CN105722496A - 包含hlb<8的糖的脂肪酸酯或液体烷基聚葡糖苷和c8-c18支链烷烃的两相组合物 - Google Patents
包含hlb<8的糖的脂肪酸酯或液体烷基聚葡糖苷和c8-c18支链烷烃的两相组合物 Download PDFInfo
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- CN105722496A CN105722496A CN201480059943.XA CN201480059943A CN105722496A CN 105722496 A CN105722496 A CN 105722496A CN 201480059943 A CN201480059943 A CN 201480059943A CN 105722496 A CN105722496 A CN 105722496A
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Abstract
本发明涉及由分离并透明的水相和油相组成的用于局部施用的组合物,其包含至少一种在室温下和在大气压力下为液体,HLB<8并选自糖的脂肪酸酯和烷基聚葡糖苷的表面活性剂、至少一种包含8至18个碳原子的支链烷烃和相对于所述组合物的总重量的0至4重量%的硅油。根据本发明的组合物在振荡后使得能够获得乳状液,其再快速分离成具有完美清晰界面的两个透明相并且没有保持附着在透明容器壁上的液滴出现。根据本发明的组合物具有相同的卸妆效力和更好的感官性质,并且特别地,其在皮肤上留下较少的油腻残留物。
Description
本发明涉及由两个分离的相(水相和油相)组成的用于局部施用的组合物,其容易通过振荡乳化并在停止振荡后经历快速相分离。本发明还涉及所述组合物在化妆品或皮肤病学中的用途,且尤其用于对皮肤(身体和面部皮肤两者),且特别是嘴唇和/或眼部进行卸妆、清洁和/或护理,和/或用于护发的用途。
由两个分离的相,尤其是在静置时分离而非一个相乳化在另一个中的水相和油相组成的这类组合物通常被称作“两相组合物”。它们与乳状液的区别在于,在静置时,这两个相是分离的而非一个相乳化在另一个中。因此,这两个相在静置时被单个界面分开,而在乳状液中,一个相以大量液滴的形式分散在另一个相中,且界面因此是多重的,这些界面通常用乳化表面活性剂和/或乳化聚合物稳定化。两相组合物的使用需要预先振荡以形成临时乳状液。这种乳状液必须具有足够的品质和稳定性以能均匀施用这两个相,但使得在静置时,这两个相变得快速分离并恢复它们的初始状态,这种现象更常被称作“相分离”。
两个相在使用后的快速相分离(或分层)是两相组合物的所需品质之一。具体而言,由于各种原因,获得快速相分离是合意的,尤其是因为两个相的不良分离被使用者视为是不美观的。
此外,越来越寻求具有清澈,即透明的组合物,因为在水的情况下,透明度是纯度和因此清洁度的象征。因此使用者特别喜欢透明组合物,这些组合物通常在透明容器中存在,且两个相的不透明性不利于美观。
在两相组合物中例如以合适的量使用硅油,例如环戊硅氧烷可以使得可以获得由两个分离的不混溶相组成的两相组合物,两个相在振荡后形成乳状液,同时保持两相组合物的所需性质,即快速相分离成两个透明相。
例如在文献EP 0 370 856和EP 0 603 080中已描述了基于环状硅油的两相组合物,其尤其用于卸除眼妆。
此外,消费者越来越寻求基于天然成分或天然来源的成分形成的化妆产品,特别是不含任何挥发性聚硅氧烷化合物的产品。
文献FR 2 939 662尤其提出由两个分离的不混溶相组成的基于非硅油的两相组合物,两个相在振荡后形成乳状液,同时保持两相组合物的所需性质,即快速相分离成具有清晰界面的两个透明相。
但是,取决于所用的非硅油,对水相和脂肪相两者而言,可能形成小液滴,其保持附着在透明容器壁上。这种现象在视觉上不可接受。
因此需要由两个分离的不混溶相组成的,包含极少或不含聚硅氧烷化合物的两相组合物,其在振荡后产生乳状液,同时保持两相组合物的所需性质,即在恢复静置后快速相分离成具有清晰界面的两个透明相,而没有保持附着在透明容器壁上的液滴出现。
令人惊讶地,申请人已经发现,通过使用包含8至18个碳原子的支链烷烃和在室温(20-25℃)下和在大气压力下为液体,HLB < 8并选自糖衍生物的表面活性剂的组合,可以获得在振荡后产生乳状液并经历再快速相分离成具有完全清晰界面的两个透明相并且没有保持附着在透明容器壁上的液滴出现的包含极少或不含聚硅氧烷化合物的透明两相组合物。
更特别地,本发明的一个主题是由分离并透明的水相和油相组成的组合物,其包含至少一种在室温(20-25℃)下和在大气压力(760 mmHg或1.013 × 105 Pa)下为液体,HLB < 8并选自糖的脂肪酸酯和烷基聚葡糖苷的表面活性剂、至少一种包含8至18个碳原子的支链烷烃和相对于所述组合物的总重量的0至4重量%的硅油。
根据本发明的组合物具有相同的卸妆效力和更好的感官性质,并且特别地,其在皮肤上留下较少的油腻残留物。
由于根据本发明的组合物意在用于局部施用,其含有生理上可接受的介质,即与皮肤、粘膜、头发和头皮相容的介质。
根据本发明的组合物包含分离的至少水相和油相。这两个相是分离的,即它们在静置时可看出彼此叠加且两者之间的界面完全清晰。它们在静置时透明,并在使用前振荡该组合物时,所得混合物由一个相在另一个相中的乳状液组成。这两个相可以或可以不是有色的。
在下文中,表述“至少一种”等同于“一种或多种”,且除非另行指明,数值范围的界限包括在该范围内。
词语“透明”是指该相具有小于或等于300 NTU的浊度。可以通过其浊度测量组合物的透明度,且NTU(比浊法浊度单位)是用于测量组合物的浊度的单位。可以例如用来自Hach Company的2100P型号浊度计进行浊度测量,用于该测量的管标为AR397A cat 24347-06。在室温(20℃至25℃)下进行测量。根据本发明的组合物的两个分离的相具有通常为0.1至300 NTU,且优选1至100 NTU的浊度。
水相
根据本发明的组合物的水(或亲水)相有利地包含水。
水相的量可以为相对于该组合物的总重量的50重量%至80重量%,且优选55重量%至70重量%。水量可以占水相的全部或一部分,且其通常为相对于该组合物的总重量的至少50重量%。
所用的水可以是无菌去矿质水和/或花水,如玫瑰水、矢车菊水、洋甘菊水或椴树花(lime blossom)水,和/或天然泉水或矿泉水,例如:Vittel水、Vichy盆地水、Uriage水、Roche Posay水、Bourboule水、Enghien-les-Bains水、Saint Gervais-les-Bains水、Néris-les-Bains水、Allevar-les-Bains水、Digne水、Maizières水、Neyrac-les-Bains水、Lons-le-Saunier水、Eaux Bonnes水、Rochefort水、Saint Christau水、Fumades水、Tercis-les-bains水和Avene水。水相还可包含重构的(reconstituted)泉水,即含有重构泉水特性的微量元素,如锌、铜、镁等的水。
根据本发明的组合物的水(或亲水)相还可含有任何水溶性或水可分散性添加剂。尤其可提到的水溶性添加剂是包含2至8个碳原子的多元醇。术语“多元醇”应被理解为是指包含至少两个游离羟基的任何有机分子。可提到的多元醇的实例包括甘油、二醇,例如丁二醇、丙二醇、异戊二醇、二丙二醇、己二醇、聚乙二醇和聚丙二醇。根据本发明的一个特定实施方案,该多元醇选自甘油和己二醇。该多元醇优选是己二醇。
多元醇可以以相对于该组合物的总重量的0.1重量%至60重量%,优选0.5重量%至50重量%,还更好为2重量%至30重量%,且甚至还更好为3重量%至20重量%的含量存在于根据本发明的组合物中。
还可提到的水溶性添加剂包括初级醇(primary alcohol),即包含1至6个碳原子的醇,如乙醇和异丙醇。其优选是乙醇。这种醇可以以相对于该组合物的总重量的例如小于或等于40重量%,且优选0.1重量%至20重量%的量存在。当根据本发明的组合物用作身体或头发产品时,这样的醇的添加可以尤其合适。
油相
油相通常占相对于该组合物的总重量的20重量%至50重量%,优选25重量%至45重量%,且还更好为30重量%至40重量%。
根据本发明的组合物的油相包含至少一种包含8至18个碳原子,且优选12至16个碳原子的支链烷烃。
根据一个特定实施方案,包含8至18个碳原子的一种或多种支链烷烃选自C8-C18异烷烃(也称作异链烷烃),如异十二烷、异癸烷或异十六烷,例如Exxon Chemical公司以商品名Isopar出售的异链烷烃或Presperse公司以商品名Permethyl出售的油,和Ineos公司出售的异十六烷和异十二烷。
根据本发明的一个特定实施方案,包含8至18个碳原子的一种或多种支链烷烃以相对于油相的总重量的至少等于40重量%,且优选45重量%至100重量%的量存在于该组合物中。
此外,根据本发明的组合物包含相对于该组合物的总重量的少于4重量%的硅油,优选少于3%,更优选少于2%,还更好为少于1重量%,且甚至还更好为少于0.5重量%的硅油。根据本发明的组合物优选不含硅油。
术语“硅油”是指含有至少一个硅原子,且尤其含有Si-O基团的油。
可提到的硅油的实例包括挥发性硅油,如环聚二甲基硅氧烷(INCI名:环聚二甲基硅氧烷(cyclomethicone)),如环戊硅氧烷、环己硅氧烷、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;线性聚硅氧烷,如七甲基己基三硅氧烷、七甲基辛基三硅氧烷、六甲基二硅氧烷、八甲基三硅氧烷、十甲基四硅氧烷或十二甲基五硅氧烷;非挥发性硅油,如聚甲基硅氧烷(PDMS)和苯基聚甲基硅氧烷,如苯基聚三甲基硅氧烷(phenyltrimethicone)、苯基聚二甲基硅氧烷、苯基三甲基甲硅烷氧基二苯基硅氧烷、二苯基聚二甲基硅氧烷、二苯基甲基二苯基三硅氧烷、2-苯基乙基三甲基甲硅烷氧基硅酸酯(2-phenylethyltrimethyl siloxysilicate)和聚甲基苯基硅氧烷;用脂肪酸、脂肪醇或聚氧化烯改性的聚硅氧烷,和它们的混合物。
根据本发明的组合物还可包含至少一种不同于包含8至18个碳原子的支链烷烃的附加非硅油。该一种或多种附加非硅油可选自不同于包含8至18个碳原子的支链烷烃的挥发性或非挥发性基于烃的油。
术语“基于烃的油“是指基本由碳和氢原子和可能氧和氮原子形成或甚至由其组成并且不含硅或氟原子的油;其可含有酯、醚、胺或酰胺基团。
术语“挥发性”是指在室温和大气压力下在与皮肤接触小于1小时时可蒸发的化合物。挥发性油是在室温下为液体,尤其在室温和大气压力下具有非零蒸气压,特别具有0.13Pa至40 000 Pa(10-3至300 mmHg),优选1.3 Pa至13 000 Pa(0.01至100 mmHg),且优选1.3Pa至1300 Pa(0.01至10 mmHg)的蒸气压的挥发性化妆品油。
可用于本发明的组合物的非硅油的实例包括:
- 植物来源的基于烃的油,如全氢鲨烯、包含4至10个碳原子的脂肪酸的液体甘油三酯,如庚酸或辛酸甘油三酯,或例如葵花油、玉米油、大豆油、葫芦油(marrow oil)、葡萄籽油、芝麻籽油、榛子油、杏仁油、澳洲坚果油、阿拉拉油(arara oil)、芫荽油、蓖麻油、鳄梨油、辛酸/癸酸甘油三酯,如Stearineries Dubois公司出售的那些或Dynamit Nobel公司以Miglyol 810、812和818为名出售的那些,荷荷巴油和乳木果油;
- 合成酯和醚,尤其是脂肪酸和/或脂肪醇的合成酯和醚,例如式R1COOR2和R1OR2的油,其中R1代表含有7至29个碳原子的脂肪酸残基且R2代表含有3至30个碳原子的基于支链或非支链烃的链,例如鸭子尾脂腺油(purcellin oil)、异壬酸异壬酯、肉豆蔻酸异丙酯、棕榈酸异丙酯、棕榈酸2-乙基己酯、硬脂酸2-辛基十二烷基酯、硬脂酸异鲸蜡醇酯、芥酸2-辛基十二烷基酯或异硬脂酸异硬脂醇酯;羟基化酯,例如乳酸异硬脂醇酯、羟基硬脂酸辛酯、羟基硬脂酸辛基十二烷基酯、苹果酸二异硬脂醇酯、柠檬三异鲸蜡醇酯和脂肪醇的庚酸酯、辛酸酯和癸酸酯;多元醇酯,例如丙二醇二辛酸酯、新戊二醇二庚酸酯和二乙二醇二异壬酸酯;和季戊四醇酯,例如季戊四醇四异硬脂酸酯;
- 不同于包含8至18个碳原子的支链烷烃的矿物或合成来源的挥发性或非挥发性直链或支链烃及其衍生物,如液体凡士林和氢化聚异丁烯,如Parleam®油;包含7至17个碳原子的挥发性直链烷烃,如十一烷或十三烷;
- 含有8至26个碳原子的在室温下为液体的脂肪醇,例如辛基十二烷醇、2-丁基辛醇、2-己基癸醇、2-十一烷基十五烷醇或油醇。
根据本发明的一个特定实施方案,该组合物包含至少一种选自下列基于烃的油的附加非硅油:
包含8至30个碳原子的脂肪酸酯,如新戊酸异癸酯、肉豆蔻酸异丙酯、棕榈酸异丙酯、棕榈酸2-乙基己酯、硬脂酸2-辛基十二烷基酯或硬脂酸异鲸蜡醇酯;直链烃,如Parleam®油和液体凡士林,包含7至17个碳原子的挥发性直链烷烃,如十一烷或十三烷。在包含7至17个碳原子,特别是9至15个碳原子,且更特别是11至13个碳原子的挥发性直链烷烃中,可以提到例如Cognis专利申请WO 2007/068 371或WO 2008/155 059中所述的烷烃(相差至少一个碳的不同烷烃的混合物)。这些烷烃由脂肪醇获得,该脂肪醇本身由椰油或棕榈油获得。
作为适用于本发明的直链烷烃的实例,可以提到正庚烷(C7)、正辛烷(C8)、正壬烷(C9)、正癸烷(C10)、正十一烷(C11)、正十二烷(C12)、正十三烷(C13)和正十四烷(C14)及其混合物。根据一个特定实施方案,该挥发性直链烷烃选自正壬烷、正十一烷、正十二烷、正十三烷和正十四烷及其混合物。
根据一个优选实施方案,可以提到Cognis公司的专利申请WO 2008/155 059的实施例1和2中获得的正十一烷(C11)和正十三烷(C13)的混合物。
根据本发明的另一特定实施方案,该组合物不含任何附加非硅油。在这一实施方案中,该组合物仅包含选自包含8至18个碳原子的支链烷烃(单独或作为混合物)的油。
在本发明的组合物,合计所有油,一种或多种油的总量可以例如为相对于该组合物的总重量的20重量%至50重量%,且优选30重量%至45重量%,且挥发油的总量可以例如为相对于该组合物的总重量的0至50重量%,优选5重量%至40重量%,且还更好为5重量%至30重量%。
根据本发明的一个特定实施方案,水相和油相之间的重量比为55/45至80/20,且还更好为50/50至70/30。
根据所需化妆品性能(cosmeticity)调节这一重量比并使该组合物具有小于4℃的凝固点。
表面活性剂
根据本发明的组合物包含至少一种在室温(20-25℃)下和在大气压力(760 mmHg或1.013 × 105 Pa)下为液体,HLB < 8并选自糖的脂肪酸酯和烷基聚葡糖苷的表面活性剂。
术语“HLB”是本领域技术人员公知的并且是指表面活性剂的亲水-亲脂平衡。可以通过Griffin法或Davies法确定根据本发明使用的一种或多种表面活性剂的HLB或亲水-亲脂平衡。
标度为0至20(不包括界限,否则该分子不再是表面活性剂)。该值越高,在水中的溶解度越大,反之亦然,该值越低,该表面活性剂对油的亲合力越大。
在出版物J. Soc. Cosm. Chem. 1954 (第5卷),第249-256页中定义了GriffinHLB值,或根据实验并如作者F. Puisieux和M. Seiller的,标题为Galenica 5: Les systèmes dispersés - Tome I - Agents de surface et émulsions - Chapitre IV -Notions de HLB et de HLB critique出版物, 第153-194页 - 段落1.1.2. Détermination de HLB par voie expérimentale [Experimental determination ofHLB], 第164-180页中所述确定HLB。
优选应考虑计算的HLB值。
计算的HLB被定义为是下列系数:
计算的HLB = 20 × 亲水部分的摩尔质量 / 总摩尔质量
Davies HLB在于合计表面活性剂的各结构基团作出的亲水和亲脂贡献:
HLB = ∑ HLB亲水基团 - ∑ HLB疏水基团 + 7
因此,该表面活性剂的HLB等于亲水基团的HLB值之和减去疏水基团的HLB值之和再加上7。
存在各种标准基团的HLB表,其尤其可见于下列专著:Surfactants inCosmetics, 第二版, surfactant science series第68卷,Martin M.Rieger & LindaD.Rhein编辑, 第134页, 表4。
根据本发明的一个特定实施方案,在室温下和在大气压力下为液体,HLB < 8的一种或多种表面活性剂包含一个或多个包含11至44个碳原子,优选12至24个碳原子,甚至更优选16至22个碳原子,且还更好为18至20个碳原子的基于直链或支链、饱和或不饱和烃的链。
术语“基于烃的链”是指基本由碳和氢原子和可能氧和氮原子形成或甚至由其组成并且不含任何硅或氟原子的基团;其可含有酯、醚、胺或酰胺基团。
糖的脂肪酸酯
一种或多种糖的脂肪酸酯可以是脂肪酸和糖或烷基糖的单酯或多酯。它们可以被氧烯化(oxyalkylenated),例如氧乙烯化和/或氧丙烯化,或聚甘油化(polyglycerolated)。
它们尤其可选自任选具有一个或多个不饱和度的C11-C22,且优选C12-C20脂肪酸和蔗糖(蔗糖(saccharose))、麦芽糖、葡萄糖、果糖或木糖的酯或酯的混合物,和任选具有一个或多个不饱和度的C11-C22,且优选C12-C20脂肪酸和(C1-C4烷基)葡萄糖,如甲基葡萄糖的酯或酯的混合物,和它们的混合物。
根据一个特定实施方案,形成可根据本发明使用的酯的脂肪单元的C11-C22(优选C12-C20,甚至更优选C14-C20,且还更好为C16-C18)脂肪酸包含含有11至22个碳原子(优选12至20个碳原子,甚至更优选14至20个碳原子,且还更好为16至18个碳原子)的基于直链或支链、饱和或不饱和烃的链。该酯的脂肪单元尤其可选自硬脂酸酯、山嵛酸酯、椰油酸酯、花生四烯酸酯、棕榈酸酯、肉豆蔻酸酯、月桂酸酯、癸酸酯和油酸酯,及其混合物。优选使用油酸酯。
根据另一特定实施方案,一种或多种糖的脂肪酸酯的糖单元可包含C1-C4烷基。其选自例如蔗糖、麦芽糖、葡萄糖、果糖、甘露糖、半乳糖、阿拉伯糖、木糖、乳糖、海藻糖和甲基葡萄糖。优选使用蔗糖、葡萄糖和甲基葡萄糖,且甚至更优选甲基葡萄糖。
根据本发明的一个优选实施方案,形成可根据本发明使用的酯的脂肪单元的C11-C22(优选C12-C20,甚至更优选C14-C20,且还更好为C16-C18)脂肪酸包含含有11至22个碳原子(优选12至20,甚至更优选14至20,且还更好为16至18)的基于不饱和直链烃的链。
根据一个优选实施方案,一种或多种糖的脂肪酸酯由其脂肪单元包含含有12至24个碳原子,且优选16至20个碳原子的基于不饱和直链烃的链的脂肪酸和(C1-C4烷基)糖的反应产生。
一种或多种糖的脂肪酸酯优选是二酯。
糖的脂肪酸酯特别选自甲基葡萄糖二油酸酯。
可提到的甲基葡萄糖二油酸酯的实例是Lubrizol公司以Glucate DO Emulsifier为名出售的产品,经Davies法计算的其HLB值等于-1.275。
烷基聚葡糖苷
本发明上下文中所用的一种或多种烷基聚葡糖苷可以或可以不是聚烷氧基化的。
根据一个特定实施方案,它们选自具有下列通式的化合物:
RO-(G)a
其中R是指包含12至44个碳原子的基于饱和或不饱和的直链或支链烃的链,基团G是指包含5至6个碳原子的糖残基且a是1至10,优选1至5的数值,且a甚至更优选等于1。
根据一个特定实施方案,R是指包含12至44个碳原子,优选16至36个碳原子,且还更好为18至22个碳原子的支链烷基。
根据另一特定实施方案,该糖残基选自葡萄糖、右旋糖、蔗糖、果糖、半乳糖、麦芽糖、麦芽三糖、乳糖、纤维二糖、甘露糖、核糖、葡聚糖、塔罗糖、阿洛糖、木糖、左旋葡聚糖、纤维素、淀粉和甲基葡萄糖。该糖残基更优选是指木糖。
该一种或多种烷基聚葡糖苷尤其可选自包含12至44个碳原子的脂肪醇和葡萄糖、麦芽糖、蔗糖、木糖或果糖的醚或醚的混合物,和包含12至44个碳原子的脂肪醇和甲基葡萄糖的醚或醚的混合物。
该醚的脂肪单元尤其可选自鲸蜡基、山嵛基、花生基、硬脂基、棕榈基、肉豆蔻基、月桂基、十六酰基和辛基十二烷基单元及其混合物,如鲸蜡硬脂基。其优选是辛基十二烷基。
根据本发明的一个特定实施方案,该一种或多种烷基聚葡糖苷选自具有下式的化合物:
R’O-G
其中R’是指包含12至44,优选16至36,且还更好为18至22个碳原子的饱和支链烷基,且基团G是指包含5至6个碳原子的糖残基,优选木糖残基。
该烷基聚葡糖苷特别是辛基十二烷基木糖苷,如SEPPIC公司以Fluidanov 20 X为名以由75%辛基十二烷醇和25%辛基十二烷基木糖苷组成的混合物形式出售的产品。经由Davies法计算的这种表面活性剂的HLB值为3.425。
根据一个特定实施方案,适用于本发明的在室温下和在大气压力下为液体,HLB <8的一种或多种表面活性剂选自甲基葡萄糖二油酸酯和辛基十二烷基木糖苷。
在室温下和在大气压力下为液体,HLB < 8的一种或多种表面活性剂通常以相对于该组合物的总重量的0.001重量%至1重量%,且优选相对于该组合物的总重量的0.005重量%至0.025重量%的活性材料量存在于该组合物中。
附加表面活性剂
根据本发明的组合物可任选在一个或另一个相中包含不同于如上定义的表面活性剂的至少一种附加表面活性剂。当其含有附加表面活性剂时,这种表面活性剂可以是阴离子、非离子或两性类型,但其优选为非离子和/或阴离子类型。其优选存在于亲水相中。
作为活性材料计的一种或多种表面活性剂的量应该是使得两个相在静置时保持分离并且不混合形成乳状液的量。这一量通常应该为相对于该组合物的总重量的小于或等于1.5重量%。其可以为例如相对于该组合物的总重量的0.01重量%至1.5重量%,优选0.025重量%至1重量%,且还更好为0.05重量%至0.5重量%。
根据一个优选实施方案,根据本发明的组合物包含相对于该组合物的总重量的小于2重量%,优选小于1重量%的附加表面活性剂,且其还更好为不含附加表面活性剂。
在附加非离子表面活性剂中,特别优选的是:
- 山梨糖醇的聚氧乙烯化脂肪酯,如ICI公司以Tween 20为名出售的产品;
- 聚氧乙烯化脂肪醇,如Gerland公司以Remcopal 21912 AL为名出售的产品;
- 聚氧乙烯化烷基酚,如Röhm & Haas公司以Triton X 100为名出售的产品;
- 环氧乙烷和环氧丙烷的缩合物,如ICI公司以Synperonic PE为名出售的那些,且特别是标作L 31、L 64、F 38、F 88、L 92、P 103、F 108和F 127的那些;
- 甘油或聚甘油的脂肪酸酯,例如甘油异硬脂酸酯、聚(3-甘油)二异硬脂酸酯或甘油辛酸酯;
- 聚乙二醇和/或聚丙二醇和甘油的醚,如甘油聚醚-7、甘油聚醚-26和PPG-24甘油聚醚-24;
- 衍生自a) 脂肪酸和b) 聚乙二醇和/或聚丙二醇甘油醚的反应的酯,例如甘油聚醚-2椰油酸酯或甘油聚醚-25 PCA异硬脂酸酯;
- 不同于上文定义的那些的蔗糖的脂肪酸酯,其包含12至30个碳原子或特别是14至20个碳原子,所述酯可能包含2至5个脂肪链,例如蔗糖二硬脂酸酯或蔗糖三硬脂酸酯;
- 不同于上文定义的那些的烷基聚葡糖苷,优选为包含含有6至30个碳原子,且优选8至16个碳原子的烷基并包含优选含有1.2至3个糖单元的亲水(葡糖苷)基团的那些。可提到的实例包括癸基葡糖苷(烷基- C9/C11-聚葡糖苷(1.4)),例如Kao Chemicals公司以Mydol10®为名出售的产品、Cogins公司以Plantaren 2000 UP®为名出售的产品和SEPPIC以Oramix NS 10®为名出售的产品;辛酰基/癸酰基葡糖苷,例如SEPPIC公司以Oramix CG110®为名出售的产品;月桂基葡糖苷,例如Cognis公司以Plantaren 1200 N®和Plantacare 1200®为名出售的产品;椰油基葡糖苷,例如Cognis公司以Plantacare 818/UP®为名出售的产品;例如SEPPIC公司以Montanov 68为名、Goldschmidt公司以Tego-CareCG90为名和Henkel公司以Emulgade KE3302为名出售的任选作为与十六十八醇的混合物的十六十八烷基葡糖苷;例如以花生醇和山嵛醇和花生基葡糖苷的混合物的形式,由SEPPIC公司以Montanov 202为名出售的花生基葡糖苷;例如以与鲸蜡醇和硬脂醇的混合物(35/65)的形式,由SEPPIC公司以Montanov 82为名出售的椰油酰基乙基葡糖苷;及其混合物;
- 聚合物乳化剂,如疏水改性的菊粉,例如Beneo Bio-Based Chemicals公司出售的Inutec SP1。
在阴离子表面活性剂中,尤其可提到:
- 烷基硫酸酯、烷基醚硫酸酯和它们的盐,尤其是它们的钠盐,例如Henkel公司以Texapon ASV为名出售的月桂基聚氧乙烯醚硫酸钠/月桂基聚氧乙烯醚硫酸镁/月桂基聚氧乙烯醚-8硫酸钠/月桂基聚氧乙烯醚-8硫酸镁的混合物;Henkel公司以Sipon AOS 225或Texapon N702 Pate为名出售的月桂基醚硫酸钠(70/30 C12-14) (2.2 EO)、Henkel公司以Sipon LEA 370为名出售的月桂基醚硫酸铵(70/30 C12-14) (3 EO);Rhodia Chimie公司以Rhodapex AB/20为名出售的(C12-C14)烷基醚(9 EO)硫酸铵;
- 烷基磺基乙酸盐,如Stepan公司以Lathanol LAL为名出售的烷基磺基乙酸盐;
- 烷基磺基琥珀酸盐,例如Witco公司以Setacin 103 Special和Rewopol SB-FA 30 K4为名出售的氧乙烯化(3 EO)月桂醇单磺基琥珀酸盐(70/30 C12/C14)、ZschimmerSchwarz公司以Setacin F Special Paste为名出售的C12-C14醇半磺基琥珀酸酯的二钠盐、Henkel公司以Standapol SH 135为名出售的氧乙烯化(2 EO)油酰胺基磺基琥珀酸二钠、Sanyo公司以Lebon A-5000为名出售的氧乙烯化(5 EO)月桂酰胺基单磺基琥珀酸盐、Witco公司以Rewopol SB CS 50为名出售的氧乙烯化(10 EO)月桂基柠檬酸酯单磺基琥珀酸酯的二钠盐,和Witco公司以Rewoderm S 1333为名出售的蓖麻油酸单乙醇酰胺单磺基琥珀酸酯的二钠盐;
- 例如通过脂肪链缩合到谷物,且尤其是小麦和燕麦的氨基酸上而得到的多肽,例如Croda公司以Aminofoam W OR为名出售的水解月桂酰小麦蛋白的钾盐、Maybrook公司以May-Tein SY为名出售的水解椰油酰大豆蛋白的三乙醇胺盐、SEPPIC公司以Proteol Oat为名出售的月桂酰燕麦氨基酸的钠盐、Deutsche Gelatine公司以Geliderm 3000为名出售的接枝到椰油脂肪酸上的胶原水解物,和SEPPIC公司以Proteol VS 22为名出售的用氢化椰油酸酰化的大豆蛋白;
- 氨基酸衍生物,例如肌氨酸盐,且尤其是酰基肌氨酸盐,如Ciba公司以Sarkosyl NL97为名出售或SEPPIC公司以Oramix L 30为名出售的月桂酰肌氨酸钠,Nikkol公司以Nikkol Sarcosinate MN为名出售的肉豆蔻酰肌氨酸钠、Nikkol公司以NikkolSarcosinate PN为名出售的棕榈酰肌氨酸钠;丙氨酸盐(alaninate),如Nikkol公司以Sodium Nikkol Alaninate LN 30为名出售或Kawaken公司以Alanone ALE为名出售的N-月桂酰-N-甲基酰胺基丙酸钠,和Kawaken公司以Alanone ALTA为名出售的N-月桂酰-N-甲基丙氨酸三乙醇胺;N-酰基谷氨酸盐,如Ajinomoto公司以Acylglutamate CT-12为名出售的三乙醇胺单椰油酰基谷氨酸盐和Ajinomoto公司以Acylglutamate LT-12为名出售的三乙醇胺月桂酰谷氨酸盐;天冬氨酸盐,如Mitsubishi公司以Asparack LM-TS2为名出售的三乙醇胺N-月桂酰天冬氨酸盐和三乙醇胺 N-肉豆蔻酰天冬氨酸盐的混合物;甘氨酸衍生物,如N-椰油酰甘氨酸钠和N-椰油酰甘氨酸钾,如Ajinomoto公司以Amilite GCS-12和AmiliteGCK-12为名出售的产品;
- 磺酸盐,例如α-烯烃磺酸盐,如Stepan公司以Bio-Terge AS-40为名出售、Witco公司以Witconate AOS Protégé和Sulframine AOS PH 12为名出售或Stepan公司以Bio-TergeAS-40 CG为名出售的α-烯烃磺酸钠(C14-C16),Clariant公司以Hostapur SAS 30为名出售的仲烯烃磺酸钠(secondary sodium olefinsulfonate);或直链烷基芳基磺酸盐,如Manro公司以Manrosol SXS30、Manrosol SXS40和Manrosol SXS93为名出售的二甲苯磺酸钠;
- 羟乙基磺酸盐,尤其是酰基羟乙基磺酸盐,如椰油酰羟乙基磺酸钠,如Jordan公司以Jordapon CI P为名出售的产品。
在两性或两性离子表面活性剂中,尤其可提到:
- 烷基酰胺基烷基胺衍生物,如Rhodia Chimie公司以Miranol C2M Conc NP为名以盐水溶液的形式出售的N-椰油酰基-N-羧基甲氧基乙基-N-羧甲基乙二胺N-二钠(CTFA名:椰油酰两性基二乙酸二钠(Disodium cocoamphodiacetate));N-椰油酰基-N-羟乙基-N-羧甲基乙二胺N-钠(CTFA名:椰油酰两性基乙酸钠)和椰油酸乙醇酰胺的混合物(CTFA名:椰油酰胺(Cocamide)DEA);
- 甜菜碱,例如椰油酰基甜菜碱,如Henkel公司以Dehyton AB-30为名出售的产品,月桂基甜菜碱,如Clariant公司以Genagen KB为名出售的产品,氧乙烯化(10 EO)月桂基甜菜碱,如Shin Nihon Rica公司以Lauryl Ether (10 EO) Betaine为名出售的产品,或氧乙烯化(10 EO)硬脂基甜菜碱,如Shin Nihon Rica公司以Stearyl Ether (10 EO) Betaine为名出售的产品;
- 烷基酰胺基丙基甜菜碱及其衍生物,例如Sanyo公司以Lebon 2000 HG为名出售或Albright & Wilson公司以Empigen BB为名出售的椰油酰胺基丙基甜菜碱、Witco公司以Rewoteric AMB12P为名出售的月桂酰胺基丙基甜菜碱,如椰油酰胺基丙基甜菜碱,例如Goldschmidt公司以Tego Betaine为名出售的产品;
- 咪唑啉衍生物,如Chimex公司以Chimexane HD为名出售的产品。
辅助剂
根据本发明的组合物还可含有常规化妆品辅助剂或添加剂,其将取决于它们的亲水或亲脂性质在一个或另一个相中,例如亲水胶凝剂、防腐剂和杀菌剂、染料、软化剂、缓冲剂、保湿剂、UV遮蔽剂(或防晒剂),电解质,如氯化钠或pH调节剂,例如柠檬酸或氢氧化钠及其混合物。
取决于根据本发明的组合物的所需粘度,可以在其中并入一种或多种亲水胶凝剂。可提到的亲水胶凝剂的实例包括改性或未改性的羧基乙烯基聚合物,如Noveon公司以Carbopol(INCI名:卡波姆)为名出售的产品;聚丙烯酰胺;任选交联和/或中和的2-丙烯酰胺基-2-甲基丙磺酸均聚物和共聚物,如Clariant公司以Hostacerin AMPS为名出售的聚(2-丙烯酰胺基-2-甲基丙磺酸)(INCI名:聚丙烯酰二甲基牛磺酸酰胺铵(ammoniumpolyacryldimethyltauramide));可以或可以不被改性的多糖生物聚合物,如黄原胶、瓜尔胶、藻酸盐和纤维素;和它们的混合物。当它们存在时,这些胶凝剂必须以使得其不改变根据本发明的组合物的性质的量引入。可提到的亲脂胶凝剂包括烯烃共聚物,例如以下类型的“二嵌段”、“三嵌段”或“放射状”类型的嵌段共聚物:聚苯乙烯/聚异戊二烯或聚苯乙烯/聚丁二烯类型,如BASF公司以Luvitol HSB®为名出售的产品,聚苯乙烯/共聚(乙烯-丙烯)类型,如Shell Chemical Co.公司以Kraton®为名出售的产品,或聚苯乙烯/共聚(乙烯-丁烯)类型,和三嵌段和放射状(星形)共聚物在异十二烷中的混合物,如Penreco公司以Versagel®为名出售的那些,例如丁烯/乙烯/苯乙烯三嵌段共聚物和乙烯/丙烯/苯乙烯星形共聚物在异十二烷中的混合物(Versagel M 5960)。
胶凝剂可以以相对于该组合物的总重量的0.05重量%至10重量%,且优选0.1重量%至5重量%的活性材料含量存在。
可用的防腐剂包括所涉及领域中常用的任何防腐剂,例如对羟基苯甲酸酯、苯氧乙醇、葡萄糖酸氯己定和聚六亚甲基双胍盐酸盐(CTFA名:聚氨基丙基双胍)。根据本发明的一个优选实施方案,该组合物含有单独或作为与其它防腐剂的混合物的聚六亚甲基双胍盐酸盐。
可用的杀菌剂的一个实例是甘油基单(C3-C9)烷基或(C3-C9)烯基醚,在文献中,特别在E. Baer, H.O.L. Fischer - J. Biol. Chem. 140-397-1941中描述了其制造。在这些甘油基单(C3-C9)烷基或(C3-C9)烯基醚中,优选使用3-[(2-乙基己基)氧基]-1,2-丙二醇、3-[(庚基)氧基]-1,2-丙二醇、3-[(辛基)氧基]-1,2-丙二醇和3-[(烯丙基)氧基]-1,2-丙二醇。根据本发明更特别优选的甘油基单(C3-C9)烷基醚是Schulke & Mayr G.m.b.H.公司以商品名Sensiva SC 50出售的3-[(2-乙基己基)氧基]-1,2-丙二醇(INCI名: 乙基己基甘油)。
在软化剂中,特别可提到尿囊素和红没药醇、浮游生物和某些植物提取物,如玫瑰提取物和草木樨提取物。
可提到的电解质包括磷酸二氢钾或磷酸氢二钾、氯化钠、硫酸镁和EDTA二钠。
一种或多种盐的量可以例如为相对于该组合物的总重量的0至5重量%,优选0.1重量%至2重量%,且还更好为0.5重量%至1重量%。
根据本发明,该组合物还可优选在亲水相中包含例如相对于该组合物的总重量的0.025重量%至5重量%的比例的相分离剂(dephasing agent)。
可提到的相分离剂的实例包括如文献EP-A-603 080中所述的烷基二甲基苄基氯化铵,且尤其是苯扎氯铵和含有其的混合物;如文献EP-A-847 746中所述的包含季铵基团的烷氧基化烷基葡糖苷,且尤其是月桂基甲基葡糖醇聚醚-10(gluceth-10)羟丙基二甲基氯化铵;乙烯基吡咯烷酮聚合物和共聚物,且尤其是如文献WO-A-99/56704中所述的聚乙烯基吡咯烷酮/十六碳烯共聚物;和它们的混合物。
当存在这样的试剂时,表面活性剂与相分离剂之间的比率优选为0.005/1至200/1,且还更好为0.01/1至120/1.
作为可用于本发明的组合物的活性剂,可提到的实例包括酶(例如乳过氧化物酶、脂肪酶、蛋白酶、磷脂酶、纤维素酶);类黄酮;保湿剂,如蛋白水解物;透明质酸钠;抗炎剂;低聚原花青素;维生素,如维生素A(视黄醇)、维生素E(生育酚)、维生素C(抗坏血酸)、维生素B5(泛醇)、维生素B3(烟酰胺)、这些维生素的衍生物(特别是酯)及其混合物;脲;咖啡因;脱色剂,如曲酸、氢醌和咖啡酸;水杨酸及其衍生物;α-羟基酸,如乳酸和羟基乙酸及其衍生物;类视黄醇,如类胡萝卜素和维生素A衍生物;氢化可的松;褪黑素;藻类、真菌、植物、酵母、细菌的提取物;甾族化合物;抗菌活性剂,如2,4,4’-三氯-2’-羟基二苯基醚(或三氯生)、3,4,4’-三氯碳酰替苯胺(或三氯卡班)和上述酸,且特别是水杨酸及其衍生物;张紧剂;神经酰胺;精油;和它们的混合物;和适合该组合物的最终用途的任何活性剂。
可以以已知方式将上述组合物置于(conditioned)具有单一隔室的瓶中。使用者随后必须振荡该瓶,然后将其内容物倒在棉片上。也可以将该产品置于“泵动瓶(pump-action bottle)”类型的瓶中。根据一个特定实施方案,其是通常由聚对苯二甲酸乙二醇酯(PET)制成的透明容器。
根据本发明的组合物可用于任何局部施用;其尤其可组成化妆品或皮肤病学组合物。其特别可用于皮肤、嘴唇和/或眼部的护理、清洁和/或卸妆,以及用作护发组合物。
因此,本发明的一个主题还有如上定义的化妆品组合物用于皮肤、嘴唇和/或眼部的护理、卸妆和/或清洁和/或用于护发的化妆用途。
本发明的一个主题还有用于皮肤、嘴唇和/或眼部或头发的卸妆、清洁和/或护理的化妆方法,其特征在于将如上定义的化妆品组合物施用到皮肤、嘴唇和/或眼部或头发。
根据本发明的一个优选实施方案,该组合物是用于皮肤、嘴唇和/或眼部的清洁和/或卸妆的组合物。
根据本发明的组合物的下列实施例作为示例给出而非限制性的。除非另行提到,其中的量作为起始材料的重量百分比给出。化合物名称作为化学名或INCI名给出。
实施例
对比例1至3。
制备下列组合物。
组合物 | 1(本发明) | 2(本发明) | 3(对比) |
EDTA二钠 | 0.11 | 0.11 | 0.11 |
磷酸钾 | 0.46 | 0.46 | 0.46 |
磷酸氢二钾 | 0.23 | 0.23 | 0.23 |
氯化钠 | 0.2885 | 0.2885 | 0.2885 |
异十六烷 | 16.92 | 16.92 | 16.92 |
染料 | 0.06 | 0.06 | 0.06 |
芳香剂 | 0.02 | 0.02 | 0.02 |
聚氨基丙基双胍(来自Arch Personal Care的Cosmocil CQ) | 0.29 | 0.29 | 0.29 |
己二醇 | 0.29 | 0.29 | 0.29 |
水 | 55.97 | 55.97 | 55.85 |
异十二烷 | 25.25 | 24.9 | 25.36 |
癸基葡糖苷(来自SEPPIC的Oramix NS 10) | - | - | 0.115 AM |
辛基十二烷醇(和)辛基十二烷基木糖苷(来自SEPPIC的Fluidanov 20 X) | - | 0.115 AM | |
甲基葡萄糖二油酸酯(来自Lubrizol的Glucate DO Emulsifier) | 0.115 AM | - | - |
在组合物3的情况下,在将该组合物放在PET容器中时,在振荡并快速相分离成两个分离的透明相后,可以看见附着在容器壁上的在脂肪相侧和水相侧两者中的液滴。用根据实施例3的组合物进行相同试验,其中用Poloxamer 184(Faconnier出售)替代癸基葡糖苷。在振荡并快速相分离后在容器壁上也观察到液滴。
用根据本发明的组合物1和2,在容器壁上没有可见液滴。
实施例4至6 - 根据本发明的卸妆组合物
制备下列组合物。
以下列方式制备组合物4至6:
每一操作都在不加热的情况下进行。逐一加入水相的起始材料,然后磁力搅拌容纳它们的烧杯直至完全均化和溶解。对脂肪相的起始材料完成相同操作。然后使这两个相接触,不搅拌。
上述各组合物4至6在使用前振荡以使这两个油相和水相暂时乳化,然后将它们施用到棉片上,然后施用到面部和/或眼部以卸妆。该产品具有良好的感官性质并观察到良好的卸妆效力。在使用后,该产品快速分离成两个透明相,具有完全清晰界面并且没有保持附着在透明容器壁上的液滴出现。
Claims (15)
1.由分离并透明的水相和油相组成的组合物,其包含至少一种在室温(20-25℃)下和在大气压力(760 mmHg或1.013 × 105 Pa)下为液体,HLB < 8并选自糖的脂肪酸酯和烷基聚葡糖苷的表面活性剂、至少一种包含8至18个碳原子,且优选12至16个碳原子的支链烷烃和相对于所述组合物的总重量的0至4重量%的硅油。
2.根据权利要求1的组合物,其中所述在室温下和在大气压力下为液体,HLB < 8的一种或多种表面活性剂包含一个或多个含有11至44个碳原子,优选12至24个碳原子,甚至更优选16至22个碳原子,且还更好为18至20个碳原子的基于直链或支链、饱和或不饱和烃的链。
3.根据权利要求1或2的组合物,其中所述一种或多种糖的脂肪酸酯是脂肪酸和糖或烷基糖的单酯或多酯,所述酯可以被氧烯化,例如氧乙烯化和/或氧丙烯化,或聚甘油化。
4.根据权利要求3的组合物,其中所述一种或多种糖的脂肪酸酯选自具有包含11至22个碳原子,优选12至20个碳原子,甚至更优选14至20个碳原子,且还更好为16至18个碳原子的基于直链或支链、饱和或不饱和烃的链的C11-C22,优选C12-C20,甚至更优选C14-C20,且还更好为C16-C18脂肪酸和糖或烷基糖的单酯或二酯。
5.根据权利要求3或4的组合物,其中所述一种或多种糖的脂肪酸酯选自蔗糖、麦芽糖、葡萄糖、果糖、甘露糖、半乳糖、阿拉伯糖、木糖、乳糖、海藻糖或甲基葡萄糖的脂肪酸酯,优选蔗糖、葡萄糖和甲基葡萄糖的脂肪酸酯,优选甲基葡萄糖的脂肪酸酯。
6.根据权利要求1至5任一项的组合物,其中所述一种或多种糖的脂肪酸酯由其脂肪单元包含含有12至24个碳原子,且优选16至20个碳原子的基于不饱和直链烃的链的脂肪酸和(C1-C4烷基)糖的反应产生。
7.根据权利要求1至6任一项的组合物,其中所述糖的脂肪酸酯是甲基葡萄糖二油酸酯。
8.根据权利要求1至7任一项的组合物,其中所述一种或多种烷基聚葡糖苷选自具有下列通式的化合物:
RO-(G)a
其中R是指包含12至44个碳原子,优选16至36个碳原子,且还更好为18至22个碳原子的基于饱和或不饱和、直链或支链烃的链,优选支链烷基,基团G是指包含5至6个碳原子的糖残基且a是1至10,优选1至5的数值,且a甚至更优选等于1。
9.根据权利要求8的组合物,其中所述糖残基选自葡萄糖、右旋糖、蔗糖、果糖、半乳糖、麦芽糖、麦芽三糖、乳糖、纤维二糖、甘露糖、核糖、葡聚糖、塔罗糖、阿洛糖、木糖、左旋葡聚糖、纤维素、淀粉和甲基葡萄糖,优选木糖。
10.根据权利要求1至9任一项的组合物,其中所述一种或多种烷基聚葡糖苷选自具有下式的化合物:
R’O-G
其中R’是指包含12至44,优选16至36,且还更好为18至22个碳原子的饱和支链烷基,且基团G是指包含5至6个碳原子的糖残基,优选木糖残基。
11.根据权利要求8至10任一项的组合物,其中所述烷基聚葡糖苷是辛基十二烷基木糖苷。
12.根据权利要求1至11任一项的组合物,其中所述包含8至18个碳原子的一种或多种支链烷烃选自C8-C18异烷烃,如异十二烷、异癸烷或异十六烷。
13.根据权利要求1至12任一项的组合物,其中所述包含8至18个碳原子的一种或多种支链烷烃以相对于油相的总重量的至少等于40重量%,且优选45重量%至100重量%的量存在于所述组合物中。
14.根据权利要求1至13任一项的组合物用于皮肤、嘴唇和/或眼部的护理、卸妆和/或清洁和/或用于护发,优选用于皮肤、嘴唇和/或眼部的卸妆和/或清洁的化妆用途。
15.用于皮肤、嘴唇和/或眼部的卸妆、清洁和/或护理,优选用于皮肤、嘴唇和/或眼部的卸妆和/或清洁的化妆方法,其中将根据权利要求1至13任一项的组合物施用到皮肤、嘴唇和/或眼部。
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FR1360530A FR3012330B1 (fr) | 2013-10-29 | 2013-10-29 | Composition biphase comprenant un ester d'acide gras et de sucre ou un alkylpolyglucoside liquide, de hlb < 8, et un alcane ramifie en c8-c18 |
PCT/EP2014/072907 WO2015062993A1 (en) | 2013-10-29 | 2014-10-24 | Two-phase composition comprising a fatty acid ester of sugar or a liquid alkyl polyglucoside, with an hlb < 8, and a c8-c18 branched alkane |
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- 2014-10-24 EP EP14795977.9A patent/EP3062761B1/en active Active
- 2014-10-24 RU RU2016120762A patent/RU2678104C2/ru active
- 2014-10-24 US US15/033,196 patent/US10016348B2/en active Active
- 2014-10-24 JP JP2016527270A patent/JP6486918B2/ja active Active
- 2014-10-24 CN CN201480059943.XA patent/CN105722496B/zh active Active
- 2014-10-24 ES ES14795977.9T patent/ES2681436T3/es active Active
- 2014-10-24 WO PCT/EP2014/072907 patent/WO2015062993A1/en active Application Filing
- 2014-10-24 BR BR112016009115-9A patent/BR112016009115B1/pt active IP Right Grant
- 2014-10-24 MX MX2016005048A patent/MX357373B/es active IP Right Grant
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Patent Citations (4)
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US5871758A (en) * | 1996-12-11 | 1999-02-16 | E-L Management Corp. | Dual phase cosmetic composition |
US6297204B1 (en) * | 1998-07-01 | 2001-10-02 | L'oreal | Two-phase cosmetic and/or dermatologic composition which is useful in particular for removing make-up from the eyes |
DE19945503A1 (de) * | 1999-09-23 | 2001-04-05 | Henkel Kgaa | Mehrphasiges Reinigungsmittel mit antimikrobieller Wirkung |
FR2939662A1 (fr) * | 2008-12-17 | 2010-06-18 | Oreal | Composition biphase transparente sans silicones |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN115151237A (zh) * | 2019-09-19 | 2022-10-04 | 化工产品开发公司Seppic | 具有良好喷雾特性的稳定加香组合物 |
CN115605177A (zh) * | 2020-04-30 | 2023-01-13 | Lvmh研究公司(Fr) | 加香组合物 |
Also Published As
Publication number | Publication date |
---|---|
EP3062761B1 (en) | 2018-06-06 |
EP3062761A1 (en) | 2016-09-07 |
JP6486918B2 (ja) | 2019-03-20 |
BR112016009115B1 (pt) | 2020-11-10 |
FR3012330B1 (fr) | 2015-10-23 |
JP2016535047A (ja) | 2016-11-10 |
MX2016005048A (es) | 2016-07-19 |
RU2016120762A3 (zh) | 2018-07-25 |
CN105722496B (zh) | 2020-04-28 |
ZA201602677B (en) | 2017-07-26 |
MX357373B (es) | 2018-07-06 |
US10016348B2 (en) | 2018-07-10 |
FR3012330A1 (fr) | 2015-05-01 |
RU2016120762A (ru) | 2017-12-06 |
RU2678104C2 (ru) | 2019-01-23 |
WO2015062993A1 (en) | 2015-05-07 |
ES2681436T3 (es) | 2018-09-13 |
US20160256367A1 (en) | 2016-09-08 |
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