之高級脂肪酸皂。 (b-1)月桂酸 本發明之高級脂肪酸皂係相對於形成高級脂肪酸皂之脂肪酸總重量而含有30～80質量%之由月桂酸所形成之脂肪酸皂。 (b-2)肉豆蔻酸 本發明之高級脂肪酸皂係相對於形成高級脂肪酸皂之脂肪酸總重量而含有5～30質量%之由月桂酸所形成之脂肪酸皂。 (b-3)棕櫚酸及硬脂酸 本發明之高級脂肪酸皂相對於形成高級脂肪酸皂之脂肪酸總重量而含有5～35質量%之由選自棕櫚酸及硬脂酸中之至少一種所形成之脂肪酸皂。若棕櫚酸及硬脂酸之合計調配量超過35質量%，則有無法獲得充分之低溫穩定性之情形。於冬季之寒冷地區等尤其要求低溫穩定性之環境下使用之情形時，較佳為將棕櫚酸及/或硬脂酸之調配量設為5～30質量%，更佳為5～25質量%，進而較佳為5～20質量%。 所謂選自棕櫚酸及硬脂酸之至少一種，包括包含棕櫚酸或硬脂酸之僅一者之態樣、及包含棕櫚酸與硬脂酸之兩者之態樣。於包含棕櫚酸與硬脂酸之兩者之態樣中，較佳為將棕櫚酸與硬脂酸之調配量比率[棕櫚酸/硬脂酸]設為0.4～2.5之範圍。該數值範圍包括0.4～2.5所含之任意範圍(例如0.4～2.0或1.0～2.0等)及該範圍中所含之所有數值。 本發明之清潔劑組合物藉由除調配月桂酸(碳數12)及肉豆蔻酸(碳數14)以外，亦調配棕櫚酸(碳數16)及/或硬脂酸(碳數18)，可獲得持續性良好之泡質，並且低溫穩定性亦優異。 一般而言，認為若增加高級脂肪酸之鏈長(碳數)則容易引起結晶析出，鑒於此，藉由除調配自先前起通用之月桂酸及肉豆蔻酸以外，亦調配碳數較多之棕櫚酸及/或硬脂酸，會提高低溫穩定性之情況係從業者無法預測之效果。 作為將高級脂肪酸陰離子中和之抗衡陽離子，較佳為設為鹼金屬陽離子，尤佳為設為鉀陽離子。本發明之(a)高級脂肪酸皂中不包括脂肪酸之精胺酸鹽及甲基牛磺酸鹽。 本發明之清潔劑組合物中之(b)高級脂肪酸皂之調配量為4～15質量%，較佳為5～12質量%，更佳為5～10質量%，進而較佳為6～8質量%。此處，所謂高級脂肪酸皂之調配量意指高級脂肪酸與中和劑(例如氫氧化鉀)之合計調配量。 於本發明之清潔劑組合物中，(a)月桂基二甲基胺基乙酸甜菜鹼之調配量與(b)高級脂肪酸皂之調配量之比率[(a)/(b)]為0.4～1.5，該調配量比率進而較佳為設為0.5～1.2之範圍內。若該調配量比率未達0.4，則無法獲得充分之低溫穩定性。 (c)多元醇 本發明之清潔劑組合物較佳為除調配(a)月桂基二甲基胺基乙酸甜菜鹼、及(b)高級脂肪酸皂之必須成分以外，亦調配多元醇。 可調配之多元醇可選自通常調配至化粧料等中者，例如可列舉：甘油、丙二醇、二丙二醇、1,3-丁二醇、乙二醇、聚乙二醇、山梨糖醇等。 多元醇之調配量並無特別限定，通常為10～50質量%，較佳為20～50質量%，更佳為25～40質量%。 多元醇中，藉由調配IOB＝3～4之多元醇，可提高自起泡器噴出之泡之彈力性，故而較佳。作為IOB＝3～4之多元醇，可例示：雙甘油、丙二醇等。 IOB＝3～4之多元醇之調配量相對於組合物總重量通常為0.1～10質量%，較佳為0.5～8質量%，更佳為1～5質量%。 本發明之清潔劑組合物亦可於不阻礙本發明之效果之範圍內含有液體清潔劑組合物中通常使用之其他任意成分，作為其他任意成分之具體例，可列舉：油分、聚矽氧類、低級或高級醇類、羊毛脂衍生物、蛋白衍生物、各種藥劑、殺菌劑、防腐劑、pH值調節劑、抗氧化劑、金屬離子封阻劑、螯合劑、動植物萃取物或其衍生物、色素、香料、顏料、有機或無機粉體、黏土礦物等。可任意地選擇該等之一種或兩種以上而調配。 本發明之清潔劑組合物並無限定，例如以使用B型旋轉黏度計於30℃之溫度下所測得之黏度為40 mPa・s以下、較佳為30 mPa・s以下、更佳為20 mPa・s左右之低黏度液體之形式提供。 本發明之清潔劑組合物可使用上述之必須成分及任意成分，並基於常法而製造。 所製備之本發明之清潔劑組合物係收容於具有多孔質膜之無氣體類型之泡噴出容器中。本發明中所使用之無氣體類型之泡噴出容器只要為將特定量之液體清潔劑組合物與特定量之空氣混合並以泡狀態於使用時自容器噴出者，則可為公知之任一類型。具體而言，例如可列舉：藉由用手指擠壓軟質容器之主體部而使用之擠壓起泡器、藉由用手指按壓具備壓頭機構之蓋之頭部而使用之壓頭起泡器等。並且於使用時，藉由使將容器內之液體清潔劑組合物與空氣混合而成之混合物通過多孔質膜(1片至複數片)，而使該液體清潔劑組合物自容器噴出口以泡狀噴出。 作為壓頭起泡器容器之多孔質膜，例如可列舉海綿、燒結體、網狀物等，就使用性等方面而言，較佳為薄壁之網狀物。作為網目之尺寸，較佳為使用30～400目左右者。對於本發明之清潔劑組合物，較佳為使用具備兩片多孔質膜之容器，即便將一多孔質膜設為200目，將另一多孔質膜設為305目之較細之網目，亦不產生堵塞，可獲得良好之泡質。 本發明之清潔劑組合物係作為收容於壓頭起泡器容器中之毛髮或皮膚之清潔劑，以洗面乳、沐浴乳、洗手乳、洗髮精等形態適宜地提供。 [實施例] 以下，列舉具體例而更詳細地說明本發明，但該等不對本發明之技術範圍進行任何限定。 再者，以下之實施例等中之調配量只要無特別說明，則為質量%。 以下述表之各例中所記載之組成，依據常法而製備清潔劑。 對於各例中所獲得之清潔劑，針對以下之項目，依據下述基準進行評價。 (1)低溫穩定性 將所製備之清潔劑組合物填充至硬質玻璃之小玻璃瓶中，於保持為各溫度(-10～5℃)之評價室中保存24小時及1週後，以目視觀察清潔劑組合物之低溫穩定性，根據下述評價基準進行評價。 A：良好(無析出物、沈澱物，無外觀之變化；無引起堵塞之可能性) B：不良(有析出物、沈澱物，有品質上之問題；有引起堵塞之可能性) 若為通常之使用環境，則只要於使至少於-5℃～＋5℃下24小時及於＋5℃下結束1週之保存之時間點之評價為「A」，則具備可作為商品提供而言充分之特性。 (2)使用性試驗 針對將收容於壓頭起泡器容器(網目200×305)中之各例之清潔劑組合物噴出為泡狀而實際使用時之泡質(泡之持續性、泡之彈力性)，由專業官能檢查員進行評價。評價係依據以下之基準而實施。 [評價基準] A：非常優異 B：優異 C：較差 再者，評價結果為A或B者具備作為商品提供而言充分之特性。 (3)黏度測定 針對各例中所製備之清潔劑組合物，使用B型黏度計(轉子No.1，60 rpm)，測定30℃之黏度。將測定結果示於各表。 [表1]
[表2]
[表3]
[表4]
[表5]
根據上述之表1～4所示之結果，含有以本發明特定之比率包含月桂酸及肉豆蔻酸、以及棕櫚酸及/或硬脂酸的高級脂肪酸，並且以特定比率含有N-月桂基二甲基胺基乙酸甜菜鹼之實施例之清潔劑組合物於低溫穩定性方面優異，不僅不會引起起泡器容器之堵塞，所產生之泡之持續性亦優異。另一方面，棕櫚酸與硬脂酸均不包含之比較例1於泡之持續性方面較差。於脂肪酸之調配比率不滿足本發明之要件之(棕櫚酸及硬脂酸之合計調配量超過35質量%)比較例2～4、及N-月桂基二甲基胺基乙酸甜菜鹼與高級脂肪酸皂之調配量比率超出本發明之範圍(0.4～1.5)之比較例5中，未獲得充分之低溫穩定性。 (b)高級脂肪酸皂之調配量小於4質量%之比較例6亦與比較例1同樣地泡之持續性較差，組合物之黏度超過30 mPa・s之比較例7難以利用壓頭起泡器進行噴出。又，將N-月桂基二甲基胺基乙酸甜菜鹼換為椰子醯胺丙基甜菜鹼(椰子油脂肪醯胺丙基甜菜鹼)之比較例8成為低溫穩定性較差者。又，若與以合計30質量%以上包含棕櫚酸及硬脂酸作為形成高級脂肪酸皂之脂肪酸之實施例9相比，則於其調配量為20～30質量%之實施例4及6～8、進而20質量%以下之實施例2、3及5中，確認到即便於更嚴酷之低溫條件下亦變得難以產生析出等，成為尤其適於冬季之寒冷地區等之使用者。 根據表5所示之結果，確認作為IOB＝3～4之多元醇之雙甘油(IOB＝3.50)並非為了獲得本發明之效果所必須(實施例12)，但調配IOB＝3～4之多元醇會提高自起泡器噴出之泡之彈力性(實施例13及14)。Hereinafter, the present invention will be described in detail. (a) Lauryl dimethylaminoacetic acid betaine. The lauryl dimethylamino acetic acid betaine (also described as N-lauryl dimethylamino acetic acid betaine) used in the present invention has the following A compound of the structure represented by the formula (1). C 12 H 25 -N + (CH 3 ) 2 -CH 2 COO - (1) The amount of lauryl dimethylaminoacetic acid betaine in the detergent composition of the present invention is formulated with the following higher fatty acid soaps. The amount is usually 2 to 20% by mass, preferably 2.5 to 18% by mass, and more preferably 3 to 15% by mass, based on the amount, but is not limited thereto, and may be included in the above range. The range is, for example, 2 to 9% by mass, 3 to 8% by mass, or 4 to 7% by mass. (b) Higher Fatty Acid Soap The detergent composition of the present invention contains a higher fatty acid soap as a cleansing component. The higher fatty acid soap of the present invention is formed from a salt of a fatty acid anion having 5 to 25 carbon atoms and a counter cation. The fatty acid having 5 to 25 carbon atoms is a linear or branched saturated or unsaturated monovalent hydrocarbon group, for example, a carboxylic acid having a structure in which a carboxyl group is bonded to an alkyl group or an alkylene group, and the above hydrocarbon group may be used. It is optionally substituted by a hydroxyl group or the like. Examples of the fatty acid having 5 to 25 carbon atoms include caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, undecanoic acid, lauric acid, decenoic acid, undecylenic acid, and myrcenoic acid. 2-ethylbutyric acid, isovaleric acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, isophthalic acid, 3,5,5-trimethylhexanoic acid, tridecanoic acid, tetramethylguanidine Acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lauric acid, wax acid, myristic acid, palmitoleic acid, oleic acid, anti-oleic acid, giant whale Acid, erucic acid, shark acid, linoleic acid, anti-linoleic acid, linoleic acid, arachidonic acid, 2-hexyl decanoic acid, isostearic acid, 12-hydroxystearic acid, coconut oil fatty acid, hydrogenation Coconut oil fatty acid, palm oil fatty acid, hydrogenated palm oil fatty acid, palm kernel oil fatty acid, hydrogenated palm kernel oil fatty acid, tallow fatty acid, hydrogenated tallow fatty acid, and the like. In the present invention, among the fatty acids having 5 to 25 carbon atoms, higher fatty acids formed from linear saturated fatty acids having 8 to 20 carbon atoms or 12 to 18 carbon atoms are preferably used. That is, the fatty acid soap used in the present invention includes a form which does not contain a fatty acid soap formed of a branched fatty acid or an unsaturated fatty acid. The detergent composition of the present invention contains linear saturatedness of at least one selected from the group consisting of (b-1) lauric acid and (b-2) myristic acid and (b-3) selected from palmitic acid and stearic acid. A fatty acid soap formed by a fatty acid. (b-1) Lauric Acid The higher fatty acid soap of the present invention contains 30 to 80% by mass of a fatty acid soap formed of lauric acid with respect to the total weight of the fatty acid forming the higher fatty acid soap. (b-2) Myristic Acid The higher fatty acid soap of the present invention contains 5 to 30% by mass of a fatty acid soap formed of lauric acid with respect to the total weight of the fatty acid forming the higher fatty acid soap. (b-3) Palmitic acid and stearic acid The higher fatty acid soap of the present invention is contained in an amount of 5 to 35% by mass based on the total weight of the fatty acid forming the higher fatty acid soap, and is formed of at least one selected from the group consisting of palmitic acid and stearic acid. Fatty acid soap. When the total amount of palmitic acid and stearic acid is more than 35% by mass, sufficient low-temperature stability cannot be obtained. In the case of use in an environment where low temperature stability is particularly required in cold regions in winter, it is preferred to set the amount of palmitic acid and/or stearic acid to 5 to 30% by mass, more preferably 5 to 25% by mass. Further, it is preferably 5 to 20% by mass. The at least one selected from the group consisting of palmitic acid and stearic acid includes the aspect comprising only one of palmitic acid or stearic acid, and the aspect comprising both palmitic acid and stearic acid. In the case of containing both palmitic acid and stearic acid, it is preferred to set the ratio of palmitic acid to stearic acid [palmitic acid/stearic acid] to a range of 0.4 to 2.5. The range of values includes any range (eg, 0.4 to 2.0 or 1.0 to 2.0, etc.) contained in 0.4 to 2.5 and all values contained in the range. The detergent composition of the present invention is also formulated with palmitic acid (carbon number 16) and/or stearic acid (carbon number 18) in addition to lauric acid (carbon number 12) and myristic acid (carbon number 14). A foam having good persistence can be obtained, and the low-temperature stability is also excellent. In general, it is considered that if the chain length (carbon number) of the higher fatty acid is increased, crystallization is likely to occur. In view of this, in addition to the lauric acid and myristic acid which have been conventionally used, the palm having a larger carbon number is also blended. Acids and/or stearic acid, which increase the stability of low temperatures, are unpredictable effects. The counter cation which neutralizes the higher fatty acid anion is preferably an alkali metal cation, and more preferably a potassium cation. The (a) higher fatty acid soap of the present invention does not include the arginine of the fatty acid and the methyl taurate. The blending amount of the (b) higher fatty acid soap in the detergent composition of the present invention is 4 to 15% by mass, preferably 5 to 12% by mass, more preferably 5 to 10% by mass, still more preferably 6 to 8% by mass. quality%. Here, the blending amount of the higher fatty acid soap means the total blending amount of a higher fatty acid and a neutralizing agent (for example, potassium hydroxide). In the detergent composition of the present invention, the ratio of (a) the amount of lauryl dimethylaminoacetic acid betaine to the amount of (b) the higher fatty acid soap [(a)/(b)] is 0.4 ～. 1.5. The blending ratio is further preferably in the range of 0.5 to 1.2. If the blending ratio is less than 0.4, sufficient low temperature stability cannot be obtained. (c) Polyol The detergent composition of the present invention is preferably formulated with a polyol in addition to the essential components of (a) lauryl dimethylaminoacetate betaine and (b) higher fatty acid soap. The polyol to be blended may be selected from those usually formulated into cosmetics, and examples thereof include glycerin, propylene glycol, dipropylene glycol, 1,3-butylene glycol, ethylene glycol, polyethylene glycol, sorbitol, and the like. The blending amount of the polyol is not particularly limited, but is usually 10 to 50% by mass, preferably 20 to 50% by mass, and more preferably 25 to 40% by mass. Among the polyols, by blending a polyol having an IOB of 3 to 4, the elasticity of the bubbles ejected from the bubbler can be improved, which is preferable. The polyhydric alcohol having IOB = 3 to 4 may, for example, be diglycerin or propylene glycol. The blending amount of the polyol having IOB = 3 to 4 is usually 0.1 to 10% by mass, preferably 0.5 to 8% by mass, and more preferably 1 to 5% by mass based on the total weight of the composition. The detergent composition of the present invention may contain other optional components which are usually used in the liquid detergent composition insofar as the effects of the present invention are not inhibited. Specific examples of the other optional components include oils and polyoxins. , lower or higher alcohols, lanolin derivatives, protein derivatives, various pharmaceutical agents, fungicides, preservatives, pH adjusters, antioxidants, metal ion blockers, chelating agents, animal and plant extracts or derivatives thereof, Pigments, perfumes, pigments, organic or inorganic powders, clay minerals, etc. One or two or more of these may be arbitrarily selected and formulated. The detergent composition of the present invention is not limited, and for example, the viscosity measured at a temperature of 30 ° C using a B-type rotational viscometer is 40 mPa·s or less, preferably 30 mPa·s or less, more preferably 20 or less. Available in the form of a low viscosity liquid around mPa·s. The detergent composition of the present invention can be produced by a usual method using the above-mentioned essential components and optional components. The prepared detergent composition of the present invention is contained in a bubble-free container having a gas-free type having a porous film. The non-gas type bubble ejection container used in the present invention may be any known type as long as a specific amount of the liquid detergent composition is mixed with a specific amount of air and ejected from the container in a bubble state at the time of use. . Specifically, for example, a blister bubbler used by squeezing a bubbler with a finger to press a main body of a soft container and pressing a head having a cap of a ram mechanism with a finger is exemplified. Wait. And in use, the liquid detergent composition is sprayed from the container discharge port by passing a mixture of the liquid detergent composition in the container and air through a porous film (1 piece to a plurality of pieces). Squirting. Examples of the porous film of the indenter bubbler container include a sponge, a sintered body, a mesh, and the like, and a thin-walled mesh is preferable in terms of usability and the like. As the size of the mesh, it is preferred to use about 30 to 400 mesh. In the detergent composition of the present invention, it is preferred to use a container having two porous membranes, and even if one porous membrane is set to 200 mesh, the other porous membrane is set to a fine mesh of 305 mesh. There is also no clogging, and good foam quality can be obtained. The detergent composition of the present invention is suitably provided as a cleansing agent for hair or skin contained in a container of a head bubbler, in the form of a face lotion, a shower gel, a hand lotion, a shampoo, and the like. [Examples] Hereinafter, the present invention will be described in more detail by way of specific examples, which are not intended to limit the scope of the invention. In addition, the blending amount in the following examples and the like is % by mass unless otherwise specified. A cleaning agent was prepared according to the usual method by the composition described in each of the following tables. For the cleaning agents obtained in the respective examples, the following items were evaluated based on the following criteria. (1) Low-temperature stability The prepared detergent composition was filled in a small glass bottle of hard glass, and stored in an evaluation room maintained at each temperature (-10 to 5 ° C) for 24 hours and 1 week, and visually observed. The low temperature stability of the detergent composition was observed and evaluated according to the following evaluation criteria. A: Good (no precipitates, precipitates, no change in appearance; no possibility of causing clogging) B: Poor (precipitated, precipitated, quality problems; possibility of causing clogging) In the use environment, if it is evaluated as "A" at a time point of at least -5 ° C to +5 ° C for 24 hours and at +5 ° C for one week, the product can be provided as a product. . (2) Usability test The detergent composition of each of the examples contained in the indenter bubbler container (mesh 200×305) was sprayed into a bubble shape, and the foam quality in actual use (bubble persistence, bubble generation) Elasticity), evaluated by a professional inspector. The evaluation was carried out based on the following criteria. [Evaluation Criteria] A: Very excellent B: Excellent C: Inferior, the evaluation result is that A or B has sufficient characteristics as a product supply. (3) Viscosity measurement For the detergent composition prepared in each example, a viscosity of 30 ° C was measured using a B-type viscometer (rotor No. 1, 60 rpm). The measurement results are shown in the respective tables. [Table 1] [Table 2] [table 3] [Table 4] [table 5] According to the results shown in Tables 1 to 4 above, higher fatty acids containing lauric acid and myristic acid, and palmitic acid and/or stearic acid in a specific ratio of the present invention are contained, and N-lauryl II is contained in a specific ratio. The detergent composition of the example of methylaminoacetic acid betaine is excellent in low-temperature stability, and does not cause clogging of the bubbler container, and the resulting foam is excellent in durability. On the other hand, Comparative Example 1 in which palmitic acid and stearic acid were not contained was inferior in the sustainability of the bubble. The compounding ratio of the fatty acid does not satisfy the requirements of the present invention (the total blending amount of palmitic acid and stearic acid exceeds 35% by mass) Comparative Examples 2 to 4, and N-lauryldimethylaminoacetic acid betaine and higher fatty acid In Comparative Example 5 in which the blending ratio of the soap was outside the range of the present invention (0.4 to 1.5), sufficient low-temperature stability was not obtained. (b) Comparative Example 6 in which the amount of the higher fatty acid soap was less than 4% by mass was also inferior in the durability of the foam in the same manner as in Comparative Example 1, and the comparative example 7 in which the viscosity of the composition exceeded 30 mPa·s was difficult to utilize the indenter bubbler. Spray out. Further, Comparative Example 8 in which N-lauryldimethylaminoacetic acid betaine was changed to coconut amphetamine propyl betaine (coconut oil fatty amidoxime betaine) was inferior in low-temperature stability. In addition, in comparison with Example 9 in which palmitic acid and stearic acid are contained in a total amount of 30% by mass or more as a fatty acid forming a higher fatty acid soap, Examples 4 and 6 to 8 in which the amount is 20 to 30% by mass are used. Furthermore, in the examples 2, 3, and 5 of 20% by mass or less, it has been confirmed that it is difficult to cause precipitation even under more severe low-temperature conditions, and it is particularly suitable for users in cold regions such as winter. According to the results shown in Table 5, it was confirmed that diglycerin (IOB = 3.50) which is a polyol having IOB = 3 to 4 is not necessary for obtaining the effects of the present invention (Example 12), but the ratio of IOB = 3 to 4 is adjusted. The alcohol increases the elasticity of the bubbles ejected from the bubbler (Examples 13 and 14).