CN115443174B - 含有低分子量无定形级聚乳酸树脂的化妆品组合物 - Google Patents
含有低分子量无定形级聚乳酸树脂的化妆品组合物 Download PDFInfo
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- CN115443174B CN115443174B CN202180016111.XA CN202180016111A CN115443174B CN 115443174 B CN115443174 B CN 115443174B CN 202180016111 A CN202180016111 A CN 202180016111A CN 115443174 B CN115443174 B CN 115443174B
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- cosmetic composition
- polylactic acid
- acid resin
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- water
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- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
化妆品组合物含有某些聚乳酸树脂作为成膜剂。该聚乳酸树脂在该组合物中在低水平下是有效的,并且与化妆品组合物中常用的许多有机成分相容。该化妆品组合物可以被配制为喷雾剂、化妆水、霜剂或糊剂。
Description
技术领域
本发明涉及化妆品组合物。
背景技术
化妆品是施加到皮肤以改变其外观、执行保护功能和/或执行愈合或其他医疗功能的产品。这些产品通常被配制为含有水相和油相的乳液。当水相是连续的且油相是不连续的并且分散在水相中时,该乳液被称为水包油乳液。相反,其中油相是连续的且不连续的水相分散在油相中的乳液被称为油包水乳液。
化妆品通常被配制为含有“成膜剂”,其典型地是聚合物,这些聚合物施加到皮肤上并且去除挥发物后在皮肤上产生柔韧且有粘着力的膜。在其他功能中,该膜可以用作基质,该基质将活性成分保持在需要其功能的皮肤表面上或附近。成膜剂通常用于减少污迹和帮助防止转移。例如,如在美国专利号6,342,209和6,726,900中所述,已经提出多种聚合物材料用作化妆品的成膜剂。
现已发现某些聚乳酸树脂是化妆品中的有用成膜剂。
发明内容
因此,在一方面,本发明是一种化妆品组合物,该化妆品组合物包含(组分1)以下中的至少一种:(i)水不混溶性有机化合物,其具有最高达1000g/mol的分子量、不大于60℃的熔融温度、以及在101kPa压力下至少100℃的沸腾温度,和(ii)水不混溶性硅酮;以及(组分2)无定形级聚乳酸树脂,其含有按重量计至少70%的乳酸重复单元并且具有不大于65℃的玻璃化转变温度,其中该聚乳酸树脂具有1000至12,000g/mol的数均分子量并且含有在具有2至24个碳原子和1至8个羟基的含羟基引发剂化合物去除羟基后的残基,该聚乳酸树脂占该化妆品组合物总重量的0.1%至10%并且溶解在组分1或油相中,组分1也溶解在该油相中。
具体实施方式
已经发现具有列举特性的聚乳酸树脂在化妆品中作为成膜剂表现良好。
本文使用术语“聚乳酸树脂”表示具有按重量计至少70%的聚合乳酸重复单元(即,具有结构-OC(O)CH(CH3)-的重复单元)的聚合物,不管那些乳酸单元如何形成聚合物。任何乳酸重复单元可以是L或D构型。聚乳酸树脂可以含有按重量计至少75%、至少80%或至少85%的乳酸单元。
聚乳酸树脂可以进一步含有衍生自与丙交酯或乳酸可共聚的其他单体的重复单元,这些单体如环氧烷(包括环氧乙烷、环氧丙烷、环氧丁烷、氧杂环戊烷等)、环状内酯(包括己内酯等)、乙交酯、羟基酸(如3-羟基丁酸和3-羟基己酸)或碳酸酯(包括碳酸亚乙酯等)。衍生自这些其他单体的重复单元可以以嵌段、准随机和/或无规排列存在。这些其他重复单元合适地占聚乳酸的按重量计最高达25%、最高达15%、最高达10%、最高达5%或最高达2%,并且可以不存在。
聚乳酸树脂含有具有1至8个羟基和2至24个碳原子的引发剂化合物的残基。引发剂化合物是具有至少一个羟基的分子,其在聚合过程中与乳酸或丙交酯分子反应以引发聚合物生长,引发剂化合物反应后的残基结合到聚乳酸分子中。去除羟基后的引发剂优选具有最高达400g/mol的分子量。
有用的引发剂化合物包括一元醇,其优选是脂肪族的。此类一元醇可以是直链的、支链的和/或环状的、饱和的或不饱和的,并且更优选含有6至20个碳原子。实例包括1-丙醇、2-丙醇、1-丁醇、1-戊醇、1-己醇、2-乙基-1-丁醇、2-乙基-1-己醇、正辛醇、正癸醇、2-乙基-1-辛醇、正十二烷醇、2-乙基-1-癸醇、正十四烷醇、2-乙基-1-十二烷醇、正十六烷醇、2-乙基-1-十四烷醇、1-十八烷醇、2-乙基-1-十六烷醇、以上未具体提及的各种格尔伯特(Guerbet)醇、顺式-9-十八烯-1-醇、1-二十烷醇(1-icosonol)和1-二十二烷醇(1-docosonol)。具有至少6个或至少8个碳原子和最高达18个碳原子的那些有时提供特别的优势。
可用作引发剂的多羟基化合物包括乙二醇、丙二醇、二甘醇、二丙二醇、三甘醇、三丙二醇、甘油、三羟甲基丙烷、季戊四醇、1,4-丁二醇、1,6-己二醇、1,6-辛二醇、具有10至24个碳原子和最高达400g/mol的分子量的聚醚多元醇等。在一些实施例中,多羟基化合物是具有3至9个碳原子和2至4个羟基的直链或支链脂肪族多元醇。
在一些实施例中,引发剂不含羧基(-COOH)或羧酸根(-COO-)基团。
引发剂残基优选占聚乳酸树脂的重量的不超过30%、不超过20%或不超过12%。
聚乳酸树脂是无定形级的。出于本发明的目的,如果作为纯材料(即,不与任何其他材料组合),当在70℃至140℃范围内的任何温度下静态(即,在没有施加应变的情况下)加热一小时时,聚乳酸树脂形成不超过5J/g的PLA微晶,则聚乳酸树脂被认为是无定形级的。结晶度是在聚乳酸树脂的样品上测量的,该样品已经预先加热到至少220℃以熔化任何微晶,并且然后通过快速冷却至室温(23±3℃)来骤冷。然后将骤冷的样品加热至70℃至140℃范围内的温度,恒温保持一小时,并且再次通过冷却至室温骤冷。然后使用差示扫描量热法(DSC)方便地测量结晶度。此种结晶度的量在此以J/g表示,即样品中聚乳酸晶体的熔融焓(以焦耳为单位)除以样品中一种或多种聚乳酸的重量(以克为单位)。用于进行DSC测量的方便测试方案是在运行Star V.6.0软件的Mettler Toledo DSC 821e热量计或等效装置上在空气中以20℃/分钟将5-10毫克样品从25℃加热至225℃。
聚乳酸树脂的数均分子量为1000g/mol至12,000g/mol,如通过凝胶渗透色谱法相对于线性聚苯乙烯标准物所测量的。优选的最小数均分子量为至少2000g/mol,并且优选的最大数均分子量为最高达10,000g/mol、最高达8000g/mol、或最高达6000g/mol。
作为纯材料,聚乳酸树脂可以具有不大于65℃、不大于55℃、不大于50℃或不大于40℃的玻璃化转变温度,如通过差示扫描量热法以20℃/分钟的升温速率所测得的,玻璃化转变温度作为转变斜率的中点。
聚乳酸树脂中的乳酸单元可以是L-或D-对映异构体或其混合物。当L-和D-乳酸单元都存在时,它们可以规则地、随机地或伪随机地分布在聚乳酸树脂分子中。
在一些实施例中,聚乳酸树脂通过聚合丙交酯制成。此种聚乳酸树脂可以是L-丙交酯、D-丙交酯、外消旋丙交酯、内消旋丙交酯或其中任何两种或更多种的混合物的聚合物。聚乳酸树脂可以是含有75%至100%内消旋丙交酯和0%至25%的另一种丙交酯(L-丙交酯、D-丙交酯和/或外消旋丙交酯)的单体混合物的聚合物。在某些实施例中,聚乳酸树脂含有基于乳酸单元的总重量,20%至80%、优选40%至60%的一种乳酸对映异构体(即,L-或D-乳酸单元)和相反地80%至20%、优选60%至40%的另一种乳酸对映异构体。
替代地,聚乳酸树脂可以通过其他方法制备,如乳酸、乳酸盐或乳酸烷基酯的直接聚合;酯交换方法,其中低聚乳酸与引发剂化合物反应;或者各种固态聚合方法。
在某些实施例中聚乳酸树脂由以下结构表示:
其中y是1至8,尤其是1至6或1至4,并且x是正数,使得聚乳酸树脂具有如前所述的分子量。R是如前所述的含羟基引发剂化合物去除羟基后的残基。R优选含有2至24个碳原子,并且优选没有羧基或羧酸酯基团。当y大于1时,R优选含有3至9个碳原子。当y是1时,R优选含有6至20、6至18或8至18个碳原子。
聚乳酸树脂可以例如占化妆品组合物的按重量计0.25%至10%。在一些实施例中,聚乳酸树脂占化妆品组合物重量的最高达8%、最高达6%、最高达5%、最高达4%或最高达3%,并且其按重量计至少0.5%。
化妆品组合物含有(组分1)以下中的至少一种:(i)水不混溶性有机化合物,其具有最高达1000g/mol的分子量、不大于50℃的熔融温度、以及在101kPa压力下至少100℃的沸腾温度;和(ii)水不混溶性硅酮化合物。聚乳酸树脂溶解在组分1中或溶解在油相中,组分1也溶解在该油相中。
组分1化合物可以占化妆品组合物总重量的至少2%、至少5%、至少10%或至少20%,并且可以占其最高达99%、最高达90%、最高达70%、最高达60%或最高达50%。
如果在25℃下,材料在水中的溶解度不超过1重量份/100重量份水,则该材料被认为是“水不混溶性的”。
此类水不混溶性有机化合物的实例包括(a)非离子有机化合物,其具有至少190g/mol且最高达1000g/mol的分子量、至少一个酰胺基或酯基、以及含有至少8个碳原子的烷基链。水不混溶性有机化合物(a)包括各种脂肪酸酯、脂肪酸酰胺和酯、或脂肪醇的酯,它们中的每一种都可以是天然存在的(如动物或植物油)或合成的。具体的实例包括甘油三酯(如三庚酸甘油酯),各种动物脂肪和植物油(如椰子油、乳木果油、橄榄油、摩洛哥坚果油、低芥酸菜籽油、棕榈油、白芒花籽油和鳄梨油),以及癸酸/辛酸甘油三酯;从植物或植物油原料制备的单或二乙酰化的单或二脂肪酸甘油酯;二羧酸的C3-24(尤其是C6-24)二烃基酯(如二(辛烯基)琥珀酸酯、二(乙基己基)环烷酸酯、二(乙基己基)邻苯二甲酸酯、癸二酸二异丙酯和癸二酸二正丁酯);以及C6-24脂肪酸的C6-24烷基酯(如棕榈酸乙基己基酯)。
此类水不混溶性有机化合物的其他实例包括(b)C8-50烷烃或此类烷烃的混合物,其包括各种矿物油和链烷烃,其中烷烃或烷烃混合物在23℃下可以是液体或固体,(c)具有8个或更多个碳原子(如8至50或8至24个碳原子)的脂肪醇,(d)不包括在(a)至(c)中的任一项中的蜡,其包括例如天然蜡(如蜂蜡、米糠蜡、杨梅蜡、羊毛脂、巴西棕榈蜡、小烛树蜡、豆科蜡、甘蔗蜡、霍霍巴蜡、表皮蜡、地蜡和椰子蜡)以及合成蜡(如石蜡和微晶蜡),(e)水不混溶性有机UV吸收剂,其包括胡莫柳酯、辛水杨酯、奥克立林、甲氧基肉桂酸辛酯、阿伏苯宗、辛基甲氧基肉桂酸酯和乙基己基水杨酸酯,以及(f)水不混溶性C2-7直链脂肪族二羧酸的C3-24二烷基酯(如己二酸二异丙酯、己二酸二正丁酯、丁二酸二异丙酯和丁二酸二正丁酯)。
水不混溶性硅酮化合物包括非离子有机硅酮(如六甲基二硅氧烷、八甲基三硅氧烷、十甲基四硅氧烷、八甲基环四硅氧烷、十甲基环五硅氧烷),和直链或支链的聚二甲基硅氧烷(PDMS)油(如六甲基二硅氧烷、八甲基三硅氧烷、十甲基四硅氧烷、十二甲基五硅氧烷)、聚甲基氢硅氧烷(PMHS)油、以及其他液体环聚二甲基硅氧烷。
化妆品组合物可以含有一种或多种表面活性剂(乳化剂或润湿剂),特别是当存在水相时。此类表面活性剂可以存在,例如,以防止油相和水相的分离和/或润湿颜料或其他微粒固体的表面,如此它们可以分散到组合物中。表面活性剂可溶于组分(1)中,可溶于或可自分散于水中,或两者。表面活性剂可以是非离子的、阴离子的、阳离子的或两性离子的,或者它们中任意两种或更多种的混合物。有用的表面活性剂的实例包括脱水山梨糖醇酯(如脱水山梨糖醇单油酸酯、脱水山梨糖醇硬脂酸酯、脱水山梨糖醇月桂酸酯、脱水山梨糖醇倍半油酸酯、脱水山梨糖醇三硬脂酸酯、脱水山梨糖醇棕榈酸酯和脱水山梨糖醇三油酸酯);乙氧基化和酯化的脱水山梨糖醇(如聚山梨醇酯20、聚山梨醇酯60和聚山梨醇酯80);脂肪酸乙氧基化物;环氧丙烷/环氧乙烷嵌段共聚物;乙氧基化的胺;乙氧基化的脂肪酸酰胺、泊洛沙姆、甘油的单和二脂肪酸酯(如单硬脂酸甘油酯、单油酸甘油酯和单月桂酸甘油酯);C2-C6多元醇(如丙二醇、乙二醇、二甘醇、二丙二醇、1,4-丁二醇、季戊四醇、三羟甲基丙烷、三羟甲基乙烷)的单脂肪酸酯;烷基酚乙氧基化物;脂肪族(优选直链C4-12)二羧酸和亚烷基醚或聚醚一元醇的二元酯(此种二元酯的实例是琥珀酸二(乙氧基乙基)酯);烷基多苷;氧化胺;二酰化脂肪酸单甘油酯;等。当存在时,一种或多种表面活性剂可以占化妆品组合物总重量的1%至40%。在相同的基础上,优选的量是1%至20%或2%至15%。
在一些实施例中,化妆品组合物包含至少一种非离子表面活性剂,其可溶于化妆品组合物中存在的一种或多种水不混溶性化合物中。此种表面活性剂可以具有最高达12、优选最高达10的亲水亲油平衡值。当存在水相时,化妆品组合物可以包含至少一种额外的非离子表面活性剂,其可溶于或可自分散于水中,并且具有至少10、优选至少12的亲水亲油平衡值。本发明的化妆品组合物可以包含至少一种非离子表面活性剂(其具有最高达12的亲水亲油平衡值且可溶于化妆品组合物中存在的一种或多种水不混溶性化合物中),以及至少一种不同非离子表面活性剂(其具有至少10、优选至少12的亲水亲油平衡值且可溶于或可自分散于水中)。
化妆品组合物可以含有水相。水相包括水和任选的一种或多种溶于水中的水溶性成分。当存在时,水相可以占化妆品组合物总重量的0.5%至95%。在具体实施例中,水相可以占化妆品组合物总重量的至少1%、至少5%、至少10%或至少20%,并且可以占例如其最高达80%、最高达60%或最高达50%。水相的重量包括任何可溶于水或可自分散于水中的表面活性剂的重量。水本身可以占例如化妆品组合物总重量的5%至80%,5%至60%,或5%至50%。
当存在水相时,化妆品组合物可以采取水包油乳液或油包水乳液的形式。油相包括如上定义的组分1和聚乳酸树脂。此种乳液可以具有分散在油相和水相之一或两者中的微粒材料。就重量而言,水相或油相可能是主要的。产品的物理形式可以是例如低粘度、可喷雾的液体、霜剂、化妆水(lotion)或糊剂。
当存在时,水相可以含有一种或多种水溶性成分(例如像一种或多种湿润剂、一种或多种水溶性聚合物);一种或多种水混溶性溶剂、一种或多种pH调节剂和一种或多种水溶性防晒剂。这些水溶性成分典型地溶解在化妆品组合物中存在的水中。
有用的湿润剂包括亚烷基二醇和聚亚烷基二醇,尤其是具有最高达8个碳原子和最高达130g/mol分子量的那些,如丙二醇、1,4-丁二醇、1,5-戊二醇、1,2-戊二醇、1,6-己二醇、1,2-己二醇和1,8-辛二醇。其他有用的湿润剂包括甘油、三乙酸甘油酯和具有最高达10个碳原子的α-羟基酸,如乳酸、乙醇酸、2-羟基癸酸、2-羟基辛酸及其具有最高达10个碳原子的低聚物。当存在时,一种或多种湿润剂可以占化妆品组合物总重量的1%至40%。在相同的基础上,优选的量是2%至30%或5%至25%。
水溶性聚合物可以用作增稠剂、分散剂、润肤剂,和/或执行一种或多种其他功能。水溶性聚合物的实例包括苯乙烯-顺丁烯二酸酐树脂或其酯,在每种情况下其具有最高达7000g/mol的重均分子量;水溶性纤维素醚;瓜尔胶、麦芽糖糊精、黄原胶、羟丙基淀粉磷酸酯、苯乙烯-丙烯酸共聚物;乙烯-丙烯酸共聚物、聚丙烯酸、聚(乙二醇)、聚(乙烯吡咯烷酮)和聚(乙烯醇)、果胶、糊精、几丁质和角叉菜胶。当存在时,一种或多种水溶性聚合物可以占例如化妆品组合物总重量的0.05%至5%,在相同的基础上,优选的量是0.1%至2%。
本发明的化妆品组合物可以含有一种或多种有机溶剂,这些溶剂可以与水混溶或可以不与水混溶。此类溶剂的实例包括具有零个或一个羟基、没有羧基或羧酸酯基团以及最高达150g/mol的分子量的化合物。水不混溶性溶剂包括例如具有最高达6个碳原子的烷烃、苯、甲苯和二甲苯。水混溶性溶剂包括乙醇、甲醇、1-丙醇、2-丙醇、叔丁醇、吡啶、丙酮、甲基乙基酮、乙醚、甘醇二甲醚和二甘醇二甲醚。如果存在的话,这些可以占化妆品组合物总重量的最高达50%、优选最高达20%、最高达10%、最高达5%、或最高达2%,并且可以不存在。当存在时,有机溶剂通常用作一种或多种其他成分的载体,和/或用于降低化妆品组合物整体的粘度,或降低化妆品组合物的油相或水相的粘度。
pH调节剂包括氨基酸如精氨酸以及各种有机和无机酸以及碱,如氢氧化钠、氢氧化钾、盐酸、磷酸、磷酸二氢钠、磷酸氢二钠、氢氧化铵、碳酸钠、碳酸氢钠等。
苯基苯并咪唑磺酸(恩素利唑)是有用的水溶性防晒剂。
化妆品组合物可以含有一种或多种颜料。出于本发明的目的,颜料是具有超过100℃的熔化或分解(如果它不熔化)温度并且不溶于化妆品组合物的其余成分的微粒固体。颜料可以是无机的(如二氧化钛、氧化铁红、氧化铁黄、氧化铁黑、氧化锌、炭黑、偏硼酸钡、偏硼酸钙、铬黄、氧化铬绿、氧化亚铜、米洛丽蓝、钼铬橙、群青、铬酸锌、磷酸锌、活性炭、石墨等),或者可以是有机颜料(如甲苯胺红、栗色、红湖C、萘酚红、DNA橙、汉萨黄、联苯胺黄、酞菁蓝或酞菁绿)。当施加组合物时,某些颜料可以在化妆品组合物中执行额外的功能。例如,二氧化钛和氧化锌是UV阻断剂,并且因此可用于防晒产品。此类颜料可以占例如化妆品组合物总重量的0.1%至60%。优选的量是1%至25%或1%至15%。防晒产品可以含有按重量计5%至60%的二氧化钛和/或氧化锌。
化妆品组合物可以进一步含有一种或多种任选的功能性成分,如配制其用于特定用途所需要的。这些可以配制成油相或水相(当存在时)或两者。有用的功能性成分的实例包括防腐剂、电解质、香料或其他香水、香料增溶剂、螯合剂、润肤剂、蛋白质水解产物和其他蛋白质衍生物、抗衰老或抗皱配制品、痤疮治疗剂、皮肤增白剂、药剂和推进剂。在一些情况下,一种成分可以在化妆品组合物中执行两种或更多种功能。
具体的此类功能性成分包括葫芦[6]脲和竹[6]脲;水杨酸、辅酶Q10、苯甲酸-4-甲基苯亚甲基、西诺沙酯、辛基异羟肟酸、二氧苯酮、邻氨基苯甲酸薄荷酯、美索利SX、多甲曲唑、奥克立林、水杨酸乙基己酯、巴马特O,对氨基苯甲酸(PABA)、苯基苯并咪唑磺酸、舒利苯酮、三乙醇胺水杨酸钛、水杨酸、维甲酸(包括称为维甲酸的全反式异构体)、过氧化苯甲酰、对苯二酚、熊果酮(包括含有它们的植物提取物)、曲酸、壬二酸、甘草次酸、乙酰丙酸、2-氰基-3,3-二苯基丙烯酸、苯并三唑基丁基苯酚磺酸钠、2-氰基-3,3-二苯基丙烯酸乙酯、2-叔丁基-6-(5-氯-2H-苯并三唑-2-基)-对甲酚、2-(2-H-苯并三唑-2-基)-4-甲基苯酚、二苯甲酮-12、冰片酮或2-苯并三唑基-4-叔辛基苯酚、二羟基丙酮、赤藓酮糖、二羟基丙酮-邻-乙酸乙酯、角黄素、阿法美诺肽、米诺地尔、5-α还原酶抑制剂(如度他雄胺或酮康唑)、吡啶硫酮锌、硫化硒、克霉唑、茶树油、或吡罗克酮醇胺、抗组胺剂、哌醋甲酯、羟甲唑啉、盐酸四氢唑啉、裸盖菇素、茶树油、吡罗克酮醇胺、洗必泰、奥替尼定、三氯生、3,5-二溴-4-羟基苯磺酸钠(地泼罗酮)、硫代乙醇酸钙、硫代乙醇酸钠、硫代乙醇酸、硫代乙醇酸铵、硫代乙醇酸丁酯、硫代乙醇酸乙醇胺、硫代乙醇酸甘油酯、硫代乙醇酸异辛酯、硫代乙醇酸异丙酯、硫代乙醇酸镁、硫代乙醇酸甲酯、硫代乙醇酸钾、铝锆四氯羟基乙酸、水合氯化铝、氯化铝、间苯二酚(“雷琐辛”)、1-萘酚、对氨基苯酚、对苯二胺(及其盐)、4-氨基-2-羟基甲苯、苯氧乙醇、N,N-二乙基-间甲苯酰胺、p-薄荷糖-3,8-二醇(柠檬桉树精油中的活性剂)、荆芥内酯(猫薄荷油)、香茅油、氯菊酯、印楝油或沼泽桃金娘提取物。
有用的香料的实例包括衍生自以下的精油:浆果、五香粉、杜松、种子、杏仁、茴香、芹菜、小茴香、肉豆蔻油、树皮、肉桂、肉桂、黄樟、木材、樟脑、雪松、花梨木、檀香、沉香、根茎、高良姜、生姜、叶子、罗勒、月桂叶、肉桂、鼠尾草、桉树、柠檬草、千层、牛至、广藿香、薄荷、松树、迷迭香、留兰香、茶树、百里香、冬青、树脂、乳香、没药、花、洋甘菊、快乐鼠尾草、丁香、香味天竺葵、啤酒花、牛膝草、茉莉、薰衣草、麦卢卡、马郁兰、玫瑰、迷迭香、罗勒、柠檬草、依兰、果皮、佛手柑、葡萄柚、柠檬、酸橙、橙子、橘子、根、缬草和芒果。
其他香料的实例包括呋喃酮、1-己醇、顺-3-己烯-1-醇、薄荷醇、己醛、顺-3-己烯醛、糠醛、果酮、乙酸己酯、甲基苯基缩水甘油酸乙酯、甲酸甲酯、乙酸甲酯、丁酸甲酯、甲基丁酸酯、乙酸乙酯、丁酸乙酯、乙基丁酸酯、乙酸异戊酯、丁酸戊酯、戊基丁酸酯、戊基戊酸酯、安息香、黑胡椒、白千层油、香菜、胡萝卜籽、芫荽、丝柏、莳萝、茴香、蜡菊、薰衣草素、柠檬维雷纳、蜂香、绿花白千层、玫瑰草、苦橙叶、万寿菊、香根草、二氢茉莉酮、辛-1-烯-3-酮、2-乙酰基-1-吡咯啉、6-乙酰基-2,3,4,5-四氢吡啶、γ-癸内酯、γ-壬内酯、δ-辛内酯、马索内酯、索托伦、乙硫醇、葡萄柚硫醇、甲硫醇、2-甲基-2-丙硫醇、月桂烯、香叶醇、橙花醇、柠檬醛(citral)、柠檬醛(lemonal)、香叶醛、橙花醛、香茅醛、香茅醇、芳樟醇、橙花油醇、柠檬烯、樟脑、松油醇、紫罗兰酮、图朱恩(thujuon)、苯甲醛、丁香酚、肉桂醛、乙基麦芽酚、茴香醚、茴香脑、草蒿脑、百里酚、硫乙胺、三甲胺、尸胺、吡啶、吲哚、粪臭素、香叶醇、乙酸香叶酯、芳樟醇、乙酸芳樟酯、四氢芳樟醇、香茅醇、乙酸香茅酯、二氢月桂烯醇、乙酸二氢月桂烯酯、四氢月桂醇、松油醇、乙酸松油酯、壬二酚、醋酸正丙酯、2-苯乙醇、乙酸2-苯乙酯、苯甲醇、乙酸苄酯、水杨酸苄酯、苯甲酸苄酯、乙酸苯乙烯烯丙酯、水杨酸戊酯、二甲基苄基甲醇、乙酸三氯甲基苯甲醇酯、乙酸对叔丁基环己酯、乙酸异壬酯、乙酸香根草酯、香根草醇、α-正戊基肉桂醛,α-己基肉桂醛,2-甲基-3-(对叔丁基苯基)-丙醇、2-甲基-3-(对异丙基苯基)-丙醛、3-(叔丁基苯基)-丙醛、乙酸三环癸烯酯、丙酸三环癸烯酯、4-(4-羟基-4-甲基戊基)-3-环己烯甲醛、4-(4-甲基-3-戊烯基)-3-环己烯甲醛、4-乙酰氧基-3-戊基四氢吡喃、二氢茉莉酸甲酯、2-正庚基环戊酮、3-甲基-2-戊基环戊酮、正癸醛、9-癸烯醇-1、异丁酸苯氧基乙酯、苯乙醛二甲基缩醛、苯乙醛二乙缩醛、香叶腈、香茅腈、乙酸雪松酯、3-异樟脑环己醇、雪松基甲醚、异长叶松酮、奥贝丁腈、奥贝平、天芥菜碱、香豆素、丁香酚、香兰素、二苯醚、羟基香茅醛、紫罗兰酮、甲基紫罗兰酮、异甲基紫罗兰酮、铁烯、顺式-3-己烯醇及其酯、茚满麝香、四氢化萘麝香、异色满麝香、大环酮、大环内酯麝香、乙烯十三烷酯、芳香硝基麝香、佛手柑油、芫荽油、二甲基庚醇、二甲基苄基卡宾基乙酸酯、乙酸香叶酯、乙酸香茅酯、玫瑰合成、波旁老鹳草、希蒂莺(hedione)、异丁香酚、甲基丁香酚苯乙烯烯丙基乙酸酯、茎酮(stemone)、玫瑰氧化拉埃沃、醛C-ll十一环、2,6-二甲基-2-烷氧基辛-7-醇的衍生物、眩晕油、岩兰草醇、香根草酯、乙酸酯、夸亚克木油、邻氨基苯甲酸酯、水杨酸苄酯、苯甲酸苄酯、橡树苔、丁香酚、乙酸对叔丁基环己基酯和香豆素。
本发明的化妆品组合物可配制为例如防晒剂、粉底、遮瑕膏、唇膏、唇彩、润唇膏、睫毛膏、眼线膏、腮红、修容粉、润肤露、妆前乳、高光、发胶、抗皱霜或化妆水或散粉。此种化妆品组合物可以采取固体(如棒、条、粉末等)、液体、糊剂、霜剂或软膏的物理形式,视其预期用途而定。油相和水相(当存在时)各自在23℃下可以是液体或固体,尽管优选至少一相(更优选两相)在该温度下是液体或糊状物。水相和油相中的任一者或两者都可以含有固体物质如颜料的颗粒,该固体物质不溶于每一相。
通过将聚乳酸树脂溶解在一种或多种水不混溶性化合物中以产生油相来方便地制备化妆品组合物。这可在例如40℃至100℃的温度下方便地进行,以熔化或软化材料,从而促进混合和溶解。一种或多种表面活性剂可以组合到油相中。然后在一个或多个额外的混合步骤中将油相与剩余的成分(如果有的话)组合。这些混合步骤可以方便地在例如10℃至100℃的温度下进行。
聚乳酸树脂本身往往有点粘,并且通常将其方便地加热至90℃或更高以促进其与其他材料的组合。对于化妆品制造来说,这样的温度有时过高,通常优选将温度限制在80℃或更低。因此,通常方便地以与一种或多种其他成分、尤其是组分1材料和/或可溶于组分1材料的表面活性剂的预混物形式提供聚乳酸树脂。此种预混物可进一步含有一种或多种溶剂和/或湿润剂(如上所述),但优选含有按重量计不超过5%或不超过2%的水(如果有的话)。然后可以将预混物与化妆品配制品的其他成分、特别是水相组合,以生产化妆品。
预混物可以通过热软化聚乳酸树脂并将热软化的聚乳酸树脂与其他预混物成分组合来制备。温度高到足以形成部分或完全均匀的混合物;70℃至100℃是合适的。冷却后的预混物典型地是蜡或油状固体或半固体。冷却至室温后可能发生一些相分离。制备此种预混物的优点是,与将聚乳酸与那些其他成分直接组合相比,它可以在稍微降低的温度下容易地与化妆品配制品的其他成分组合,这是因为与聚乳酸树脂本身相比,它的粘度较低。这允许在配制化妆品时使用较低的温度,同时仍然获得良好且高度均匀的产品。因此,使用预混物允许在配制化妆品时使用较低的温度,这可以带来另外的优点,如较少变色、较少产生不希望的气味和更好的产品稳定性,尤其是当使用可能对热敏感的天然成分时。
此种预混物可以占聚乳酸树脂的例如按重量计至少1%、优选至少5%或至少10%,并且其最高达50%、最高达40%或最高达30%。
在一些实施例中,此种预混物包括至少一种C2-C6多元醇(如丙二醇、乙二醇、二甘醇、二丙二醇、1,4-丁二醇、季戊四醇、三羟甲基丙烷、三羟甲基乙烷)的单脂肪酸酯。此种单脂肪酸酯的脂肪酸基团可以含有例如6至24或8至18个碳原子,并且可以是饱和的或不饱和的。脂肪酸基团的具体实例包括硬脂酸酯、油酸酯和月桂酸酯。丙二醇单油酸酯、丙二醇单硬脂酸酯、丙二醇单月桂酸酯、单硬脂酸甘油酯、单油酸甘油酯和单月桂酸甘油酯可用作单脂肪酸酯。当存在时,此种单脂肪酸酯可以占例如预混物总重量的至少25%或至少40%或至少50%,并且可以占例如其总重量的多达80%或多达75%。
在一些实施例中,此种预混物包括如前所述的组分1材料。当存在时,此种组分1材料可以占例如预混物总重量的至少1%、至少2%、至少5%或至少10%,并且其最高达60%或最高达50%。
在一些实施例中,此种预混物含有如前所述的湿润剂或溶剂。当存在时,此种溶剂或湿润剂可以占例如预混物总重量的至少1%、至少5%或至少10%,并且可以占其最高达50%或其最高达33%。
在具体的实施例中,此种预混物含有(1)按重量计1%至50%的聚乳酸树脂,(2)按重量计25%至75%的至少一种C2-C6多元醇(如丙二醇、乙二醇、二甘醇、二丙二醇、1,4-丁二醇、季戊四醇、三羟甲基丙烷、三羟甲基乙烷)的单脂肪酸酯,和至少一种组分1材料,优选至少一种甘油三酯和/或至少一种脂肪族(优选具有最高达12个碳原子的直链脂肪族)二羧酸的C3-24二烷基酯(并且尤其是至少一种植物油或动物脂肪),和(3)按重量计1%至50%的至少一种组分1材料,尤其是植物油或动物脂肪,其中(1)、(2)和(3)一起占预混物总重量的至少80%、至少90%或至少95%且最高达100%。此种预混物可以含有例如按重量计最高达20%、最高达10%或最高达5%的不同于(2)的表面活性剂。
在其他具体的实施例中,此种预混物含有(1)按重量计1%至50%的聚乳酸树脂,(2)5%至50%的至少一种溶剂或湿润剂,和(3)按重量计1%至50%的至少一种组分1材料,优选至少一种甘油三酯和/或至少一种脂肪族(优选具有最高达12个碳原子的直链脂肪族)二羧酸的C3-24二烷基酯(并且尤其是至少一种植物油或动物脂肪),其中(1)、(2)和(3)一起占预混物总重量的至少80%、至少90%或至少95%且最高达100%。此种预混物可以含有例如按重量计最高达20%、最高达10%或最高达5%的表面活性剂。
在其他具体的实施例中,此种预混物含有(1)按重量计1%至50%的聚乳酸树脂,(2)按重量计25%至75%的至少一种C2-C6多元醇(如丙二醇、乙二醇、二甘醇、二丙二醇、1,4-丁二醇、季戊四醇、三羟甲基丙烷、三羟甲基乙烷)的单脂肪酸酯,和(3)按重量计5%至50%的至少一种溶剂或湿润剂,其中(1)、(2)和(3)一起占预混物总重量的至少80%、至少90%或至少95%且最高达100%。此种预混物可以含有例如按重量计最高达20%、最高达10%或最高达5%的不同于(2)的表面活性剂。
在又其他具体的实施例中,此种预混物含有(1)按重量计1%至50%的聚乳酸树脂,(2)按重量计25%至75%的至少一种C2-C6多元醇(如丙二醇、乙二醇、二甘醇、二丙二醇、1,4-丁二醇、季戊四醇、三羟甲基丙烷、三羟甲基乙烷)的单脂肪酸酯,(3)按重量计1%至60%的至少一种组分1材料,优选至少一种甘油三酯和/或至少一种脂肪族(优选具有最高达12个碳原子的直链脂肪族)二羧酸的C3-24二烷基酯(并且尤其是至少一种植物油或动物脂肪),和(4)按重量计1%至50%的至少一种溶剂或湿润剂,其中(1)、(2)和(3)一起占预混物总重量的至少80%、至少90%或至少95%且最高达100%。此种预混物可以含有例如按重量计最高达20%、最高达10%或最高达5%的不同于(2)的表面活性剂。
本发明的代表性防晒配制品可以是包含以下成分的混合物。可以存在额外的组分。
代表性防晒配制品
此种防晒剂可以通过组合水相成分(水溶性成分);将油相成分(油溶性UV吸收剂、水不混溶性溶剂、聚乳酸树脂)与表面活性剂分别组合,将氧化锌与水相或油相共混,并且然后将油相和水相组合来制备。该产品是水包油乳液,其中悬浮有氧化锌颗粒。
本发明的代表性粉底配制品可以是以下成分的混合物。可以存在额外的成分。
代表性粉底配制品
*基于总配制品重量。
本发明的代表性唇膏配制品可以是以下成分的混合物。可以存在额外的成分。
代表性唇膏配制品
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*基于总配制品重量。
本发明的化妆品可以以与为相同目的配制的常规化妆品相同的一般方式使用。它们可以以适合其预期用途的方式应用。
以下实例说明本发明,但并不旨在以任何方式限制本发明。除非另有指示,否则所有份数和百分比都按重量计。
实例1和2以及对比样品A
含有有机和无机UV吸收剂的水包油防晒剂(对比样品A和实例1和2)如下制备:
水分散性预混物通过将按重量计10份1,3-丙二醇、0.2份黄原胶、0.2份瓜尔胶、2份恩素利唑、0.5份L-精氨酸、1份苯丙醇/辛二醇/1,3-丙二醇混合物(Sensiva PA 40,来自美国新泽西州费尔菲尔德舒美公司(Schulke,Inc.))和(仅对于对比样品A)2份麦芽糖糊精(水溶性成膜剂)组合以形成粘性的均匀混合物来制备。然后将预混物加热至70℃,并将其添加到49.1份水中,并且均质化以产生水相。
油/表面活性剂预混物通过在70℃下将7.5份胡莫柳酯、2.5份辛水杨酯、5份奥克立林、5份环烷酸二(乙基己基)酯、2份阴离子表面活性剂(Dracorin GOC,来自德之馨公司(Symrise AG))、3份聚氧乙烯(20)脱水山梨糖醇单月桂酸酯,和(仅对于实例1和2)2份测试成膜剂组合来单独制备。将20份氧化锌与油/表面活性剂预混物组合,并且将所得分散体与上述水相组合并均质化以产生白色防晒配制品。
实例1中的成膜剂是通过将约90%内消旋丙交酯和10%L-丙交酯的混合物聚合到季戊四醇上制备的2296g/mol Mn聚合物(“PLA-1”)。PLA-1具有26℃的玻璃化转变温度并且含有约94%的乳酸单元。约55%的乳酸单元是L-乳酸单元。
实例2中的成膜剂是通过将约90%内消旋丙交酯和10%L-丙交酯的混合物聚合到1-十八烷醇上制备的3614g/mol Mn聚合物(“PLA-2”)。PLA-2具有14℃的玻璃化转变温度并且含有约93%的乳酸单元。约55%的乳酸单元是L-乳酸单元。(对于PLA 1和PLA 2的额外的物理特性数据,参见表2。)
根据21CFR§201.357(i)(2011)中阐述的方法,对每种防晒剂进行SPF(防晒系数)测试。将0.05克的测试防晒剂施加到聚甲基丙烯酸甲酯板上。使用圆周运动涂抹30秒,使用竖直运动涂抹15秒,并且然后使用水平运动涂抹15秒。在SPF测试之前,将涂覆的板置于黑暗的箱中15分钟。
在最初的SPF测试后,将涂覆的板置于搅拌的30℃水浴中20分钟。然后将板移出,并且允许其在空气中干燥。然后将干燥板再次进行SPF测试。SPF测试的结果如表1中所示。
表1
*对比
洗涤前,实例1和2与对比样品相比,表现相当或更好。在SPF测试中的良好表现表明当施加防晒剂时成膜;当没有形成良好的膜时,获得的结果要差得多。在板被洗涤后,实例1和2比对比样品表现好得多。更好的耐洗性再次表明良好的膜形成。
实例3-9
水包油防晒剂实例3-9以下面的一般方式制备。水分散性预混物通过将20份1,3-丙二醇、0.5份黄原胶/瓜尔胶混合物、2份恩素利唑、0.5份L-精氨酸、1.0份Sensive PA 40和2份麦芽糖糊精组合来制备。将所得混合物与47份80℃水组合,并保持在80℃。这产生水相。
油/表面活性剂/氧化锌相通过在75℃下将10份在辛酸/癸酸甘油三酯载体中的氧化锌的50%分散体、7.5份胡莫柳酯、2.5份辛水杨酯、5份奥克立林、5份棕榈酸乙基己基酯、2份脱水山梨醇油酸酯、3份聚(丙二醇)60脱水山梨醇单月桂酸酯和2份成膜剂混合来制备。每种情况中的成膜剂是通过将约90%内消旋丙交酯和10%L-丙交酯的混合物聚合到引发剂上制备的聚乳酸树脂,如表2中所述。然后防晒剂通过将75℃的油/表面活性剂/氧化锌相添加到80℃的水相中并均质化来制备。
表2
实例 | PLA样品 | 引发剂 | Mn,g/mol | Tg,℃ | %丙交酯单位 |
3 | PLA-3 | 月桂醇 | 2907 | 16.4 | 93.6 |
4 | PLA-4 | 1-十八烷醇 | 5256 | 25 | 94.9 |
5 | PLA-5 | 辛醇 | 5261 | 33 | 97.5 |
6 | PLA-6 | 辛醇 | 2588 | 17 | 95.0 |
7 | PLA-7 | 辛醇 | 1134 | -6.5 | 88.5 |
8 | PLA-8 | 1-十八烷醇 | 1165 | 11 | 76.9 |
9 | PLA-2 | 1-十八烷醇 | 3615 | 14.1 | 92.6 |
防晒剂实例3-9中的每一个的布氏粘度是在23℃下使用变速法用#27锭子确定的。如前所述,在每种情况下测量SPF。结果如表3中所示。
表3
表3中的SPF数据揭示了聚乳酸树脂的引发剂的长度与SPF值之间的相关性。通常,较长的引发剂链长度对应于较好的SPF值。PLA分子量影响粘度,但对SPF值几乎没有影响。
实例10和11
粉底实例10和11以下面的一般方式制备。将40份1,3-丙二醇、2份苯乙烯马来酸酐共聚物(MSA 1800,来自克雷威利公司(Cray Valley))、6份恩素利唑、16份二氧化钛颗粒和2份Sensive PA 40组合。单独地,将0.4份黄原胶、6份改性玉米淀粉(ICB 3000,来自泰莱公司(Tate and Lyle))和3份辛烯基琥珀酸淀粉钠/葫芦脲混合物(Aqstar M1,英国剑桥安道拓公司(Aqdot Company))组合。然后将两种混合物一起均质化。向均质化的材料中添加1.4份氧化铁红、4.2份氧化铁黄和0.4份氧化铁黑(从制作化妆品颜色公司(Making CosmeticColor)可获得)的混合物,然后进一步均质化。然后将所得混合物与71.6份80℃的水共混。结果是颜料在水相中的分散体。
单独地,将30份由大豆原料制备的二乙酰化单甘油酯、2.5份鲸蜡醇、1.5份辛烯基琥珀酸淀粉钠/葫芦脲混合物、4份油酸甘油酯柠檬酸酯和辛酸/癸酸甘油三酯的混合物、1份气相二氧化硅和4份聚乳酸树脂在75℃下组合以产生油/表面活性剂相。然后将75℃的油/表面活性剂相共混到80℃的水性颜料分散体中,并均质化以产生粉底。
实例10和11中的聚乳酸树脂分别是PLA-1和PLA-2。
实例10和11如前所述,在洗涤之前和之后都进行了SPF等级评价。结果如表4中所示。
表4
两种PLA成膜剂都赋予粉底配制品良好的耐洗性。
实例12-18以及对比样品B
粉底组合物(实例12-18)以下面的一般方式制备。预混物通过将20份1,3-丙二醇、1份SMA/MA共聚物、0.7份羟丙基淀粉磷酸酯、0.3份瓜尔胶和2份麦芽糖糊精组合来制备。单独地,形成含有0.3份氧化铁红、1份氧化铁黄、0.1份氧化铁黑和8份二氧化钛的颜料混合物。将颜料混合物和预混物组合直至均匀,并且然后与42.5份85℃的水组合。这产生了颜料分散在其中的水相。
油/表面活性剂相通过将5份琥珀酸二庚酯/辛酰基甘油癸二酸共聚物混合物(LexfeelN50,殷度斯公司(Inolex,Inc.))、2份鲸蜡醇、1份辛烯基琥珀酸淀粉钠/葫芦素混合物(Aqstar M1,英国剑桥安道拓公司)、10份三庚酸甘油酯/C13-16链烷烃混合物(Lexfeel,来自殷度斯公司)、2.0份脱水山梨糖醇油酸酯、2.0份聚乙二醇60脱水山梨糖醇单月桂酸酯、0.1份气相二氧化硅和2份成膜剂(除了在对比样品B中,其中省略了成膜剂)混合来制备。如表5中所示,在每种情况下的成膜剂都是聚乳酸树脂。然后防晒剂通过将85℃的水相与75℃的油/表面活性剂相组合并均质化来制备。
粘度和SPF等级以前述方式在每个样品上确定。转移阻力是通过使用脚趾涂抹器将预称重的粉底样品施加到人类受试者前臂的2cm×2cm的方形部分上,并允许其干燥一分钟来确定的。重新称量涂抹器,以计算施加到皮肤上的粉底量。然后将称重的3cm×3cm的组织施加到所施加的粉底上,并拖动3cm。然后对组织重新称重,以测量去除的粉底量。然后将转移的量计算为100%×(去除的重量÷施加的重量)。
测试的结果如表5中所示。
表5
实例 | PLA树脂 | 粘度,cP | SPF等级 | 转移,% |
12 | PLA-3 | 514 | 4.3 | 14.9 |
13 | PLA-4 | 2355 | 5.8 | 17.6 |
14 | PLA-5 | 1058 | 4.6 | 15.7 |
15 | PLA-6 | 290 | 2.9 | 17.0 |
16 | PLA-7 | 526 | 3.0 | 21.4 |
17 | PLA-8 | 2655 | 3.8 | 26.3 |
18 | PLA-2 | 1465 | 3.9 | 21.8 |
B* | 无 | 2155 | 3.4 | 43% |
*对比。
所有的聚乳酸树脂都示出是有效的成膜剂,如特别是通过与对照物(对比样品B)相比优异的转移阻力所示。作为对比,当测试其他方面相同但缺少成膜剂的粉底配制品时,质量转移为43.1%。
实例19-20以及对比样品C
油包水防晒配制品如下制备:在室温下将10份丙二醇、1份辛基异羟肟酸、0.5份乳酸锌和0.2份L-精氨酸与49.3份水混合以形成水相。单独地,油/表面活性剂/氧化锌相通过将19份C15-C19烷烃混合物(Emogreen L15,赛比克股份公司(Seppic S.A.))、1份DracorinGOC和1份三(聚甘油基-3/月桂基)氢化三油酸酯混合来制备。将15份氧化锌添加到混合物中,并分散直至均匀。将油/表面活性剂/氧化锌相加热至75℃,添加3份成膜剂(如表6中所示),并且混合直至均匀。在75℃下将水相与油相组合,并混合直至均质化,以产生嫩白化妆水。洗涤之前和之后的粘度和SPF都如前所述进行测量。结果如表6中。
表6
*对比。
实例19和20相对于对比样品C的SPF等级的增加表明PLA树脂在该配制品中是有效的成膜剂。
实例21-22
仅包含无机防晒剂的水包油防晒配制品如下制备:将0.3份黄原胶、10份丙二醇、1份辛基异羟肟酸/辛酸甘油酯混合物、0.5份L-精氨酸和1份水解玉米淀粉羟乙基醚与43.2份水混合,直至均质化以形成水相。将水相加热至75℃。油/表面活性剂/氧化锌相通过将20份异链烷烃混合物(Lexfeel WOW)、15份氧化锌、3份如表7所示的成膜剂、1份DracorinGOC、3份山嵛酰乳酸钠在75℃下组合并混合直至均匀来制备。将这些相混合并均质化。如前所述测量粘度和SPF(洗涤之前和之后),其中结果如表7中所示。
表7
实例23和24
唇膏配制品如下生产:如表8中所示,将30.8份蓖麻油、16份辛酸/癸酸甘油三酯、17份异二十烷、5份摩洛哥坚果油、3.5份微晶蜡、3.5份地蜡、7份小烛树蜡、3份巴西棕榈蜡和1份成膜剂在80℃-95℃下组合,以形成熔融蜡相。单独地,将1份红色7号D&C湖和11份云母组合,并且然后混合到熔融蜡相中。将0.2份生育酚和1份对羟基苯甲酸酯-DU(56%丙二醇、3%对羟基苯甲酸丙酯、11%对羟基苯甲酸甲酯和30%重氮烷基脲的混合物)混合,并且然后与熔融的蜡相组合。将所得的唇膏配制品倒入唇膏模具中,并在冷冻机中固化。
以前述方式测试唇膏的转移阻力。硬度和渗透力根据ASTM D1321-10测量。结果如表8中所示。
表8
样品 | %转移 | 硬度(重力) | 7mm的渗透力 |
PLA-1 | 12 | 442 | 131 |
PLA-2 | 13 | 380 | 126 |
实例24-33以及对比样品A
对比样品A:将20份椰子油和3份PLA-1分别加热至90℃并用手混合。所得混合物在该温度下目测是均匀的。当在80℃下重复该实验时,混合物仅部分是均匀的,而当在70℃下制备混合物时,混合物是完全不均匀的。当椰子油和PLA-1在80℃下以3:1的比例混合时,所得混合物是完全不均匀的。
实例24:单硬脂酸甘油酯和椰子油以68/32的重量比组合。当将20克该混合物和3份PLA-1分别加热至70℃并组合时,获得完全均匀的混合物。当混合比为3:1时,获得类似的结果。冷却后,这些混合物部分相分离,但在70℃下容易与水相组合,以产生化妆品配制品。
实例25:单油酸甘油酯和椰子油以84/16的比率组合。当将20克该混合物和3份PLA-1分别加热至70℃并组合时,获得部分不均匀的混合物;在80℃时,混合物是完全均匀的。当混合比为3:1时,在70℃和80℃的混合温度下均可获得部分不均匀的混合物。冷却后,这些混合物部分相分离,但在70℃至80℃下容易与水相组合,以产生化妆品配制品。
实例26:单油酸甘油酯和单月桂酸甘油酯以63/37的比率组合。当将20克该混合物和3份PLA-1分别加热至70℃并组合时,获得部分不均匀的混合物;在80℃时,混合物是完全均匀的。当混合比为3:1时,在70℃和80℃的混合温度下均可获得完全均匀的混合物。冷却后,这些混合物部分相分离,但在70℃至80℃下容易与水相组合,以产生化妆品配制品。
实例27:丙二醇单油酸酯和椰子油以99/1的比率组合。当将20克该混合物和3份PLA-1分别加热至80℃并组合时,获得完全均匀的混合物。冷却后,这些混合物部分相分离,但在80℃下容易与水相组合,以产生化妆品配制品。
实例28:单硬脂酸甘油酯和椰子油以63/37的比率组合。当将20克该混合物和3份PLA-1分别加热至80℃并组合时,获得部分不均匀的混合物。冷却后,这些混合物部分相分离,但在70℃至80℃下容易与水相组合,以产生化妆品配制品。
实例29:丙二醇单油酸酯和椰子油以55/45的比率组合。当将20克该混合物和3份PLA-1分别加热至80℃并组合时,获得部分不均匀的混合物。冷却后,这些混合物部分相分离,但在80℃下容易与水相组合,以产生化妆品配制品。
实例30:单硬脂酸甘油酯和椰子油以68/32的比率组合。当将20克该混合物和3份PLA-4分别加热至80℃并组合时,获得部分不均匀的混合物。当混合比为3:1时,在70℃和80℃下均获得部分不均匀的混合物。冷却后,这些混合物部分相分离,但在70℃-80℃下容易与水相组合,以产生化妆品配制品。
实例31:单油酸甘油酯和椰子油以84/16的比率组合。当将20克该混合物和3份PLA-4分别加热至70℃并组合时,获得部分不均匀的混合物;在80℃时,混合物是完全均匀的。冷却后,这些混合物部分相分离,但在70℃至80℃下容易与水相组合,以产生化妆品配制品。
实例32:单油酸甘油酯和单月桂酸甘油酯以63/37的比率组合。当将20克该混合物和3份PLA-4分别加热至80℃时,获得部分不均匀的混合物。当混合比为3:1时,获得类似的结果。冷却后,这些混合物部分相分离,但在80℃下容易与水相组合,以产生化妆品配制品。
实例33:丙二醇单油酸酯和椰子油以99/1的比率组合。当将20克该混合物和3份PLA-4分别加热至80℃并组合时,获得完全均匀的混合物。冷却后,这些混合物部分相分离,但在80℃下容易与水相组合,以产生化妆品配制品。
实例34和35
实例34:将6.0份椰子油、10.2份单硬脂酸甘油酯和5.4份PLA-4组合,加热至80℃保持一小时,并且冷却至室温,以形成预混物。
单独地,水相通过将44.55份水、0.55份黄原胶和9.9份1,3-丙二醇混合来制备。
化妆水是通过将预混物加热至80℃并将其与18份椰子油、1.8份油酸甘油酯柠檬酸酯和3.6份硬脂醚-21表面活性剂组合以产生油相来制备。水相被单独加热到相同的温度。在约400rpm的温和搅拌条件下,将油相缓慢倒入水相中。将搅拌速率提高到1000rpm,并在相组合后继续搅拌5分钟。得到的产品是均匀的抗相分离的化妆水。
以相同的方式制备实例35,除了用PLA-1代替PLA-4。获得了类似的结果。
Claims (19)
1.一种用于将膜施加在唇部、皮肤或睫毛上的化妆品组合物,该化妆品组合物包含组分1和组分2,其中组分1包含以下中的至少一种:(i) 水不混溶性有机化合物,其具有最高达1000 g/mol的分子量、不大于60°C的熔融温度、以及在101 kPa压力下至少100°C的沸腾温度,和 (ii) 水不混溶性硅酮化合物;以及组分2包含无定形级聚乳酸树脂,其含有按重量计至少70%的乳酸重复单元并且具有不大于65°C的玻璃化转变温度,其中该聚乳酸树脂具有1000至12,000 g/mol的数均分子量并且含有在具有1至4个羟基的直链或支链脂肪族醇去除羟基后的残基,当该直链或支链脂肪族醇具有1个羟基时,该直链或支链脂肪族醇具有8至18个碳原子,并且当该直链或支链脂肪族醇具有大于1个羟基时,该直链或支链脂肪族醇具有3至9个碳原子,该聚乳酸树脂占该化妆品组合物总重量的0.1%至10%并且溶解在组分1或油相中,组分1也溶解在该油相中。
2.如权利要求1所述的化妆品组合物,其中,基于该聚乳酸树脂中乳酸单元的总重量,该聚乳酸树脂含有20%至80%的一种乳酸对映异构体和相应的80%至20%的另一种乳酸对映异构体。
3.如权利要求1所述的化妆品组合物,其中,该聚乳酸树脂是内消旋丙交酯的聚合物,或者是含有至少75%内消旋丙交酯和至多25%的另一种丙交酯的丙交酯混合物的共聚物。
4.如权利要求1或2所述的化妆品组合物,其中,该聚乳酸树脂进一步含有至少一种与丙交酯或乳酸可共聚的其他单体的重复单元。
5.如权利要求1或2所述的化妆品组合物,其中,该聚乳酸树脂由以下结构表示:
其中y是1至4,x是正数,使得该聚乳酸树脂具有1000至12,000 g/mol的数均分子量,并且R是具有y个羟基的直链或支链脂肪族醇去除羟基后的残基,其中当y为1时,R具有8至18个碳原子,并且当y大于1时,R具有3至9个碳原子。
6.如权利要求1至3中任一项所述的化妆品组合物,其中,该聚乳酸树脂具有2000至8000 g/mol的数均分子量。
7.如权利要求1至3中任一项所述的化妆品组合物,其中,该直链或支链脂肪族醇是具有8至18个碳原子的直链或支链脂肪族一元醇。
8.如权利要求1至3中任一项所述的化妆品组合物,其中,该直链或支链脂肪族醇是具有3至9个碳原子和2至4个羟基的直链或支链脂肪族醇。
9.如权利要求1至3中任一项所述的化妆品组合物,其中,组分1包括脂肪酸酯、脂肪醇或有机防晒剂中的一种或多种。
10.如权利要求1至3中任一项所述的化妆品组合物,其为水包油或油包水乳液。
11.如权利要求9所述的化妆品组合物,其含有按重量计5%至90%的水。
12.如权利要求9所述的化妆品组合物,其进一步包含至少一种水溶性聚合物。
13.如权利要求1至3中任一项所述的化妆品组合物,其进一步包含至少一种乳化剂。
14.如权利要求1至3中任一项所述的化妆品组合物,其进一步含有至少一种微粒颜料。
15.如权利要求1至3中任一项所述的化妆品组合物,其进一步包含氧化锌和二氧化钛中的至少一种。
16.如权利要求1至3中任一项所述的化妆品组合物,其进一步包含至少一种具有3至6个碳原子和最高达125 g/mol的分子量的多元醇。
17.如权利要求1至3中任一项所述的化妆品组合物,其含有至少一种有机UV吸收剂。
18.如权利要求1至3中任一项所述的化妆品组合物,其是防晒剂,该防晒剂具有根据21CFR §201.357(i) (2011)中描述的方法测量的至少5的防晒系数。
19.如权利要求1至3中任一项所述的化妆品组合物,其是防晒剂,该防晒剂具有根据21CFR §201.357(i) (2011)中描述的方法测量的至少20的防晒系数。
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US202062979556P | 2020-02-21 | 2020-02-21 | |
US62/979,556 | 2020-02-21 | ||
PCT/US2021/018658 WO2021168170A1 (en) | 2020-02-21 | 2021-02-19 | Cosmetic compositions containing low molecular weight amorphous grade polylactic acid resin |
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- 2021-02-19 JP JP2022549136A patent/JP2023515407A/ja active Pending
- 2021-02-19 CN CN202180016111.XA patent/CN115443174B/zh active Active
- 2021-02-19 WO PCT/US2021/018658 patent/WO2021168170A1/en unknown
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EP1633797A1 (en) * | 2003-12-04 | 2006-03-15 | Samyang Corporation | Biodegradable branched polylactide derivativescapable of forming polymeric micelles, and their preparation method and use |
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US20230087601A1 (en) | 2023-03-23 |
CN115443174A (zh) | 2022-12-06 |
KR20230005125A (ko) | 2023-01-09 |
JP2023515407A (ja) | 2023-04-13 |
EP4106881A1 (en) | 2022-12-28 |
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