CN108472224B - α凝胶形成用组合物和α凝胶组合物 - Google Patents
α凝胶形成用组合物和α凝胶组合物 Download PDFInfo
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- CN108472224B CN108472224B CN201780008407.0A CN201780008407A CN108472224B CN 108472224 B CN108472224 B CN 108472224B CN 201780008407 A CN201780008407 A CN 201780008407A CN 108472224 B CN108472224 B CN 108472224B
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- polyoxyethylene
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Abstract
本发明要解决的课题在于,提供不存在随时间着色、晶体析出等的稳定性高的α凝胶形成组合物、和使用其的α凝胶组合物。α凝胶组合物,其包含,(A)1种或2种以上的碳原子数为16以上的高级脂肪族醇和/或高级脂肪酸25~50质量%,(B)特定的聚氧乙烯甾醇醚40~70质量%,(C)特定的聚氧乙烯二烷基酯和/或醚5~20质量%,所述组合物通过添加水而生成。
Description
相关申请
本申请要求2016年1月27日提交的日本特许申请2016-013181号的优先权,在此并入其中。
技术领域
本发明涉及α凝胶形成用组合物和α凝胶组合物、特别是凝胶形成物质的改良。
背景技术
一直以来,为了保持化妆品、医药部外品、医药品等皮肤外用剂的乳化稳定性,使用了采用高级脂肪族醇、高级脂肪酸与亲水性表面活性剂所形成的α凝胶的含α凝胶的皮肤外用剂。这样的α凝胶通过高粘度而使皮肤外用剂达到稳定,但涂布中存在滑腻的感触,在稳定性方面也存在高级醇、高级脂肪酸容易随时间以晶体形式析出等问题点(例如参照非专利文献1)。
此外,发现较多粘度随时间上升的情况,还研究了将双链型的阳离子表面活性剂等用作粘度上升防止剂,但无法得到充分良好的稳定性(例如参照非专利文献2)。进一步,防止来自皮肤内部的水分蒸散(阻挡)的效果也不充分。
此外,为了防止来自皮肤内部的水分蒸散,使用了包含神经酰胺类、二烷基季铵盐或磷脂质等双链型化合物和甾醇类的同样的制剂(例如专利文献1);包含磷脂质、聚氧乙烯甾醇醚类、高级醇的制剂(例如专利文献2、非专利文献3),但磷脂质类存在着色、气味等问题点,神经酰胺存在晶体容易析出的问题点。
现有技术文献
专利文献
专利文献1:日本特许第5690074号
专利文献2:日本特许第4495941号
非专利文献
非专利文献1:Kei Watanabe等人,J.Oleo Sci.,61,29-34(2012)
非专利文献2:Makoto Uyama等人,J.Oleo Sci.,62,9-16(2013)
非专利文献3:绀野义一,日本化妆品技术者会志,45,83-91(2011)。
发明内容
发明要解决的课题
本发明鉴于前述现有技术而进行,其要解决的课题在于,提供不存在随时间着色、晶体析出等的稳定性高的α凝胶形成组合物和使用其的α凝胶组合物。
用于解决问题的手段
为了解决前述课题,本发明人等进行深入研究的结果发现,通过以特定的比例包含高级脂肪族醇和/或高级脂肪酸、聚氧乙烯甾醇醚、以及具有2个碳原子数为16以上的疏水基团的聚氧乙烯二烷基酯和/或醚,形成新型α凝胶组合物,从而完成了本发明。
即,本发明所涉及的α凝胶形成用组合物的特征在于,包含:
(A)1种或2种以上的碳原子数为16以上的高级脂肪族醇和/或高级脂肪酸25~50质量%
(B)下述通式(I)所示的聚氧乙烯甾醇醚40~70质量%
(I)
(其中,通式I中R表示胆固醇和/或植物甾醇残基,n表示5~20的整数);
(C)下述通式(II)所示的聚氧乙烯二烷基酯和/或醚5~20质量%
(II)
(其中,通式II中R1和R2是碳原子数为16~24的直链脂肪族酸残基或直链脂肪族醇残基,n是4~15的整数),
所述组合物添加至水相中而形成凝胶。
此外,本发明所涉及的α凝胶组合物的特征在于,前述(A)~(C)在水相中形成。
此外,上述的α凝胶组合物中,适合的是,相对于α凝胶组合物中的有效成分,含有0.1~10质量%的具有氮原子的双链型两亲性物质。
此外,前述凝胶组合物中,适合的是,前述具有氮原子的双链型两亲性物质包含选自磷脂质、卵磷脂、溶血卵磷脂、神经酰胺、二烷基季铵盐中的一种或二种以上。
α凝胶形成用组合物中,碳原子数为16以上的高级脂肪族醇和/或高级脂肪酸的配混量在全部有效成分中适合为25~50质量%。作为碳原子数为16以上的高级脂肪族醇的例子,可以举出鲸蜡醇、鲸蜡硬脂醇、硬脂醇、山萮醇、鲨肝醇等。作为高级脂肪酸的例子,可以举出棕榈酸、硬脂酸、山萮酸等。
此外,前述α凝胶形成用组合物中,(I)的聚氧乙烯甾醇醚适合为作为疏水基团具有植物甾醇、胆固醇、麦角固醇的聚氧乙烯甾醇醚,聚氧乙烯链适合为5~30摩尔。作为例子,可以举出聚氧乙烯(5摩尔)植物甾醇(例如日光ケミカルズ公司制,Nikkol BPS-5)、聚氧乙烯(10摩尔)植物甾醇(例如日光ケミカルズ公司制,Nikkol BPS-10)、聚氧乙烯(20摩尔)植物甾醇(例如日光ケミカルズ公司制,Nikkol BPS-20)、聚氧乙烯(30摩尔)植物甾醇(例如日光ケミカルズ公司制,Nikkol BPS-30)、聚氧乙烯(10摩尔)胆固醇(例如日本エマルジョン公司制,Emalex CS-10)等。作为配混量,在全部有效成分中适合为40~70质量%。
前述α凝胶形成用组合物中,(II)的聚氧乙烯二烷基酯和/或醚适合具有碳原子数为16~24的直链脂肪族酸残基或直链脂肪族醇残基,聚氧乙烯链适合为4~15摩尔。作为例子,可列举聚氧乙烯(4摩尔)二硬脂酸(例如日本エマルジョン公司制,Emalex 200DIS)、聚氧乙烯(6摩尔)二硬脂酸(例如日本エマルジョン公司制,Emalex 300DIS)、聚氧乙烯(8摩尔)二硬脂酸(例如日本エマルジョン公司制,Emalex 400DIS)、聚氧乙烯(12摩尔)二硬脂酸(例如日本エマルジョン公司制,Emalex 600DIS)、硬脂酸硬脂醇聚氧乙烯醚-4(例如日本エマルジョン公司制,Emalex SWS-4)、硬脂酸硬脂醇聚氧乙烯醚-6(例如日本エマルジョン公司制,Emalex SWS-6)、硬脂酸硬脂醇聚氧乙烯醚-9(例如日本エマルジョン公司制,EmalexSWS-9)、聚氧乙烯(8摩尔)二山萮基醚等。应予说明,聚氧乙烯链与烷基的键合方式可以为酯也可以为醚,此外,可以包括该两者。作为配混量,在全部有效成分中适合为5~20质量%。
磷脂质、卵磷脂、溶血卵磷脂、神经酰胺、二烷基季铵盐等具有氮原子的双链型两亲性物质的配混量相对于α凝胶组合物中的有效成分适合为0.1~10质量%。如果为0.1质量%以下,则效果差,在10质量%以上的配混的情况中,容易引起着色、晶体析出等稳定性方面的问题。
此外,皮肤外用剂组合物中,前述α凝胶组合物可以配混任意的量,但一般而言,在皮肤外用剂中,以α凝胶组合物中的有效成分计,适合为0.1~20质量%。
发明效果
本发明所涉及的α凝胶组合物和以配混其为特征的皮肤外用剂组合物在涂布中是清爽的,在涂布后防止来自皮肤内部的水分蒸散(阻挡)的效果高,即使与磷脂质、卵磷脂、溶血卵磷脂、神经酰胺、二烷基季铵盐等具有氮原子的双链型两亲性物质一起配混,也不会随时间的经过引起着色、晶体析出等稳定性的问题。
附图说明
图1是本发明所涉及的25℃下制作的聚氧乙烯(6摩尔)二硬脂酸-硬脂醇-聚氧乙烯(10摩尔)植物甾醇的有效成分50质量%溶剂水的三成分系的相平衡图。
图2是本发明所涉及的图1的★标记的X射线散射谱。
图3是本发明所涉及的聚氧乙烯(6摩尔)二硬脂酸-硬脂酸-聚氧乙烯(10摩尔)植物甾醇=2:2:6的50质量%溶剂水的X射线散射谱。
具体实施方式
以下,针对本发明的构成进行详细描述。
本发明所涉及的α凝胶组合物通过下述方式得到:使1种或2种以上的碳原子数为16以上的高级脂肪族醇和/或高级脂肪酸25~50质量%、聚氧乙烯甾醇醚40~70质量%、以及聚氧乙烯二烷基酯和/或醚5~20质量%在70~80℃下熔融,向其中以40~90质量%的比例添加70~80℃的离子交换水并搅拌后,将其冷却,从而得到。此外,通过下述方式得到:使1种或2种以上的碳原子数为16以上的高级脂肪族醇和/或高级脂肪酸25~50质量%、聚氧乙烯甾醇醚40~70质量%、以及聚氧乙烯二烷基酯和/或醚5~20质量%在70~80℃下熔融后,添加磷脂质、卵磷脂、溶血卵磷脂、神经酰胺、二烷基季铵盐等具有氮原子的双链型两亲性物质并熔融,向其中以40~90质量%的比例添加70~80℃的离子交换水并搅拌后,将其冷却,从而得到。应予说明,α凝胶一般而言是指高级脂肪族醇和亲水性表面活性剂在水中形成的聚集体、并采取α结构(福岛正二著“鲸蜡醇的物理化学”フレグランスジャーナル公司)的凝胶。
作为α凝胶组合物的具体例,分别选择1种或2种以上的碳原子数为16以上的高级脂肪族醇和/或高级脂肪酸硬脂醇,作为聚氧乙烯甾醇醚的聚氧乙烯(10摩尔)植物甾醇(例如日光ケミカルズ公司制,Nikkol BPS-10),作为聚氧乙烯二烷基酯和/或醚的聚氧乙烯(6摩尔)二硬脂酸(例如日本エマルジョン公司制,Emalex 300DIS),将它们的混合物在70~80℃下制成一相后,以全部有效成分量达到全体的60质量%的比例的方式添加加热至相同温度的离子交换水,将冷却至室温而得到的三成分系的相平衡图示于图1。图1中,斜线部分是示差量热分析仪中的熔点峰为1个的情况中的X射线分析的结果,是得到了表示α凝胶的散射峰(图2)的区域。应予说明,图2是图1的★标记所示的组合物的X射线散射谱。
此外,将硬脂醇改变为硬脂酸,也同样地得到了表示α凝胶的X射线散射谱(图3)。由图1可知,在硬脂醇25~50质量%、聚氧乙烯(10摩尔)植物甾醇40~70质量%、聚氧乙烯(6摩尔)二硬脂酸5~20质量%的区域确认形成α凝胶。
本发明中,可以仅由上述3个成分构建α凝胶,但根据改善皮肤粗糙等目的,也可以一起配混磷脂质、卵磷脂、溶血卵磷脂、神经酰胺、二烷基季铵盐等具有氮原子的双链型两亲性物质。
本发明的皮肤外用剂中使用的油成分没有特别限定,可以适当配混例如液体油脂、固体油脂、蜡类、烃油、高级脂肪酸、合成酯油、硅油等,进一步,还可以将部分高级醇溶解于前述油成分中从而乳化。作为相对于目标的含有α凝胶的皮肤外用剂的配混量,没有特别限定,优选为0.05~50质量%。0.05质量%以下的情况中,作为皮肤外用剂的效果差,如果大于50质量%,则使用感受变差。
作为液体油脂,可以举出例如鳄梨油、山茶油、海龟油、澳洲坚果油、玉米油、貂油、橄榄油、菜籽油、蛋黄油、芝麻油、杏仁油、小麦胚芽油、山茶花油、蓖麻油、亚麻仁油、红花油、棉籽油、紫苏子油、大豆油、花生油、茶籽油、香榧油、米糠油、中国桐油、日本桐油、荷荷巴油、胚芽油、三甘油等。
作为固体油脂,可以举出例如可可脂、椰子油、马油、氢化椰子油、棕榈油、牛脂、羊脂、硬化牛脂、棕榈仁油、猪油、牛骨油、木蜡仁油、硬化油、牛蹄油、木蜡、氢化蓖麻油等。
作为蜡类,可以举出例如蜂蜡、小烛树蜡、棉蜡、巴西棕榈蜡、杨梅蜡、虫蜡、鲸蜡、褐煤蜡、糠蜡、羊毛脂、木棉蜡、乙酰化羊毛脂、液态羊毛脂、甘蔗蜡、羊毛脂脂肪酸异丙酯、月桂酸己酯、还原羊毛脂、霍霍巴蜡、硬质羊毛脂、虫胶蜡、聚氧乙烯羊毛脂醇醚、聚氧乙烯羊毛脂醇乙酸酯、聚氧乙烯胆固醇醚、羊毛脂脂肪酸聚乙二醇酯、聚氧乙烯氢化羊毛脂醇醚、棕榈酸鲸蜡酯。
作为烃油,可以举出例如液体石蜡、地蜡、角鲨烷、姥鲛烷、石蜡、白地蜡、角鲨烯、凡士林、微晶蜡等。
作为高级脂肪酸,可以举出例如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山萮酸、油酸、十一碳烯酸、妥尔油酸、异硬脂酸、亚油酸、亚麻酸、二十碳五烯酸(EPA)、二十二碳六烯酸(DHA)等。
作为合成酯油,可以举出例如辛酸鲸蜡酯、肉豆蔻酸肉豆蔻基酯、三(2-乙基己酸)甘油酯、四(2-乙基己酸)季戊四醇酯、丁二酸二辛酯、二新戊酸三丙二醇酯等。
作为硅油,可以举出例如链状聚硅氧烷(例如二甲基聚硅氧烷、甲基苯基聚硅氧烷、二苯基聚硅氧烷等);环状聚硅氧烷(例如八甲基环四硅氧烷、十甲基环五硅氧烷、十二甲基环六硅氧烷等)、形成三维网格结构的硅酮树脂、硅酮橡胶、各种改性聚硅氧烷(氨基改性聚硅氧烷、聚醚改性聚硅氧烷、烷基改性聚硅氧烷、氟改性聚硅氧烷等)、丙烯酸硅酮类等。
本发明所涉及的含有α凝胶的皮肤外用剂可以用于例如能够应用于皮肤、头发等身体的皮肤化妆产品、洗发产品、皮肤清洗产品、头发造型产品等。
此外,本发明所涉及的含有α凝胶的皮肤外用剂中,除了上述必须成分之外,还可以以不对稳定性造成影响的范围的配混量配混通常在化妆品、医药品等中使用的成分。作为所述成分,可以举出例如粉末成分、两性表面活性剂、离子性表面活性剂、非离子表面活性剂、保湿剂、增稠剂、覆膜剂、紫外线吸收剂、金属离子螯合剂、pH调节剂、皮肤营养剂、维生素、抗氧化剂、抗氧化助剂、香料等。
作为粉末成分,可以举出例如无机粉末(例如滑石、高岭土、云母、绢云母(Sericite)、白云母、金云母、合成云母、红云母、黑云母、蛭石、膨润土、水辉石、锂藻土(laponite)、碳酸镁、碳酸钙、硅酸铝、硅酸钡、硅酸钙、硅酸镁、硅酸锶、钨酸金属盐、镁、二氧化硅、沸石、硫酸钡、煅烧硫酸钙(烧石膏)、磷酸钙、氟磷灰石、羟基磷灰石、陶瓷粉末、金属皂(例如肉豆蔻酸锌、棕榈酸钙、硬脂酸铝)、氮化硼等);有机粉末(例如聚酰胺树脂粉末(尼龙粉末)、聚乙烯粉末、聚甲基丙烯酸甲酯粉末、聚苯乙烯粉末、苯乙烯与丙烯酸的共聚物树脂粉末、苯并胍胺树脂粉末、聚四氟乙烯粉末、纤维素粉末等);无机白色颜料(例如二氧化钛、氧化锌等);无机红色系颜料(例如氧化铁(氧化铁红)、钛酸铁等);无机褐色系颜料(例如γ-氧化铁等);无机黄色系颜料(例如氧化铁黄、黄土等);无机黑色系颜料(例如氧化铁黑、低价氧化钛等);无机紫色系颜料(例如锰紫、钴紫等);无机绿色系颜料(例如氧化铬、氢氧化铬、钛酸钴等);无机蓝色系颜料(例如群青、普鲁士蓝等);珠光颜料(例如氧化钛涂布的云母、氧化钛涂布的氯氧化铋、氧化钛涂布的滑石、着色氧化钛涂布的云母、氯氧化铋、鱼鳞箔等);金属粉末颜料(例如铝粉末、铜粉末等);锆、钡或铝色淀等有机颜料(例如红色201号、红色202号、红色204号、红色205号、红色220号、红色226号、红色228号、红色405号、橙色203号、橙色204号、黄色205号、黄色401号、和蓝色404号等有机颜料、红色3号、红色104号、红色106号、红色227号、红色230号、红色401号、红色505号、橙色205号、黄色4号、黄色5号、黄色202号、黄色203号、绿色3号和蓝色1号等);天然色素(例如叶绿素、β-胡萝卜素等)等。
作为两性表面活性剂,可以举出例如咪唑啉系两性表面活性剂(例如2-十一烷基-N,N,N-(羟基乙基羧基甲基)-2-咪唑啉钠、2-椰油酰基-2-咪唑鎓氢氧化物-1-羧基乙氧基二钠盐等);甜菜碱系表面活性剂(例如2-十七烷基-N-羧基甲基-N-羟基乙基咪唑鎓甜菜碱、月桂基二甲基氨基乙酸甜菜碱、烷基甜菜碱、酰胺甜菜碱、磺基甜菜碱等)等。
作为离子性表面活性剂,可以举出N-酰基甲基牛磺酸盐、N-酰基谷氨酸盐、烷基硫酸盐、聚氧乙烯烷基硫酸盐、脂肪酸皂、烷基季铵盐等。
作为亲油性非离子表面活性剂,可以举出例如脱水山梨糖醇脂肪酸酯类(例如脱水山梨糖醇单油酸酯、脱水山梨糖醇单异硬脂酸酯、脱水山梨糖醇单月桂酸酯、脱水山梨糖醇单棕榈酸酯、脱水山梨糖醇单硬脂酸酯、脱水山梨糖醇倍半油酸酯、脱水山梨糖醇三油酸酯、五(2-乙基己酸)二甘油脱水山梨糖醇酯、四(2-乙基己酸)二甘油脱水山梨糖醇酯等);甘油聚甘油脂肪酸酯类(例如单棉籽油脂肪酸甘油酯、单芥酸甘油酯、倍半油酸甘油酯、单硬脂酸甘油酯、α,α'-油酸焦谷氨酸甘油酯、单硬脂酸甘油苹果酸酯等);丙二醇脂肪酸酯类(例如单硬脂酸丙二醇酯等);氢化蓖麻油衍生物;甘油烷基醚等。
作为亲水性非离子表面活性剂,可以举出例如聚氧乙烯脱水山梨糖醇脂肪酸酯类(例如聚氧乙烯脱水山梨糖醇单油酸酯、聚氧乙烯脱水山梨糖醇单硬脂酸酯、聚氧乙烯脱水山梨糖醇单油酸酯、聚氧乙烯脱水山梨糖醇四油酸酯等);聚氧乙烯山梨醇脂肪酸酯类(例如聚氧乙烯山梨醇单月桂酸酯、聚氧乙烯山梨醇单油酸酯、聚氧乙烯山梨醇五油酸酯、聚氧乙烯山梨醇单硬脂酸酯等);聚氧乙烯甘油脂肪酸酯类(例如聚氧乙烯甘油单硬脂酸酯、聚氧乙烯甘油单异硬脂酸酯、聚氧乙烯甘油三异硬脂酸酯等聚氧乙烯单油酸酯等);聚氧乙烯脂肪酸酯类(例如聚氧乙烯二硬脂酸酯、聚氧乙烯单二油酸酯、二硬脂酸乙二醇酯等);聚氧乙烯烷基醚类(例如聚氧乙烯月桂基醚、聚氧乙烯油基醚、聚氧乙烯硬脂基醚、聚氧乙烯山萮基醚、聚氧乙烯2-辛基十二烷基醚、聚氧乙烯胆甾烷醇醚等);Pluronic型类(例如Pluronic等);聚氧乙烯・聚氧丙烯烷基醚类(例如聚氧乙烯・聚氧丙烯鲸蜡基醚、聚氧乙烯・聚氧丙烯2-癸基十四烷基醚、聚氧乙烯・聚氧丙烯单丁基醚、聚氧乙烯・聚氧丙烯氢化羊毛脂、聚氧乙烯・聚氧丙烯甘油醚等);四聚氧乙烯・四聚氧丙烯乙二胺缩合物类(例如Tetronic等);聚氧乙烯蓖麻油氢化蓖麻油衍生物(例如聚氧乙烯蓖麻油、聚氧乙烯氢化蓖麻油、聚氧乙烯氢化蓖麻油单异硬脂酸酯、聚氧乙烯氢化蓖麻油三异硬脂酸酯、聚氧乙烯氢化蓖麻油单焦谷氨酸单异硬脂酸二酯、聚氧乙烯氢化蓖麻油马来酸等);聚氧乙烯蜂蜡・羊毛脂衍生物(例如聚氧乙烯山梨醇蜂蜡等);烷醇酰胺(例如椰子油脂肪酸二乙醇酰胺、月桂酸单乙醇酰胺、脂肪酸异丙醇酰胺等);聚氧乙烯丙二醇脂肪酸酯;聚氧乙烯烷基胺;聚氧乙烯脂肪酸酰胺;蔗糖脂肪酸酯;烷基乙氧基二甲基胺氧化物;三油基磷酸等。
作为天然的水溶性高分子,可以举出例如植物系高分子(例如阿拉伯胶、黄蓍胶、半乳聚糖、瓜尔胶、角豆胶、刺梧桐树胶、刺槐豆胶、罗望子胶、卡拉胶、果胶、琼脂、榅桲籽(榅桲)、褐藻胶(褐藻提取物)、淀粉(大米、玉米、马铃薯、小麦)、甘草酸);微生物系高分子(例如黄原胶、葡聚糖、琥珀酰葡聚糖、茁霉多糖等);动物系高分子(例如胶原、酪蛋白、白蛋白、明胶等)等。
作为半合成的水溶性高分子,可以举出例如淀粉系高分子(例如羧基甲基淀粉、甲基羟基丙基淀粉等);纤维素系高分子(甲基纤维素、乙基纤维素、甲基羟基丙基纤维素、羟基乙基纤维素、纤维素硫酸钠、二烷基二甲基铵硫酸纤维素、羟基丙基纤维素、羧基甲基纤维素、羧基甲基纤维素钠、结晶纤维素、纤维素末和这些高分子的疏水改性化合物<例如:将一部分进行硬脂氧基改性>和这些高分子的阳离子改性化合物等);藻酸系高分子(例如藻酸钠、藻酸丙二醇酯等);果胶酸钠等。
作为合成的水溶性高分子,可以举出例如乙烯基系高分子(例如聚乙烯醇、聚乙烯基甲基醚、聚乙烯基吡咯烷酮、羧基乙烯基聚合物等);聚氧乙烯系高分子(例如聚乙二醇20,000、40,000、60,000的聚氧乙烯聚氧丙烯共聚物等);聚(二甲基二烯丙基卤化铵)型阳离子性高分子(例如Merquat100,美国メルク公司制);二甲基二烯丙基卤化铵和丙烯酰胺的共聚物型阳离子性聚合物(例如Merquat 550,美国メルク公司制);丙烯酸系高分子(例如聚丙烯酸钠、聚丙烯酸乙酯、聚丙烯酰胺等);聚乙烯亚胺;阳离子聚合物;硅酸AlMg(VEEGUM)等。
作为紫外线吸收剂,可以举出例如苯甲酸系紫外线吸收剂(例如对氨基苯甲酸(以下简称为PABA)、PABA单甘油酯、N,N-二丙氧基PABA乙基酯、N,N-二乙氧基PABA乙酯、N,N-二甲基PABA乙酯、N,N-二甲基PABA丁酯、N,N-二甲基PABA乙酯等);邻氨基苯甲酸系紫外线吸收剂(例如N-乙酰基邻氨基苯甲酸高䓝酯等);水杨酸系紫外线吸收剂(例如水杨酸戊酯、水杨酸䓝酯、水杨酸高䓝酯、水杨酸辛酯、水杨酸苯酯、水杨酸苯甲酯、对异丙醇苯基水杨酸酯等);桂皮酸系紫外线吸收剂(例如辛基肉桂酸酯、4-异丙基肉桂酸乙酯、2,5-二异丙基肉桂酸甲酯、2,4-二异丙基肉桂酸乙酯、2,4-二异丙基肉桂酸甲酯、对甲氧基肉桂酸丙酯、对甲氧基肉桂酸异丙酯、对甲氧基肉桂酸异戊酯、对甲氧基肉桂酸辛酯(对甲氧基肉桂酸2-乙基己酯)、对甲氧基肉桂酸2-乙氧基乙酯、对甲氧基肉桂酸环己酯、α-氰基-β-苯基肉桂酸乙酯、α-氰基-β-苯基肉桂酸2-乙基己酯、甘油单-2-乙基己酰基-二对甲氧基肉桂酸酯等);二苯甲酮系紫外线吸收剂(例如2,4-二羟基二苯甲酮、2,2'-二羟基-4-甲氧基二苯甲酮、2,2'-二羟基-4,4'-二甲氧基二苯甲酮、2,2',4,4'-四羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-甲氧基-4'-甲基二苯甲酮、2-羟基-4-甲氧基二苯甲酮-5-磺酸盐、4-苯基二苯甲酮、2-乙基己基-4'-苯基-二苯甲酮-2-甲酸酯、2-羟基-4-正辛氧基二苯甲酮、4-羟基-3-羧基二苯甲酮等);3-(4'-甲基苯甲叉基)-d,l-樟脑、3-苯甲叉基-d,l-樟脑;2-苯基-5-甲基苯并噁唑;2,2'-羟基-5-甲基苯基苯并三唑;2-(2'-羟基-5'-叔辛基苯基) 苯并三唑;2-(2'-羟基-5'-甲基苯基苯并三唑;二茴香酰基甲烷;4-甲氧基-4'-叔丁基二苯甲酰基甲烷;5-(3,3-二甲基-2-降冰片叉基)-3-戊烷-2-酮等);三嗪系紫外线吸收剂(例如2-4[(2-羟基-3-十二烷基氧基丙基)氧基]-2-羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-4[(2-羟基-3-十三烷基氧基丙基)氧基]-2-羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪等)。
作为金属离子螯合剂,可以举出例如1-羟基乙烷-1,1-二膦酸、1-羟基乙烷-1,1-二膦酸四钠盐、依地酸二钠、依地酸三钠、依地酸四钠、柠檬酸钠、聚磷酸钠、偏磷酸钠、葡糖酸、磷酸、柠檬酸、抗坏血酸、丁二酸、依地酸、乙二胺羟基乙基三乙酸三钠等。
作为pH调节剂,可以举出例如乳酸-乳酸钠、柠檬酸-柠檬酸钠、丁二酸-丁二酸钠等缓冲剂等。
作为维生素类,可以举出例如维生素A、B1、B2、B6、C、E和其衍生物、泛酸和其衍生物、生物素等。
作为抗氧化剂,可以举出例如生育酚类、二丁基羟基甲苯、丁基羟基苯甲醚、没食子酸酯类等。
作为抗氧化助剂,可以举出例如磷酸、柠檬酸、抗坏血酸、马来酸、丙二酸、丁二酸、富马酸、脑磷脂、六偏磷酸盐、植酸、乙二胺四乙酸等。
作为其他可配混成分,可以举出例如防腐剂(尼泊金乙酯、尼泊金丁酯、1,2-烷二醇、苯氧基乙醇、甲基氯异噻唑啉酮等);消炎剂(例如甘草酸衍生物、甘草次酸衍生物、水杨酸衍生物、目柏醇、氧化锌、尿囊素等);美白剂(例如虎耳草提取物、熊果苷等);各种提取物(例如黄柏、黄连、紫草根、芍药、当药、桦木、鼠尾草、枇杷、胡萝卜、芦荟、锦葵、鸢尾花、葡萄、薏苡、丝瓜、百合、番红花、川芎、生姜、小连翘、芒柄花、大蒜、辣椒、陈皮、当归、海藻等)、赋活剂(例如蜂王浆、感光素、胆固醇衍生物等);血行促进剂(例如壬酸香草酰胺、烟酸苯甲基酯、烟酸β-丁氧基乙基酯、辣椒素、姜辣素、斑蝥酊、鱼石脂、鞣酸、α-冰片、烟酸生育酚酯、肌醇六烟酸酯、环扁桃酯、桂利嗪、苄唑啉、乙酰胆碱、维拉帕米、千金藤素、γ-谷维素等);抗脂溢剂(例如硫、二甲噻蒽等);抗炎剂(例如凝血酸、硫代牛磺酸、亚牛磺酸等);芳族醇(苯甲基醇、苯甲基氧基乙醇等)等。
此外,在不损害稳定性的范围内,还可以适当配混其他香料、擦洗剂等。
实施例
以下,通过实施例进一步详细说明本发明,但本发明不被这些所限定。应予说明,在没有特别记载的情况下,配混量全部用质量%表示。
[α凝胶的阻挡效果的比较]
在70℃下用超声均化器制备以下的实施例、比较例所涉及的组合物,冷却后,在纸上各自以5mg/cm2的比例均匀涂布并放置1天。在恒温恒湿室(23℃,相对湿度= 45%)中,在25mL容积小瓶中加入5mL的水后,立刻在小瓶的盖部上夹持该滤纸并固定,随时间测定水分蒸发量。将单位时间的水分蒸发量(衰减质量%)定义为水分蒸发速度常数(%/小时)。因此,水分蒸发速度常数(%/小时)越小,则保持水分的能力越高。
实施例1
配混量
(1)硬脂醇 12.5%
(2)聚氧乙烯(10摩尔)植物甾醇 30.0%
(3)聚氧乙烯(6摩尔)二硬脂酸 7.5%
(4)离子交换水 50.0%。
实施例2
配混量
(1)硬脂酸 12.5%
(2)聚氧乙烯(10摩尔)植物甾醇 30.0%
(3)聚氧乙烯(6摩尔)二硬脂酸 7.5%
(4)离子交换水 50.0%。
实施例3
配混量
(1)山萮醇 15.0%
(2)聚氧乙烯(20摩尔)植物甾醇 30.0%
(3)聚氧乙烯(4摩尔)二硬脂酸 5.0%
(4)离子交换水 50.0%。
比较例1
配混量
(1)山萮醇 34.1%
(2)N-硬脂酰基甲基牛磺酸钠 15.9%
(3)离子交换水 50.0%。
比较例2
配混量
(1)山萮醇 30.0%
(2)聚氧乙烯(20摩尔)山萮基醚 20.0%
(3)离子交换水 50.0%。
比较例3
配混量
(1)硬脂醇 12.5%
(2)聚氧乙烯(10摩尔)植物甾醇 30.0%
(3)大豆氢化レシノール 7.5%
(4)离子交换水 50.0%。
结果
结果示于表1。由表1可知,本发明的α凝胶(实施例1~3)与使用山萮醇和N-硬脂酰基甲基牛磺酸钠、山萮醇和聚氧乙烯(20摩尔)山萮基醚、硬脂醇和聚氧乙烯(10摩尔)植物甾醇和大豆氢化レシノール的比较例1~3的α凝胶基剂相比,阻挡效果高。
表1. 各α凝胶基剂的阻挡效果
[粘度稳定性试验]
进一步,将实施例1~3、比较例1~3的基剂各自在75℃下用离子交换水稀释至10倍,保存于0~50℃的各温度下,对于随时间的粘度,在30℃下保持30分钟以上后,用B型粘度计测定粘度(mPa・s)。
结果
结果示于表2。由表可知,实施例1~3和比较例3中,粘度稳定,但比较例1、2中,发现随时间的增粘。应予说明,粘度稳定的比较例3确认到变臭。
表2. 实施例1~3和比较例1~3的粘度随时间的经过的变化
[气味稳定性]
将实施例4~6、比较例4~6的基剂各自在75℃下用离子交换水稀释至10倍,保存于50℃的各温度下,通过专门小组以下述判定基准判定1个月后的气味。
判定基准
○:没有问题、△:略微变臭、×:变臭。
实施例4
配混量
(1)硬脂醇 12.5%
(2)聚氧乙烯(10摩尔)植物甾醇 30.0%
(3)聚氧乙烯(6摩尔)二硬脂酸 6.0%
(4)大豆氢化レシノール 1.5%
(5)离子交换水 50.0%。
实施例5
配混量
(1)硬脂酸 12.5%
(2)聚氧乙烯(10摩尔)植物甾醇 30.0%
(3)聚氧乙烯(6摩尔)二硬脂酸 7.0%
(4)神经酰胺III 0.5%
(5)离子交换水 50.0%。
实施例6
配混量
(1)山萮醇 15.0%
(2)聚氧乙烯(20摩尔)植物甾醇 30.0%
(3)聚氧乙烯(4摩尔)二硬脂酸 4.8%
(4)二硬脂基季铵氯化物 0.2%
(5)离子交换水 50.0%。
比较例4
配混量
(1)山萮醇 34.1%
(2)N-硬脂酰基甲基牛磺酸钠 14.4%
(3)大豆氢化レシノール 1.5%
(4)离子交换水 50.0%。
比较例5
配混量
(1)山萮醇 30.0%
(2)聚氧乙烯(20摩尔)山萮基醚 19.5%
(3)神经酰胺III 0.5%
(4)离子交换水 50.0%。
比较例6
配混量
(1)硬脂醇 12.5%
(2)聚氧乙烯(10摩尔)植物甾醇 30.0%
(3)二硬脂基季铵氯化物 7.5%
(4)离子交换水 50.0%。
结果
结果示于表3。由表3可知,通过使用本发明的α凝胶组合物,磷脂质、卵磷脂、溶血卵磷脂、神经酰胺、二烷基季铵盐等具有氮原子的双链型两亲性物质的变臭消失。
表3. 各α凝胶基剂的气味判定结果
以下,举出更具体的实施例,针对本发明进行进一步说明,但本发明不限定于此。
实施例7
乳液 配混量(质量%)
(1)硬脂醇 1.3
(2)聚氧乙烯(10摩尔)植物甾醇 3.0
(3)聚氧乙烯(6摩尔)二硬脂酸 0.6
(4)双丙甘醇 5.0
(5)香料 0.1
(6)四(2-乙基己酸)季戊四醇酯 2.0
(7)α烯烃低聚物 3.0
(8)二甲基聚硅氧烷 2.0
(信越化学株式会社制,Silicone KF96-A6T)
(9)精制凡士林 1.0
(10)1,3-丁二醇 2.0
(11)苯氧基乙醇 0.5
(12)甘油 4.0
(13)羧基乙烯基聚合物 0.03
(14)氢氧化钾 0.01
(15)凝血酸 0.1
(16)柠檬酸 0.02
(17)柠檬酸钠 0.08
(18)离子交换水 余量。
(制造方法)
通过常规方法乳化,得到上述乳液。所得乳液的阻挡效果高,清爽,粘度稳定性和气味稳定性良好。
实施例8
美容液 配混量(质量%)
(1)N-硬脂酰基甲基牛磺酸钠 0.01
(2)硬脂醇 0.13
(3)聚氧乙烯(10摩尔)植物甾醇 0.3
(4)聚氧乙烯(6摩尔)二硬脂酸 0.06
(5)液体石蜡 0.78
(6)甲基苯基聚硅氧烷 0.2
(信越化学株式会社制,Silicone KF56)
(7)香料 0.02
(8)聚氧乙烯(14摩尔)聚氧丙烯(7摩尔)二甲基醚 0.5
(9)甘油 3.0
(10)双丙甘醇 5.0
(11)1,3-丁二醇 3.0
(12)柠檬酸 0.02
(13)柠檬酸钠 0.08
(14) EDTA2Na・2H2O 0.01
(15)一般醇95%(一般アルコール95%) 5.0
(16)苯氧基乙醇 0.5
(17)离子交换水 余量。
(制造方法)
通过常规方法乳化,得到上述美容液。所得美容液的阻挡效果高,清爽,粘度稳定性和气味稳定性良好。
实施例9
乳液 配混量(质量%)
(1)硬脂醇 1.3
(2)聚氧乙烯(10摩尔)植物甾醇 3.0
(3)聚氧乙烯(6摩尔)二硬脂酸 0.6
(4)大豆氢化レシノール 0.2
(5)异戊二醇 4.5
(6)1,4-丁二醇 1.5
(7)香料 0.09
(8)三硬脂酸甘油酯 2.5
(9)角鲨烷 4.5
(10)二甲基聚硅氧烷 1.0
(信越化学株式会社制,Silicone KF96-A6T)
(11)丙二醇 7.0
(12)赤藓醇 1.3
(13)达纳炸药用甘油 6.0
(14)苯氧基乙醇 0.3
(15)黄原胶 0.5
(16)六偏磷酸钠 0.03
(17)离子交换水 余量。
(制造方法)
通过常规方法乳化,得到上述乳液。所得乳液的阻挡效果高,清爽,粘度稳定性和气味稳定性良好。
实施例10
防晒霜 配混量(质量%)
(1)山萮醇 1.5
(2)聚氧乙烯(20摩尔)植物甾醇 3.0
(3)聚氧乙烯(4摩尔)二硬脂酸 0.5
(4)神经酰胺II 0.2
(5)双丙甘醇 6.0
(6)香料 0.08
(7)三(2-乙基己酸)甘油酯 2.0
(8)丁二酸二(2-乙基己基)酯 3.0
(9)对甲氧基肉桂酸2-乙基己基 5.0
(10)阿伏苯宗 3.0
(11)双乙基己氧基苯酚甲氧基苯基 1.0
三嗪
(12)1,3-丁二醇 5.0
(13)苯氧基乙醇 0.5
(14)甘油 9.0
(15)EDTA-三钠盐 0.1
(16)赤藓醇 0.1
(17)柠檬酸 0.02
(18)柠檬酸钠 0.08
(19)离子交换水 余量。
(制造方法)
通过常规方法乳化,得到上述防晒霜。所得防晒霜的阻挡效果高,清爽,粘度稳定性和气味稳定性良好。
实施例11
霜剂 配混量(质量%)
(1)硬脂醇 2.5
(2)聚氧乙烯(10摩尔)植物甾醇 6.0
(3)聚氧乙烯(6摩尔)二硬脂酸 1.2
(4)1,3-丁二醇 6.5
(5)香料 0.05
(6)二甲基聚硅氧烷 7.4
(信越化学株式会社制,Silicone KF96-A6T)
(7)角鲨烷 4.0
(8)精制凡士林 1.0
(9)双丙甘醇 5.0
(10)苯氧基乙醇 0.5
(11)甘油 7.0
(12)EDTA-三钠盐 0.1
(13)母菊提取物 0.1
(14)柠檬酸 0.02
(15)柠檬酸钠 0.08。
(制造方法)
通过常规方法乳化,得到霜剂。所得霜剂的阻挡效果高,清爽,粘度稳定性和气味稳定性良好。
Claims (5)
2.α凝胶组合物,其将权利要求1所述的(A)~(C)配混在水中而制备。
3.根据权利要求2所述的α凝胶组合物,其特征在于,相对于α凝胶组合物中的有效成分,还含有0.1~10质量%的具有氮原子的双链型两亲性物质。
4.根据权利要求3所述的α凝胶组合物,其特征在于,具有氮原子的双链型两亲性物质为选自磷脂质、卵磷脂、溶血卵磷脂、神经酰胺、二烷基季铵盐中的一种或二种以上。
5.皮肤外用剂组合物,其特征在于,配混有权利要求2所述的α凝胶组合物。
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- 2017-01-06 EP EP17743889.2A patent/EP3417845B1/en active Active
- 2017-01-18 TW TW106101682A patent/TWI740882B/zh active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1228109A (zh) * | 1997-05-30 | 1999-09-08 | 株式会社资生堂 | 凝胶剂和凝胶组合物 |
CN1385457A (zh) * | 2001-05-11 | 2002-12-18 | 潘里科合伙公司 | 凝胶组合物 |
CN1944482A (zh) * | 2006-09-21 | 2007-04-11 | 北京科技大学 | 一种凝胶注模成型用凝胶组合物及其制备方法 |
CN107693844A (zh) * | 2016-08-07 | 2018-02-16 | 李媚 | 一种组合物凝胶与应用 |
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TWI740882B (zh) | 2021-10-01 |
EP3417845A4 (en) | 2019-07-03 |
KR102757341B1 (ko) | 2025-01-17 |
AU2017212886A1 (en) | 2018-08-16 |
CN108472224A (zh) | 2018-08-31 |
EP3417845A1 (en) | 2018-12-26 |
JP2017132709A (ja) | 2017-08-03 |
JP6426635B2 (ja) | 2018-11-21 |
RU2018128456A3 (zh) | 2020-02-27 |
US20210100732A1 (en) | 2021-04-08 |
RU2018128456A (ru) | 2020-02-27 |
US11033479B2 (en) | 2021-06-15 |
BR112018015257A2 (pt) | 2018-12-18 |
KR20180104091A (ko) | 2018-09-19 |
BR112018015257B1 (pt) | 2021-11-16 |
EP3417845B1 (en) | 2021-03-31 |
RU2732289C2 (ru) | 2020-09-15 |
TW201801710A (zh) | 2018-01-16 |
WO2017130655A1 (ja) | 2017-08-03 |
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