CN104427965A - 包含紫外线辐射吸收性聚酯的防晒剂组合物 - Google Patents
包含紫外线辐射吸收性聚酯的防晒剂组合物 Download PDFInfo
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- CN104427965A CN104427965A CN201380034715.2A CN201380034715A CN104427965A CN 104427965 A CN104427965 A CN 104427965A CN 201380034715 A CN201380034715 A CN 201380034715A CN 104427965 A CN104427965 A CN 104427965A
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Abstract
本发明提供了组合物,其包含基本上均匀地分布在连续水相中的油相,所述油相包含防晒剂,其中防晒剂以有效地向所述组合物提供约10或更高的SPF的量包含UV吸收性聚酯,并且所述组合物为如下物质的聚合反应产物:包含UV吸收性三唑、二酯、二醇和四元醇的单体;烷基化的聚乙烯吡咯烷酮;以及选自阴离子乳化剂和/或非离子乳化剂的乳化剂,其中组合物基本上不含非聚合的UV吸收性防晒剂,并且在不存在UV吸收性聚酯的情况下具有小于2的SPF。
Description
技术领域
本发明涉及包含UV吸收性聚酯的局部可接受的防晒剂组合物。
背景技术
长时间暴露于诸如来自太阳的紫外线(UV)辐射,可导致形成光皮肤病和红斑,以及增加皮肤癌诸如黑素瘤的风险,并加速皮肤老化,诸如皮肤失去弹性和起褶皱。
许多防晒剂组合物可商购获得,这些组合物具有不同的为身体屏蔽紫外光的能力。然而,提供具有强效UV辐射保护性并抗水洗的防晒剂组合物依然存在许多挑战。
如果对防晒剂组合物还有其他约束的话,则会进一步加大获得防水防晒剂的挑战。本发明提供防水、美学的防晒剂组合物,其包含聚合物的防晒剂化合物(即,紫外线辐射吸收性聚酯),并且其基本上不含非聚合的UV吸收性防晒剂。
发明内容
本发明的组合物包括包含防晒剂的不连续油相,其中防晒剂以有效地向组合物提供约10或更高的SPF的组合物的量包含UV吸收性聚酯。油相基本上均匀地分布在连续水相中。UV吸收性聚酯为包含UV吸收性三唑、二酯、二醇与四元醇的单体的聚合反应产物。组合物包括烷基化的聚乙烯吡咯烷酮和乳化剂,其中乳化剂选自阴离子乳化剂和非离子乳化剂。组合物基本上不含非聚合的UV吸收性防晒剂并且在不存在UV吸收性聚酯的情况下具有小于2的SPF。
具体实施方式
除非另有定义,否则本文使用的所有技术和科学术语都具有本发明所属技术领域普通技术人员公知的相同含义。除非另外指明,否则如本文所用的所有烃基团(例如,烷基、烯基)基团可为直链或支链的基团。除非另外指明,如本文所用的术语“分子量”指重均分子量(Mw)。
除非另有定义,否则所有的浓度指按所述组合物的重量计的浓度。另外,除非另有具体定义,否则相对于一类成分的术语“基本上不含”,是指特定成分(一种或多种)以小于该特定成分被用以有效提供其将以其他方式使用的有益效果或属性所需的浓度存在,例如,约1%或更少,或约0.5%或更少。
如本文所用,“UV吸收性”是指吸收在紫外线光谱(290nm-400nm)的一些部分中的辐射的材料或化合物,例如聚合物的或非聚合的防晒剂或化学部分,诸如针对上述定义的紫外线光谱内的至少一个波长具有至少约1000mol-1cm-1的消光系数的一种材料或化合物。使用下文所述的体外方法测定本文公开并受权利要求书保护的SPF值。
UV吸收性聚酯
本发明的实施例涉及包括防晒剂的组合物,其中防晒剂包含UV吸收性聚酯。此类聚酯可以被表征为多元醇、多元酸、多元酸酐和/或聚酯的聚合反应(例如,酯化反应和/或酯交换反应)产物。所谓“聚酯”,其意指具有多个重复单元的聚合物,这些重复单元中的每个包含酯官能团,[-COO-]。这样,UV吸收性聚酯可包含一个或多个“聚酯主链”部分,每个聚酯主链部分具有通过如本文所述聚合作用衍生出的一个或多个酯官能团。如本文所用,“UV吸收性聚酯”可包含可由于聚合过程而存在的残余游离单体。
根据某些实施例,UV吸收性聚酯为复合物。所谓“复合物”,其意指UV吸收性聚酯包含末端一官能化合物。UV吸收性聚酯用一官能酸类、酸酐类、一官能醇类、一官能环氧衍生物类和/或一官能酯类完全地或部分地封端(通过反应)。
根据某些实施例,UV吸收性聚酯为交联的。所谓“交联”,其意指UV吸收性聚酯具有三个或更多个末端基团,每个基团对UV吸收性聚酯的支链封端。因此,UV吸收性聚酯可使用总共具有至少三个官能团(例如四个官能团)的一种或多种多官能单体来制备。
根据某些实施例,UV吸收性聚酯包含多个独立的聚酯部分,其中每个聚酯部分由UV吸收性部分封端(terminated)或“封端(capped)”。可用于根据本发明的组合物的UV吸收性聚酯在美国专利申请公开US2011/0104078A1中有所描述。具体地,根据所述专利申请的方案6并且如下文另外定义的UV吸收性聚酯可用于本发明的组合物,其中本发明的组合物基本上不含非聚合的UV吸收性防晒剂。
UV吸收性聚酯之所以是UV吸收性的,是因为其包含如下文讨论的UV吸收性部分并因此吸收在紫外线光谱(290nm-400nm)的一些部分中的辐射,诸如针对上述定义的紫外线光谱内的至少一个波长具有约1000mol-1cm-1或更大(例如大于10,000或100,000或1,000,000mol-1cm-1)的消光系数的一种。UV吸收性部分可主要在紫外线光谱的UV-A部分(320nm至400nm)中吸收或主要在紫外线光谱的UV-B部分(290nm至320nm)中吸收。具体地,UV吸收性部分的合适示例包括UV吸收性三唑。所谓“UV吸收性三唑”,其意指包含具有两个碳原子和三个氮原子的五元杂环的UV吸收性部分。典型的UV吸收性三唑为苯丙三唑,其包含所提及的与六元碳环芳族环稠合在一起的五元杂环。UV吸收性三唑的示例包括例如由式(II)或式(III)表示的化合物:
(II)
(Ⅲ)
其中R14为任选的C1-C18烷基或氢;R15和R22独立地任选为可用苯基基团取代的C1-C18烷基,并且R21为任选的官能团诸如可包含含有甲基基团的酯键的C1-C8烷基。UV吸收性三唑可连接到独立的聚酯部分。
聚酯部分可各自包含或由诸如下面的(IV)或(V)的n个重复单元组成:
(IV)
(V)
在结构(IV)和(V)中:R和R’表示烃类诸如具有独立在C1-C100,诸如C4-C50,诸如C6-C40的范围内的碳链长的烷基、芳基,或芳烷基链(饱和或不饱和);n为独立聚酯部分中的每个的聚合度,且可在1至约20(诸如1至约10,诸如1至约5)的范围内。总聚合度,即,UV吸收性聚酯中所有聚酯部分n的总和,可在4至约25(诸如约5至约20,诸如5至约10)的范围内。
根据某些实施例,通过使用例如下面的条件和检测系统执行凝胶渗透色谱法,测定UV吸收性聚酯具有约2,000或更大的重均分子量(Mw),如约4,000或更大,如约4,000至约4,500。
Mw的测定可使用下面的凝胶渗透色谱法(GPC)方法和设备进行。合适的液相色谱系统为Agilent 1100/1200系列高效液相色谱法系统,其中的硬件包括5个模块;G1379A脱气器、G1310A型号等度泵、1110自动液体采样器型号G1313A、G1316A型号恒温柱隔室,和G1362A型号折射率检测器(RID)。使用Agilent LC Chemstation软件,修订版本B.03.02来控制系统。系统配有两个瓦里安中孔GPC色谱柱(Varian MesoPore GPC),300×7.5mm,3um,多孔。样品在ACS HPLC等级四氢呋喃(THF)中溶解至约1.0mg/ml的浓度。THF含有250ppm丁基化羟基甲苯(BHT)作为氧化抑制剂。THF在被用作移动相溶剂和溶解溶剂之前使用0.45um的微孔(Millipore)过滤器进行过滤。通过系统中的真空脱气器对溶剂连续脱气。移动相流速为1mL/min。在色谱柱隔室中的两个色谱柱的组保持在45℃。注入体积为200微升。运行时间为三十分钟。
使用分别具有162、580、1110、1530、2340、3790、5120、7210、12830和19640道尔顿的分子量的10个窄分子量分布聚苯乙烯标准物,来执行GPC色谱柱的校准。标准物可购自Agilent-Varian。注入每个标准物,且摩尔质量针对洗脱体积线性回归以提供校准线。聚酯的分子量计算使用Agilent Chemstation软件的添加件Agilent GPC插件修订版本B.01.01进行测定。以道尔顿单位给出的具有创造性的聚酯的所有结果均相对于聚苯乙烯标准物。
在某些实施例中,为了增强抗水性和铺展性,UV吸收性聚酯可具有低的水溶解度。所谓“水溶解度”,其意指聚酯可放置于100克去离子水并搅拌以获得澄清溶液并且在环境温度下在视觉上保持均匀且透明达24小时的最大重量百分比(相对于聚酯加上水)。例如,在某些实施例中,UV吸收性聚酯的水溶解度可为约3%或更小,如约1%或更小。
适用于本发明组合物的UV吸收性聚酯可通过本领域技术人员已知的各种方式合成,例如,带有UV吸收性部分的内酯(环状酯)的开环;具有酸功能性和醇功能性的UV吸收性单体的缩合反应(例如,“A-B”缩合反应)使多元醇官能单体和多元酸官能单体缩合,其中之一或二者包含UV吸收性部分;等。
制备UV吸收性聚酯的一个具体合适方法为通过酯交换反应,诸如通过使多官能羟基发生反应,例如,四元醇(具有四个醇官能团的分子)、二醇、二羧酸和酯官能的UV吸收性单体。例如,三个中每个均不存在UV吸收性部分的单体(例如二醇、四元醇和二羧酸)可与第四单体(例如具有酯功能性的UV吸收性三唑)反应以生产UV吸收性聚酯。单体的摩尔比可以被选择,使得各种单体对的比例为约0.25:1至约4:1。根据一个实施例,UV吸收性单体(例如UV吸收性三唑)相对于反应中使用的所有单体的摩尔总数(包括UV吸收性单体)的摩尔份数被选择为约0.39至约0.60,或约0.37至约0.42。根据另一个实施例,该摩尔份数被选择为约0.45或更小。
一个具体合适的UV吸收性聚酯通过以下单体的酯交换反应形成:(1)二聚二醇,C36H72O,CAS号147853-32-5,其为C36二醇;(2)二-三羟甲基丙烷,C12H26O5,CAS号23235-61-2,其为衍生自三羟甲基丙烷二聚反应的四官能醇(四元醇);(3)己二酸二甲酯,C8H14O4,CAS号627-93-0,己二酸的甲基酯;以及(4)苯丙酸,3-(2h-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羟基-甲酯,C20H23N3O3,CAS号84268-33-7,UV吸收性单体(包括UV吸收性三唑)。二聚二醇在美国专利US 7,427,640中有所描述。
根据某些实施例,防晒剂由或基本上由如本文定义的UV吸收性聚酯组成。根据某些其他实施例,防晒剂可包含除了如本文定义的那些UV吸收性聚酯之外的另外的UV吸收性聚合物和/或非UV吸收性、光散射的颗粒。另外的UV吸收性聚合物是可以被表示为具有周期性地重复(例如,至少两次)的一个或多个结构单元以生成分子的分子,并且可以是除了在本说明书中定义并受权利要求书保护的那些之外的UV吸收性聚酯。
另外的UV吸收性聚合物可具有大于约1500的分子量。合适的另外的UV吸收性聚合物的示例包括亚苄基丙二酸硅氧烷,其包括在Bernasconi等人的美国专利6,193,959中描述的那些。具体合适的亚苄基丙二酸酯包括可从Heerlen,Netherlands的DSM(Royal DSM N.V.)商购获得的“ParsolSLX”。其他另外合适的UV吸收性聚合物公开于US 6,962,692;US 6,899,866;和/或US 6,800,274中;包括己二酸、与2,2-二甲基-1,3-丙二醇的聚合物、3-[(2-氰基-1-氧代-3,3-二苯基-2-丙烯基)氧基]-2,2-二甲基丙基2-辛基十二酯;以商品名“POLYCRYLENE”出售,可从Chicago,Illinois的HallStar Company商购获得。当被使用时,此类另外的UV吸收性聚合物可以约1%或更大(例如约3%或更大)的浓度使用。
非UV吸收性、光散射的颗粒不在UV光谱中吸收,但可通过散射入射的UV辐射增强SPF。非UV吸收性、光散射的颗粒的示例包括具有约0.1微米至约10微米的尺寸例如平均直径的固体颗粒。在某些实施例中,非UV吸收性、光散射的颗粒为包含或基本上由有机聚合物或玻璃组成的中空颗粒。合适的有机聚合物包括丙烯酸聚合物,其包括丙烯酸/苯乙烯共聚物,如以SUNSPHERES得知并且可从Midlanda,Michigan的DowChemical商购获得的那些。合适的玻璃包括硼硅酸盐玻璃,如在名称为,“AESTHETICALLY AND SPF IMPROVED UV-SUNSCREENSCOMPRISING GLASS MICROSPHERES(包含玻璃微球体的美学和SPF改善的UV防晒剂)”的公布的美国专利申请US20050036961A1中描述的那些。
局部用组合物
在一个实施例中,提供了适用于以局部/美容用途施用于人体(例如,角质表面如皮肤、毛发、嘴唇或指/趾甲)尤其是皮肤的组合物。组合物包含一种或多种本文所述的UV吸收性聚酯。如上面讨论的,尤其在不存在或基本不存在如本文所述的其他UV吸收性聚合物或非聚合的UV吸收性防晒剂药剂的情况下,UV吸收性聚酯的浓度足够提供约10或更高的SPF。因此,UV吸收性聚酯的浓度可为约5重量%至约50重量%,如组合物的约7%至约40%,如组合物的约10%至约25%。在某些实施例中,UV吸收性聚合物的浓度为组合物的约10%或更大,如约15%或更大,如约25%或更大。根据其中防晒剂药剂基本上由UV吸收性聚酯组成的某些实施例,UV吸收性聚酯的浓度可为约15%或更大。
如果存在非UV吸收性防晒剂药剂,其浓度可为约1%或更大,如从约1%至约10%,如从约2%至约5%。在其中UV防晒剂还包含如上讨论量的非UV吸收性防晒剂的某些实施例中,本发明的组合物可具有约20或更高的SPF。
本发明的组合物基本上不含非聚合的UV吸收性防晒剂。所谓“基本上不含非聚合的UV吸收性防晒剂”,其意指如通过下文所述的体外方法测定的,在不存在UV吸收性聚酯的情况下,组合物不包含有效地向组合物提供大于2的SPF的量的非聚合的UV吸收性防晒剂药剂。例如,本发明的组合物将包含约1%或更少或者约0.5%或更少的此类非聚合的UV吸收性防晒剂药剂。在不存在UV吸收性聚酯的情况下,组合物将具有小于2的SPF。组合物基本上不含的非聚合的UV吸收性防晒剂药剂的一个示例通常可以被表征为“有机的”(主要包含或仅包含选自碳、氢、氧和氮的原子),并且具有不可限定的重复单元且通常具有约600道尔顿或更小(如约500道尔顿或更小,如小于400道尔顿)的分子量。此类化合物,有时被称为“单体、有机UV吸收性剂”,的示例包括但不限于:甲氧基肉桂酸酯衍生物如甲氧基肉桂酸辛酯和异戊基甲氧基肉桂酸酯;樟脑衍生物如4-甲基亚苄基樟脑、樟脑烷基苄基二甲基铵硫酸二甲酯和对苯二亚甲基二樟脑磺酸;水杨酸酯衍生物如水杨酸辛酯、水杨酸三乙醇胺和胡莫柳酯;磺酸衍生物如苯基苯并咪唑磺酸;苯酮衍生物如双羟华酮、磺异苯酮和羟甲氧二苯酮;苯甲酸衍生物如氨基苯甲酸和辛基二甲基对-氨基苯甲酸;氰双苯丙烯酸辛酯和其他β,β-二苯基丙烯酸酯;二辛基丁酰胺基三嗪酮;辛基三嗪酮;丁基甲氧基二苯甲酰甲烷;甲酚曲唑三硅氧烷;以及邻氨基苯甲酸薄荷酯。
组合物基本上不含的其他非聚合的UV吸收性防晒剂药剂可包括紫外线吸收性颗粒,如某些无机氧化物,其包括二氧化钛、氧化锌和某些其他过渡金属氧化物。此类紫外屏蔽颗粒通常为直径为约0.1微米至约10微米的固体颗粒。
本发明的组合物可用于多种美容用途,尤其是用以保护皮肤免受UV辐射。因此组合物可制成多种递送形式。这些形式包括但不限于悬浮体、分散体、溶液或者水溶性或水不溶性基材(例如,如有机或无机的粉末、纤维或膜的基材)上的涂料。合适的产品形式包括洗剂、霜剂、凝胶剂、棒剂、喷剂、软膏剂、摩丝和粉盒/粉末。组合物可用于各种最终用途,如娱乐或日用防晒剂、保湿剂、化妆品/彩妆、清洁剂/调色剂、抗衰老产品或它们的组合。本发明的组合物可使用化妆品制剂领域普通技术人员熟知的方法制备。
本发明的组合物包含连续水相,其中包含UV吸收性聚酯的不连续油相基本上均匀地分布在所述连续水相中。在某些实施例中,UV吸收性聚酯溶解而不是分散或悬浮在油相内。油相可继而稳定在水相内。油相可以平均直径为约1微米至约1000微米,如约1微米至约100微米的离散液滴或单元存在。
水相和油相的相对浓度可变化。在某些实施例中,水相按重量计百分比为约10%至约90%,如约40%至约80%,如50%至约80%;其中余量为油相。
组合物中包含的水的百分比可在约20%至约90%范围内,如约20%至约80%,如约30%至约70%,如约51%至约80%,如约51%至约70%,如约51%至约60%。
局部用载体
可将组合物中的一种或多种UV吸收性聚酯与“美容上可接受的局部用载体”,即,能使其他成分分散或溶解在其中并具有可接受的特性使得其可安全地局部使用的局部用载体组合。这样,组合物还可包含化妆品化学领域已知的多种功能成分中的任何成分,例如润肤剂(包括油和蜡)以及常用于个人护理组合物中的其他成分,如其他功能成分中的保湿剂、增稠剂、遮光剂、芳香剂、染料、UV吸收性聚酯的溶剂等成分。UV吸收性聚酯的溶剂的合适的示例包括以CETIOL CC得自宾Ambler,Pennsylvania的Cognis Corporation的碳酸二辛酯。为了提供合意的美观,在本发明的某些实施例中,组合物基本上不含挥发性溶剂;具体地,C1-C4醇类如乙醇和异丙醇。
此外,组合物可基本上不含将使得组合物不适于局部使用的成分。这样,组合物可基本上不含溶剂如挥发性溶剂,具体地不含挥发性有机溶剂如酮、二甲苯、甲苯等。
成膜聚合物
本发明的组合物包含成膜聚合物。当溶解、乳化或分散在一种或多种稀释剂中时,成膜聚合物在与液体载体一起铺展到光滑基材如玻璃上并让液体载体蒸发时,可形成连续或半连续的膜。这样,聚合物可在玻璃上以如下方式干燥,其中在该聚合物铺展开的区域上其应主要是连续的,而不是形成多个离散的岛状结构。根据本文所述的本发明实施例,通过在皮肤上涂敷组合物而形成的薄膜的平均厚度可小于约100微米,如小于约50微米。
与聚合物的UV吸收聚合物相比,成膜聚合物通常不吸收可测量的紫外辐射并因此不满足UV吸收性聚合物的要求。然而,通过改善成膜性,成膜聚合物可增强组合物的UV防护性(UV-A、UV-B或二者)和/或增强组合物的防水性或抗水性。
成膜聚合物为烷基化的聚乙烯吡咯烷酮,如乙烯基吡咯烷酮和α-烯烃的共聚物,如乙烯基吡咯烷酮和长链(例如,C16至C30)α-烯烃的共聚物,例如,GANEX V220、GANEX V216、GANEX WP660)。在一个尤其值得注意的实施例中,成膜聚合物由20%的乙烯基吡咯烷酮和80%的C16烯烃(1-十六碳烯)形成,如GANEX V216。GANEX成膜聚合物可从New Jerseya,Wayne的IISP Specialty Chemicals(Ashland SpecialtyIngredients)商购获得。
本发明的组合物可包含另外的成膜聚合物,其包括天然聚合物如多糖或蛋白质以及合成聚合物如聚酯、聚丙烯酸类、聚氨酯、乙烯基聚合物、聚磺酸酯、聚脲、聚恶唑啉等。另外的成膜聚合物的具体的示例包括例如氢化的二聚体亚油醇基/二甲基碳酸酯共聚物,其以COSMEDIA DC购自Amblera,Pennsylvania的Cognis Corporation;以及水可分散的聚酯,其包括可按EASTMAN AQ 38S从Eastman Chemical商购获得的那些。
存在于组合物中成膜聚合物的量可为约0.1%至约5%,或约0.3%至约3%,或约0.1%至约2.5%。
水包油乳化剂
本发明的组合物包含一种或多种水包油(O/W)乳化剂,所述水包油乳化剂选自阴离子乳化剂和非离子乳化剂。所谓“乳化剂”,其意指适用于在连续水相中乳化离散的油相液滴的多种分子中的任何分子。所谓“低分子量乳化剂”,其意指分子量为约2000道尔顿或更小,如约1000道尔顿或更小的乳化剂。当室温下向纯去离子水添加至0.5%或更低浓度的O/W型乳化剂时,O/W型乳化剂可能够将纯去离子水的表面张力降至45达因/厘米。O/W乳化剂可具有约8或更大,如约10或更大的亲水亲油平衡值(HLB)。
在某些实施例中,组合物包含一种或多种阴离子乳化剂。阴离子乳化剂合适的化学类示例为烷基、芳基或烷基芳基或以下部分的酰基改性型式:硫酸盐、醚硫酸盐、单甘油醚硫酸盐、磺酸盐、磺基琥珀酸盐、醚磺基琥珀酸盐、磺基琥珀酰胺酸盐、酰胺基磺基琥珀酸盐、羧酸盐、酰胺基醚羧酸盐、琥珀酸盐、肌氨酸盐、氨基酸、牛磺酸盐、磺基乙酸盐和磷酸盐。值得注意的阴离子乳化剂为磷酸和鲸蜡醇的酯的盐,如磷酸和鲸蜡醇的酯的混合物的钾盐(例如,1-十六醇、磷酸二氢酯、单钾盐)。一个值得注意的示例为十六烷基磷酸钾,氢化的棕榈酸甘油酯,其以商品名EMULSIPHOS从Holzminden,Germany的Symrise获得。
在某些实施例中,一种或多种阴离子乳化剂的浓度为约0.5%至约6%,如约1%至约4%,如约1%至约2.5%。
在本发明的另一个实施例中,组合物包含一种或多种非离子乳化剂。非离子乳化剂的示例包括脂肪酰胺、单甘油酯;脱水山梨糖醇酯;多元醇酯的聚氧乙烯衍生物;烷基葡糖苷或多聚葡糖苷;多甘油酯;非交联硅氧烷共聚物如烷氧基或烷基聚二甲基硅氧烷共聚醇、具有侧链亲水部分的硅氧烷如具有侧链聚醚基团或甘油聚合物基团的直链硅氧烷;包含至少一个亲水部分的交联弹性体固体有机聚硅氧烷:聚乙二醇、聚丙二醇、或多甘油酯。根据一个实施例,非离子乳化剂不具有醇官能团。根据本发明的一个实施例,非离子乳化剂的分子量为约10,000道尔顿或更小,如约7000道尔顿或更小。
根据一个实施例,非离子表面活性剂为脂肪酸的酯,如各种饱和或不饱和、直链或支化的,C7-C22非乙氧基化的,脂族酸。脂肪酸可具有14至约22个碳原子,如约16至18个碳原子。根据一个实施例,非离子乳化剂为聚醚,如选自甘油的脂肪酸酯(如甘油基硬脂酸酯)、聚乙二醇脂肪酸酯(如PEG-100硬脂酸酯)以及它们的组合。
从非离子表面活性剂中具体排除的为油-胶凝聚合物,如能够与矿物油在25℃形成凝胶的聚合物,如当油-胶凝聚合物与矿物油混合至约0.25重量%至2.0重量%的油-胶凝聚合物的浓度时,所得的混合物具有约5帕斯卡(Pa)或更大的屈服应力,如约10Pa或更大,如约10Pa至约1100Pa。油-胶凝聚合物的示例为C2-C4烷基纤维素聚合物,如乙基纤维素,其为包含长链聚合物的纤维素的乙基醚,所述长链聚合物由通过乙缩醛键合接合在一起的葡糖酐单元组成。油-胶凝聚合物的其他示例为二丁基乙基己醇基谷氨酰胺(dibutyl ethylheaxanoyl glutamide)和二丁基月桂酰基谷氨酰胺(dibutyl lauroyl glutamide)。
非离子乳化剂的浓度可在约1%至约10%的范围内,如约2%至约6%,如约2%至约4%。
在某些实施例中,除了上述讨论的乳化剂(一种或多种)以外,组合物包含另外的乳化剂如两性乳化剂、阳离子乳化剂和/或聚合物的乳化剂中的一种或多种。合适的化学类两性乳化剂的示例包括烷基甜菜碱、氨基烷基甜菜碱烷基两性乙酸酯(alkylamphoacetates);酰胺基烷基磺基甜菜碱(amidoalkyl sultaines);两性磷酸酯;磷酰化的咪唑啉;羧烷基烷基多元胺;烷基亚氨基-二丙酸盐;烷基两性(单或二)甘氨酸盐;烷基两性丙酸盐;N-烷基β-氨基丙酸;以及烷基聚氨基羧酸盐。合适的化学类阳离子乳化剂的示例包括烷基季铵盐、苄基季铵盐、酯季铵盐、乙氧基化的季铵盐和烷基胺。合适的化学类聚合物乳化剂的示例包括基于丙烯酰氨烷基磺酸的共聚物,如Clariant Corporation的AVC和HMB;以及Grant Industries,Inc的Granthix APP。
在某些实施例中,组合物包含用于防止或减轻干燥并用于保护皮肤的润肤剂,以及增溶的UV吸收性聚酯。合适的润肤剂包括矿物油、凡士林、植物油(例如三甘油酯如辛酸/癸酸甘油三酯)、蜡和脂肪酯的其他混合物,其中脂肪酯包括但不限于甘油的酯(例如,棕榈酸异丙酯、肉豆蔻酸异丙酯),以及硅氧烷油如聚二甲基硅氧烷。在某些实施例中,三甘油酯(例如辛酸/癸酸三甘油酯(triclycerides))和二醇类的酯(例如肉豆蔻酸异丙酯)的混合物可用于增溶UV吸收性聚酯。
在某些实施例中,组合物包含适用于提供颜色或遮盖力的颜料。颜料可为适用于有色化妆品的一种,其包括施用于毛发、指/趾甲和/或皮肤尤其是脸部的组合物。有色化妆组合物包括但不限于粉底、遮瑕膏、打底膏(primer)、腮红、睫毛膏、眼影膏、眼线膏、唇膏、指甲油和调色保湿剂。
适用于提供颜色或遮盖力的颜料可由包括红和黄氧化铁的氧化铁、二氧化钛、群青颜料和铬或氢氧化铬颜色、以及它们的混合物构成。颜料可为色淀颜料,例如,沉淀于惰性粘合剂如不溶性盐上的有机染料,如被指定为D&C和FD&C蓝、棕、绿、橙、红、黄等的偶氮、靛青类、三苯甲烷、蒽醌和黄嘌呤染料。色淀颜料的示例包括红#6、红#7、黄#5和蓝#1。颜料可为干涉颜料。干涉颜料的示例包括含有云母基材、氯氧化铋基材和二氧化硅基材的那些,例如可作为CHROMALITE颜料(BASF)商购获得的云母/氯氧化铋/氧化铁颜料;涂布于云母上的二氧化钛和/或氧化铁,如商购获得的FLAMENCO颜料(BASF);云母/二氧化钛/氧化铁颜料,包括商购获得的KTZ颜料(Kobo products)、CELLINI珍珠颜料(BASF);和含硼硅酸盐的颜料,如REFLECKS颜料(BASF)。
本发明的组合物可还包含一种或多种其他美容活性剂(一种或多种)。“美容活性剂”为对皮肤具有美容或治疗效果的化合物,例如治疗皱纹、粉刺或增亮皮肤的试剂。美容活性剂通常以组合物的约0.001重量%至约20重量%,例如组合物的约0.01重量%至约10重量%,如组合物的约0.1重量%至约5重量%的量存在于本发明的组合物中。
在某些实施例中,组合物的pH为约4.0至约8.0,如约5.5至约7.0。
抗水性可使用例如如下所示的体外抗水性测试来测量。相比于具有较低抗水性值的组合物,其倾向于指示组合物的膜对于被用水去除具有较小的抗性,组合物较高的抗水性值倾向于指示组合物的膜对于被用水去除具有较大的抗性。申请人已经认识到,本发明的组合物具有惊人地与其关联的高抗水性值。例如,在某些实施例中,组合物的抗水性值(WRV)为约65%或更大。在某些其他实施例中,组合物表现出约80%或更大的WRV,如约90%或更大。
本发明的组合物可使用普通技术人员熟知的混合和共混方法制备。在本发明的一个实施例中,制备本发明组合物的方法包括通过混合至少UV吸收性聚酯与任选的油可溶或油可混溶的成分来制备油相;并通过混合水与任选的水可溶或水可混溶的成分来制备水相。然后可将油相与水相以足以使油相基本上均匀地分散在水相中使得水相连续而油相不连续的方式混合。
本发明的组合物可通过局部施用于哺乳动物来使用,例如通过直接平铺、涂搽或铺展组合物到人的皮肤或毛发上来使用。
在本发明方法和以下的实例中使用了下面的抗水性测试。
抗水性测试:
给定制剂的抗水性潜能根据下面示出的抗水性测试进行测量。虽然大于80%的WRV被认为是甚至更可取的,并且大于90%的WRV被认为是甚至更可取的,但大于65%的WRV被认为是特别高的。
抗水性测试以如下方式进行。对于每个样品,将产品施加于PMMA板,并且根据下面所述的程序、体外SPF方法测量初始SPF。在15分钟干燥周期后,立即用蓝菲(labphere)仪器测量初始SPF,然后将涂覆一种防晒剂的PMMA板连接到包括4个推进器类型混合刀片的18英寸的杆。将混合杆+板浸渍到3L烧杯的去离子水中。混合刀片以35rpm精确地旋转20分钟。20分钟后对板除水并且允许风干2小时。在干燥板上读取最终SPF。通过最终SPF除以初始SPF并乘以100计算WRV。将新鲜的3L去离子水用于每个板。
防晒因子(SPF)可使用下面的体外SPF测试方法进行测试。测量其上未施加任何测试材料的PMMA板(基材)的基线透射率。测试样品通过提供聚合物样品来制备。共混物也可通过此方法测试。聚酯(一种或多种)可以无需任何另外的添加剂进行测试;也可使用溶剂体系或作为可包含溶剂和/或另外成分的个人护理组合物的一部分。
每个样品单独地施加到PMMA板(购自Marseillea,France的Helioscience),施加密度为2微升溶液/平方厘米基材,操作人员用手指将其摩擦成均匀的薄层,并让其干燥。让样品干燥15分钟,然后用校准的UV-1000S UV透射分析仪(LabsphereNorth Sutton,N.H.,USA)测量吸光度。使用吸光度测定值计算SPF和PFA指数(基于UVA的生物保护因子)。
可使用本领域已知的方法计算SPF和PFA–参见用于SPF的计算的下面的公式(1):
其中:
E(λ)=红斑作用光谱
I(λ)=自UV源接收的光谱辐照度
A0(λ)=UV暴露之前测试产品层的平均单色吸光度
dλ=步进波长(1nm)
实例
下面的实例示出了本发明的组合物的制备和功效。
实例I
下面的实例示出了本发明的某些组合物的高抗水性。发明组合物(E1-E3)包含UV吸收性聚酯,其基本上不含UV屏蔽化合物,并且还包含烷基化的聚乙烯吡咯烷酮以及阴离子或非离子乳化剂。这些发明实例如表1所示制备并在下面描述。
发明实例E1通过下面的方法制备:通过向主容器中加入水并于混合下加热至70℃-75℃制备水相。加入PEMULEN TR-2并混合直至溶解。加入EUXYL PE9010并混合直至溶解。通过向容器中装入CETIOL CC并混合来制备油相。在60℃下,将UV吸收性聚酯添加到容器中。将ARLACEL 165和GANEX 216添加到油相中,并且在持续混合下将混合物加热至约80℃直至均匀。以中等剪切将受热的油相添加到水相中。在冷却过程中继续进行中等混合。在约40℃时,将二氧化硅轻轻地加入到制剂中。
发明实例E2通过下面的方法制备。通过向主容器中加入水并于混合下加热至75℃-80℃制备水相。将EUXYL PE9010添加到水相中。通过向容器中装入CETIOL CC并混合来制备油相。在60℃下,加入UV吸收性聚酯。将ARLACEL 165和GANEX 216加入到油相中,并且在连续混合下将混合物加热至约75℃-80℃直至均匀。以中等剪切将受热的油相加入到水相中。在冷却过程中继续进行中等混合。在约40℃时,将二氧化硅和Cosmedia ATH轻轻地加入到制剂中。
发明实例E3通过下面的方法制备。通过向主容器中加入水并于混合下加热至75℃-80℃制备水相。通过向容器中加入CETIOL CC并混合来制备油相。在60℃下,加入UV吸收聚合物。加入EMULSIPHOS、CRODACOL C95和GANEX 216,并且在混合下将混合物加热至约75℃-80℃。以中等剪切将热油相加入到水相中。在冷却过程中继续进行中等混合。在约40℃时,将二氧化硅轻轻地加入到制剂中。随后,将EUXYL PE9010混合到制剂中。
表1:发明实例
PEMULEN TR-2为丙烯酸酯/C10-30烷基丙烯酸酯交联聚合物,购自Wickliffea,Ohio的Noveon/Lubrizol)。CETIOL CC为碳酸二辛酯,购自Ludwigshafen,Germany)的科宁公司,现为BASF公司。EUXYL PE 9010为苯氧基乙醇和乙基己基甘油,购自Northvale,New Jersey的Tri-K Industries。GANEX V-216为乙烯基吡咯烷酮和C16α-烯烃的共聚物,购自Wayne,New Jersey的ISP Specialty Chemicals。ARLACEL 165veg为甘油基硬脂酸酯(和)PEG-100硬脂酸酯,购自Edisona,New Jersey的禾大公司Croda。CRODACOL C95为一系列饱和脂肪醇类,购自Edisona,New Jersey的Croda PLC)。EMULSIPHOS为十六烷基磷酸钾和氢化棕榈酸甘油酯,购自Holzminden,Germany的Symrise。
UV吸收性聚酯由如下四种单体制备:(1)二聚二醇,C36H72O,CAS号147853-32-5(在下面的表1中称为“DDO”);(2)二-三羟甲基丙烷,C12H26O5,CAS号23235-61-2(“DITMP”);(3)己二酸二甲酯,C8H14O4,CAS号627-93-0(“DMA”);以及(4)苯丙酸,3-(2h-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羟基-,甲酯,C20H23N3O3,CAS号84268-33-7(“三唑”)。四种单体(DDO:DITMP:DMA:三唑)的摩尔比为:3.4:2.1:4.0:6.0。因此,UV吸收性聚酯的UV吸收性三唑的摩尔份数为约0.39。重均分子量估计为约4192。所得的UV吸收性聚酯与足够量的碳酸二辛酯(CETIOL CC)混合以形成UV吸收性聚酯溶液,其为80重量%的UV吸收性聚酯和20重量%的碳酸二辛酯。
除了发明实例E1-E3,比较例C1-C5如表2所示制备并且在下面描述。
表2:比较例,C1-C5
COSMEDIA ATH为氢化的二聚体二亚油基/二甲基碳酸酯共聚物,购自Ambler,Pennsylvania的Cognis Corporation。EMULFREE CBG为丁二醇、异硬脂醇和乙基纤维素的椰油酸单酯和椰油酸二酯的混合物;购自Parisa,France的Gattefosse其他成分如本说明书的其他部分描述。
比较例C1-C2通过如下方法制备:通过向主容器中加入水并于混合下加热至70℃-75℃制备水相。加入EUXYL PE9010(C2)或PHENONIP XB(C1)并混合直至溶解。缓慢加入PEMULEN并快速混合直至均匀。乳化前,水相被部分中和。通过向容器中装入CETIOL CC并混合来制备油相。加入CRODACOL C95并进行加热处理。在60℃下,加入UV吸收性聚酯。分别加入EMULFREE CBG(C1)和EMULFREE加上GANEX 216(C2),且连续混合5分钟,并将混合物加热至约80℃直至均匀。以中等剪切将受热的油相加入到水相中。用氢氧化钠将pH调节至6.5,并且继续进行中等混合5分钟。在减小的混合速度下,将混合物缓慢冷却至室温。
比较例C3和C4通过如下方法制备:通过向主容器中加入水并混合加热至75℃-80℃来制备水相。加入黄原胶并混合直至溶解。通过向容器中装入CETIOL CC并混合来制备油相。在60℃下,加入UV吸收性聚酯。加入ARLACEL 165,并且在混合下,将混合物加热至约75℃-80℃直至均匀。以中等剪切将受热的油相加入到水相中。在冷却过程中继续进行中等混合。在约40℃下,将二氧化硅轻轻地加入到制剂中。随后,将EUXYL PE9010混合到制剂中。比较例C4与C3相同,不同的是在方法结束时加入1%的COSMEDIA ATH。
比较例C5通过如下方法制备:通过向主容器中加入水并于混合下加热至75℃-80℃制备水相。加入PEMULEN TR-2并混合直至溶解。通过向容器中加入CETIOL CC并混合来制备油相。在60℃下,加入UV吸收性聚酯。加入EMULSIPHOS和CRODACOL C95,并且在混合下将混合物加热至约75℃-80℃。以中等剪切将受热的油相加入到水相中。在冷却过程中继续进行中等混合。在约40℃下,将二氧化硅轻轻地加入到制剂中。随后,将EUXYL PE 9010混合到制剂中。
发明实例E1-E3和比较例C1-C5的WRV使用如上所述的抗水性测试来测定,结果报道于表3。对于除C4和C5以外的全部示例,均在三个独立的板上执行抗水性测试,其中测试只在单个PMMA板上进行。
表3:抗水性测试
抗水性测试的结果指示,烷基化的聚乙烯吡咯烷酮成膜剂(GANEX216)的添加显著改善了包含阴离子或非离子乳化剂的组合物的抗水性。例如,如通过比较E3和C5所示,烷基化的聚乙烯吡咯烷酮改善了具有阴离子乳化剂EMULSIFPHOS的组合物的抗水性;或如通过比较E1和C3或通过比较E2和C4所示,烷基化的聚乙烯吡咯烷酮改善了具有非离子乳化剂ARLACEL的组合物的抗水性。然而,烷基化的聚乙烯吡咯烷酮成膜剂并不导致不包含这些类型乳化剂的任一种(实例C1和C2)的组合物抗水性的增大。此外,如通过比较C4和C3所示,使用含有氢化的二亚油酸基/二甲基碳酸酯共聚物(COSMEDIA ATH)而不含有烷基化的聚乙烯吡咯烷酮的成膜剂,不改善抗水性。
令人意外的是,仅当具体的乳化剂(非离子和阴离子)与成膜剂组合使用时,包含UV吸收性聚酯且基本上不含或不含常规的非聚合的UV吸收性防晒剂的组合物提供足够的抗水性。
应理解,虽然已结合本发明的具体实施方式描述了本发明,但前面的描述旨在示出而非限制本发明的范围。
Claims (18)
1.一种组合物,包含:
连续水相,
基本上均匀地分布于所述水相中的不连续油相,所述油相包含防晒剂,所述防晒剂以有效地向所述组合物提供约10或更高的SPF的量包含UV吸收性聚酯,其中UV吸收性聚酯为包含UV吸收性三唑、二酯、二醇和四元醇的单体的聚合反应产物,
烷基化的聚乙烯吡咯烷酮;和
选自阴离子乳化剂和非离子乳化剂的水包油乳化剂,
其中所述组合物基本上不含非聚合的UV吸收性防晒剂,并且在不存在所述UV吸收性聚酯的情况下具有小于2的SPF。
2.根据权利要求1所述的组合物,包含约5%至约50%的所述UV吸收性聚酯。
3.根据权利要求1所述的组合物,其具有约20或更高的SPF。
4.根据权利要求1所述的组合物,其中所述防晒剂基本上由所述UV吸收性聚酯组成。
5.根据权利要求1所述的组合物,包含约12%或更多的所述UV吸收性聚酯。
6.根据权利要求1所述的组合物,包含约7%或更多的所述UV吸收性聚酯。
7.根据权利要求1所述的组合物,其中所述UV吸收性聚酯具有约4,000或更大的重均分子量。
8.根据权利要求1所述的组合物,其具有约20或更高的SPF。
9.根据权利要求1所述的组合物,其中所述UV吸收性三唑、所述二酯、所述二醇和所述四元醇发生反应,使得UV吸收性三唑的摩尔份数相对于在所述反应中使用的单体的摩尔总数为约0.39至约0.60。
10.根据权利要求1所述的组合物,其中所述UV吸收性三唑、所述二酯、所述二醇和所述四元醇发生反应,使得UV吸收性三唑的摩尔份
数相对于在所述反应中使用的所有单体的摩尔总数为约0.37至约0.42。
11.根据权利要求1所述的组合物,其中所述水包油乳化剂为阴离子乳化剂。
12.根据权利要求1所述的组合物,其中所述水包油乳化剂为非离子乳化剂。
13.根据权利要求11所述的组合物,其中所述非离子乳化剂具有约10,000道尔顿或更小的分子量。
14.根据权利要求1所述的组合物,其中所述水包油乳化剂以约0.5重量%至约6重量%的浓度存在。
15.根据权利要求1所述的组合物,其中所述水包油乳化剂以约1重量%至约4重量%的浓度存在。
16.根据权利要求1所述的组合物,其中所述烷基化的聚乙烯吡咯烷酮以约0.3重量%至约3重量%的浓度存在。
17.根据权利要求1所述的组合物,其中所述烷基化的聚乙烯吡咯烷酮以约1重量%至约2.5重量%的浓度存在。
18.根据权利要求1所述的组合物,其中所述UV吸收性聚酯为UV吸收性三唑、己二酸二甲酯、二聚二醇和二-三羟甲基丙烷的所述聚合反应产物,其中所述UV吸收性三唑、己二酸二甲酯、二聚二醇和二-三羟甲基丙烷发生反应,使得UV吸收性三唑的摩尔份数相对于在所述反应中使用的单体的摩尔总数为约0.39至约0.60。
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-
2012
- 2012-12-11 US US13/710,531 patent/US20140004057A1/en not_active Abandoned
-
2013
- 2013-06-18 CA CA2877464A patent/CA2877464C/en active Active
- 2013-06-18 ES ES13731623.8T patent/ES2642887T3/es active Active
- 2013-06-18 IN IN10613DEN2014 patent/IN2014DN10613A/en unknown
- 2013-06-18 CN CN201380034715.2A patent/CN104427965A/zh active Pending
- 2013-06-18 AU AU2013280908A patent/AU2013280908B2/en active Active
- 2013-06-18 KR KR1020157001810A patent/KR102099074B1/ko active IP Right Grant
- 2013-06-18 EP EP13731623.8A patent/EP2866770B1/en active Active
- 2013-06-18 RU RU2015102579A patent/RU2648756C2/ru active
- 2013-06-18 BR BR112014032792A patent/BR112014032792A8/pt not_active Application Discontinuation
- 2013-06-18 WO PCT/US2013/046316 patent/WO2014004169A2/en active Application Filing
-
2014
- 2014-12-10 US US14/565,909 patent/US9592190B2/en active Active
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Also Published As
Publication number | Publication date |
---|---|
CA2877464C (en) | 2021-06-01 |
RU2015102579A (ru) | 2016-08-20 |
BR112014032792A8 (pt) | 2022-08-16 |
IN2014DN10613A (zh) | 2015-09-11 |
WO2014004169A2 (en) | 2014-01-03 |
AU2013280908A1 (en) | 2015-01-22 |
US9592190B2 (en) | 2017-03-14 |
US20150093341A1 (en) | 2015-04-02 |
CA2877464A1 (en) | 2014-01-03 |
ES2642887T3 (es) | 2017-11-20 |
RU2648756C2 (ru) | 2018-03-28 |
AU2013280908B2 (en) | 2018-02-15 |
KR102099074B1 (ko) | 2020-04-09 |
KR20150023866A (ko) | 2015-03-05 |
WO2014004169A3 (en) | 2014-09-25 |
BR112014032792A2 (pt) | 2017-06-27 |
EP2866770B1 (en) | 2017-08-23 |
US20140004057A1 (en) | 2014-01-02 |
EP2866770A2 (en) | 2015-05-06 |
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