201110990 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種水中油型乳化組成物。詳而言之係 關於一種含有特定紫外線吸收劑與極性油之水中油型乳化 組成物。本發明之水中油型乳化組成物可較佳地利用作為 防曬化妝料。 【先前技術】 防曬化妝料之重要的紫外線吸收波長區域為UV_A區 域（320〜400nm)與UV-B區域（290〜320nm)。而一般認為 UV-A區域（320〜400nm)之紫外線會侵害造成皮膚變黑，但 並不會如UV-B區域（290〜320nm)之紫外線般引起曬傷，促 進皮膚老化。然而，然而，近年來逐漸了解，UV_B區域的 紫外線相較而言，只會到達皮膚的表面部分，相對於此， UV-A區域的紫外線，會到達皮膚的深處，不僅是皮膚老 化，亦為誘發皮膚癌的原因。 至今為止所使用之化妝料用紫外線吸收劑若由其構造 來分類，有（1)苯甲酸衍生物、（2)甲氧基桂皮酸衍生物、（3) 二苯基酮衍生物、（4)二苯甲醯基f烷衍生物、（5)水陽酸衍 生物等。近年來尤其大多使用（2)與（4)之紫外線吸收劑 然而，上述所例舉之紫外線吸收劑從實用面來看則各 有問《s例如（1)之本甲酸衍生物方面，例如對二f基胺基 苯甲酸-2-乙基己酯為液狀、透明，雖有使用容易性這樣的 優點，但含有該等衍生物則有安全性的顧慮，近年來未被 使用。且極大吸收波長在290nm附近，僅吸收UV_B區域 201110990 之紫外線。 (2) 之桂皮酸竹生物方面，現在市售之防罐（sun care)化 妝品中最常被使用之紫外線吸收劑有對甲氧基桂皮酸_2-乙 基己基酯。極大吸收波長在31 Onm附近，吸收區域不及於 UV-A區域。且因曰光會發生變質而於著色性、紫外線防紫 效果持續性方面有問題。 (3) 之二苯基酮衍生物方面，例如2-經基-4 -甲氧基二笨 基酮橫跨UV-A、UV-B區域皆有吸收，對皮膚外用劑基劑 之溶解性亦較為良好，但極大吸收波長約靠近UV-B區域， 吸光度也不太大。且近年來被質疑其基本骨格之構造物（二 笨基酿I)為環境荷爾蒙而對於其之使用敬而遠之。 (4) 之二苯甲醯基曱烷衍生物方面，於皮膚外用劑中常 使用4-第三丁基-4，-曱氧基二苯曱醯基曱烷。極大吸收在 360nm附近，吸光度亦大，而作為UV A區域之紫外線吸收 劑為相當優異。然而，在光安定性方面有問題，且對皮膚 外用劑用之油分之相溶性差，僅能少量混合。 (5) 之水陽酸衍生物方面，係使用有水陽酸辛酯。於 UV-B區域具有極大吸收波長，為油狀，雖然對石蠟油等之 相溶性優異但因為吸光度低，故並未實用化。 因此，在UV-B區域方面，大多使用（2)之對曱氧基桂 皮酸-2-乙基己酯，關於UV_A區域則大多使用⑷之仁第三 丁基-4’-甲氧基二苯甲醯基甲烧。尤其近年來對於uv_A區 域之紫外線吸收的要求提高了。 另一方面，紫外線吸收劑之中有具有黏腻性者，而當 4 201110990 ，合於重視使用感之防曬化妝料中時，有時成為極大的問 題。亦即，為了發揮較高之紫外線吸收效果，而大量配合 紫外線吸收劑時，其之使用感會極度地惡化。因此，有時 會無法以所希望之配合量來配合所要之紫外線吸收劑。 又，—般從確保廣範圍吸收區域之觀點來看，係於防 曬化妝料中配合複數種紫外線吸收劑。 然而，配合紫外線吸收劑之防曬化妝料的情況時，其 使用感有時會降低。而優異之使用感乃對化妝料強烈要求 之重要要素，故即使為了要確保廣範圍的吸收區域，通常 仍不會配合複數種尤其是三種或四種以上不同的紫外線吸 收劑。 另一方面，配合於化妝料中作為紫外線吸收劑之二苯 曱酸基曱燒衍生物會因暴露於光造成在紫外線照射下之w 吸收能降低。為了確保抑制此現象之光安定性，係開發有 一種併用苯曱醯基曱烷衍生物與其他紫外線吸收劑即α _氰 基-/5 ,占_二苯基丙稀酸酯之技術（專利文獻1) ^ 又，併用有紫外線吸收劑之三嗪衍生物與二苯甲 醯基甲烷衍生物之化妝料中，若存在有4_第三丁基_'4，_甲氧 基二苯甲S基甲&，則、經紫外線照射嗓衍生物會嚴 重地發生化學性劣化。因此’為了確保三嗪衍生物與 二苯甲醯基甲烷衍生物之光安定性，係開發有一種併用α_ 氰基-/3，/3 -二笨基丙烯酸酯之技術（專利文獻2)。 然而，藉由併用複數種紫外線吸收劑來確保紫外線吸 收劑本身之光安定性之技術方面仍有問題。其原因在於固 201110990 體形態之紫外線吸收劑大部分與化妝料基材即油分之相溶 性低而難溶’故為了安定地將其配合於化妝料中，則必須 大量配合相溶性優異之特定油分。而若大量配合此種特定 油分，則會成為招致化妝料安定性（尤其是水中油型乳化化 妝料之乳化安定性）降低或使用感降低之要因。 如上所述’紫外線吸收劑之併用乃招致化妝料安定性 降低與使用感降低之要因，故通常於防曬化妝料中不會配 合複數種（尤其是四種以上之）不同的紫外線吸收劑。 又於水中油型乳化組成物中配合有四種以上紫外線 吸收劑的情況時，對於其乳化安定性（尤其是低温時對紫外 線吸收劑之溶解安定性）之探討報告少。 專利文獻1 :日本專利第2975682號公報 專利文獻2 :日本專利第3714632號公報 【發明内容】 為了獲得較高之對於UV-A區域及UV_B區域之紫外線 防紫能，必須平衡良好地配合紫外線吸收劑之U V _ A吸收劑 與UV-B吸收劑。 然而，一般之UV-A吸收劑大多為難溶性，故為了將其 溶解必須配合大量的高極性油分，而難以獲得安定之水中 油型乳化組成物之基劑。 又，當欲製造配合有四種以上紫外線吸收劑之水中油 型乳化組成物即防釀化妝料時’其問題點在於乳化安定性 或其之使用感會降低。 本發明人有寥於上述觀點’針對具有優異紫外線吸收 6 201110990 效果且乳化安定性與使用感皆優異之防曝化妝料進行努力 研究之結果’發現若組合配合高達四種特定之紫外線吸收 劑與特疋化妝料成分’則可提供一種發揮優異紫外線防禦 效果且乳化安定性與使用感優異之水中油型乳化組成物及 防曬化妝料，而完成了本發明。 本發明之目的係提供一種具有優異紫外線吸收效果且 乳化女疋性與使用感優異之水中油型乳化組成物及防曬化 妝料。 亦即，本發明係提供一種水中油型乳化組成物，其特 徵在於含有以下（a)〜⑴。 (a) 奥克立林 (b) 雙乙基己氧基苯酚甲氧基苯基三嗪 (c) 一乙基胺基羥基笨甲醯基苯甲酸己酯 (d) 4-第三丁基-4，-甲氧基二苯甲醯基甲烷 (e) 水溶性局分子 (f) 水膨潤性黏土礦物 (g) IOB為0_〇5以上之油分 (h) 高級脂肪酸 (i) 界面活性劑 ⑴水 又，本發明係提供一種吐述之水中油型乳化組成物， 其中’上述⑴水膨潤性黏土礦物之含量為相對於水中油型 乳化組成物總量為〇. 0 1〜4質量％。 進而，本發明係提供一種上述之水中油型乳化組成 7 201110990 物’其中’上述（g)I〇B為〇 〇5 ^上之油分在油相中所佔之 比例為20〜75質量〇/0。 又’本發明係提供—箱 種上述之水中油型乳化組成物， 其中’上述（e)水溶性高分子為多糖類。 物 中 嗪 進而’本發明係提供一種上述之水中油型乳化組成 其中’上述⑷咖為以上之油分為醋油。201110990 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to an oil-in-water emulsion composition. More specifically, it relates to an oily emulsified composition containing a specific ultraviolet absorber and a polar oil. The oil-in-water emulsion composition of the present invention can be preferably used as a sunscreen cosmetic. [Prior Art] The important ultraviolet absorption wavelength regions of the sunscreen cosmetic are the UV_A region (320 to 400 nm) and the UV-B region (290 to 320 nm). It is generally believed that ultraviolet rays in the UV-A region (320 to 400 nm) cause skin blackening, but do not cause sunburn as in the UV-B region (290 to 320 nm), which promotes skin aging. However, in recent years, it has been gradually understood that the ultraviolet rays in the UV_B region will only reach the surface portion of the skin. In contrast, the ultraviolet rays in the UV-A region will reach the depth of the skin, not only the skin aging, but also To induce skin cancer. The ultraviolet absorber for cosmetics used so far is classified according to its structure, and is (1) a benzoic acid derivative, (2) a methoxycinnamic acid derivative, (3) a diphenyl ketone derivative, (4). a benzoic acid f alkane derivative, (5) a salicylic acid derivative or the like. In recent years, the ultraviolet absorbers of (2) and (4) have been used in many cases. However, the ultraviolet absorbers exemplified above have practical problems in terms of "s, for example, (1) of the present formic acid derivative, for example, Di-f-amino-aminobenzoic acid 2-ethylhexyl ester is liquid and transparent, and although it has an advantage of ease of use, the use of such derivatives has safety concerns and has not been used in recent years. And the maximum absorption wavelength is around 290nm, and only absorbs the ultraviolet rays of the UV_B region 201110990. (2) For the cinnamic acid bamboo organism, the most commonly used ultraviolet absorber in the commercially available sun care cosmetics is p-methoxycinnamate 2-ethylhexyl ester. The maximum absorption wavelength is around 31 Onm, and the absorption area is not as good as the UV-A area. Furthermore, there is a problem in the persistence of coloring property and ultraviolet anti-purple effect due to deterioration of the twilight. (3) In terms of the diphenyl ketone derivative, for example, 2-transyl-4-methoxybisphenyl ketone is absorbed across the UV-A and UV-B regions, and is soluble in the external base of the skin. It is also relatively good, but the absorption wavelength is close to the UV-B region, and the absorbance is not too large. In recent years, it has been questioned that its basic skeleton structure (two stupid base I) is an environmental hormone and its use is far removed. (4) In terms of the benzoyl decane derivative, 4-tert-butyl-4,-decyloxydiphenylfluorenyl decane is often used in the external preparation for skin. The maximum absorption is around 360 nm, and the absorbance is also large, and the ultraviolet absorber as the UV A region is quite excellent. However, there is a problem in light stability, and the compatibility with the oil for the external preparation for skin is poor, and only a small amount can be mixed. (5) In terms of the salicylic acid derivative, octyl salicylate is used. It has an extremely high absorption wavelength in the UV-B region and is oily. Although it is excellent in compatibility with paraffin oil or the like, it is not practical because it has low absorbance. Therefore, in the UV-B region, (2) p-methoxy cinnamic acid 2-ethylhexyl ester is mostly used, and in the UV_A region, (4) is preferably used as the third butyl-4'-methoxy group. Benzopyrene is burnt. In particular, the demand for ultraviolet absorption in the uv_A region has increased in recent years. On the other hand, among the ultraviolet absorbers, there is a problem of stickiness, and when 4 201110990 is used in a sunscreen cosmetic which emphasizes the use of the feeling, it sometimes becomes a great problem. In other words, in order to exert a high ultraviolet absorbing effect and a large amount of the ultraviolet absorbing agent is blended, the feeling of use thereof is extremely deteriorated. Therefore, sometimes it is impossible to match the desired ultraviolet absorber with the desired amount. Further, in view of ensuring a wide range of absorption regions, a plurality of ultraviolet absorbers are blended in the sunscreen cosmetic. However, in the case of a sunscreen cosmetic containing a UV absorber, the feeling of use may be lowered. Excellent use is an important factor in the strong demand for cosmetics, so even in order to ensure a wide range of absorption areas, it is usually not suitable for a plurality of types, especially three or more different types of ultraviolet absorbers. On the other hand, the diphenyl phthalate-based smoldering derivative which is incorporated as an ultraviolet absorbing agent in a cosmetic material has a decrease in w absorption energy under ultraviolet irradiation due to exposure to light. In order to ensure the light stability of this phenomenon, a technique of combining a phenyl decyl decane derivative with other ultraviolet absorbers, α _ cyano-/5 , _ diphenyl acrylate, has been developed (patent 1) ^ In addition, in the cosmetic material containing a triazine derivative of ultraviolet absorber and a benzhydrylmethane derivative, if there is 4_t-butyl- 4,-methoxybenzophenone S-based &, the ultraviolet-irradiated hydrazine derivative will seriously deteriorate chemically. Therefore, in order to secure the photostability of the triazine derivative and the benzhydrylmethane derivative, a technique of using α-cyano-/3,/3-diphenyl acrylate in combination has been developed (Patent Document 2). However, there are still problems in the technical aspect of ensuring the light stability of the ultraviolet absorber itself by using a plurality of ultraviolet absorbers in combination. The reason is that most of the ultraviolet absorbers in the form of solid 201110990 have low compatibility with the base material of the cosmetic material, that is, it is difficult to dissolve. Therefore, in order to stably mix it into the cosmetic, it is necessary to mix a large amount of the specific oil having excellent compatibility. . On the other hand, if a large amount of such a specific oil component is blended, it will be a cause of a decrease in the stability of the cosmetic material (especially, the emulsification stability of the oily emulsified cosmetic material) or a decrease in the feeling of use. As described above, the combination of the ultraviolet absorbing agents causes a decrease in the stability of the cosmetic material and a decrease in the feeling of use. Therefore, a plurality of (particularly four or more) different ultraviolet absorbing agents are usually not contained in the sunscreen cosmetic. Further, when four or more kinds of ultraviolet absorbers are blended in the oil-type emulsified composition in water, there are few reports on the emulsion stability (especially the solubility stability of the ultraviolet absorber at low temperatures). Patent Document 1: Japanese Patent No. 2975682 Patent Document 2: Japanese Patent No. 3714632 [Summary of the Invention] In order to obtain a high ultraviolet anti-violet energy for the UV-A region and the UV_B region, it is necessary to balance the ultraviolet absorption well. UV _ A absorbent and UV-B absorbent. However, most of the general UV-A absorbents are poorly soluble, so that it is necessary to mix a large amount of highly polar oil in order to dissolve them, and it is difficult to obtain a base of an oily emulsified composition in a stable water. Further, when it is desired to produce an oil-in-water emulsion composition containing four or more types of ultraviolet absorbers, that is, an anti-stuffing cosmetic material, the problem is that the emulsion stability or the feeling of use thereof is lowered. The inventors of the present invention have made an effort to study the results of an effort to study an anti-exposure cosmetic having excellent ultraviolet absorption 6 201110990 effect and excellent emulsion stability and use feeling, and found that if a combination of up to four specific ultraviolet absorbers is combined with The present invention has been completed by providing an oil-in-water emulsion composition and a sunscreen cosmetic which exhibit excellent ultraviolet protection effects and excellent emulsion stability and use feeling. SUMMARY OF THE INVENTION An object of the present invention is to provide an oil-in-water emulsified composition and a sunscreen cosmetic which have excellent ultraviolet absorbing effects and are excellent in emulsification and sensation. That is, the present invention provides an oil-in-water emulsion composition characterized by containing the following (a) to (1). (a) octocrylene (b) bisethylhexyloxyphenol methoxyphenyl triazine (c) monoethylamino hydroxy benzoyl benzoic acid hexyl ester (d) 4-tert-butyl -4,-methoxydibenylmethane methane (e) Water-soluble host molecule (f) Water-swellable clay mineral (g) Oil with IOB of 0_〇5 or more (h) Higher fatty acid (i) Interfacial activity (1) Water In addition, the present invention provides a water-in-oil type emulsified composition, wherein the content of the above (1) water-swellable clay mineral is 〇. 0 1~4 by mass relative to the oil-type emulsified composition in water. %. Further, the present invention provides the above-mentioned oil-in-water emulsified composition 7 201110990, wherein the ratio of the oil component in the above (g) I 〇 B is 〇〇 5 ^ in the oil phase is 20 to 75 mass 〇 / 0. Further, the present invention provides a tank oil type emulsified composition according to the above, wherein the (e) water-soluble polymer is a polysaccharide. The present invention provides a water-in-oil type emulsified composition as described above. wherein the above (4) coffee is a vinegar oil.
又本發明係提供一稽卜；+，+ U 檀上边之水中油型乳化組成物，其 上述（a)奥克立林、（b)譬pr奠p备 、J雙乙基己氧基苯酚甲氧基苯基三 ⑷二乙基胺基經基苯甲醜基苯甲酸己_、⑷4_第三丁 基_4，_甲氧基二苯甲醯基甲烷之合計含量相對於水中油型 乳化組成物總量為1 〇〜2 5質量0/〇。 進而本發明係提供一種防曬化妝料，其係由上述之水 中油型乳化組成物所構成。 本發明可提供-種水中油型乳化組成物，其係具有優 異之紫外線吸收效果，且乳化安定性與使用感優異。 【實施方式】 以下詳述本發明。 「紫外線吸收劑」 本發明所配合之四種紫外線吸收劑為（a)奥克立林 (〇ct〇cryiene)、（b)雙乙基己氧基苯酚甲氧基苯基三嗪、（c) 二乙基胺基羥基苯曱醯基笨曱酸己酯、（幻4_第三丁基_4，_ 甲氧基二苯甲醯基曱烷（第三丁基曱氧基二苯甲醯基曱 烷）。皆為習知之紫外線吸收劑。 (a)奥克立林（2-乙基己基2_氰基_3,3二苯基丙烯酸 201110990 醋），市售有例如「Pars〇1340」（DSM Nutritional Products)。 (b) 雙乙基己氧基本紛甲乳基苯基三唤，市售有例如 「TINOSORB S」（Ciba Specialty Chemicals)。 (c) 二乙基胺基羥基苯曱醯基苯曱酸己酯，市售有例如 「UvinulA plus granular」（BASF JAPAN)。 (d) 4-第三丁基_4’_曱氧基二苯甲醯基曱烷市售有例如 「Parsol 1789」（DSM Nutritional Products)。 上述四種之紫外線吸收劑的各配合量可依製品不同而 適當決定。所配合之四種的合計量相對於水中油型乳化組 成物總量通常為iMO質量％，較佳為5〜30質量％，更佳為 10〜25質量％。其之合計量若未滿1質量％，則無法發揮充 刀之务、外線吸收效果，又，若超過40質量％，則會產生霉占 腻性。 「水溶性高分子」 本發明中所用之（e)水溶性高分子可舉出例如：多糖類 之二仙膠、印尼卡拉膠、果膠、聚甘露糖、卡特蘭多醣、 硫酸軟骨素、澱粉、半乳聚糖、硫酸皮膚素（dermatan sulfate)、 肝糖、***膠、硫酸肝素（heparan sulfate)、透明質酸、 透明質酸鈉、黄蓍膠（Tragant gum)、硫酸角質素（keratan sulfate)、軟骨素、硫酸黏液素、羥基乙基瓜爾豆膠、羥基 曱基瓜爾豆膠、瓜爾豆膠、刺槐豆膠（car〇b gum)、聚葡萄 糖、硫酸角質素（keratosulfate)、刺槐豆膠、玻ί白酿聚糖、 卡洛寧酸、幾丁質、幾丁聚糖、羥基甲基幾丁質、榲棹（quince) 子、殿粉（米、玉蜀黍、馬鈴薯、小麥）、甘草酸（glycyrrhizin)、 201110990 葡聚糖 '及洋菜等。 纖維素糸南分子可舉出 甲基經基丙基纖維素、經基 經基丙基纖維素、經基甲基 結晶纖維素、纖維素末等。 •甲基纖維素、乙基纖維素、 乙基纖維素、纖維素硫酸鈉、 纖維素、羥基甲基纖維素鈉、 乙嫦基系高分子可舉出聚乙婦醇、聚乙婦基甲基驗、 聚乙烯基吡咯烷酮、羥基乙烯基聚合物等。 丙稀酸系高分子可舉出聚丙烯酸酸鈉、聚丙稀酸乙 酯、聚丙烯醯胺等。 曰水溶性高分子之配合量相對於水中油型乳化組成物總 罝通常為0.01〜5質量％ ,較佳為〇川〜丨質量％，更佳為 0.1〜0.5質量配合量若未滿〇〇1質量％，則組成物之乳 化安定性會變差，又，若超過5質量％則使用感黏腻。 「水膨潤性黏土礦物」 本發明中所用之（f)水膨潤性黏土礦物為屬於膨潤石屬 之層狀妙Sic鹽礦物’ 一般而言有蒙脫石（montmorillonite)、 铭膨潤石（beidellite)、鐵膨潤石（nontronite)、鎮膨潤石 (saponite)、鐘膨潤石（hectorite)、皂土（bentonite)等。該等 可為天然或合成物。市售品有庫尼皮亞、思美庫通（音譯， 皆為kunimine工業公司製）、LAPONITE(laporte公司製）、 合成鈉型氟金雲母（撒卜雲母E:大東化成者製比佳姆、 烏魯托拉、古拉组盧思（音譯，BinderBuilt公司製）等。其中 尤佳為庫尼皮亞、思美庫通。 水膨潤性黏土礦物之配合量相對於水中油型乳化組成 10 201110990 物總里，通常為0.0 1〜4質量％，較佳為0.01〜2質量。/〇，更 佳為O’OIM質量％β配合量若未滿G G1 f量％，則組成物 之乳化安定性會變差，又，若超過4質量❶/◦,則皮膚上之塗 抹性會變差。 「IOB為0.05以上之油分」 本發明中所用之油分為I〇B為〇 05以上之極性油，較 佳為IOB為〇.05〜〇·8之酯油。具體可舉出例如：異壬酸異 壬S曰、肉豆蔻酸異丙酯、；2_乙基己酸十六院酯、肉莖蔻酸辛 基十一烧酯、棕櫊酸異丙酯、硬脂酸丁酯、月桂酸己醋、 肉莖蔻酸肉莖蔻酯、油酸癸酯、二曱基辛酸己基癸酯、乳 酸十六烷酯、乳酸肉笪蔻基、乙酸羊毛脂、硬脂酸異十六 烧酯、異硬脂酸異十六烷酯、12_羥基硬脂酸膽固醇酯、二 -2-乙基己酸乙二醇酯、二新戊四醇脂肪酸酯、單異硬脂酸 Ν -院基一醇醋、二癸酸新戊二醇自旨、頻果酸二異硬脂g旨、 二-2-庚基十一烷酸甘油酯、三_2_乙基己酸三羥甲基丙烷 酯、三異硬脂酸三經甲基丙烧酯、四_ 2 -乙基己酸新戊四醇 酯、三-2-乙基己酸甘油酯、三異硬脂酸三羥甲基丙烷酯、 2-乙基己酸十六烧酯、棕撋酸2-乙基己酯、萘二叛酸二乙 基己酯、苯甲酸（碳數12-1 5)烧基酯、絲堪硬脂醇異壬酸酯 (cetearyl isononanoate)、三（辛酸或癸酸）甘油醋 ' (二辛酸/ 癸酸）丁二醇酯、三肉菫蔻酸甘油酯、三2·庚基十一酸甘油 醋、蓖麻油脂肪酸甲醋、油酸油酿、Cetostearic alcohol、 乙醯甘油酯、粽櫚酸2_庚基十一烷酯、己二酸二異丁酯、 N-月桂醯-L-谷氨酸-2-辛基十二烷酯、己二酸二2·庚基十一 201110990 烧醋 '乙基月桂酯、癸二酸二2-乙基己酯、肉莖缝酸2_己 基癸基、棕櫚酸2·己基癸酯、己二酸2_己基癸酯、癸二酸 二異丙酿、琥拍酸二2-乙基己酯、乙酸乙酯、乙酸丁醋、 乙酸戊酯、擰檬酸三乙酯、對曱氧基桂皮酸2_乙基己酯、 二新戊酸三丙二醇酯等，其中尤佳為異壬酸異壬酯、2_乙基 己酸甘油酯、2 -乙基己酸十六烧酯、癸二酸二異丙酯等。 其中所謂 ΙΟΒ 値係 lnorganic/〇rganic Balance(無機性/ 有機性比）的簡稱，表示無機性値對有機性値之比率之值， 表示有機化合物之極性程度之指標。I〇B値具體而言係表示 成「1〇3值=無機性値/有機性値」。此處，關於「無機性値」、 「有機性値」，例如分子中碳原+ i個時「有機性値」為 2〇,分子中經基i個時「無機性値」為i⑽，設定依據各種 原子或官能基H機性値，」、「有機性値」，藉由將有 機化合物中所有的原子及官能基#「無機性値」' 「有機 性値」加總起來，可算中兮女城！ 人u 斤出忒有拽化合物之IOB値（例如參照 1957年藤田所著之「化學 楚η坐 μ / ’、' 予域」第11卷、第號、第 719頁〜第725頁）。 IOB為〇.〇5以上夕沾八 Α β 乏油刀之配合量相對於水中油型乳化 組成物總量，通常為1〜7〇晳β ^ 為夏％，李又佳為3〜50質量〇/〇，更 佳為5〜30質量％。 又’ IOB為〇·〇5以卜♦ 上之油分於油相中所佔之比例較佳 t20〜75質量％。所謂油相係指包含本發明中所用之⑷〜⑷ 紫外線吸收劑、界面活性劑之油性成分。 （）⑷ 「高級脂肪酸」 12 201110990 本發明中，由水中油型乳化組成物之乳化安定性觀點 來看，進而配合（h)高級脂肪酸為佳。具體而言可舉出例如 月桂酸、肉1蔻酸、棕櫊酸、硬脂酸、二十二烷酸、油酸、 十一烷烯酸、妥爾油酸（tall 〇ii acid)、異硬脂酸、亞麻油酸、 次亞麻油酸等。其中尤佳為使用硬脂酸、二十二烷酸。高 級脂肪酸亦可於水中油型乳化組成物中形成高級脂肪酸肥 息0 本發明中，高級脂肪酸之配合量對於水中油型乳化組 成物總量’通常為0.1〜10質量％，較佳為〇.丨〜5質量％，更 佳為0.5〜2質量％。 「界面活性劑」 本發明中，為了製造水中油型乳化組成物，係配合有⑴ 界面活性劑。本發明中所用之界面活性劑可適當地決定， 但較佳係使用親油性非離子界面活性劑及/或親水性非離子 界面活性劑。以下例示本發明中可使用之界面活性劑。Further, the present invention provides a water-in-oil emulsified composition on the upper side of the +, + U sandalwood, wherein the above (a) octocrylene, (b) 譬pr, and bis-ethylhexyloxyphenol The total content of methoxyphenyl tris(4)diethylamino group via benzyl benzoylbenzoic acid hexyl, (4) 4 - tert-butyl-4, methoxy benzophenhydryl methane relative to the oil type in water The total amount of the emulsified composition is 1 〇~2 5 mass 0/〇. Further, the present invention provides a sunscreen cosmetic comprising the above oily emulsified composition. The present invention can provide an oil-in-water emulsion composition which has an excellent ultraviolet absorbing effect and is excellent in emulsion stability and use feeling. [Embodiment] The present invention will be described in detail below. "Ultraviolet absorber" The four types of ultraviolet absorbers to be used in the present invention are (a) octocrylene (b) bisctyl phenyl phenyl triazine, (c) bisethylhexyloxyphenol methoxy phenyl triazine, (c) Diethylamino hydroxyphenyl decyl hexanoate, (Phantom 4 - Ternyl -4-, methoxy benzoyl decyl decane (t-butyl decyloxy diphenyl) All are known as UV absorbers. (a) Okrinin (2-ethylhexyl 2 - cyano-3,3 diphenyl acrylate 201110990 vinegar), commercially available, for example, "Pars〇 1340" (DSM Nutritional Products) (b) Diethylhexyloxy sulfonyl phenyl sulfonate, commercially available, for example, "TINOSORB S" (Ciba Specialty Chemicals). (c) Diethylamino hydroxybenzene Mercaptobenzoic acid hexyl ester is commercially available, for example, as "Uvinul A plus granular" (BASF JAPAN). (d) 4-Terbutyl-4-4'-decyloxybenzophenanthrane is commercially available, for example. "Parsol 1789" (DSM Nutritional Products) The amount of each of the above four types of UV absorbers can be appropriately determined depending on the product. The total amount of the four types of blending is relative to the oil type in water. The total amount of the emulsified composition is usually iMO% by mass, preferably 5 to 30% by mass, more preferably 10 to 25% by mass. If the total amount is less than 1% by mass, the filling process and the external absorption are not exhibited. When the amount is more than 40% by mass, moldy greasyness is generated. "Water-soluble polymer" (e) The water-soluble polymer used in the present invention may, for example, be a polysaccharide of dimentin or an Indonesian caramel. Gum, pectin, polymannose, carterin, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, transparent Sodium sulphate, tragant gum, keratan sulfate, chondroitin, sulphate sulfate, hydroxyethyl guar gum, hydroxy guar guar gum, guar gum, locust bean Car〇b gum, polydextrose, keratosulfate, locust bean gum, botanic glycan, carlinic acid, chitin, chitosan, hydroxymethyl chitin, Quin (quince) child, temple powder (rice, jade, horse bell , wheat), glycyrrhizic acid (glycyrrhizin), 201110990 dextran' and amaranth, etc. Cellulose 糸南 molecules can be exemplified by methyl propyl cellulose, propyl propyl cellulose, transmethyl Crystalline cellulose, cellulose powder, etc. • Methyl cellulose, ethyl cellulose, ethyl cellulose, sodium cellulose sulfate, cellulose, sodium hydroxymethyl cellulose, and ethylene-based polymer Ethyl alcohol, polyethylidene methylation, polyvinylpyrrolidone, hydroxyvinyl polymer, and the like. Examples of the acrylic acid polymer include sodium polyacrylate, ethyl acrylate, and polypropylene decylamine. The blending amount of the water-soluble polymer is usually 0.01 to 5% by mass based on the total mass of the oil-based emulsified composition in water, preferably 〇川~丨% by mass, more preferably 0.1 to 0.5 by mass. When the amount is 1% by mass, the emulsification stability of the composition is deteriorated, and if it exceeds 5% by mass, the feeling is sticky. "Water-swellable clay mineral" (f) The water-swellable clay mineral used in the present invention is a layered Sic salt mineral belonging to the genus Banyanite. Generally, there are montmorillonite and beendelite. , nontronite, saponite, hectorite, bentonite, etc. These may be natural or synthetic. Commercially available products are Cunipia, Simi Coton (transliteration, all made by Kunimine Industries), LAPONITE (made by Laporte), and synthetic sodium-type fluorophlogopite (Sab Mica E: Dadonghuacheng Bibi , Ulutola, Gula group Lusi (transliteration, BinderBuilt company), etc. Among them, especially for Cunipia, Sime Chongtong. The amount of water-swelling clay minerals relative to the oil-type emulsified composition in water 10 In the total amount of 201110990, it is usually 0.01 to 4 mass%, preferably 0.01 to 2 mass. /〇, more preferably O'OIM mass%β, if less than G G1 f, the emulsification of the composition The stability will be deteriorated, and if it exceeds 4 mass ❶/◦, the spreadability on the skin will be deteriorated. "IOB is 0.05 or more oil." The oil used in the present invention is classified into I 〇 B which is a polarity of 〇 05 or more. The oil, preferably IOB, is an ester oil of 〇.05~〇·8. Specific examples thereof include isoindole isoindole S, isopropyl myristate, and 2-hexylhexanoate , meat stem octyl eleven-burning ester, isopropyl palmitate, butyl stearate, lauric acid vinegar, meat stem citrate Oxalic acid oleate, hexyl decyl octyl octanoate, cetyl lactate, decyl lactic acid, lanolin acetate, isohexadecyl stearate, isohexadecyl isostearate, 12-hydroxyl hard Cholesterol fatty acid ester, ethylene glycol di-2-ethylhexanoate, fatty acid ester of dipentaerythritol, bismuth monoisostearate-homo-alcoholic acid, neopentyl glycol dipentoxide Di-isostearate, di-2-heptyl undecanoic acid glyceride, tris-ethylhexanoic acid trimethylolpropane ester, triisostearic acid trimethyl methacrylate , tetra-2-ethylhexanoic acid pentaerythritol ester, tris-2-ethylhexanoic acid glyceride, trimethylolpropane triisostearate, hexadecyl 2-ethylhexanoate, brown 2-ethylhexyl phthalate, diethylhexyl naphthalene dicarboxylate, benzoic acid (carbon number 12-1 5) alkyl ester, cetoaryl isononanoate, tris(octanoic acid) Or citric acid) glycerol vinegar ' (dioctanoic acid / citric acid) butylene glycol ester, tri-glyceric acid glyceride, tri- 2 · heptyl undecanoic acid glycerin, castor oil fatty acid methyl vinegar, oleic acid oil, Cetostearic Alcohol, acetamidine, palmitic acid 2_heptyl ten Alkyl ester, diisobutyl adipate, N-laurel-L-glutamic acid-2-octyldodecyl ester, adipic acid di 2·heptyl eleven 201110990 vinegar 'ethyl lauryl ester, Di-2-ethylhexyl sebacate, 2_hexyldecyl chondronate, 2·hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl azelaic acid, sodium succinate 2-ethylhexyl ester, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, 2-ethylhexyl decyl cinnamate, tripropylene glycol dipivalate, etc. Preferably, isodecyl isononanoate, 2-ethylhexanoic acid glyceride, hexadecyl 2-ethylhexanoate, diisopropyl sebacate and the like. The abbreviation of lnorganic/〇rganic Balance (inorganic/organic ratio) refers to the value of the ratio of inorganic cerium to organic cerium, and indicates the degree of polarity of the organic compound. Specifically, I 〇 B 表示 is expressed as "1 〇 3 value = inorganic 値 / organic 値". Here, regarding "inorganic enthalpy" and "organic enthalpy", for example, "organic enthalpy" is 2 碳 in the molecule, and "inorganic 値" is i (10) in the molecule. According to various atomic or functional groups H, "organic enthalpy", by adding all the atoms and functional groups #""inorganic 値" and "organic 値" in the organic compound, it can be counted as Female city! The human I 忒 IO IO 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値 値IOB is 〇. 〇5 上 沾 沾 Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α 乏 Α 乏 乏 乏 乏 乏 乏 乏 乏 乏 乏 乏 乏 乏 乏〇, more preferably 5 to 30% by mass. Further, the ratio of the oil in the IOB is 〇·〇5 to 卜 ♦ is preferably t20 to 75 mass%. The oil phase refers to an oil component containing the (4) to (4) ultraviolet absorber and the surfactant used in the present invention. (4) "Advanced fatty acid" 12 201110990 In the present invention, it is preferable to further (h) a higher fatty acid from the viewpoint of the emulsion stability of the oil-in-water emulsion composition. Specific examples thereof include lauric acid, meat monodecanoic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oleic acid, and different Stearic acid, linoleic acid, sublinoleic acid, and the like. It is especially preferred to use stearic acid or behenic acid. The higher fatty acid may also form a higher fatty acid fertilizer in the oily emulsified composition of the water. In the present invention, the amount of the higher fatty acid is generally 0.1 to 10% by mass, preferably 〇.丨 5% by mass, more preferably 0.5 to 2% by mass. "Interfacial Active Agent" In the present invention, in order to produce an oily emulsified composition in water, (1) a surfactant is blended. The surfactant used in the present invention can be appropriately determined, but it is preferred to use a lipophilic nonionic surfactant and/or a hydrophilic nonionic surfactant. The surfactant which can be used in the present invention is exemplified below.
親水性非離子性界面活性劑可舉出例如：p〇E烷基醚、 POE烷基苯醚、poe · POP烷基醚、p〇E脂肪酸g旨、p〇E 去水山梨醇脂肪酸酯、POE甘油脂肪酸酯、p〇E蓖麻油或 硬化蓖麻油衍生物、POE蜜蠟·羊毛脂衍生物、烷基醇醯 胺、POE丙二醇脂肪酸酯、:p〇E烷基胺、p〇E脂肪酸醯胺、 蔗糖脂肪酸酯、聚醚變性聚矽氧等。該等可單獨使用一種 或組合二種以上使用。 其中，「POE」表示聚氧乙烯、r P〇p」表示聚氧丙烯， 有時會記載成以下形式。Examples of the hydrophilic nonionic surfactant include p〇E alkyl ether, POE alkyl phenyl ether, poe POP alkyl ether, p〇E fatty acid g, p〇E sorbitan fatty acid ester. , POE glycerol fatty acid ester, p〇E castor oil or hardened castor oil derivative, POE beeswax lanolin derivative, alkyl decylamine, POE propylene glycol fatty acid ester, : p〇E alkylamine, p〇 E fatty acid decylamine, sucrose fatty acid ester, polyether modified polyoxo, and the like. These may be used alone or in combination of two or more. Here, "POE" means polyoxyethylene and r P〇p" means polyoxypropylene, and may be described in the following form.
13 201110990 上述親水性非離子性界面活性劑之中，尤佳為HIB 8以 上之環氧乙烷加成型非離子性界面活性劑，可舉出例如 POE(10〜50 |耳）植物固醇_、p〇E(1G〜5G莫耳）二氫化膽固 醇越、P0E(1G〜5G莫耳）2_辛基十二;^基鱗、p〇E(1()〜5G莫耳） 癸基十四烷基醚、POE(1〇〜5〇莫耳）油醚、ρ〇Ε(ι〇〜5〇莫耳） 十六烷基醚、P〇E(5〜30莫耳）P0P(5〜3〇莫耳）2癸基十四烷 基趟、P〇E(1〇〜50莫耳）p〇p(2〜3〇莫耳）十六烷基醚、 POE(20〜60莫耳）去水山梨醇單油酸酯、ρ〇Ε(ι〇〜6〇莫耳）去 水山梨醇單異硬脂酸酯、p〇e〇〇〜8〇莫耳）甘油單異硬脂酸 酯、POE(10〜30莫耳）甘油單硬脂酸酯、ρ〇Ε(2〇〜ι〇〇)硬化 麻油衍生物等 親油性非離子界面活性劑可舉出例如：去水山梨醇單 油酸醋、去水山梨醇倍半油酸醋、去水山梨醇三油酸醋' 去水山梨醇單異硬脂酸醋、去水山梨醇倍半異硬脂酸酯； 甘油單油酸醋、甘油單異硬脂酸醋、甘油二異硬脂酸自旨、 甘油單芥酸二甘油單油酸酯、二甘油二油酸酯、二甘油單 異硬脂酸醋、二甘油二異硬脂酸酯、十甘油五油酸酯、十 甘油五異硬脂酸酯、十甘油十油酸酯、十甘油十異硬脂酸 酯、蔗糠單油酸酯、P〇E(2莫耳）單油酸酯、p〇E(6莫耳）二 異硬脂酸酯、P〇E(3〜10莫耳）蓖麻油衍生物等。、— 界面活性劑之配合量可適當地決定，相對於水中油型 乳化組成物總量，通常為ο·ι〜10質量％，較佳為〇 ι〜5質量 %，更佳為〇·5~3質量％。 里 201110990 旦發明中，⑴水的配含相對於水中油型乳化組成物總 里較佳為5G〜9G質量％。於水中，⑷水溶性高分子、⑴水 膨潤性黏土礦物等水性成分會而形成水相。 本發明之水中油裂乳化組成物中除了上述必須成分以 外二亦可孝見需要適當配合通常於化妝料所使用《成分並以 通二方法來製造’該通常於化妝料所使用之成分例如粉 士成：、液體油脂、固體油脂、I、烴油、高級脂肪酸、 冋級醇聚矽氧油、陰離子界面活性劑、陽離子界面活性 劑、兩性界面活性劑、保濕劑、增黏劑、被膜劑、金屬離 子螯合劑、低級醇' 多元醇、糖、胺基酸、有機胺、高分 子礼化液、pH調整劑、皮膚營養劑、維他命、抗氧化劑、 抗乳化助劑、香料等。 本發明之水中油型乳化組成物可較佳地利用作為防曬 化妝料。車乂佳4 w/〇乳液之防曬霜、防曬乳化液、防曬化 妝水等之製品。 實施例 以下藉由實施例更具體說明本發明。13 201110990 Among the above hydrophilic nonionic surfactants, an ethylene oxide addition nonionic surfactant having a HIB of 8 or more is preferable, and for example, POE (10 to 50 | ear) phytosterol is exemplified. , p〇E (1G~5G molar) dihydrogenated cholesterol, P0E (1G~5G molar) 2_octyl 12; ^ base scale, p〇E (1 () ~ 5G molar) Tetraalkyl ether, POE (1〇~5〇莫耳) oil ether, ρ〇Ε(ι〇~5〇莫耳) cetyl ether, P〇E (5~30 mol) P0P (5~ 3 〇 Mo Er) 2 癸 十四 十四 趟 趟, P 〇 E (1 〇 ~ 50 Mo) p 〇 p (2 ~ 3 〇 Mo) cetyl ether, POE (20 ~ 60 Mo) Sorbitan monooleate, ρ〇Ε(ι〇~6〇莫耳) sorbitan monoisostearate, p〇e〇〇~8〇mole) glycerol monoisostearate Examples of the lipophilic nonionic surfactant such as POE (10 to 30 mol) glycerin monostearate, ρ〇Ε(2〇~ι〇〇) hardened sesame oil derivative, and the like, for example, sorbitan monooleate Sour vinegar, sorbitan sesquiole vinegar, sorbitan trioleate vinegar sorbitol monoisostearic acid vinegar, to the water mountain Alcohol sesquiisostearate; glycerol monooleate, glycerol monoisostearate, glyceryl diisostearate, glycerol monoerucic acid diglyceride monooleate, diglyceryl dioleate, Diglycerol monoisostearate, diglyceryl diisostearate, decaglyceryl pentaoleate, decaglyceryl pentaisostearate, decaglycerin decaoleate, decaglyceryl sesquiisolactate, Cane monooleate, P〇E (2 mol) monooleate, p〇E (6 mol) diisostearate, P〇E (3 to 10 mol) castor oil derivatives, etc. . The amount of the surfactant may be appropriately determined, and is usually ο·ι 10 mass%, preferably 〇ι 5 mass%, more preferably 〇·5, based on the total amount of the oil-type emulsified composition in the water. ~3 mass%. In the invention of 201110990, (1) the water content is preferably from 5 G to 9 G% by mass based on the oil-type emulsified composition in the water. In water, an aqueous component such as (4) a water-soluble polymer or (1) a water-swellable clay mineral forms an aqueous phase. In addition to the above-mentioned essential components, the oil-cracked emulsified composition of the present invention may be succinctly required to be appropriately blended with the "components used in cosmetics" and manufactured by the method of the second method. Shicheng:, liquid grease, solid oil, I, hydrocarbon oil, higher fatty acid, sulfonated alcohol polyoxygenated oil, anionic surfactant, cationic surfactant, amphoteric surfactant, moisturizer, tackifier, film , metal ion chelating agent, lower alcohol 'polyol, sugar, amino acid, organic amine, polymer liquefied liquid, pH adjuster, skin nutrient, vitamins, antioxidants, anti-emulsification additives, spices and so on. The oil-in-water emulsion composition of the present invention can be preferably used as a sunscreen cosmetic. Che Yujia 4 w/〇 lotion sunscreen lotion, sunscreen lotion, sunscreen makeup water and other products. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples.
本發明並不限定於該等實施例。實施例中之配合量酯 亦沒有特別定義即表示質量％。 S 、下表1」及「表2」之A(水相）與B(油相）分別加 熱至7〇 C Μ吏之完全溶解。於b中加人A，以乳化機進行 乳化並冷卻以製得水中油型乳化組成物（霜狀防曬化妝料）。 「乳化安定性」 經由將所得之組成物封入50ml之螺紋管（screw 15 201110990 tube) ’保存於5〇。〇4週伴在 巧保存之後之外觀來評價乳化安定性。 <評價：> 保持為一層之狀態時：〇 難以辨認時：x 3其結果’表1中可明瞭：僅配合有⑷水溶性高分子（三 骖）之比較例！及2發生分離，才目對於此，添加有少量之 ()黏土礦物（膨潤石’ smec出〇)之實施例1則 無損於使用感且安定性良好者。 于 攸表2可明瞭：僅配合有⑷水溶性高分子（三仙膠）之比 較例3係發生分離β再者入= 一 丹有配σ —仙膠作為一種之（e)水溶性 且進而配合琥珀醯聚糖（succin〇glycan)或卡波姆 (⑽瞻r)作為另一種之⑷水溶性高分子之比較例w則 、了刀離之外’亦損及使用感。相對於此’添加有⑴水膨 '【县土 bentonite)之貫施例2〜5則獲得安定性 子者此之中’實施例2〜3使用感亦良好。 「使用感」 <評價> 經由女性專門評審員1〇名實際於肌膚上塗 對塗佈的良好度（輕鬆度）以下述標準進行評價。… 〇：8名以上評價為塗佈輕鬆。 △ . 3〜7名評價為塗佈輕鬆。 X : 2名以下評價為塗佈輕鬆。 201110990 表1 比較例1 比較例2 實施例1 水相 CD離子交換水 剩餘量 剩餘量 剩餘量 一般醇95度合成 5.0 5.0 5,0 1,3-丁二醇 5.0 5.0 5.0 甘油 5.0 5.0 5.0 (e)三仙膠 0.1 0.3 0.1 (0思美庫通(kunimine工業公司製） — — 0.1 三乙醇胺 0.25 0.25 0.25 EDTA-3Na-H20 0.1 0.1 0.1 苯氧基乙醇 0.5 0.5 0.5 油相 (i)甘油單硬脂酸酯 1,5 1.5 1.5 (i)POE甘油異硬脂酸酯 1.5 1.5 1.5 (h)二十二烧酸 、 1 1 1 聚乙烯基吡咯烷嗣/二十烯共聚物 2.0 2.0 2.0 鲨肝醇(batyl alcohol) 0.5 0.5 0.5 二十二醇 1 1 1 (g)異壬酸異壬酯 10 10 10 (g)2-乙基己酸甘油酯 5 5 5 (a)奥克立林 10 10 10 (b)雙乙基己氧基笨酚曱氧基苯基三嗪 3 3 3 (C)二乙基胺基羥基苯甲醯基苯甲酸己酯 3 3 3 (d)4-第三丁基-4’-甲氧基二苯曱醯基曱烷 3 3 3 Dimethicodiethylbenzal malonate 5 5 5 香料 適量 適量 適量 合計 100 100 100 評價 乳化安定性 X X 〇 使用感 〇 〇 〇The invention is not limited to the embodiments. The compounding amount of the ester in the examples is also not specifically defined, i.e., represents % by mass. S, Table 1" and "Table 2" A (aqueous phase) and B (oil phase) are respectively heated to 7 〇 C 完全 and completely dissolved. Adding A to b, emulsification and cooling with an emulsifier to obtain an oily emulsified composition (creamy sunscreen cosmetic) in water. "Emulsifying stability" was carried out at 5 Torr by enclosing the obtained composition in a 50 ml screw tube (screw 15 201110990 tube). The emulsion stability was evaluated after 4 weeks of appearance after careful preservation. <Evaluation:> When the state is maintained as one layer: 〇 When it is difficult to recognize: The result of x 3 ' It is clear in Table 1 that only the comparative example of (4) water-soluble polymer (three oxime) is blended! In the case of the separation of 2 and 2, the addition of a small amount of () clay mineral (bentonite smec) to the first embodiment is not detrimental to the feeling of use and good stability. In Table 2, it can be understood that only Comparative Example 3 with (4) water-soluble polymer (Sanxianjiao) is separated and β is added. = Yidan is equipped with σ-xiancyl as one kind of (e) water-soluble and further In combination with amber sucrose (succin〇glycan) or carbomer ((10) ru), the comparative example of (4) water-soluble polymer w, and the knife is also damaged. In contrast to the examples 2 to 5 in which (1) water swelling [[soil bentonite] was added, the stability was obtained. The results of the examples 2 to 3 were also good. "Essence of use" <Evaluation> Applicable to the skin by a female expert reviewer 1 The evaluation of the goodness of the application (easyness) was evaluated by the following criteria. ... 〇: 8 or more evaluations are easy to apply. △ . 3 to 7 were evaluated as easy to apply. X: The following two evaluations are easy to apply. 201110990 Table 1 Comparative Example 1 Comparative Example 2 Example 1 Water phase CD ion exchange water Residual amount Remaining amount Remaining amount General alcohol 95 degree synthesis 5.0 5.0 5,0 1,3-butanediol 5.0 5.0 5.0 Glycerin 5.0 5.0 5.0 (e ) Sanxianjiao 0.1 0.3 0.1 (0 Simei Kutong (Kunimine Industrial Co., Ltd.) — 0.1 Triethanolamine 0.25 0.25 0.25 EDTA-3Na-H20 0.1 0.1 0.1 Phenoxyethanol 0.5 0.5 0.5 Oil phase (i) Glycerol single hard Fatty acid ester 1,5 1.5 1.5 (i) POE glyceryl isostearate 1.5 1.5 1.5 (h) Twenty two burned acid, 1 1 1 polyvinylpyrrolidinium / eicosene copolymer 2.0 2.0 2.0 Shark liver Batyl alcohol 0.5 0.5 0.5 eicosyl alcohol 1 1 1 (g) isodecyl isononanoate 10 10 10 (g) 2-ethylhexanoic acid glyceride 5 5 5 (a) octocrylene 10 10 10 (b) bisethylhexyloxyphenol phenoxy phenoxy phenyl triazine 3 3 3 (C) diethylamino hydroxy benzoyl benzoic acid hexyl ester 3 3 3 (d) 4-third butyl Base-4'-methoxydiphenyl decyl decane 3 3 3 Dimethicodiethylbenzal malonate 5 5 5 Proper amount of the right amount 100 100 100 Evaluation of emulsion stability XX 〇 Use sensation
17 201110990 表2 比較例3 比較例4 比較例5 實施例2 實施例3 實施例4 實施例5 水相 0)離子交換水 剩餘量 剩餘量 剩餘量 剩餘量 剩餘量 剩餘量 齣餘量 醇95度合成 5.0 5.0 5.0 5.0 5.0 5.0 5.0 1，3-丁二醇 5.0 5.0 5,0 5.0 5.0 5.0 5.0 甘油 5.0 5,0 5.0 5.0 5.0 5.0 5.0 (e)三仙膠 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (e)琥珀醯聚糖 — 0.3 — — — — — (e)卡波姆 — — 0.3 — — — — (❸皂土 — — — 0.1 0.5 1 2 三乙醇胺 0.25 0.25 0.45 0.25 0,25 0.25 0.25 EDTA-3Na-H20 0.1 0.1 0.1 0,1 0.1 0.1 0.1 苯氧基己醇 0.5 0.5 0.5 0.5 0.5 0.5 0.5 油相 ⑴甘油單硬脂酸酯 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (i)POE甘油異硬脂酸酯 1.5 1.5 1.5 1.5 1.5 Γ 1.5 1.5 (h)二十二烷酸 1 1 1 1 1 1 I 聚乙烯基吡咯烷酮/二十烯共聚物 2.0 2.0 2.0 2.0 2.0 2.0 2.0 鲨肝醇(batyl alcohol) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 二十二醇 1 1 1 1 1 1 1 (g)異壬酸異壬酯 10 10 10 10 10 10 10 (g)2-乙基己酸甘油酯 ’ 5 5 5 5 5 5 5 (a)奥克立林 5 5 5 5 5 5 5 (b)雙乙基己氧基苯酚甲氧基苯基三嗪 3 3 3 3 3 3 3 (C)二乙基胺基羥基苯甲醯基苯曱酸己酯 3 3 3 3 3 3 3 (d)4-第三丁基-4’-甲氧基二苯甲醯基曱烷 3 3 3 3 3 3 3 Dimethicodiethylbenzal malonate 3 3 3 3 3 3 3 _香料 適量 適量 適量 適量 適量 適量 適量 合計 100 100 100 100 100 100 100 評價 安定性 X X X 〇 〇 〇 〇 使用感 〇 X X 〇 〇 〇 Δ 「紫外線吸收效果」 將實施例1、2及比較例6的試樣50 // L以2mg/cm2之 比例均勻地塗佈於尼龍製之膜（5x5cm)，放置1 5分鐘後’以 分光光度計（U-41 〇〇 :日立製作所）測定吸光度。結果示於 圖。由圖1可明瞭實施例1及2之UV吸收能遠比比較例617 201110990 Table 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Example 2 Example 3 Example 4 Example 5 Water phase 0) Ion exchange water remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount of alcohol 95 degrees Synthesis 5.0 5.0 5.0 5.0 5.0 5.0 5.0 1,3-butanediol 5.0 5.0 5,0 5.0 5.0 5.0 5.0 Glycerin 5.0 5,0 5.0 5.0 5.0 5.0 5.0 (e) Sanxianjiao 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (e) Amber xylan — 0.3 — — — — — (e) Carbomer – 0.3 — — — — (❸❸土— — — 0.1 0.5 1 2 Triethanolamine 0.25 0.25 0.45 0.25 0,25 0.25 0.25 EDTA-3Na- H20 0.1 0.1 0.1 0,1 0.1 0.1 0.1 Phenoxyhexanol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Oil phase (1) Glycerol monostearate 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (i) POE glyceryl isostearate 1.5 1.5 1.5 1.5 1.5 Γ 1.5 1.5 (h) Behenic acid 1 1 1 1 1 1 I Polyvinylpyrrolidone / icosene copolymer 2.0 2.0 2.0 2.0 2.0 2.0 2.0 batyl alcohol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 icosdiol 1 1 1 1 1 1 1 (g) isodecyl isononanoate 10 10 10 10 10 10 10 10 (g) 2-ethylhexanoic acid glycerol ' 5 5 5 5 5 5 5 (a) octocrylene 5 5 5 5 5 5 5 (b) bisethylhexyloxyphenol methoxyphenyl triazine 3 3 3 3 3 3 3 (C) Ethylamino hydroxybenzimidyl benzoic acid hexyl ester 3 3 3 3 3 3 3 (d) 4-tert-butyl-4'-methoxydibenzofuranyl decane 3 3 3 3 3 3 3 Dimethicodiethylbenzal malonate 3 3 3 3 3 3 3 _Spices, right amount, right amount, right amount, right amount, right amount, total amount 100 100 100 100 100 100 100 100 Evaluation of stability XXX 〇〇〇〇 Sense of use XX 〇〇〇 Δ "UV absorption effect" will be implemented Samples 50, L, and L of Example 1, 2 and Comparative Example 6 were uniformly applied to a film made of nylon (5 x 5 cm) at a ratio of 2 mg/cm 2 and left for 15 minutes to 'by spectrophotometer (U-41 〇〇 : Hitachi, Ltd.) The absorbance was measured. The results are shown in the figure. It can be understood from Fig. 1 that the UV absorption energy of Examples 1 and 2 is much higher than that of Comparative Example 6.
優異。又’比較例之 SPE(Sun Protection Factor)為 34 ’ P A(Protection Grade of UVA)具有+++之功能，故實施例1及 2之防曬化妝料為spf3〇以上PA + + +以上，確認到具有較 高之SPF與PA功能。 18 201110990 其中，將比較例6之處方示於表3。比較例6係用以比 較紫外線吸收效果之基準處方，係具有SPF30、PA+ + +之優 異紫外線吸收機能之處方。 表3 比較例6 ①水 剩餘量 乙醇 7 甘油 2 卡波姆 0.3 (e)三仙膠 0.2 (i)聚氧乙烯硬化蓖麻油 1.5 (i)聚醚變性聚矽氧 1 十甲基環戊矽氧烷 12 異硬脂酸 1 (g)異壬酸異壬酯 2 氧化鈦 5 曱氧基桂皮酸辛酯 5 (a)奥克立林 2 (C)二乙基胺基羥基苯甲醯基苯曱酸己酯 0.5 EDTA-3Na 0.5 苯氧基乙醇 0.5 「紫外線吸收劑之溶解度」 分別調查（b)雙乙基己氧基苯酚曱氧基苯基三嗪、（c)二 乙基胺基羥基苯甲醯基苯曱酸己酯、（d)4-第三丁基-4’ -甲氧 基二苯甲醯基甲烷各1.5質量％於0°C之對各種油分的溶解 性。 其結果，IOB値為0之油分雖觀察到沉澱，但0.05以 上之值的油分則未觀察到沉澱。亦即，可瞭解到（b)〜(d)之 紫外線吸收劑對IOB値為0.05以上之油分的溶解性優異。 因此，本發明中，可獲得紫外線吸收劑不會析出且安定之 水中油型乳化組成物。Excellent. In addition, the SPE (Sun Protection Factor) of the comparative example has a function of +++ for 34' PA (Protection Grade of UVA), so the sunscreen cosmetics of Examples 1 and 2 are spf3〇 or more and PA + + + or more, and it is confirmed. Has a higher SPF and PA function. 18 201110990 Among them, the case of Comparative Example 6 is shown in Table 3. Comparative Example 6 is a standard prescription for comparing the ultraviolet absorbing effect, and has an excellent ultraviolet absorbing function of SPF 30 and PA + + +. Table 3 Comparative Example 6 1 Remaining amount of water Ethanol 7 Glycerol 2 Carbomer 0.3 (e) Sanxian Gum 0.2 (i) Polyoxyethylene hardened castor oil 1.5 (i) Polyether denatured polyoxyl 1 Tetramethylcyclopentanyl Oxane 12 isostearic acid 1 (g) isodecyl isononanoate 2 titanium oxide 5 octyl octyl cinnamate 5 (a) octocrylene 2 (C) diethylamino hydroxybenzimidylbenzene Hexyl decanoate 0.5 EDTA-3Na 0.5 phenoxyethanol 0.5 "Solubility of UV absorber" Separately investigated (b) bisethylhexyloxyphenol decyloxy phenyl triazine, (c) diethylamino hydroxy group The solubility of each of the oil fractions of 1.5% by mass of each of benzoyl benzoyl hexanoate and (d) 4-tert-butyl-4'-methoxydibenzopyrenemethane at 0 °C. As a result, although precipitation was observed in the oil fraction having an IOB 0 of 0, no precipitation was observed in the oil having a value of 0.05 or more. In other words, it is understood that the ultraviolet absorbers of (b) to (d) are excellent in solubility in oils having an IOB 0.05 of 0.05 or more. Therefore, in the present invention, it is possible to obtain an oily emulsified composition in which the ultraviolet absorber does not precipitate and is stable.
19 201110990 表4 新協朗Ί (音譯， 商品名） 液體石 蠟 奧克立 林 2-乙基 己酸十 六院S旨 2-乙基 己酸甘 油酷 癸 —~異丙 S旨 IOB值 0 0 0.33 0.13 0.35 0.4 雙己基己氧基苯酚甲氧基苯基三嗪 X X 〇 〇 〇 〇 二乙基胺基羥基苯甲醯基苯甲酸己酯 X X 〇 〇 〇 〇 4-第三丁基·4’-甲氧基二苯甲醯基甲烷 X X 〇 〇 〇 〇 (〇：0°C時未觀察到沉澱。X : (TC時觀察到沉澱） 「實施例6」防曬乳液 二丙二醇 5 三仙膠 0.1 皂土 1 硬脂酸 0.5 棕櫚酸 0.5 異硬脂酸聚氧化乙烯甘油醋 1 單硬脂酸甘油酯 1 單硬脂酸聚氧乙烯甘油酯 1 聚乙烯基吡咯烷酮/二十烯共聚物 1 二新戊酸三丙二醇 5 四2-乙基己酸新戊四醇酯 2 癸二酸異丙醋 2 奥克立林（Octocrylene) 5 雙乙基己氧基苯酚甲氧基苯基三嗪 2 二乙基胺基羥基苯f醯基苯甲酸己酯 2 4-第三丁基-4’-曱氧基二苯甲醯基甲烷 2 20 201110990 對曱氧基桂皮酸2-乙基己酯 5 乙基己基三嗪 0.5 六偏填酸納（sodium hexametaphosphate) 〇. l EDTA-3Na 0.1 三乙醇胺 適量 防腐劑 適量 精製水 殘餘量 香料 適量 「實施例7」防曬乳液 甘油 5 三仙膠 0.3 思美庫通（kunimine工業公司） 0.5 硬脂酸 〇_5 異硬脂醆 〇 _ 5 硬脂醇 2 聚氧乙烯硬化蓖麻油 1 單硬脂酸聚氧乙烯甘油酯 1 三曱基矽氧基石夕酸 1 環聚二曱基石夕氧烧（CyCl〇methicone) 3 辛醯基聚二甲基矽氧烷（caprylylmethicone) 3 乙基己酸十六烧酯 2-乙基己酸2-乙基己酯 3 奥克立林（Octocrylene) 5 21 201110990 雙乙基己氧基苯酚甲氧基苯基三嗪 2 二乙基胺基羥基笨曱醯基苯甲酸己酯 2 4-第三丁基-4’-甲氧基二苯曱醯基曱烷 2 苯基苯并味α坐續酸 1 維他命 C 配糖體（Ascorbic Acid 2-Glucoside) 2 EDTA-3Na 0.1 氫氧化鉀 適量 防腐劑 適量 精製水 殘餘量 香料 適量 「實施例8」防曬乳液 醇 5 二丙二醇 5 三仙膠 0.1 皂土 1 單硬脂酸甘油酯 1 異硬脂酸聚氧乙烯甘油酯 1 二十二烷酸 1 二十二醇 2 三曱基矽氧基矽酸 1 環聚二甲基矽氧烷 3 二聚二甲基矽氧烷 2 肉苴蔻酸異丙酯 5 22 201110990 棕櫚酸辛酯 5 琥珀酸二乙基己酯 i 聚氧乙稀聚氧丙烯二醇 1 奥克立林（Octocrylene) 5 雙乙基己氧基笨酚甲氧基苯基三嗪 2 二乙基胺基羥基笨曱醯基苯曱酸己酯 2 4-第三丁基_4，-曱氧基二苯曱醯基曱烷 2 經基甲氧基二苯基酮績酸鈉 1 亞曱基雙苯并。塞。坐四曱基丁基笨紛 2 EDTA-3Na 〇 ^ 二乙醇胺 防腐劑 精製水 香料 適量 適量 殘餘量 適量 (產業利用性） 本發明可提供一種水中油型乳化組成物，齊具有優異 之紫外線吸收效果’且乳化安定性與使用感優異。本發明 之水中油型礼化組成物可較佳地被利用於作為防曬化妝 料。 【圖式簡單說明】 圖1係實施例與比較例之吸光度曲線。 【主要元件符號說明】 無 2319 201110990 Table 4 Xinxie Langyi (transliteration, trade name) Liquid paraffin octoberin 2-ethylhexanoic acid 16th Institute S 2-ethylhexanoic acid glycerin 癸 ~ ~ ~ isopropyl S the purpose IOB value 0 0 0.33 0.13 0.35 0.4 bishexyl hexyloxyphenol methoxy phenyl triazine XX 〇〇〇〇 diethylamino hydroxy benzoyl benzoic acid hexyl ester XX 〇〇〇〇 4-third butyl · 4' -Methoxydibenzoylmethane methane XX 〇〇〇〇 (〇: No precipitation was observed at 0 ° C. X : (precipitation was observed at TC) "Example 6" Sunscreen lotion Dipropylene glycol 5 Sanxian Gum 0.1 Bentonite 1 stearic acid 0.5 palmitic acid 0.5 isostearic acid polyoxyethylene glycerin vinegar 1 glyceryl monostearate 1 polyoxyethylene glyceryl monostearate 1 polyvinylpyrrolidone / hexene copolymer 1 new Tripropylene glycol valerate 5 tetraethyl 2-ethylhexanoate pentaerythritol 2 isopropyl vinegar 2 octacrylene 5 bisethylhexyloxyphenol methoxyphenyl triazine 2 Aminoamino hydroxybenzene hexyl benzoic acid hexyl ester 2 4-tert-butyl-4'-nonyloxybenzhydryl methane 2 20 201110990 2-Ethylhexyl citrate 2 Ethylhexyl triazine 0.5 Sodium hexametaphosphate 〇. l EDTA-3Na 0.1 Triethanolamine Appropriate amount of preservatives Appropriate amount of refined water Residual amount of flavor "Example 7 Sunscreen lotion glycerin 5 Sanxianjiao 0.3 Simei Kutong (kunimine industrial company) 0.5 Stearic acid 〇_5 Isostearin 醆〇 5 Stearyl alcohol 2 Polyoxyethylene hardened castor oil 1 Monostearic acid polyoxyethylene Glyceryl ester 1 Trimethyl decyloxy oxalate 1 Cyclic polydecyl ketone (CyCl 〇methicone) 3 octadecyl polydimethyl methoxy hydride (caprylylmethicone) 3 ethylhexanoic acid hexadecanoate 2-ethyl 2-ethylhexyl hexanoate 3 Octorcylene 5 21 201110990 Diethylhexyloxyphenol methoxyphenyl triazine 2 Diethylaminohydroxy hydroxy adenyl benzoate 2 4 -T-butyl-4'-methoxydiphenylnonanoxane 2 Phenylbenzo-flavored α-sucrose acid 1 Ascorbic Acid 2-Glucoside 2 EDTA-3Na 0.1 Potassium Hydroxide Appropriate amount of preservatives, amount of refined water, residual amount of spices, "Example 8", sunscreen lotion alcohol 5 dipropylene 5 Sanxianjiao 0.1 Bentonite 1 Monostearate 1 Isostearic acid polyoxyethylene glyceride 1 Dodecanoic acid 1 Ethylene glycol 2 Tridecyl decyloxy decanoic acid 1 Cyclopolydimethyl Oxane 3 Dimer dimethyl oxane 2 Isopropyl citrate 5 22 201110990 Octyl palmitate 5 diethylhexyl succinate i polyoxyethylene polyoxypropylene diol 1 octoline ( Octocrylene) 5 bisethylhexyloxyphenol methoxy phenyl triazine 2 diethylamino hydroxy alum phenyl phthalate 2 4-tert-butyl _4,- decyl diphenyl Mercaptodecane 2 by sodium methoxy diphenyl ketone sodium 1 fluorenyl bisbenzo. Plug. Sodium tetradecyl butyl 2 EDTA-3Na 〇 ^ diethanolamine preservative refined water flavor appropriate amount of residual amount (industrial use) The present invention can provide an oily emulsified composition, which has excellent ultraviolet absorption effect 'And the emulsion stability and the feeling of use are excellent. The oil-in-water ritual composition of the present invention can be preferably utilized as a sunscreen cosmetic. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an absorbance curve of an example and a comparative example. [Main component symbol description] None 23