201223550 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種uv防護化妝料。更詳細而言，本發 明係關於-種可不高濃度地調配油溶性紫外線吸收劑而獲 得較高之SPF的水中油型乳化化妝料，尤其是防曬化妝 料。 【先前技術】 於皮膚護理、身體護理方面，保護皮膚不受紫外線傷害 為重要課題之-，UV防護化妝料之主要目的在於將紫外 線對皮膚ie成之不良影響抑制於最小限度。作為UV防護 化妝料之種之防曬化妝料（sunscreen cosmetics)係藉由調 配紫外線吸收劑或紫外線散射劑等截斷UVA(uhravi〇iet A，長波紫外線）及UVB(ultravi〇let b，巾波紫外線），而保 護肌膚不受紫外線傷害的化妝料（非專利文獻丨）。 作為UV防護化妝料、尤其是防曬化妝料之基劑，通常 使用水中油型乳化系基劑、油中水型乳化系基劑、油性基 劑等。水中油型乳化基劑若為提高SpF(sun pr〇tecti〇n factor防曬係數）而增加油溶性紫外線吸收劑之調配量， 則存在產生黏腻感’失去水中油型乳化基劑本來具有的 「水潤之使用感」之特徵的情形。 另一方面’為維持水中油型乳化基劑之水潤感並達成較 向之SPF亦採用調配水溶性紫外線吸收劑之方式，但存 在由於構成水溶性紫外線吸收劑之鹽之影響而乳化物之穩 & &降低的@題°為解決此種問題，業界進行了使用親水 159558.doc 201223550 性較高之界面活性劑（PEG脂肪酸甘油酯系界面活性劑 專）（專利文獻丨）、調配院基曱基牛確酸鹽（專利文獻2)等嘗 試，取得了一定程度之效果。 又’專利文獻3中記載藉由調配體質顏料，且將高級醇 與界面活性劑之總量及比率設為特定範圍内，則無黏腻感 而為水潤之使用感，並且可達成較高之SPF。然而，要獲 得穩定且使用性良好之製劑必需調配高級醇。 另一方面，水中油型乳化基劑亦存在若高濃度地調配 醇’則會破壞乳化粒子’難以獲得充分穩定之基劑的問 題’但專利文獻4中揭示有如下之酵-水中油型乳化組合 物，並記載其具有賦予頭髮光澤感、柔軟性、潤澤感且使 梳通性良好的效果，該醇·水中油型乳化組合物之特徵在 於：其含有油分、50重量％以上之低級醇、水、作為乳化 劑之下述通式所示之聚醚改質聚矽氧之一種或兩種以上： [化1] CH3 H3C—SI-<!h3 _ CH3 _ 0SI ( h3 ^3 • Μ m Us ch3 osi — ch3 CHs201223550 VI. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a uv protective cosmetic. More specifically, the present invention relates to an oil-in-water emulsified cosmetic which can obtain a high SPF without a high concentration of an oil-soluble ultraviolet absorbing agent, particularly a sunscreen cosmetic. [Prior Art] Protecting the skin from UV rays in skin care and body care is an important issue - the main purpose of UV protective cosmetics is to minimize the adverse effects of UV rays on skin. Sunscreen cosmetics, which are UV protective cosmetics, are cut off by UVA (uhravi〇iet A, UVB) and UVB (ultravi〇let b, UVB) by blending UV absorbers or UV scattering agents. A cosmetic that protects the skin from UV rays (Non-patent literature). As the base of the UV protective cosmetic, especially the sunscreen cosmetic, an oily emulsified base in water, an aqueous emulsified base in oil, an oily base, and the like are usually used. If the oil-based emulsion base is used to increase the amount of the oil-soluble UV absorber to increase the SPF (sun pr〇tecti〇n factor), there is a feeling of stickiness, which is inherent in the oil-borne emulsion base. The case of the characteristics of the sense of use of water. On the other hand, in order to maintain the water sensation of the oil-based emulsion base in water and to achieve a more SPF, a water-soluble ultraviolet absorber is also used, but there is an emulsion due to the influence of the salt constituting the water-soluble ultraviolet absorber. Stabilization && lowering @题° In order to solve this problem, the industry has used surfactants with high hydrophilicity 159558.doc 201223550 (PEG fatty acid glyceride surfactants) (patent literature), blending Attempts have been made to achieve a certain degree of effect by the use of the base 曱 牛 牛 确 ( (Patent Document 2). Further, in Patent Document 3, by setting the body pigment and setting the total amount and ratio of the higher alcohol and the surfactant to a specific range, there is no sticky feeling, and the feeling of moisturizing is high, and a higher feeling can be achieved. SPF. However, it is necessary to formulate a higher alcohol in order to obtain a stable and usable formulation. On the other hand, in the case of the oil-based emulsion base, there is a problem that if the alcohol is blended at a high concentration, the emulsified particles are destroyed, and it is difficult to obtain a sufficiently stable base. However, Patent Document 4 discloses the following fermentation-oil emulsification. In the composition, it is described that it has an effect of imparting a glossy feeling, a softness, a moist feeling to the hair, and a good combing property. The alcohol/water-oil emulsion composition is characterized in that it contains an oil component and a lower alcohol of 50% by weight or more. , water, or one or two or more kinds of polyether modified polyoxane represented by the following formula as an emulsifier: [Chemical 1] CH3 H3C-SI-<!h3 _ CH3 _ 0SI (h3 ^3 • Μ m Us ch3 osi — ch3 CHs
(i»2)3〇(C3lkO)a (C2H4〇)bH (上述式中，m為50〜1000之整數’ 11為1〜4〇之整數，&為 5〜50之整數，b為5〜50之整數），並且實質上不含其他界面 活性劑。 然而’由於專利文獻4中記載之組合物中含有非常多之 低級醇，故而難以應用於通常之皮膚護理基劑中。 J59558.doc 201223550 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開2008-162930號公報 [專利文獻2]日本專利特開2002-284638號公報 [專利文獻3]曰本專利特開2010-189281號公報 [專利文獻4]國際公開第WO97/002888號手冊 [非專利文獻] [非專利文獻1]「新化妝品學」第2版，光井武夫編， 2001年，南山堂發行，第497〜504頁 【發明内容】 [發明所欲解決之問題] 本發明之目的在於提供一種水中油型乳化化妝料，其不 高濃度地調配防曬化妝料中成為黏膩感之主要原因之油溶 性紫外線吸收劑，即便不添加水溶性紫外線吸收劑亦可達 成較高之SPF ’並且穩定性優異。 [解決問題之技術手段] 本發明者等人為解決上述課題反覆進行努力研究，結果 發現，藉由組合調配⑷聚醚改質聚石夕氧、(B)特定量之體 質顏料、及(_V_A區域具有吸收能力之紫外線吸收 劑，則無黏腻感而為水淵之使用《，穩定且可 SPF，從而完成本發明。 向 ，其特徵 亦即，本發明係提供一 在於含有： 種水中油型防曬化妝料 (A)聚醚改質聚矽氧、 159558.doc 201223550 (B) 3〜8質量％之體質顏料、及 (C) 於UV-A區域具有吸收能力之紫外線吸收劑。 [發明之效果] 本發明之乳化化妝料由於未高濃度地調配油溶性紫外線 吸收劑，故而不黏腻’可維持水中油型乳化物所具有之水 潤之使用感，安全性優異，並且穩定且可達成較高之紫外 線遮蔽效果（高SPF)。進而，塗佈於皮膚後轉相而顯示優 異之耐水性。 【實施方式】 本發明之化妝料中之聚醚改質聚矽氧（成分A)只要為具 有聚氧伸乙基（POE，p〇lyoxyethylene)或聚氧伸丙基 (POP ’ p〇ly〇Xypropylene)等聚氧伸烷基之聚矽氧衍生物則 並無特別限定，較佳為使用選自先前以來化妝料等中所使 用者之1種或2種以上。 作為具體例，可列舉：鯨蠟基聚二甲基矽氧烷共聚醇 (eetyl dimethicone copolyol)、月桂基pEg-9聚二曱基矽烷 氧基乙基聚二甲基矽氧烷、PEG/PPG-19/19聚二甲基矽氧 烷PEG_10聚二甲基矽氧烷、PEG-9聚二甲基矽烷氧基乙 基聚一甲基矽氧烷、（聚二甲基矽氧烷/(PEG-10/15))交聯 聚 a 物聚♦氧燒-13(p〇lysilicone-13)等。 :本發月中，尤佳為分子量為5 0000以上，親水基係選 自聚氧伸乙基（P〇E)或聚氧伸丙基（POP)之聚_改質聚石夕 氧。 其中較佳為使用下述通式所表示之聚醚改質聚矽氧。 159558.doc 201223550 [化2] ch3 H3C—S 卜 (!η3 _ CH3 -081 — • ch3 ~ 0$i — ch3 • - m ch3 osi一- ch3 CR3(i»2) 3〇(C3lkO)a(C2H4〇)bH (In the above formula, m is an integer of 50 to 1000' 11 is an integer of 1 to 4, and & is an integer of 5 to 50, and b is 5 An integer of ~50) and is substantially free of other surfactants. However, since the composition described in Patent Document 4 contains a very large amount of a lower alcohol, it is difficult to apply it to a usual skin care base. [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A-2002-284638 (Patent Document 3) Japanese Patent Publication No. 2010-189281 [Patent Document 4] International Publication No. WO97/002888 Manual [Non-Patent Document] [Non-Patent Document 1] "New Cosmetics", 2nd Edition, edited by Kazuo Kazuo, 2001, issued by Nanshan Hall [pp. 497-504] [Draft of the Invention] [Problems to be Solved by the Invention] An object of the present invention is to provide an oil-in-water emulsified cosmetic which is a main cause of stickiness in a sunscreen cosmetic composition at a low concentration. The oil-soluble ultraviolet absorber can achieve a high SPF' and excellent stability even without adding a water-soluble ultraviolet absorber. [Means for Solving the Problem] The inventors of the present invention have made an effort to solve the above problems, and as a result, it has been found that a combination of (4) polyether-modified polysulfide, (B) a specific amount of extender pigment, and (_V_A region) The ultraviolet absorbing agent having an absorptive property is not viscous and is used in the water, and is stable and SPF, thereby completing the present invention. The present invention is characterized in that it provides: Sunscreen Cosmetics (A) Polyether Modified Polyoxo, 159558.doc 201223550 (B) 3 to 8 mass% of body pigments, and (C) UV absorbers having absorbency in the UV-A region. [Effects] Since the emulsified cosmetic of the present invention is formulated with an oil-soluble ultraviolet absorbing agent at a high concentration, it is not sticky and can maintain the moisturizing feeling of the oily emulsion in water, and is excellent in safety and stable and achievable. High UV shielding effect (high SPF). Further, it is applied to the skin and then phase-shifted to exhibit excellent water resistance. [Embodiment] The polyether modified polyfluorene (component A) in the cosmetic of the present invention is only required The polyoxyalkylene derivative having a polyoxyalkylene group such as POE, p〇lyoxyethylene or POP 'p〇ly〇Xypropylene is not particularly limited, and is preferably used. One or two or more kinds of users selected from cosmetics and the like have been used. Specific examples thereof include: eetyl dimethicone copolyol and lauryl pEg-9 poly Dimercaptodecyloxyethylpolydimethyloxane, PEG/PPG-19/19 polydimethyloxane PEG_10 polydimethyloxane, PEG-9 polydimethylalkoxy B Polymethyl methoxy oxane, (polydimethyl methoxy oxane / (PEG-10 / 15)) cross-linked poly-a polyoxyl-13 (p〇lysilicone-13), etc.: this month Particularly preferred is a poly-modified polyoxo oxygen having a molecular weight of more than 50,000 and a hydrophilic group selected from the group consisting of polyoxyethylene (P〇E) or polyoxypropylidene (POP). Polyether modified polyoxo represented by the following formula: 159558.doc 201223550 [Chemical 2] ch3 H3C-S Bu (!η3 _ CH3 -081 — • ch3 ~ 0$i — ch3 • - m ch3 osi one - ch3 CR3
(iH2)3〇(C3H6〇)a (C2H4〇)bH 上述式中，m為50〜looo，較佳為15〇〜1〇〇〇 , n為卜仞。 又，m:n較佳為2〇〇:ι〜5:1，尤佳為6〇:1〜15:1。 又，a為5〜50，b為5〜50，該等聚氧伸烷基在分子中之含 量並無特別限定，較理想為聚氧伸烷基之含量於總分子量 中超過2 〇重量〇/〇。 雖並無特別限定，但例如可列舉HLB(Si)為5以上且未達 10、未達9、未達8或未達7之聚醚改質聚矽氧作為尤佳之 例。 再者’本說明書中之HLB(Si)係指由下述計算式所求出 之值。 [數1] 一-MdlL乙基（POE)與聚氧伸丙基（pop)之分子詈 分子量 X 2 〇 於使用HLB(Si)為5以上之聚醚改質聚矽氧之情形時，若 調配5〜50質量％以下之乙醇，則可更穩定地乳化。 本發明中使用之聚醚改質聚矽氧亦可為市售品，例如可 列舉.商品名 BYll_〇3〇(Dow Corning Toray Silicone公司 製造：含有50質量％之PEG/PPG-19/19聚二曱基石夕氧燒及 5〇質量。/〇之環戊矽氧烷。PEG/ppG-19/i9聚二曱基石夕氧院 159558.doc 201223550 係上述通式中m=400、n=10、a=19、b=19的分子量55000 之聚謎改質聚矽氧；HLB(Si)=7)、商品名KF-6012(Shin-Etsu Silicones公司製造：PEG/PPG-20/22丁醚聚二曱基矽 氧烷）、商品名 SH3749(Shin-Etsu Silicones 公司製造： PEG/PPG-20/20聚二曱基矽氧烷）等。 本發明之化妝料中之聚醚改質聚矽氧（成分A)之調配量 為〇· 1〜10質量％，較佳為〇. 1〜5質量％，更佳為〇丨〜3質量0/〇。 於調配量未達0.1質量％之情形時，或調配超過1〇質量％之 情形時，存在無法獲得穩定之水中油型乳化物之情況。 調配於本發明之化妝料中的體質顏料（成分B)只要為通 常用於化妝料中者即可，並無特別限定。體質顏料係通常 並不以著色為目的而用於保持製品之劑形的無機顏料，藉 由調配體質顏料，可調節製品之使用性（延展性、附著性） 或光澤、色調等》 作為體質顏料之具體例’可列舉：滑石、高嶺土、雲 母、合成雲母、絹雲母、碳酸鎂、碳酸鈣、滑石/二氧化 矽/氧化鈦複合體。又，本發明中亦可組合調配2種以上體 質顏料。其中，較佳為使用選自滑石、高嶺土、雲母中之 1種或2種以上。 本發明中使用之體質顏料較佳為未經疏水化處理者。經 疏水化處理之體質顏料與未經疏水化處理之情形相比較， 存在紫外線防禦效果及乳化穩定性變差之傾向。 本發明之化妝料中之體質顏料的調配量為3〜8質量％， 較佳為4〜8質量若調配量未達3質量％則無法達成本發 159558.doc 201223550 明之目的，若調配超過8質量％ ’則存在乳化穩定性降低 之情形。 調配於本發明之化妝料中的於UV-A區域具有吸收能力 之紫外線吸收劑（成分C :以下亦簡稱為「紫外線吸收 劑」）只要為於UV-A區域（320〜400 nm之波長區域）中具有 吸收能力者則並無特別限定，為先前以來用於化妝料中者(iH2)3〇(C3H6〇)a(C2H4〇)bH In the above formula, m is 50 tolooo, preferably 15〇~1〇〇〇, and n is a dip. Further, m:n is preferably 2 〇〇: ι 5:1, and particularly preferably 6 〇: 1 to 15:1. Further, a is 5 to 50, and b is 5 to 50. The content of the polyoxyalkylene group in the molecule is not particularly limited, and it is preferred that the content of the polyoxyalkylene group exceeds 2 〇 in the total molecular weight. /〇. Although it is not particularly limited, for example, a polyether modified polyfluorene oxide having an HLB (Si) of 5 or more and less than 10, less than 9, less than 8, or less than 7 is particularly preferable. Further, HLB (Si) in the present specification means a value obtained by the following calculation formula. [Numerical 1] The molecular weight of the mono-MdlL ethyl group (POE) and the polyoxypropylidene (pop) molecular weight X 2 is in the case of using polyether modified polyfluorene with an HLB (Si) of 5 or more. When 5 to 50% by mass or less of ethanol is blended, the emulsion can be more stably emulsified. The polyether modified polyfluorene used in the present invention may also be a commercially available product, and for example, the product name BYll_〇3〇 (manufactured by Dow Corning Toray Silicone Co., Ltd.: containing 50% by mass of PEG/PPG-19/19) Polydidecyl sulphate and 5 〇 mass. / 〇 环 矽 矽 。. PEG / ppG-19 / i9 poly 曱 石 夕 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 10, a=19, b=19 molecular weight 55000 poly-mystery modified polyfluorene; HLB (Si) = 7), trade name KF-6012 (Shin-Etsu Silicones company: PEG / PPG-20 / 22 butyl ether poly Dimercaptomethoxyoxane), trade name SH3749 (manufactured by Shin-Etsu Silicones Co., Ltd.: PEG/PPG-20/20 polydidecyloxyne). The compounding amount of the polyether modified polyfluorene (component A) in the cosmetic of the present invention is 〇·1 to 10% by mass, preferably 〇. 1 to 5% by mass, more preferably 〇丨~3 by mass. /〇. When the blending amount is less than 0.1% by mass, or when the blending amount is more than 1% by mass, there is a case where a stable oil-in-water emulsion cannot be obtained. The extender pigment (ingredient B) to be blended in the cosmetic of the present invention is not particularly limited as long as it is usually used in cosmetics. The body pigment is usually used for the purpose of coloring, and is used to maintain the dosage form of the inorganic pigment. By blending the body pigment, the usability (ductility, adhesion) or gloss, color tone, etc. of the product can be adjusted. Specific examples thereof include talc, kaolin, mica, synthetic mica, sericite, magnesium carbonate, calcium carbonate, talc/cerium oxide/titanium oxide composite. Further, in the present invention, two or more kinds of extender pigments may be blended in combination. Among them, one or two or more selected from the group consisting of talc, kaolin and mica are preferably used. The extender pigment used in the present invention is preferably one which has not been hydrophobized. Compared with the case where the hydrophobized body pigment is not hydrophobized, there is a tendency that the ultraviolet protection effect and the emulsion stability are deteriorated. The blending amount of the extender pigment in the cosmetic of the present invention is 3 to 8 mass%, preferably 4 to 8 mass. If the blending amount is less than 3% by mass, the purpose of the present invention is 159,558.doc 201223550, and if the blending exceeds 8 The mass %' has a situation in which the emulsion stability is lowered. The ultraviolet absorber (component C: hereinafter also referred to as "ultraviolet absorber") having an absorption ability in the UV-A region formulated in the cosmetic of the present invention is only in the UV-A region (wavelength region of 320 to 400 nm). There is no particular limitation on those who have absorption ability, but those used in cosmetics before.
即可D 作為具體例，可列舉：甲氧基桂皮酸乙基己酯、二乙胺 基羥基苯曱醯基苯曱酸己酯、奥克立林、多晶石夕_15、雙 乙基己氧基苯盼曱氧基苯基三井、經苯曱__3、2,4 6-三 [4-( 乙基己氧基叛基）本胺基]-1，3,5 -三啡、第三丁基甲氧 基二苯曱醯基甲烷、苯并***、亞苄基樟腦（benzylidene camphor)、三甲氧基桂皮酸曱基雙（三甲基矽烷氧基）矽烷 基異戊酯、及苯基苯并咪唑磺酸等》該等可視需要適當選 擇1種或2種以上而使用。 該#之中，二乙胺基經基苯曱醯基苯曱酸己酿、雙乙基 己氧基笨酚甲氧基苯基三畊由於黏腻感較少，紫外線吸收 效果亦較高故而較佳。尤其是藉由將二乙胺基羥基苯甲醯 基苯甲酸己酯與雙乙基己氧基苯酚甲氧基苯基三畊兩種組 合調配，紫外線吸收效果進一步提高，因此較佳。 本發明之化妝料中之紫外線吸收劑的調配量為5〜3〇質量 /〇，較佳為1 0〜25質量％，更佳為丨〇〜2〇質量％。若調配量 未達5質量％則無法達成本發明之目的，若調配超過3〇質 ’則存在產生黏腻感或對皮膚之刺激性的情況。 159558.doc 201223550 尤其疋調配二乙胺基羥基苯曱醯基苯曱酸己酯及/或雙 乙基己氧基苯酚甲氧基苯基三畊作為紫外線吸收劑之情形 時’較佳為將該等之調配量設為1.1〜5質#% 〇若該等之調 配量未達1.1質量％，則難以獲得紫外線吸收效果之進一步 提同，若調配超過5質量％，則存在產生黏腻感或對皮膚 之刺激性的情況。 本發明之化妝料中除上述必需成分A〜c以外，亦可於不 妨礙本發明之效果之範圍内含有自先前以來用於化妝品中 之其他任意成分。具體而言，可列舉：增黏劑、保濕劑、 油分、緩衝劑、螯合劑、色料、防腐劑等。 s等任意成刀中，較佳為於本發明之化妝料中調配親冰 性增黏劑。作為親水性增㈣，只要為詩化妝品中者， 則並無特別限定，例如可列舉：天然之水溶性高分子、半 合成之水溶性高分子、合成之水溶性高分子等。 作為天然之水溶性高分子，例如可列舉：***膠、黃 =膠、半乳聚糖、瓜_、刺槐豆膠、刺梧桐樹膠、鹿角 菜膠、果膠、壇脂、摇梓軒（德桂「 (払梓（ma_lo))、海藻膠（褐 溱萃取物）、澱粉（稻米、玉米、$丛 T馬鈴薯、小麥）、甘草酸等 植物系高分子；三仙膠、聚結翁她 膠眾葡萄糖、琥珀醯聚糖、聚三葡 萄糖等微生物系高分子；膠原蛋白 史曰、酪蛋白' 白蛋白、明 膠等動物系高分子等β 〜π 1列舉：叛甲 、甲基經丙基殺粉等澱粉系高分子；甲基纖維素、 纖維素、乙基纖維素、甲基經丙基纖維素、經乙基〗 159558.doc 201223550 素、纖維素硫酸鈉、㈣基纖維素、》甲基纖維素納 (CMC)、結晶纖維素、纖維素粉末等纖維素系高分子；海 藻酸納、海藻酸丙二醇酿等海藻酸系高分子等。 作為合成之水溶性高分子，例如可列舉：聚乙烯醇、聚 乙烯甲醚、聚乙烯吡咯啶酮、羧乙烯聚合物(卡波姆 (__〇)等乙稀系高分子；聚乙二醇（分子量15〇〇、 4000、6000)等聚氧乙烯系高分子；聚氧乙烯-聚氧丙烯共 聚物等共聚合系高分子；聚丙烯酸鈉、聚丙烯酸乙自旨、聚 丙烯醯胺、丙烯酸-甲基丙烯酸烷基酯共聚物（商品名 「PemulenTR-Ι」）等丙烯酸系高分子；聚乙烯亞胺、陽離 子聚合物等。 於在本發明之化妝料中調配親水性增黏劑之情形時，調 配量為0.01〜5質量。/。，較佳為〇1〜3質量％。若調配量未達 〇·〇1質量％，則存在顯現不出對於提高乳化穩定性之幫助 的情況，若調配超過5質量％，則存在塗佈時觸感厚重的 情況。 本發明之化妝料可依據先前以來製造乳化物所使用之方 法而製造。例如，混合油相成分，將水相成分與體質顏料 等一同混合，使水相與油相混合並以均質攪拌機等進行乳 化’藉此可獲得本發明之水中油型乳化防曬化妝料。 [實施例] 以下，列舉具體例更詳細地說明本發明，但本發明並不 限定於以下之實施例。又，只要並無特別聲明，則以下之 實施例等中之調配量係表示質量〇/〇。 159558.doc 201223550 (實施例及比較例） 依據常法製備具有下述表1所示之組成之乳化組合物， 並對其乳化穩定性進行評價。又，對各組合物測定UV吸 收光譜。 乳化穩定性之評價方法及基準： 嘗試以表1中所示之組成製備水中油型乳化組合物，將 目視觀察之結果為獲得乳化粒子較小且穩定之水中油型乳 化物之例評價為「〇，將無法乳化之例評價為「X」。 [表1]As a specific example, D can be exemplified by ethyl hexyl cinnamate, hexyl diethyl hydroxybenzophenone benzoate, octocrylene, polycrystalline s15, diethyl Hexyloxyphenyl phenyloxy phenyl trisulfide, benzoquinone __3, 2,4 6-tris[4-(ethylhexyl ethidyl) benzylamino]-1,3,5-trimorphine, Third butyl methoxydiphenylmethylmethane, benzotriazole, benzylidene camphor, trimethoxy cinnamate bis(trimethyldecyloxy)decylisoamyl ester, and benzene For the purpose of the above-mentioned, it is necessary to use one or two or more types as appropriate. Among the #, the diethylamino group is brewed with phenyl benzoyl benzoic acid, and the diethyl hexyloxy phenol methoxy phenyl triturate has less sticky feeling and higher ultraviolet absorption effect. Preferably. In particular, by blending diethylhexyl hydroxybenzimidylbenzoate with bisethylhexyloxyphenol methoxyphenyl tritonate, the ultraviolet absorbing effect is further improved, which is preferable. The amount of the ultraviolet absorber in the cosmetic of the present invention is 5 to 3 Å by mass, preferably 10 to 25% by mass, more preferably 丨〇 2 to 2% by mass. If the amount is less than 5% by mass, the object of the present invention cannot be attained, and if it is more than 3 〇, it may cause stickiness or irritation to the skin. 159558.doc 201223550 Especially when blending diethyl hexyl hydroxyphenyl benzoyl phthalate and/or bis hexyl oxy phenol methoxy phenyl tri-methane as a UV absorber, it is better The blending amount is set to 1.1 to 5 mass%. If the blending amount is less than 1.1% by mass, it is difficult to obtain further enhancement of the ultraviolet absorbing effect. If the blending amount exceeds 5% by mass, there is a feeling of stickiness. Or irritating to the skin. In addition to the above-mentioned essential components A to c, the cosmetic of the present invention may contain other optional components used in cosmetics from the prior range without impairing the effects of the present invention. Specific examples thereof include tackifiers, humectants, oils, buffers, chelating agents, colorants, and preservatives. In any of the knives such as s, it is preferred to formulate a waxy tackifier in the cosmetic of the present invention. The hydrophilicity increase (4) is not particularly limited as long as it is a poetic cosmetic product, and examples thereof include a natural water-soluble polymer, a semi-synthetic water-soluble polymer, and a synthetic water-soluble polymer. Examples of the natural water-soluble polymer include gum arabic, yellow gum, galactan, melon _, locust bean gum, karaya gum, carrageenan, pectin, altar, and 梓 梓 (de "Gui" (払梓 (ma_lo)), seaweed gum (brown peony extract), starch (rice, corn, $ bush T potato, wheat), glycyrrhizic acid and other plant-based polymers; Sanxianjiao, agglomeration Microbial polymers such as glucose, amber xylan, and polytriglucose; collagen history, casein' albumin, gelatin and other animal polymers, etc. β ～ π 1 List: renegade, methyl propyl propyl Starch-based polymer such as powder; methyl cellulose, cellulose, ethyl cellulose, methyl propyl cellulose, ethyl 159558.doc 201223550, sodium cellulose sulfate, (tetra) cellulose, "A A cellulose-based polymer such as a cellulose nanocapsule (CMC), a crystalline cellulose or a cellulose powder; an alginic acid-based polymer such as sodium alginate or propylene glycol alginate; and examples of the water-soluble polymer to be synthesized include, for example, Polyvinyl alcohol, polyvinyl methyl ether, polyethylene Pyrrolidone, carboxyvinyl polymer (Carbomer (__〇) and other ethylene-based polymers; polyethylene glycol (molecular weight 15 〇〇, 4000, 6000) and other polyoxyethylene polymers; polyoxyethylene - A copolymerized polymer such as a polyoxypropylene copolymer; a high polyacrylic acid such as sodium polyacrylate, polyacrylic acid acrylate, polypropylene decylamine or acrylic acid-alkyl methacrylate copolymer (trade name "Pemulen TR-Ι") Molecular weight; polyethyleneimine, cationic polymer, etc. When the hydrophilic thickener is formulated in the cosmetic of the present invention, the blending amount is 0.01 to 5 mass%, preferably 〇1 to 3 mass%. When the amount is less than 质量·〇1% by mass, there is a case where the improvement of the emulsion stability is not exhibited, and when the blending amount is more than 5% by mass, the touch is heavy at the time of application. The material can be produced according to the method used in the prior art for producing an emulsion. For example, the oil phase component is mixed, the water phase component is mixed with the body pigment, and the like, and the water phase is mixed with the oil phase and emulsified by a homomixer or the like. The invention can be obtained [Embodiment] The present invention will be described in more detail below by way of specific examples, but the present invention is not limited to the following examples. Further, unless otherwise stated, the following examples and the like are used. The blending amount is a mass 〇/〇. 159558.doc 201223550 (Examples and Comparative Examples) An emulsified composition having the composition shown in the following Table 1 was prepared according to a usual method, and the emulsion stability was evaluated. The UV absorption spectrum of each composition was measured. Evaluation method and basis of emulsion stability: An oily emulsion composition in water was prepared by the composition shown in Table 1, and the result of visual observation was that the emulsion particles were small and stable. An example of the oily emulsion was evaluated as "〇, and an example in which the emulsion could not be emulsified was evaluated as "X". [Table 1]
比較例 1 比較例 2 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 比較例 3 比較例 4 離子交換水 剩餘 剩餘 剩餘 剩餘 剩餘 剩餘 剩餘 剩餘 剩餘 乙醇 15 15 15 15 15 15 15 15 15 1，3-丁二酵 5 5 5 5 5 5 5 5 5 卡波姆 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 丙烯酸/丙烯酸烷基 (C10〜30)酯共聚物 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 三乙酵胺 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 PEG/PPG-19/19 聚二甲基矽氧烷 (A成分)*1) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 環戊矽氧烷 1.5 1.5 1,5 1.5 1,5 1.5 1,5 1,5 1.5 鯨蠟酵乙基己酸酯 3 3 3 3 3 3 3 3 3 甲氧基桂皮酸乙基 己酯(C成分） 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 多晶矽-15(C成分） 5 5 5 5 5 5 5 5 5 二乙胺基羥基苯 甲醖基笨甲酸己酯 (C成分） 2 2 2 2 2 2 2 2 2 雙乙基己氧基笨酚 甲氡基笨基三畊 (C成分） 2 2 2 2 2 2 2 2 2 滑石(B成分） - 2 3 5 8 - - 10 - 雲母(B成分） - - - • - 5 - - - 高嶺土 (B成分） - - - - - - 5 - - 經疏水化處理之滑石 - - - - - - - - 5 整合劑 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 苯氧基乙酵 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 合計 100 100 100 100 100 100 100 100 100 乳化穩定性 〇 〇 〇 〇 〇 〇 〇 X X *1)商品名BYll-030(Dow Coming Toray Silicone公司製造：HLB(Si)=7) 159558.doc -12-Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 3 Comparative Example 4 Ion exchange water remaining remaining remaining remaining remaining remaining remaining ethanol 15 15 15 15 15 15 15 15 15 1 , 3-丁二酵5 5 5 5 5 5 5 5 5 Carbomer 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Acrylic acid/alkyl acrylate (C10~30) ester copolymer 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ethylamine 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 PEG/PPG-19/19 Polydimethyloxane (Component A)*1) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Cyclopentaoxane 1.5 1.5 1 ,5 1.5 1,5 1.5 1,5 1,5 1.5 cetyl ethylhexanoate 3 3 3 3 3 3 3 3 3 ethylhexyl methoxycinnamate (component C) 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Polycrystalline germanium-15 (component C) 5 5 5 5 5 5 5 5 5 Diethylaminohydroxybenzhydryl benzoic acid hexyl ester (component C) 2 2 2 2 2 2 2 2 2 Diethylhexyloxy Base phenolic methacrylate-based stupid three-plowed (C component) 2 2 2 2 2 2 2 2 2 talc (component B) - 2 3 5 8 - - 10 - mica (component B) - - - • - 5 - - - Kaolin (Part B) - - - - - - 5 - - Hydrophobized talc - - - - - - - - 5 Integrator 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Phenoxyethylacetate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Total 100 100 100 100 100 100 100 100 100 Emulsification stability 〇〇〇〇〇〇〇 XX *1) Trade name BYll-030 (manufactured by Dow Coming Toray Silicone: HLB(Si)=7) 159558.doc -12-
201223550 如根據表1中所示之結果可知般，含有聚醚改質聚矽 氧、紫外線吸收劑，且滑石、雲母、高嶺土等體質顏料之 調配量為8質量％以下的比較例1、2及實施例1〜5之組合物 之乳化穩定性優異。相對於此，於體質顏料等過剩（丨〇質 量％)調配的比較例3及調配有經疏水化處理之滑石的比較 例4之組成下’無法獲得穩定之乳化物。 另一方面，本發明之實施例1〜5之組成與未調配體質顏 料或其調配量未達3質量％之比較例1及2相比，紫外線吸 收能力顯著提高（圖1及2)〇 繼而’對上述比較例1及實施例3〜5之組合物實施紫外線 防禦效果之耐水性試驗。評價方法如下所述。 於表面經粗糙化之PMMA(聚甲基丙烯酸甲酯）板上均勻 地塗佈2 mg/cm2之組合物（比較例i或實施例3〜5)，利用分 光光度計（U-4100，曰立製作所）測定吸光度。繼而，將上 述PMMA板（塗佈有各組合物者）置於強流水中15分鐘充 分使其乾燥後，再次測定吸光度。計算出耐水性試驗後波 長3 1 0 nm之吸光度相當於耐水性試驗前同波長之吸光度之 百分多少，將其值作為UV防禦效果之殘留率（％)。 將各例中所得之UV防禦效果之殘留率示於圖3之圖中。 不含體質顏料之比較例丨中，耐水性試驗後之殘留率未達 50%，與此相對，除聚醚改質聚矽氧、紫外線吸收劑以外 亦調配有特定量滑石、雲母、高嶺土等體質顏料之實施例 3〜5中，殘留率提高至65%〜75%。 以下’示出本發明之其他實施例。 159558.doc 13_ 201223550 實施例6 :水中油型防曬化妝料 離子交換水 剩餘 乙醇 20 二丙二醇 3 丙烯酸/丙烯酸烷基（C10-30)酯共聚物 0.5 三仙膠 0.1 胺基甲基丙二醇 適量 聚氧丁烯聚氧丙烯二醇 2 PEG/PPG-19/19聚二甲基矽氧烷 2 聚乙二醇 1 環戊矽氧烷 2 氫化聚異丁烯 3 辛甲基聚矽氧烷 5 奥克立林 3 第三丁基曱氧基二苯甲醯基甲烷 1 苯并*** 1 羥苯甲酮-3 0.1 滑石 6 螯合劑 適量 對羥基苯曱酸乙酯 適量 香料 適量 實施例7 :水中油型防曬化妝料 離子交換水 剩餘 乙醇 15 159558.doc 14 201223550 1，3-丁二醇 卡波姆 7 丙烯酸/丙烯酸烷基(C10〜30)酯共聚物 0.15 胺基甲基丙醇 0.15 聚丙二醇 適量 PEG/PPG-19/19聚二曱基矽氧烷 3 聚一甲基石夕氧坑 1.5 環戊矽氧烷 1,5 二甲基聚矽氧烷 2 季戊四醇四（乙基己酸）酯 2 異十二烷 3 曱氧基桂皮酸乙基己酯 2 苯基苯并啼唾續酸 5 2,4,6-三[4-(2_乙基己氧基羰基）苯胺基]-1，3,5-三p井 2 亞苄基樟腦 0.3 二甲氧基桂皮酸曱基雙（三甲基矽烷氧基)矽烷基異戊酯 0.2 雲母 0.2 高嶺土 2 1 適量 適量 螯合劑 笨氧基乙醇 【圖式簡單說明】 圖1係表示對實施例1、4及比較例1、2之組合轨化 所測定 之UV光譜的圖。 圖2係表示對實施例2、3、5及比較例1之組合物所測定 159558.doc •15· 201223550 之uv光譜的圖。 圖3係表示實施例3〜5及比較例1之組合物的耐水性試驗 後紫外線防護效果之殘留率的圖。According to the results shown in Table 1, the blending amount of the polyether-modified polyfluorene oxide and the ultraviolet absorber, and the blending amount of the talc, mica, kaolin, and the like are 8% by mass or less, and Comparative Examples 1 and 2 and The compositions of Examples 1 to 5 were excellent in emulsion stability. On the other hand, in Comparative Example 3 in which excess amount of body pigment or the like (% by mass) was blended, and in the composition of Comparative Example 4 in which hydrophobized talc was formulated, a stable emulsion could not be obtained. On the other hand, in the compositions of Examples 1 to 5 of the present invention, the ultraviolet absorbing ability was remarkably improved as compared with Comparative Examples 1 and 2 in which the unmixed extender pigment or the blended amount thereof was less than 3% by mass (Figs. 1 and 2). The water resistance test for the ultraviolet protection effect of the composition of the above Comparative Example 1 and Examples 3 to 5 was carried out. The evaluation method is as follows. A composition of 2 mg/cm 2 (Comparative Example i or Examples 3 to 5) was uniformly coated on a surface roughened PMMA (polymethyl methacrylate) plate, and a spectrophotometer (U-4100, 曰) was used. Established by Seiko Seisakusho Co., Ltd.). Then, the above PMMA plate (applied with each composition) was placed in strong running water for 15 minutes to be sufficiently dried, and then the absorbance was measured again. The absorbance at a wavelength of 3 1 0 nm after the water resistance test was calculated as a percentage of the absorbance at the same wavelength before the water resistance test, and the value was taken as the residual ratio (%) of the UV defense effect. The residual ratio of the UV defense effect obtained in each example is shown in the graph of Fig. 3. In the comparative example containing no extender pigment, the residual ratio after the water resistance test is less than 50%, and in addition to the polyether modified polyfluorene and the ultraviolet absorber, a specific amount of talc, mica, kaolin, etc. is also blended. In Examples 3 to 5 of the extender pigment, the residual ratio was increased to 65% to 75%. The following 'shows other embodiments of the invention. 159558.doc 13_ 201223550 Example 6: Oil-based sunscreen lotion ion exchange water remaining ethanol 20 Dipropylene glycol 3 Acrylic acid/alkyl acrylate (C10-30) ester copolymer 0.5 Sanxianjiao 0.1 Aminomethyl propylene glycol Suitable amount of polyoxygen Butene polyoxypropylene diol 2 PEG/PPG-19/19 polydimethyl methoxy oxide 2 polyethylene glycol 1 cyclopentanoxane 2 hydrogenated polyisobutylene 3 octyl methyl polyoxane 5 octoberin 3 Tributyl decyloxybenzhydrylmethane 1 benzotriazole 1 hydroxybenzophenone-3 0.1 talc 6 Chelating agent appropriate amount of p-hydroxybenzoic acid ethyl ester amount of the appropriate amount of Example 7: water-based sunscreen cosmetics Ion exchange water residual ethanol 15 159558.doc 14 201223550 1,3-butanediol carbomer 7 Acrylic acid/alkyl acrylate (C10~30) ester copolymer 0.15 Aminomethyl propanol 0.15 Polypropylene glycol PEG/PPG- 19/19 polydidecyloxane 3 polymethyl oxazepine 1.5 cyclopentaoxane 1,5 dimethyl polyoxane 2 pentaerythritol tetrakis (ethylhexanoate) 2 isododecane 3 ethoxylated cinnamic acid ethylhexyl ester 2 phenyl benzindene succinic acid 5 2,4,6-three [4-(2_B Hexyloxycarbonyl)anilino]-1,3,5-trip well 2 benzylidene camphor 0.3 dimethoxy cinnamic acid decyl bis(trimethyldecyloxy)decyl isoamyl ester 0.2 mica 0.2 Kaolin 2 1 Appropriate amount of chelating agent Stupid oxyethanol [Brief Description] Fig. 1 is a graph showing the UV spectra measured for the combined orbitalization of Examples 1, 4 and Comparative Examples 1 and 2. Fig. 2 is a graph showing the uv spectrum of 159558.doc •15·201223550 measured for the compositions of Examples 2, 3, and 5 and Comparative Example 1. Fig. 3 is a graph showing the residual ratio of the ultraviolet protection effect after the water resistance test of the compositions of Examples 3 to 5 and Comparative Example 1.
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