201249467 六、發明說明： 【發明所屬之技術領域】 本發明係關於可安定地維持摻混二直鏈型陽離子界面 活性劑系統成透明乃至半透明之水中油型乳化化妝料。 _ 【先前技術】 以化妝水爲首之水系皮膚化妝料，有喜好外觀呈現半 透明乃至透明者之傾向（例如參考專利文獻1 ~2)。化妝水 係給予皮膚適當的滋潤，保持皮膚健康之原本機能之外， 近年來隨著消費者嗜好的多樣化，亦追求摻混可得到冷感 、清涼感之薄荷醇、樟腦等之冷感劑（清涼劑）者。接著·， 專利文獻3所揭示倂用冷感劑（清涼劑）及陽離子型界面活 性劑，達成提升冷感、清涼感效果之技術。 然而，尤其使用含陽離子型界面活性劑之皮膚化妝料 於臉等時，就安全性等之觀點，以使用二長鏈型陽離子界 面活性劑比單長鏈型陽離子界面活性劑適合。然而，因爲 二長鏈型陽離子界面活性劑難溶於水，所以至今仍難以不 藉由高壓乳化等之方法而簡便地製造摻混二長鏈型陽離子 界面活性劑之半透明乃至透明系之化妝水。雖然前述專利 文獻1係揭示可使用作爲陽離子界面活性劑之單長鏈型陽 離子界面活性劑、二長鏈型陽離子界面活性劑中任一種 ([0027])，但表示作爲該調製方法之於6x1 07〜18x1 07Pa之 壓力下之高壓乳化法（[0044])。另外，以實施例作爲實際 上使用的例，所具體記載者係僅使用單長鏈型陽離子界面 -5- 201249467 活性劑之例（[005 8])。前述專利文獻2中實施例等具體所 示之陽離子界面活性劑係僅單長鏈型陽離子界面活性劑。 [先前技術文獻] (專利文獻） 專利文獻1 :特開 2000- 1 9 1 530號公報（段落號碼 [0027] 、 [0044] 、 [0058]) 專利文獻2 :特開平6-27 1 42 1號公報 專利文獻3 :特開2002- 1 1 4649號公報 【發明內容】 發明所欲解決之課題 本發明係有鑑於前述傳統情況所實施者，以提供可安 定摻混二直鏈型陽離子界面活性劑系統，維持透明乃至半 透明性，而且不藉由高壓乳化等之方法，以混合攪拌等之 手段而可簡便地製造之水中油型乳化化妝料爲目的。 課題之解決手段 爲解決前述課題之本發明係提供含有0.1〜2質量％之 (A) 二直鏈型陽離子界面活性劑、0.^2質量％之 (B) HLBIO〜18之非離子界面活性劑、〇.〇1〜2質量％之（(：） 常溫（2 5°C )爲液狀之油分、1〜20質量％之（D)甘油類、及 (E)水’（C)成份之摻混量係相對於（A)成份及（B)成份之合 計摻混量爲0 · 6 5以下（質量比）之透明乃至半透明之水中油201249467 VI. Description of the Invention: [Technical Field] The present invention relates to an oil-in-water emulsified cosmetic which can stably maintain a blended two linear cation surfactant system into a transparent or translucent. _ [Prior Art] Water-based skin cosmetics, such as lotion, have a tendency to be semi-transparent or even transparent (see, for example, Patent Documents 1 to 2). The lotion is suitable for moisturizing the skin and maintaining the original function of the skin. In recent years, with the diversification of consumers' tastes, it has also sought to be a cold feeling agent such as menthol and camphor which can be mixed with cold feeling and cool feeling. (cooling agent). Next, Patent Document 3 discloses a technique for improving the feeling of cooling and cooling by using a cold sensitizer (cooling agent) and a cationic surfactant. However, in particular, when a skin cosmetic containing a cationic surfactant is used for the face or the like, it is suitable to use a two-chain type cationic surfactant than a single long chain type cationic surfactant from the viewpoint of safety and the like. However, since the two long-chain cationic surfactant is poorly soluble in water, it has been difficult to fabricate a translucent or transparent cosmetic which is blended with a long-chain cationic surfactant by a method such as high-pressure emulsification. water. Although the aforementioned Patent Document 1 discloses that any one of a single long-chain type cationic surfactant and a two-long chain type cationic surfactant which is a cationic surfactant can be used ([0027]), it is shown as 6x1 as the modulation method. High pressure emulsification method under pressure of 07~18x1 07Pa ([0044]). Further, the examples are actually used as examples, and the specific examples are those in which only a single long-chain type cation interface -5 - 201249467 active agent is used ([005 8]). The cationic surfactant specifically shown in the above examples of Patent Document 2 is a single long chain type cationic surfactant. [Prior Art Document] (Patent Document) Patent Document 1: JP-A-2000-119, 530 (Pension No. [0027], [0044], [0058] Patent Document 2: JP-A-6-27 1 42 1 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the foregoing conventional circumstances to provide a stable blending of two linear cation interfacial activities. The agent system maintains transparency and translucency, and is not intended to be easily produced by means of mixing or the like by means of high-pressure emulsification or the like. Solution to Problem The present invention for solving the above problems provides a nonionic surfactant having a (A) di-linear cation surfactant of 0.1 to 2% by mass and (B) HLBIO 〜18 of 0.1% by mass. Agent, 〇.〇1~2% by mass ((:) Normal temperature (25 °C) is liquid oil, 1~20% by mass of (D) glycerin, and (E) water '(C) ingredient The blending amount is a transparent or translucent water oil in which the total blending amount of the component (A) and the component (B) is 0·65 or less (mass ratio).
-6- 201249467 型乳化化妝料。 另外’本發明提供再含有薄荷醇及/或樟腦之前述水 中油型乳化化妝料。 發明之功效 藉由本發明提供可安定摻混二直鏈型陽離子界面活性 劑系統，維持透明乃至半透明性，而且不藉由高壓乳化等 之方法，以混合攪拌等之手段而可簡便地製造之水中油型 乳化化妝料。 用以實施發明之最佳型態 以下係詳述本發明。另外，於下述分別表示POE爲 聚氧乙烯、POP爲聚氧丙烯、PEG爲聚乙二醇。 作爲（A)成份之二長鏈型陽離子界面活性劑，適合使 用後述式（I )及/或（Π )所示之二長鏈型陽離子界面活性劑 ch3-6- 201249467 type emulsified cosmetic. Further, the present invention provides the aforementioned water-based emulsified cosmetic which further contains menthol and/or camphor. EFFECTS OF THE INVENTION The present invention provides a system for stably blending a two-linear cationic surfactant system, which maintains transparency and translucency, and can be easily produced by means of mixing and the like without being subjected to high-pressure emulsification or the like. Oil-based emulsified cosmetic in water. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Further, POE is polyoxyethylene, POP is polyoxypropylene, and PEG is polyethylene glycol, as follows. As the long-chain cationic surfactant of the component (A), a long-chain cationic surfactant ch3 represented by the following formula (I) and/or (Π) is suitably used.
I R1CO—〇—(CH2)P—N+—(CH2)p~〇-C〇Ri X" (I) [式（I )中，hCO係表示分別獨立，碳原子數12〜22，具 有〇〜3個雙鍵之脂肪族醯基；P係表示1~3之整數；r2係 表示甲基、或一（CH2)p—OH基（但是，p係如前述之定義） :X係表示鹵原子、硫酸甲酯、或磷酸甲酯。] 201249467 (R4)—N+—(R3)2 j v (II) [式（Π )中，R3係表示分別獨立，碳原子數12〜22，具有 0〜3個雙鍵之烷基；R4係表示分別獨立，碳原子數1〜3， 不具有雙鍵之烷基；Y係表示鹵原子、硫酸甲酯、或磷酸 甲酯。] 作爲前述式（I )所示之二長鏈型陽離子界面活性劑， 可列舉適合之椰油脂肪酸系esterquat之鹵化物或硫酸甲 酯。具體上可列舉二椰油醯乙基羥乙基甲基銨甲基硫酸（ 作爲市售物之「DEHYQUART L80」（Cognis Japan社製） 等）等。但是非局限於此等例者。 作爲前述式（Π )所示之二長鏈型陽離子界面活性劑， 可舉例如雙二十二烷基二甲基氯化銨、二硬脂基二甲基氯 化銨（市售物「陽離子DSV」（三洋化成工業（股）製）等）、 雙十六烷基二甲基氯化銨、雙十六十八烷基二甲基氯化銨 、二硬脂基二甲基銨硫酸甲酯、雙二十二烷基二甲基錢硫 酸甲酯、雙十六烷基二甲基銨硫酸甲酯、雙十六十八烷基 二甲基氯化銨硫酸甲酯等。但是非局限於此等例者。 (A) 成份之摻混量係本發明之化妝料總量中之0.1 ~2 質量％。以0.1〜1質量％爲宜。未達0.1質量％則提升冷感 效果之實際感覺消失，另一方面，超過2質量％時，保存 時之乳化安定性變差，並不適宜。可使用1種或2種以上 之（A)成份》 (B) 成份係HLB10〜18之非離子界面活性劑。HLB係 -8- 201249467 以後述數1 [數1] HLB= 7+ 11.7 · log(MW/MO) (但是，MW係表示親水基部之分子量，MO係表示親油基 部之分子量） 所表示之川上式所算出。HLB未達10或超過18者，將難 以縮小乳化粒子徑。 作爲（B)成份，可舉例如 單月桂酸六甘油酯（HLB 14.5)、單肉豆蔻酸六甘油酯 (HLB11)、單月桂酸十甘油酯（HLB15.5)、單肉豆蔻酸十甘 油酯（HLB14.0)、單硬脂酸十甘油酯（HLB12.0)、單異硬脂 酸十甘油酯（HLB12.0)、單油酸十甘油酯（HLB12.0)、二硬 脂酸十甘油酯（HLB9.5)、二硬脂酸十甘油酯（HLB10.0)等 之聚甘油脂肪酸酯類： 單硬脂酸P〇E(15)甘油酯（HLB13.5)、單油酸P〇E(15) 甘油酯（HLB14.5)等之POE甘油脂肪酸酯類； POE(20)山梨糖醇酐單椰油脂肪酸酯（HLB16.9)、 POE(2 0)山梨糖醇酐單棕櫚酸酯（HLB15.6)、P〇E(2 0)山梨 糖醇酐單硬脂酸酯（HLB14.9)、POE(20)山梨糖醇酐三硬脂 酸酯（HLB10.5)、POE(20)山梨糖醇酐單異硬脂酸酯 (HLB15.0)、POE(20)山梨糖醇酐單油酸酯（HLB15.0)、 POE(6)山梨糖醇酐單油酸酯（HLB10.0)、POE(2 0)山梨糖醇 201249467 酐三油酸酯（HLBl 1.0)等之POE山梨糖醇酐脂肪酸酯類； POE(6)山梨糖醇單月桂酸酯（HLB15.5)、POE(60)山梨 糖醇四硬脂酸酯（HLB13.0)、POE(30)山梨糖醇四油酸酯 (HLB11.5)、POE(40)山梨糖醇四油酸酯（HLB12.5)、 POE(60)山梨糖醇四油酸酯（HLB14.0)等之POE山梨糖醇 脂肪酸酯類； POE(10)¥€ 月旨（HLB12.0) 、 POE(20)$ 毛月旨（HLB13.0) 、POE(30)# 毛月旨（HLB1 5.0) 、 Ρ Ο E ( 5 ) # 毛月旨 @| (H L B 1 2 · 5 ) 、ΡΟΕ(ΙΟ)羊毛脂醇（HLB15.5) 、ΡΟΕ(20)羊毛脂醇 (HLB16.0)、ΡΟΕ(40)羊毛脂醇（HLB17.0)等之 ΡΟΕ 羊毛脂 、羊毛脂醇、蜂蠟衍生物類： ΡΟΕ(20)蓖麻油（HLB10.5)、ΡΟΕ(40)蓖麻油（HLB12.5) 、ΡΟΕ(50)蓖麻油（HLB14.0)、ΡΟΕ(60)蓖麻油（HLB14.0)、 ΡΟΕ(30)硬化茵麻油（HLB11.0)、ΡΟΕ(40)硬化箆麻油 (HLB13.5)、ΡΟΕ(60)硬化蓖麻油（HLB14.0)、ΡΟΕ(80)硬化 蓖麻油（HLB16.5)、ΡΟΕ(40)硬化蓖麻油（100)(HLB16.5)等 之ΡΟΕ箆麻油、硬化蓖麻油類； ΡΟΕ(ΙΟ)植物固醇（HLB12.5)、ΡΟΕ(20)植物固醇 (HLB15.5)、ΡΟΕ(30)植物固醇（HLB 1 8.0)、ΡΟΕ(30)ΡΟΡ(7) 植物固醇（HLB13.5)、Ρ〇Ε(25)植物固烷醇（HLB14.5)、 ΡΟΕ(30)膽固烷醇（HLB17.0)等之ΡΟΕ固醇、氫化固醇類 • ΡΟΕ(4·2)月桂基醚（HLB1 1.5)、ΡΟΕ(9)月桂基醚 (HLB14.5)、ΡΟΕ(5.5)十六烷基醚（HLB 1 0.5)、ΡΟΕ(7)十六I R1CO—〇—(CH2)P—N+—(CH2)p~〇-C〇Ri X" (I) [In the formula (I), the hCO system is expressed independently, and the number of carbon atoms is 12-22, which has 〇~ 3 double bond aliphatic sulfhydryl groups; P system represents an integer of 1 to 3; r2 represents a methyl group, or a (CH2) p-OH group (however, p is as defined above): X represents a halogen atom , methyl sulfate, or methyl phosphate. 201249467 (R4)—N+—(R3)2 jv (II) [In the formula (Π), R3 represents an alkyl group having 12 to 22 carbon atoms and 0 to 3 double bonds; R4 represents Separately, the number of carbon atoms is 1 to 3, and the alkyl group does not have a double bond; and the Y system represents a halogen atom, methyl sulfate, or methyl phosphate. The di-long-chain cationic surfactant represented by the above formula (I) may, for example, be a halide of a coconut fatty acid-based esterquat or a methyl sulfate. Specifically, dicocoyl ethyl hydroxyethyl methyl ammonium methyl sulphate ("DEHYQUART L80" (manufactured by Cognis Japan Co., Ltd.), etc., which is a commercially available product), etc. are mentioned. However, it is not limited to these examples. The di-long-chain cationic surfactant represented by the above formula (Π) may, for example, be didocosyldimethylammonium chloride or distearyldimethylammonium chloride (commercially available "cation" DSV" (Sanyo Chemical Industry Co., Ltd.), etc., dihexadecyldimethylammonium chloride, dihexadecyldimethylammonium chloride, distearyldimethylammonium sulfate Ester, methyl behenyl dimethyl sulphate, methyl hexadecyl dimethyl ammonium sulfate, dihexadecyl dimethyl ammonium chloride methyl sulfate, and the like. However, it is not limited to these examples. The blending amount of the component (A) is 0.1 to 2% by mass in the total amount of the cosmetic of the present invention. It is preferably 0.1 to 1% by mass. When the amount is less than 0.1% by mass, the actual feeling of the effect of improving the cold feeling disappears. On the other hand, when it exceeds 2% by mass, the emulsion stability during storage is deteriorated, which is not preferable. One or two or more kinds of (A) components (B) may be used as the nonionic surfactant of HLB10-18. HLB series -8- 201249467 hereinafter referred to as 1 [number 1] HLB = 7 + 11.7 · log (MW / MO) (however, MW represents the molecular weight of the hydrophilic base, and MO represents the molecular weight of the lipophilic base) Calculated by the formula. If the HLB is less than 10 or more than 18, it will be difficult to reduce the diameter of the emulsified particles. Examples of the component (B) include hexaglyceryl monolaurate (HLB 14.5), hexaglyceryl monomyristate (HLB11), decaglyceryl monolaurate (HLB15.5), and decaglyceryl monomyristate. (HLB14.0), decaglyceryl monostearate (HLB12.0), decaglyceryl monoisostearate (HLB12.0), decaglyceryl monooleate (HLB12.0), ten stearic acid Polyglycerol fatty acid esters such as glyceride (HLB9.5) and decaglyceryl distearate (HLB10.0): P〇E(15) glyceryl monostearate (HLB13.5), monooleic acid P 〇E(15) glycerol ester (HLB14.5) and other POE glycerol fatty acid esters; POE (20) sorbitan monocohol fatty acid ester (HLB16.9), POE (20) sorbitan single Palmitate (HLB15.6), P〇E (20) sorbitan monostearate (HLB14.9), POE (20) sorbitan tristearate (HLB10.5), POE (20) sorbitan monoisostearate (HLB15.0), POE (20) sorbitan monooleate (HLB15.0), POE (6) sorbitan monooleate (HLB10.0), POE (20) sorbitol 201249467 anhydride trioleate (HLBl 1.0) and other POE sorbitan fatty acid esters; POE (6) Sorbitol monolaurate (HLB15.5), POE (60) sorbitol tetrastearate (HLB13.0), POE (30) sorbitol tetraoleate (HLB11.5) POE (40) sorbitol tetraoleate (HLB12.5), POE (60) sorbitol tetraoleate (HLB14.0) and other POE sorbitol fatty acid esters; POE (10) ¥ Month (HLB12.0), POE(20)$ 毛月(HLB13.0), POE(30)# 毛月(HLB1 5.0), Ρ Ο E ( 5 ) #毛月旨@| (HLB 1 2 · 5 ) , ΡΟΕ (ΙΟ) lanolin alcohol (HLB15.5), ΡΟΕ (20) lanolin alcohol (HLB16.0), ΡΟΕ (40) lanolin alcohol (HLB17.0), etc. lanolin, wool Aliphals, beeswax derivatives: ΡΟΕ (20) castor oil (HLB10.5), ΡΟΕ (40) castor oil (HLB12.5), ΡΟΕ (50) castor oil (HLB14.0), ΡΟΕ (60) castor oil (HLB14.0), ΡΟΕ(30) hardened castor oil (HLB11.0), ΡΟΕ(40) hardened castor oil (HLB13.5), ΡΟΕ(60) hardened castor oil (HLB14.0), ΡΟΕ(80) hardened Castor oil (HLB16.5), bismuth (40) hardened castor oil (100) (HLB16.5), etc. castor oil, hardened castor oil; ΡΟΕ (ΙΟ) plant sterol (HLB12 .5), ΡΟΕ (20) Phytosterols (HLB15.5), ΡΟΕ (30) Phytosterols (HLB 1 8.0), ΡΟΕ (30) ΡΟΡ (7) Plant sterols (HLB13.5), Ρ〇Ε (25) Sterols such as plant hydroalkanol (HLB14.5) and hydrazine (30) cholesterol (HLB17.0), hydrogenated sterols • ΡΟΕ(4·2) lauryl ether (HLB1 1.5) , ΡΟΕ (9) lauryl ether (HLB14.5), hydrazine (5.5) cetyl ether (HLB 1 0.5), bismuth (7) sixteen
-10- 201249467 烷基醚（HLB11.5)、POE(IO)十六烷基醚（HLB13.5)、 POE(15)十六烷基醚（HLB15.5)、POE(20)十六烷基醚 (HLB17.0)、P〇E(23)十六烷基醚（HLB18.0)、p〇E(4)硬脂 醚（HLB9.0)、POE(20)硬脂醚（HLB18.0)、POE(7)油基醚 (HLB10.5)、POE(IO)油基醚（HLB14.5)、P〇E(15)油基醚 (HLB16.0)、POE(20)油基醚（HLB17.0)、P〇E(50)油基醚 (HLB18.0)、POE(IO)二十二烷基醚（HLB10.0)、P〇E(20)二 十二烷基醚（HLB16.5)、POE(30)二十二烷基醚（HLB18.0) 、POE(4)(Cl2〜C15)烷基醚（HLB10.5)、POE(10)(CI2〜Cl5) 烷基醚（HLB15.5)、POE(5)2 級烷基醚（HLB10.5) ' POE(7)2 級烷基醚（HLB12.0)、POE(9)烷基醚（HLB13.5)、 POE(12)烷基醚（HLB14.5)等之POE烷基醚類； POE(10)POP(4)十六烷基醚（HLB10.5)、POE(20) POP(8)十六烷基醚（HLB12.5)、POE(20)POP(6)癸基十四烷 基醚（HLB11.0) 、 P〇E(30)POP(6)癸基十四烷基醚 (HLB12.0)等之POE· POP烷基醚類； 單月桂酸 PEG(10)(HLB12.5)、單硬脂酸 PEG(10) (HLB11.0)、單硬脂酸 PEG(25)(HLB15.0)、單硬脂酸 PEG(40)(HLB17.5)、單硬月旨酸 P E G (4 5 ) (H LB 1 8.0)、單硬 脂酸 PEG(55)(HLB18.0)、單油酸 PEG(10)(HLB11.0)' 二 硬脂酸PEG(HLB16.5)等之PEG脂肪酸酯類； 異硬脂酸 PEG(8)甘油酯（HLB10.0)、異硬脂酸 PEG(10)甘油酯（HLB10.0)、異硬脂酸 PEG(15)甘油酯 (HLB12.0) >異硬脂酸PEG(20)甘油酯（HLB13.0)、異硬脂 -11 - 201249467 酸PEG(25)甘油酯（HLB14.0)、異硬脂酸PEG(30)甘油酯 (HLB15.0)、異硬脂酸PEG(40)甘油酯（HLB15.0)、異硬脂 酸PEG(50)甘油酯（HLB16.0)、異硬脂酸PEG(60)甘油酯 (HLB16.0)等之異硬脂酸POE甘油酯類：等。但是非局限 於此等例者。 本發明中特別就保存時安定性之觀點，其中以POE 植物固醇、POE植物固烷醇、POE膽固烷醇等之POE固 醇、氫化固醇類爲宜。可列舉作爲市售品之「NIKKOL BPS-10」、「NIKKOL BPS-20」、「NIKK0L BPS-3 0」、 「NIKKOL BPS-3007」（以上皆爲 Nikko Chemicals(股）製） 等。可使用1種或2種以上之（B)成份。 (B)成份之摻混量係本發明之化妝料總量中之0.1〜2 質fi %。以0.1〜1質量％爲宜。未達0.1質量％將難以調製 2OOnm以下之乳化粒子徑，另一方面，超過2質量％，在 使用感上會發生黏腻。 作爲（C)成份於常溫（25 °C )爲液狀之油分，只要一般 化妝料所可使用者即可，並非特別限定者，可使用例如油 脂、高級脂肪酸、酯油、烴油、高級醇、矽油等之傳統以 來化妝品所使用者。作爲具體例，可列舉後述者。 作爲油脂’可舉例如亞麻仁油、椿油、夏威夷火山豆 油、玉米油、橄欖油、酪梨油、山茶花油、蓖麻油、紅花 油、杏仁油、肉桂油、荷荷巴油、葡萄油、葵花油、杏仁 果油、菜籽油、芝麻油、小麥胚芽油、米胚芽油、米糠油 、棉籽油、大豆油、花生油、茶籽油、月見草油等^ -12- ⑧ 201249467 作爲高級脂肪酸，可舉例如庚酸、辛酸、壬酸、癸酸 、十五烷酸、十七烷酸、十九烷酸、異硬脂酸、油酸、亞 油酸、亞麻酸、花生油酸等。 作爲酯油，可舉例如四辛酸季戊四醇酯、辛酸十六烷 基酯 '月桂酸己酯、肉豆蔻酸異丙酯、肉豆蔻酸辛基十二 烷基酯、棕櫚酸辛酯、異硬脂酸異丙酯、異棕櫚酸辛酯、 油酸異癸酯、乙基己酸十六烷基酯等。 作爲烴油，可舉例如流動鏈烷烴、三十碳烷、角鯊烷 、鏈烷烴、異鏈烷烴、辛烷、癸烷、十二碳烷、異十二碳 烷、十六碳烷、異十六碳烷等。 作爲高級醇，可舉例如辛醇、異硬脂醇、油醇等。 作爲矽油，可舉例如二甲基聚矽氧烷、甲基苯基聚矽 氧烷、甲基氫聚矽氧烷等之鏈狀聚矽氧烷、八甲基環四矽 氧烷、十甲基環五矽氧烷、十二甲基環六矽氧烷等之環狀 聚矽氧烷等。 本發明中特別就乳化良好性之觀點，適合使用酯油、 高級醇、烴油等。可使用1種或2種以上之（C)成份》 (C)成份之摻混量係本發明之化妝料總量中之〇.〇1 ~2 質量％。以0 · 1〜1質量％爲宜。未達〇 · 〇 1質量％則有時不 能乳化，（A)成份析出，並不適宜，另—方面，超過2質 量％，將難以縮小乳化粒子徑。 另外，本發明中，摻混（C)成份相對於（A)成份及（B) 成份之合計摻混量成0.65以下（質量比）。超過0.65時保 存安定性差，乳化粒子徑亦變大，不能得到半透明乃至透 -13- 201249467 明性β另外，（C)成份相對於（A)成份及（B)成份之合計摻 混量之摻混比之下限値，雖非特別限定者，但就含難溶於 水的（A)成份並使安定地分散之觀點，以〇.〇5以上爲宜， 以〇 · 1以上尤佳，以0.2以上最好。 作爲（D)成份之甘醇類，只要一般化妝料所可使用者 即可，並非特別限定者，可舉例如1，3-丁二醇、二丙二醇 、聚乙二醇、乙二醇、二乙二醇、三乙二醇、1，2-丙二醇 、1，3-丙二醇、異戊二醇、1,4-丁二醇、新戊二醇、1，2-戊二醇、1，5-戊二醇、1，6-己二醇、1，4-環己烷二甲醇、 聚丙二醇' 聚仲四亞甲基二醇等。其中以使用1,3-丁二醇 、二丙二醇等尤佳。可使用1種或2種以上之（D)成份。 (D) 成份之摻混量係本發明之化妝料總量中之1〜20質 量％。以5〜15質量％爲宜。未達1質量％時將變得難以縮 小乳化粒子徑。另一方面，超過20質量％，有時會有發 黏等之損及使用觸感，並不適宜。 (E) 成份爲水。 本發明係以前述（A)〜（E)成份爲必要成份，藉由摻混 前述特定摻混量範圍之此等成份，不藉由高壓乳化法等而 可將水難溶性成份的（A)成份溶化且安定於水中油型乳化 型溶劑，形成透明乃至半透明之基劑。 另外，本發明化妝料中，所謂「透明乃至半透明」係 指透明性指標之L値爲85以上者。「L値」係可以色差 計[例如 COLOR-EYE 7000A(Gretag Macbeth 社製）]等測定 。L値係愈接近1 〇〇，透明度愈高。 -14- 201249467 另外，本發明之半透明乃至透明的水中油型乳化化妝 料係以乳化粒子徑爲200nm以下之微粒子徑爲宜，以 100nm以下尤佳。 本發明係除了前述必要成份之外，以提升冷感、清涼 感效果爲目的，可摻混冷感劑（清涼劑）。適合使用作爲冷 感劑（清涼劑）之薄荷醇、樟腦。摻混冷感劑（清涼劑）時， 摻混量係相對於化妝料整體爲0.001-1.0質量％程度爲宜 ，以0.0 1〜0.5質量％尤佳。 本發明化妝料之製造係無須如傳統之高壓乳化等之手 段，可以混合、攪拌等之手段製造。例如加熱混合 (A)〜（C)成份，以70°C程度之溫度溶解（油相）。接著，藉 由對此油相，添加、攪拌（D)成份及部份（E)成份而成之混 合水相後，添加混合部份（E)成份而可製造。 另外，（D)成份及（E)成份（部份）所成之前述混合水相 中兩成份之摻混比（質量比），就容易乳化等之觀點，以 (D) 成份：（E)成份（部份）=6 : 4〜9 : 1爲宜，以7 : 3~8 : 2 尤佳。使用添加（E)成份（部份）於（D)成份之混合水相，將 容易調製微小乳化粒子徑。若取代（D)成份及（E)成份（部 份）所成之混合水相，僅添加（D)成份後，添加（E )成份（總 量）時，不能得到微細的乳化粒子。 另外，亦可藉由於（A)〜（D)成份，以70°C程度的溫度 溶解混合部份（E)成份[(E)成份相對於（D)成份之適合質量 比與前述相同]，製作均勻系統，於其中添加混合剩餘的 (E) 成份於此，微細化乳化粒子，製造本發明之化妝料。 -15- 201249467 本發明之化妝料，於不損及本發明效果之範圍，除了 前述成份，因應需要，可適當摻混通常化妝料中作爲基劑 所摻混之保濕劑、油份（固體油脂、躐類等）、粉末成份、 水溶性高分子（天然、半合成、合成）、增黏劑、紫外線吸 收劑、金屬離子封鎖劑、低級醇（乙醇等）、糖類（單糖、 寡糖、多醣）、有機胺、pH調整劑、維生素類、抗氧化劑 、抗氧化助劑、其他可摻混的成份等。但並非局限於此等 例者。 本發明之化妝料之劑型係只要可使用於皮膚即可，並 非特別限制者，可列舉化妝水、乳液、使含浸於薄片狀基 劑之含浸液等。 【實施方式】 實施例 以下係舉實施例更具體地說明本發明，但本發明並非 受此任何限制者。摻混量如無特別記述，皆爲質量％。 [平均粒子徑] 乳化滴之平均粒子徑係使用Zetasizer NanoZS(sysmex 社製），未稀釋試樣，直接測定。 [L値（透明性）] 將調製後之試樣，使用COLOR-EYE 7000A(Gretage Macbeth社製）測定，以作爲對照組之蒸餾水的透明度爲 -16- ⑧ 201249467 ]00，算出L値。L値未達85〜98者爲半透明，98~100爲 透明。 [保存時安定性（L値變化）] 將試樣於〇 °C、2 5 °C、5 0 °C之各溫度，放置1個月後 ，測定L値，求出與剛製造後L値的差，依據該平均値 ，藉由後述評估基準進行評估。 (評估基準） ◎ : L値變化係於±5以內 〇：L値變化係於超過±5〜±10 △ : L値變化係於超過±10〜±15 -:L値（初期値）未達85 (實施例1~6 ’比較例1) 調製如後述表1所示之試樣》使用此等試樣，藉由前 述評估方法，評估平均乳化粒子徑、L値（透明性）、保存 時安定性（L値變化）。結果如表1所示。 (製法） 將（1)〜（1〇)加熱混合’以70°C溶解。於此添加（1 1)及 部份（12)(8 : 2之質量比）之混合水相，成爲65t。將此充 份攪拌後’添加混合剩餘的（1 2) ’調製試樣。 -17- 201249467 表1 比較 0施 實施 實施 實施 Κ施 ΪΓ施 例1 例1 例2 例3 例4 例5 例6 (1)棕櫚酸乙基己酯[(c)成份] 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (2)異硬脂醇[(C诚份] 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (3)二硬脂基二甲基氯化銨[(A)成份] 0.4 0.4 0.4 0.4 0.6 0.6 0.6 (4)POE(5)植物固醇(HLB9.5) 0.6 • _ • (5)P0E( 10)二十二烷基醚(HLB丨0.0)[⑼成 - 0.6 - - - - - 份] (6)POE(5)植物固醇(HLB 12.5)[(B)成份] — 0.4 • ⑺POE(20)單異硬脂酸甘油酯(HLB14.0) - - - 0.4 - - - [(B戚份] (8)POE(20)植物固醇(HLB15.5)[(B)成份] • 卸 _ • 0.3 (9)POE(20):十二烷基醚(HLB 16.5)[(B 减 - - - - - 0.3 - 份] (10)POE(30)植物固醇(HLB 丨 8_0)[(B)成份] _ 參 _ 0.2 (11)1,3-丁二醇[(D)成份] 8 8 8 8 8 8 8 剩餘 剩餘 剩餘 剩餘 剩餘 剩餘 剩餘 (12)精製水KE诚份] 量 量 ϋ Ά β 量 量 平均乳化粒子徑(nm) 451 78 68 62 101 105 157 L値(透明性） 13 93 96 95 91 92 87 保存時安定性(L値變化） 〇 ◎ ◎ 〇 〇 Δ 由表1結果顯示，本發明之化妝料（實施例1〜6)係乳 化粒子徑爲20 Onm以下，L値亦高，保存安定性亦優異。 相對於此，使用HLB未達1 0之非離子界面活性劑之比較 ^ 例1係乳化粒子徑大，L値亦低，保存時安定性亦差者。 (實施例7〜9，比較例2〜3 ) 調製如後述表2所示之試樣。使用此等試樣，藉由前 ’ 18_ ⑧ 201249467 述評估方法，評估平均乳化粒子徑、L値（初期値）、保存 時安定性。結果如表2所示。 (製法） 將U)〜（4)加熱混合，以70°C溶解。於此添加（5)及部 份（6 )(8 : 2之質量比）之混合水相，成爲65 °C。將此充份 攪拌後，添加混合剩餘的（6)，調製試樣。 表2 實施 實施 實施 比較 比較 例7 例8 例9 例2 例3 ⑴棕櫚酸乙基已酯[(C)成份] 0.12 0.20 0.24 0.28 0.40 (2)異硬脂醇[(Q成份] 0.12 0.20 0.24 0.28 0.40 (3)二硬脂基二甲基氯化銨[(A戚份] 0.40 0.40 0.40 0.40 0.40 (4)POE(10)植物固醇(HLB12.5)[⑼成份] 0.40 0.40 0.40 0.40 0.40 (5)1,3-丁二醇[(D)成份] 8 8 8 8 8 ⑹精製水猶成份] 剩餘 剩餘 剩餘 量 剩餘 剩餘 量 量 量 旦 里 平均乳化粒子徑(細） 42 68 141 341 384 L値 98 96 86 54 49 保存時安定性(L値變化） ◎ ◎ Δ - * 由表2結果顯示，（C)成份/[(A)成份+ (B)成份](質量 比）爲0.65以下之實施例7〜9可得到本發明之效果。另一 方面，前述質量比超過0.65之比較例2、3未能得到本發 明之效果。 -19- 201249467 調製如後述表3所示之試樣。使用此等試樣，藉由前 述評估方法，評估平均乳化粒子徑、L値（初期値）、保存 時安定性。結果如表3所示。 (製法） 混合（1)(剩餘部份）〜（5)，使其溶解。混合（6)〜（9)，使 其溶解，添加於（1)(剩餘部份）〜（5)之混合物（爲A相）。接 著，將（1〇)~(13)加熱混合，以70°C溶解，於此添加（14)及 部份（1)(8 : 2之質量比）之混合水相，成爲65°C。將此充 份搅拌後，確認可得到均勻相後，再於此加入（1 )的其他 部份而稀釋（爲B相）β B相係藉由水的稀釋，冷卻成4 5 °C 左右，確認形成微細粒子。接著，將B相添加混合於A 相，調製試樣。 -20- ⑧ 201249467 表3 實施例10 實施例11 ⑴精製水[(E诚份] 剩餘量 剩餘量 (2)檸檬酸 0.01 0.01 (3)檸檬酸鈉 0.04 0.04 (4)乙二胺四乙酸鹽 0.01 0.01 (5泔油 3 3 ⑹乙醇 8 8 (7)苯氧基乙醇 0.5 0.5 (8)薄荷醇 • 0.04 (9)樟腦 0.02 (1〇)棕櫚酸乙基已酯[(C)成份] 0.2 0.2 (11)異硬脂醇[(C)成份] 0.2 0.2 (12)二硬脂基二甲基氯化銨[(A戚份] 0.4 0.4 (13)POE(10)植物固醇[(B)成份] 0.4 0.4 (14)1，3-丁二醇[(D 戚份] 8 8 平均乳化粒子徑(nm) 68 70 L値 96 95 保存時安定性(L値變化） ◎ ◎ 由表3所示之實施例1 〇、實施例1 1之結果對比顯示 ，即使摻混冷感劑（清涼劑）時，仍可得到半透明乃至透明 的試樣。另外’實施例10係冷感、清涼效果優異者。 (比較例4 ~ 5 ) 調製後述表4所示之試樣。此等試樣係類似於傳統技 術欄中所舉之「專利文獻1」中實施例2，摻混二直鏈型 陽離子界面活性劑於油分量多的系統之乳膠試樣。使用此 等試樣’評估平均乳化粒子徑、外觀（目測。〇：透明〜半 透明，X :白濁）。結果如表4所示。 -21 - 201249467 (製法） 將（1)〜（6)加熱混合’以70〇c溶解。於此添加（7)後攪 拌。於此添加溶解（8)於（9)者，於70。(：攪拌（比較例5)。 比較例4係於前述攪拌後，於55Mpa之壓力下進行 高壓乳化。 表4-10- 201249467 Alkyl ether (HLB11.5), POE (IO) cetyl ether (HLB13.5), POE (15) cetyl ether (HLB15.5), POE (20) hexadecane Ether (HLB17.0), P〇E (23) cetyl ether (HLB18.0), p〇E (4) stearyl ether (HLB9.0), POE (20) stearyl ether (HLB18. 0), POE (7) oleyl ether (HLB10.5), POE (IO) oleyl ether (HLB14.5), P〇E (15) oleyl ether (HLB16.0), POE (20) oil base Ether (HLB17.0), P〇E(50) oleyl ether (HLB18.0), POE(IO) behenyl ether (HLB10.0), P〇E(20) behenyl ether (HLB16.5), POE (30) behenyl ether (HLB18.0), POE (4) (Cl2~C15) alkyl ether (HLB10.5), POE (10) (CI2~Cl5) Ether (HLB15.5), POE (5) 2nd alkyl ether (HLB10.5) ' POE (7) 2 alkyl ether (HLB12.0), POE (9) alkyl ether (HLB13.5) POE alkyl ethers such as POE (12) alkyl ether (HLB14.5); POE (10) POP (4) cetyl ether (HLB10.5), POE (20) POP (8) sixteen Alkyl ether (HLB12.5), POE (20) POP (6) mercaptotetradecyl ether (HLB11.0), P〇E (30) POP (6) mercaptotetradecyl ether (HLB12. 0) etc. POE· POP alkyl ethers; monolauric acid PEG (10) (HLB12.5), single hard Acid PEG (10) (HLB11.0), monostearic acid PEG (25) (HLB15.0), monostearic acid PEG (40) (HLB17.5), mono-hard acid PEG (4 5 ) ( PEG fatty acid esters such as H LB 1 8.0), succinic acid PEG (55) (HLB18.0), monooleic acid PEG (10) (HLB11.0)' distearic acid PEG (HLB16.5); Isostearic acid PEG (8) glyceride (HLB10.0), isostearic acid PEG (10) glyceride (HLB10.0), isostearic acid PEG (15) glyceride (HLB12.0) > Stearic acid PEG (20) glyceride (HLB13.0), isostearyl-11 - 201249467 Acid PEG (25) glyceride (HLB14.0), isostearic acid PEG (30) glyceride (HLB15.0) , isostearic acid PEG (40) glyceride (HLB15.0), isostearic acid PEG (50) glyceride (HLB16.0), isostearic acid PEG (60) glyceride (HLB16.0), etc. Isostearic acid POE glycerides: and so on. However, it is not limited to these examples. In the present invention, in particular, from the viewpoint of stability at the time of storage, POE sterols such as POE plant sterols, POE plant stanols, and POE cholesterol alcohols, and hydrogenated sterols are preferred. "NIKKOL BPS-10", "NIKKOL BPS-20", "NIKK0L BPS-3 0", and "NIKKOL BPS-3007" (all of which are manufactured by Nikko Chemicals Co., Ltd.) are commercially available. One or two or more (B) components may be used. The blending amount of the component (B) is 0.1 to 2% by mass based on the total amount of the cosmetic of the present invention. It is preferably 0.1 to 1% by mass. When it is less than 0.1% by mass, it is difficult to prepare an emulsified particle diameter of 2,00 nm or less, and on the other hand, if it is more than 2% by mass, stickiness may occur in the feeling of use. The oil component in which the component (C) is liquid at room temperature (25 ° C) is not particularly limited as long as it can be used as a general cosmetic, and for example, fats and oils, higher fatty acids, ester oils, hydrocarbon oils, and higher alcohols can be used. , oyster sauce and other traditional cosmetics users. As a specific example, the following will be mentioned. Examples of the fats and oils include linseed oil, eucalyptus oil, Hawaiian volcanic soybean oil, corn oil, olive oil, avocado oil, camellia oil, castor oil, safflower oil, almond oil, cinnamon oil, jojoba oil, grape oil, and sunflower. Oil, almond oil, rapeseed oil, sesame oil, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, tea seed oil, evening primrose oil, etc. ^ -12- 8 201249467 As a higher fatty acid, for example Such as heptanoic acid, octanoic acid, citric acid, citric acid, pentadecanoic acid, heptadecanoic acid, nonadecanic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, peanut oleic acid and the like. The ester oil may, for example, be pentaerythritol tetraoctanoate, cetyl octanoate, hexyl laurate, isopropyl myristate, octyldodecyl myristate, octyl palmitate, isostearic acid. Propyl ester, octyl isopalmatate, isodecyl oleate, cetyl ethylhexanoate, and the like. The hydrocarbon oil may, for example, be a flowing paraffin, a triacontane, a squalane, a paraffin, an isoparaffin, an octane, a decane, a dodecane, an isododecane, a hexadecane or a different. Hexadecane and the like. Examples of the higher alcohol include octanol, isostearyl alcohol, and oleyl alcohol. Examples of the eucalyptus oil include a chain polyoxyalkylene such as dimethyl polyoxyalkylene, methylphenyl polyoxyalkylene or methyl hydrogen polyoxyalkylene, octamethylcyclotetraoxane, and tenth A cyclic polyoxane such as a quinone oxetane or a dodecamethylcyclohexaoxane. In the present invention, in particular, in view of good emulsification, an ester oil, a higher alcohol, a hydrocarbon oil or the like is suitably used. The blending amount of one or more of the components (C) can be used in the total amount of the cosmetic of the present invention in the range of 〇1 to 2% by mass. It is preferably 0. 1 to 1% by mass. If it is less than 〇 · 〇 1% by mass, it may not be emulsified. (A) The precipitation of the component is not suitable. On the other hand, if it exceeds 2% by mass, it will be difficult to reduce the diameter of the emulsified particle. Further, in the present invention, the blending amount of the component (C) with respect to the total of the components (A) and (B) is 0.65 or less (mass ratio). When the content exceeds 0.65, the stability of storage is poor, the diameter of the emulsified particles is also large, and translucent or even translucent is not obtained. -201249467. In addition, the total amount of (C) component relative to the (A) component and (B) component is blended. The lower limit of the blending ratio is not particularly limited, but the viewpoint of containing the (A) component which is hardly soluble in water and allowing it to be stably dispersed is preferably 〇. 5 or more, and more preferably 〇·1 or more. It is best to use 0.2 or more. The glycol as the component (D) is not particularly limited as long as it can be used as a general cosmetic, and examples thereof include 1,3-butylene glycol, dipropylene glycol, polyethylene glycol, ethylene glycol, and the like. Ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, isoprene glycol, 1,4-butanediol, neopentyl glycol, 1,2-pentanediol, 1,5 - pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, polypropylene glycol 'polytetramethylene glycol, and the like. Among them, 1,3-butanediol, dipropylene glycol and the like are particularly preferable. One or two or more (D) components may be used. The blending amount of the component (D) is 1 to 20% by mass based on the total amount of the cosmetic of the present invention. It is preferably 5 to 15% by mass. When it is less than 1% by mass, it becomes difficult to reduce the diameter of the emulsified particles. On the other hand, when it exceeds 20% by mass, there is a case where it is sticky or the like, and it is not suitable. (E) The ingredient is water. The present invention is characterized in that the components (A) to (E) described above are essential components, and the components of the water-insoluble component (A) are not used by a high-pressure emulsification method or the like by blending the components in the specific blending amount range. It is dissolved and stabilized in an oily emulsified solvent in water to form a transparent or translucent base. Further, in the cosmetic of the present invention, "transparent or translucent" means that the L? of the transparency index is 85 or more. "L値" can be measured by a color difference meter (for example, COLOR-EYE 7000A (Gretag Macbeth)). The closer the L値 system is to 1 〇〇, the higher the transparency. Further, the translucent or transparent water-in-oil emulsion cosmetic of the present invention preferably has a particle diameter of emulsified particle diameter of 200 nm or less, and more preferably 100 nm or less. In addition to the above-mentioned essential components, the present invention can be blended with a cold sensitizer (cooling agent) for the purpose of improving the cold feeling and the cooling feeling effect. It is suitable for use as a cold sensitizer (cooling agent) of menthol and camphor. When the cold sensitizer (cooling agent) is blended, the blending amount is preferably from 0.001 to 1.0% by mass based on the total amount of the cosmetic, and particularly preferably from 0.01 to 0.5% by mass. The manufacture of the cosmetic of the present invention is not required to be carried out by means of mixing, stirring or the like as in the conventional high-pressure emulsification. For example, the components (A) to (C) are heated and mixed, and dissolved at a temperature of 70 ° C (oil phase). Then, by adding and stirring the mixed aqueous phase of the component (D) and the component (E) to the oil phase, the mixed component (E) is added to produce the mixture. In addition, the blending ratio (mass ratio) of the two components in the mixed aqueous phase formed by the component (D) and the component (E) is easily emulsified, and the component (D) is: (E) Ingredients (partial) = 6 : 4 ~ 9 : 1 is appropriate, with 7 : 3 ~ 8 : 2 is especially good. The addition of the (E) component (part) to the mixed aqueous phase of the component (D) makes it easy to prepare the microemulsified particle diameter. When the mixed aqueous phase formed by the (D) component and the (E) component (part) is substituted, only the (D) component is added, and when the (E) component (total amount) is added, fine emulsified particles cannot be obtained. In addition, the (E) component may be dissolved at a temperature of 70 ° C by the components (A) to (D) [the suitable mass ratio of the component (E) to the component (D) is the same as described above, A uniform system was prepared, and the remaining (E) component was added thereto, and the emulsified particles were finely granulated to produce the cosmetic of the present invention. -15- 201249467 The cosmetic of the present invention, in addition to the aforementioned components, may be appropriately blended with a humectant or an oil (solid fat) blended as a base in a usual cosmetic, as needed. , hydrazine, etc.), powder components, water-soluble polymers (natural, semi-synthetic, synthetic), tackifiers, UV absorbers, metal ion blockers, lower alcohols (ethanol, etc.), sugars (monosaccharides, oligosaccharides, Polysaccharides), organic amines, pH adjusters, vitamins, antioxidants, antioxidants, other blendable ingredients, etc. But it is not limited to these examples. The dosage form of the cosmetic of the present invention is not particularly limited as long as it can be applied to the skin, and examples thereof include a lotion, an emulsion, and an impregnation liquid impregnated with a sheet-like base. [Embodiment] The present invention will be more specifically described by the following examples, but the present invention is not limited thereto. The blending amount is % by mass unless otherwise specified. [Average particle diameter] The average particle diameter of the emulsified droplets was measured by using an undiluted sample using a Zetasizer NanoZS (manufactured by sysmex). [L値 (transparency)] The prepared sample was measured using COLOR-EYE 7000A (manufactured by Gretage Macbeth Co., Ltd.), and the transparency of distilled water as a control group was -16 - 8 201249467 ] 00, and L 算出 was calculated. Those with L値 not reaching 85~98 are translucent and 98~100 are transparent. [Stability at the time of storage (L値 change)] The sample was allowed to stand at each temperature of 〇 ° C, 2 5 ° C, and 50 ° C for 1 month, and then L 测定 was measured to determine the L 値 after the production. The difference is based on the average 値 and is evaluated by the evaluation criteria described later. (Evaluation criteria) ◎ : L値 change is within ±5 〇: L値 change is more than ±5~±10 △ : L値 change is more than ±10~±15 -: L値 (initial 値) 85 (Examples 1 to 6 'Comparative Example 1) Preparation of Samples as shown in Table 1 below. Using these samples, the average emulsified particle diameter, L値 (transparency), and storage time were evaluated by the above evaluation method. Stability (L値 change). The results are shown in Table 1. (Production Method) (1) to (1 〇) were heated and mixed to dissolve at 70 °C. Here, the mixed aqueous phase of (1 1) and part (12) (mass ratio of 8 : 2) was added to become 65t. After the mixture was thoroughly stirred, the remaining (1 2)' sample was mixed and mixed. -17- 201249467 Table 1 Comparison 0 Implementation Implementation Implementation Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 (1) Ethyl palmitate [(c) component] 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (2) Isostearyl alcohol [(C Cheng) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (3) distearyl dimethyl ammonium chloride [(A) component] 0.4 0.4 0.4 0.4 0.6 0.6 0.6 (4 ) POE (5) phytosterol (HLB9.5) 0.6 • _ • (5) P0E (10) behenyl ether (HLB 丨 0.0) [(9) into - 0.6 - - - - - parts] (6) POE (5) Phytosterol (HLB 12.5) [(B) Ingredients] - 0.4 • (7) POE (20) glyceryl monoisostearate (HLB14.0) - - - 0.4 - - - [(B ]份) ( 8) POE (20) phytosterol (HLB15.5) [(B) ingredient] • Unloading _ • 0.3 (9) POE (20): lauryl ether (HLB 16.5) [(B minus - - - - - 0.3 - part] (10) POE (30) phytosterol (HLB 丨 8_0) [(B) ingredient] _ _ 0.2 (11) 1,3-butanediol [(D) ingredient] 8 8 8 8 8 8 8 Residual remaining residual remaining surplus (12) Refined water KE Chengfen] Quantities ϋ 量 β Amount Average emulsified particle diameter (nm) 451 78 68 62 101 105 157 L値 (transparency) 13 93 96 95 91 92 8 7 Stability at the time of storage (L値 change) 〇 ◎ ◎ 〇〇 Δ The results of Table 1 show that the cosmetic material of the present invention (Examples 1 to 6) has an emulsified particle diameter of 20 Onm or less, and the L値 is also high, and the stability is preserved. In contrast, in the case of using a nonionic surfactant having an HLB of less than 10, the emulsified particle diameter is large, the L値 is also low, and the stability during storage is also poor. (Examples 7 to 9) Comparative Examples 2 to 3) The samples shown in Table 2 below were prepared. Using these samples, the average emulsified particle diameter, L値 (initial enthalpy), and storage time were evaluated by the evaluation method described in the previous '18_8 201249467. The results are shown in Table 2. (Production method) U)~(4) were heated and mixed, and dissolved at 70 ° C. Here, (5) and part (6) (mass ratio of 8 : 2) were added. Mix the aqueous phase to 65 °C. After the mixture was thoroughly stirred, the remaining (6) was added to prepare a sample. Table 2 Implementation Implementation Comparison Comparative Example 7 Example 8 Example 9 Case 2 Example 3 (1) Ethyl palmitate [(C) component] 0.12 0.20 0.24 0.28 0.40 (2) Isostearyl alcohol [(Q component] 0.12 0.20 0.24 0.28 0.40 (3) distearyl dimethyl ammonium chloride [(A ]) 0.40 0.40 0.40 0.40 0.40 (4) POE (10) phytosterol (HLB12.5) [(9) ingredients] 0.40 0.40 0.40 0.40 0.40 (5) 1,3-butanediol [(D) component] 8 8 8 8 8 (6) Refined water component] Residual remaining amount Remaining residual amount Amount of average emulsified particle diameter (fine) 42 68 141 341 384 L値98 96 86 54 49 Stability during storage (L値 change) ◎ ◎ Δ - * The results in Table 2 show that (C) component / [(A) component + (B) component] (mass ratio) is 0.65 or less The effects of the present invention were obtained in Examples 7 to 9. On the other hand, Comparative Examples 2 and 3 in which the mass ratio exceeded 0.65 failed to obtain the effects of the present invention. -19- 201249467 Modification of the sample shown in Table 3, which will be described later. Using these samples, the average emulsified particle diameter, L 値 (initial enthalpy), and stability during storage were evaluated by the above evaluation methods. The results are shown in Table 3. (Preparation method) Mixing 1) (Remaining part) ~ (5), dissolve it. Mix (6) ~ (9), dissolve it, add it to the mixture of (1) (remaining part) ~ (5) (for phase A) Then, (1〇)~(13) is heated and mixed, and dissolved at 70 ° C, and the mixed aqueous phase of (14) and part (1) (mass ratio of 8 : 2) is added thereto to become 65 ° C. After fully stirring this, it is confirmed that a homogeneous phase can be obtained, and then the other part of (1) is added and diluted (for phase B). The β B phase is diluted by water and cooled to about 45 ° C. Then, it was confirmed that fine particles were formed. Then, phase B was added and mixed in phase A to prepare a sample. -20- 8 201249467 Table 3 Example 10 Example 11 (1) Refined water [(E Cheng parts) Remaining amount remaining (2) Citric acid 0.01 0.01 (3) Sodium citrate 0.04 0.04 (4) Ethylenediaminetetraacetate 0.01 0.01 (5 泔 oil 3 3 (6) Ethanol 8 8 (7) Phenoxyethanol 0.5 0.5 (8) Menthol • 0.04 ( 9) Camphor 0.02 (1 〇) ethyl palmitate palmitate [(C) component] 0.2 0.2 (11) Isostearyl alcohol [(C) component] 0.2 0.2 (12) distearyl dimethyl ammonium chloride [(A) 0.4 0.4 (13) POE (10) Phytosterol [(B) Ingredients] 0.4 0.4 (14) 1,3-butanediol [(D 戚)] 8 8 Average emulsified particle diameter (nm) 68 70 L値96 95 Stability during storage (L値 change) ◎ ◎ Shown in Table 3 Example 1 Comparison of the results of Example 1 shows that even when a cold sensitizer (cooling agent) is blended, a translucent or transparent sample can be obtained. Further, Example 10 is excellent in cold feeling and cooling effect. (Comparative Examples 4 to 5) Samples shown in Table 4 below were prepared. These samples are similar to the latex sample of the system of Example 2 of "Patent Document 1" cited in the conventional art column, in which a two-chain type cationic surfactant is blended in a large amount of oil. The average emulsified particle diameter and appearance were evaluated using these samples' (visual inspection: 〇: transparent ~ semi-transparent, X: white turbid). The results are shown in Table 4. -21 - 201249467 (Preparation method) Dissolve (1) to (6) by heating and dissolve at 70 °C. After the addition of (7), the mixture was stirred. Here, the addition of (8) to (9) is added at 70. (: stirring (Comparative Example 5). Comparative Example 4 was subjected to high-pressure emulsification under a pressure of 55 MPa after the agitation described above.
比較例4 比較例5 (1)荷荷巴油（Mw600程度） 8.5 8.5 (2)環甲矽脂（Mw= 371) 3 3 (3)香油 3 3 (4)維生素E醋酸酯 0.5 0.5 (5)二硬脂基二甲基氯化銨 0.5 0.5 (6)POE(10)二十二烷基醚（hlb 10.0) 4.5 4.5 (7)乙醇 12.5 12.5 (8)甘油 5 5 (9)精製水 剩餘量 剩餘量 調製方法 高壓乳化 攪拌 平均乳化粒子徑（nm) 56 1000-10000 外觀 〇 X 由表4之結果顯示，使用二直鏈型陽離子界面活性劑 於傳統油分fi多的系統之乳膠，僅以攪拌混合步驟不能得 到半透明〜透明的外觀（比較例5)，藉由高壓乳化終於可得 到半透明〜透明的外觀（比較例4)。 後述爯表示實施例。 (質量％) 剩餘 (實施例12 :透明化妝水） (摻混成份） (1)精製水[(E)成份] -22 ⑧ 201249467 (2)EDTA-2Na · 2H2〇 0.01 (3)檸檬酸鈉 0.02 (4)甘油 3.0 (5)乙醇 8.0 (6)苯氧基乙醇 0.5 (7)薄荷醇 0.04 (8)樟腦 0.02 (9)1，3-丁二醇[(D)成份] 8.0 (1〇)異硬脂醇[(C)成份] 0.2 (H)棕櫚酸辛酯[(C)成份] 0.2 (1 2 )二椰油醯乙基羥乙基甲 基銨甲基硫酸[(A)成份] (DEHYQUART L80 : Cognis Japan 製） (13)POE(10)植物固醇[(B)成份] <製造方法> 1、 以25°C混合（1)(剩餘部份）~(8)，使其溶解。 2、 以75°C使（1)(部份）及（9)〜（13)溶解混合。 3、 緩緩添加前述2於1中，攪拌混合。 所得化妝水係乳化粒子爲2 8nm，L値爲9 8。另外，保存 時安定性亦良好。 (質量％) 剩餘 (實施例13 :透明化妝水） (摻混成份） (1)精製水[(E)成份] -23- 201249467 (2) EDTA-2Na · 2H2〇 0.01 (3) 檸檬酸 〇·〇1 (4) 檸檬酸鈉 0.04 (5) 甘油 3.0 (6) 乙醇 8.0 (7) 苯氧基乙醇 0.5 (8) 二丙二醇[(D)成份] 8.0 (9) 異硬脂醇[(C)成份] 0.2 (1〇)棕櫚酸辛酯[(C)成份] 0.2 (11) 二硬脂基二甲基氯化銨[(Α)成份] 〇.4 (12) Ρ〇Ε(10)植物固醇[(B)成份] 0.4 <製造方法> 1、 以25°C混合（1)(剩餘部份）〜（7)，使其溶解。 2、 以75 °C使（1)(部份）及（8)〜（12)溶解混合。 3、 緩緩添加前述2於1中，攪拌混合。 所得化妝水係乳化粒子爲28nm，L値爲98。另外，保存 時安定性亦良好。 產業上利用性 藉由本發明提供可安定摻混二直鏈型陽離子界面活性 劑系統，維持透明乃至半透明，而且不藉由高壓乳化等之 方法’以混合攪拌等之手段而可簡便地製造之水中油型乳 化化妝料。 -24-Comparative Example 4 Comparative Example 5 (1) Jojoba oil (degree of Mw600) 8.5 8.5 (2) cyclomethicone (Mw = 371) 3 3 (3) sesame oil 3 3 (4) Vitamin E acetate 0.5 0.5 (5 ) distearyl dimethyl ammonium chloride 0.5 0.5 (6) POE (10) behenyl ether (hlb 10.0) 4.5 4.5 (7) ethanol 12.5 12.5 (8) glycerol 5 5 (9) refined water remaining Volume Residue Modulation Method High Pressure Emulsification Stirring Average Emulsified Particle Diameter (nm) 56 1000-10000 Appearance 〇X The results of Table 4 show that the latex of the system using a two-linear cationic surfactant in a conventional oil fraction is only The stirring and mixing step did not give a translucent to transparent appearance (Comparative Example 5), and a translucent to transparent appearance was finally obtained by high pressure emulsification (Comparative Example 4). The following description shows an embodiment. (% by mass) Remaining (Example 12: Transparent lotion) (blending component) (1) Refined water [(E) component] -22 8 201249467 (2) EDTA-2Na · 2H2 〇 0.01 (3) Sodium citrate 0.02 (4) Glycerol 3.0 (5) Ethanol 8.0 (6) Phenoxyethanol 0.5 (7) Menthol 0.04 (8) Camphor 0.02 (9) 1,3-butanediol [(D) ingredient] 8.0 (1〇 Isostearol [(C) component] 0.2 (H) octyl palmitate [(C) ingredient] 0.2 (1 2 ) dicocoyl ethyl hydroxyethyl methyl ammonium methyl sulfate [(A) ingredient] (DEHYQUART L80: manufactured by Cognis Japan) (13) POE (10) phytosterol [(B) component] <Production method> 1. Mix at 25 ° C (1) (remaining portion) ~ (8), Let it dissolve. 2. Dissolve (1) (part) and (9) to (13) at 75 °C. 3. Slowly add the above 2 to 1, stir and mix. The obtained lotion-based emulsified particles were 28 nm, and L値 was 98. In addition, the stability during storage is also good. (% by mass) Remaining (Example 13: Transparent lotion) (blending component) (1) Refined water [(E) component] -23- 201249467 (2) EDTA-2Na · 2H2〇0.01 (3) Barium citrate ·〇1 (4) Sodium citrate 0.04 (5) Glycerin 3.0 (6) Ethanol 8.0 (7) Phenoxyethanol 0.5 (8) Dipropylene glycol [(D) component] 8.0 (9) Isostearyl alcohol [(C )Ingredients] 0.2 (1〇) octyl palmitate [(C) ingredient] 0.2 (11) distearyl dimethyl ammonium chloride [(Α) ingredients] 〇.4 (12) Ρ〇Ε (10) plants Sterol [(B) component] 0.4 <Production method> 1. Mix (1) (the remaining portion) to (7) at 25 ° C to dissolve. 2. Dissolve (1) (partial) and (8) to (12) at 75 °C. 3. Slowly add the above 2 to 1, stir and mix. The obtained lotion-based emulsified particles were 28 nm, and L値 was 98. In addition, the stability during storage is also good. INDUSTRIAL APPLICABILITY The present invention provides a system for stably blending a two-linear cationic surfactant system, which is transparent or even translucent, and can be easily produced by means of mixing or the like without a method such as high-pressure emulsification. Oil-based emulsified cosmetic in water. -twenty four-