CN105380810B - 化妆品组合物的稳定 - Google Patents
化妆品组合物的稳定 Download PDFInfo
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- CN105380810B CN105380810B CN201510920580.0A CN201510920580A CN105380810B CN 105380810 B CN105380810 B CN 105380810B CN 201510920580 A CN201510920580 A CN 201510920580A CN 105380810 B CN105380810 B CN 105380810B
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Abstract
本发明涉及选自(a1)二苯基丙烯酸酯和(a2)特定羟基苯基三嗪的UV吸收剂用于稳定化妆品组合物的用途,所述化妆品组合物含有(b1)特定的二苯酮衍生物、(b2)特定的苯并三唑衍生物和(b3)特定的三嗪衍生物以及选自(c1)肉桂酸衍生物和(c2)二苯甲酰基甲烷衍生物的UV滤光剂。
Description
本申请是中国专利申请201080014767.X的分案申请,该中国专利申请的申请日为2010年1月28日,发明名称是“化妆品组合物的稳定”。
技术领域
本发明涉及选自二苯基丙烯酸酯和特定羟基苯基三嗪的UV吸收剂用于稳定化妆品组合物的用途,所述化妆品组合物含有特定的二苯酮衍生物、特定的苯并三唑衍生物和特定的三嗪衍生物以及选自肉桂酸衍生物和二苯甲酰基甲烷衍生物的UV滤光剂。
背景技术
众所周知,紫外辐射(光)对人的皮肤有害。根据波长,UV辐射引起不同类型的皮肤损伤。UV-B辐射(约290-320nm)会引起晒伤并能引起皮肤癌。UV-A辐射(约320-400nm)在使皮肤变黑的同时,也会引起晒伤,并引起皮肤癌。此外,UV-B辐射的有害作用会由UV-A辐射加重。
所以,有效的防晒配料优选同时含有至少一种UV-A和UV-B滤光剂以覆盖越290-400nm的整个范围,从而防止人的皮肤受到日光的有害影响。
UV-A的影响主要由自由基来调节,例如反应性氧物质引起不同类型的向细胞DNA、类脂和蛋白质的降解。可见性的迹象通常是长期累积作用的结果。这是皮肤光老化与UV-A光有关的原因。还已经知道,正常的户外UV-A辐射可以足够有效以致引起蛋白质胶原和弹性蛋白的断裂,导致牢固性和皮肤弹性的损失。所以,日常皮肤护理的UVA防护是十分重要的。
许多UV-B滤光剂已经登记用于防晒制剂中,它们主要是3-亚苄基樟脑的衍生物、水杨酸乙基己基酯和肉桂酸酯,例如对甲氧基肉桂酸2-乙基己基酯。
一类新的有机UV滤光剂是微粒化的哌嗪二-二氨基二苯酮,它们通常与肉桂酸衍生物和/或二苯甲酰基甲烷衍生物混合使用。
不幸的是,这种在防晒组合物中组合使用的UV滤光剂的缺点是较快地发生光降解,导致丧失防止阳光损伤的作用。
所以,本发明的一个挑战是稳定这些特定的UV滤光剂组合物。
发明内容
惊奇的是,发现使用二苯基丙烯酸酯和特定的三嗪衍生物将提高含有特定微粒化三嗪衍生物和选自肉桂酸衍生物和二苯甲酰基甲烷衍生物中的UV吸收剂的组合物的化妆品和皮肤病理学(dermatological)配料的稳定性。
所以,本发明涉及选自以下的UV吸收剂用于稳定化妆品组合物的用途:
(a1)二苯基丙烯酸酯;和
(a2)下式的羟基苯基三嗪:
R1是–O-R5;-COOR6;或-CO-NHR7;
R2是–O-R8;-COOR9;或-CO-NHR10;
R3是–O-R11;-COOR12;或-CO-NHR13;
R5、R6、R7、R8、R9、R10、R11、R12和R13彼此独立地是C1-C18烷基;
R4是氢或羟基;和
x是0或1;
所述化妆品组合物含有选自以下(b1)、(b2)和(b3)的有机UV吸收剂:
(b1)下式的二苯酮衍生物:
R14和R15彼此独立地是;C1-C20烷基;C2-C20链烯基;C3-C10环烷基;C3-C10环烯基;或R14和R15与连接的氮原子一起形成5或6元杂环;
n1是1-4的数;
当n1=1时,R16是饱和或不饱和的杂环基团;羟基-C1-C5烷基;任选地被一个或多个C1-C5烷基取代的环己基;任选地被杂环基、氨基羰基或C1-C5烷基羧基取代的苯基;
n2是1-3的数;
当n1是3时,R16是烷三基;
当n1是4时,R16是烷四基;
A是-O-;或–N(R17)-;和
R17是氢;C1-C5烷基;或羟基-C1-C5烷基;
(b2)下式的苯并三唑衍生物:
T1是任选被苯基取代的C1-C12烷基;和
(b3)下式的三嗪衍生物:
R17和R21彼此独立地是氢;C1-C18烷基;或C6-C12芳基;
其中在式(4a)中,R18、R19和R20中的至少一个基团是式(4c)的基团;
R22、R23、R24、R25和R26彼此独立地是氢;羟基;卤素;C1-C18烷基;C1-C18烷氧基;C6-C12芳基;联苯基;C6-C12芳氧基;C1-C18烷硫基;羧基;-COOM;C1-C18-烷基羧基;氨基羰基;或单-或二-C1-C18烷基氨基;C1-C10酰基氨基;-COOH;
M是碱金属离子;
x是1或2;和
y是2-10的数;
并且所述化妆品组合物含有选自以下(c1)和(c2)的UV滤光剂:
(c1)肉桂酸衍生物;和
(c2)二苯甲酰基甲烷衍生物。
根据对于式(1)化合物中的基团的定义,C1-C18烷基是直链或支化的烷基,例如甲基,乙基,正丙基,异丙基,正丁基,仲丁基,叔丁基,戊基,异戊基或叔戊基,己基,2-乙基己基,庚基,辛基,异辛基,壬基,癸基,十一烷基,十二烷基,十四烷基,十五烷基,十六烷基,十七烷基或十八烷基。
根据对于式(1)化合物中的基团的定义,C1-C18烷基可以被以下基团取代:甲氧基乙基,乙氧基丙基,2-乙基己基,羟基乙基,氯丙基,N,N-二乙基氨基丙基,氰基乙基,苯乙基,苄基,对叔丁基苯乙基,对叔辛基苯氧基乙基,3-(2,4-二叔戊基苯氧基)-丙基,乙氧基羰基甲基-2-(2-羟基乙氧基)乙基,或2-呋喃基乙基。
根据对于式(1)化合物中的基团的定义,C1-C18烷氧基是例如:甲氧基,乙氧基,正丙氧基,异丙氧基,正丁氧基,仲丁氧基,叔丁氧基,戊氧基,异戊氧基或叔戊氧基,己氧基,庚氧基,辛氧基,异辛氧基,壬氧基,癸氧基,十一烷氧基,十二烷氧基,十四烷氧基,十五烷氧基,十六烷氧基,十七烷氧基或十八烷氧基。
根据对于式(1)化合物中的基团的定义,C6-C10芳基是例如萘基,优选苯基。
二苯基丙烯酸酯(a1)优选选自2-氰基-3,3-二苯基丙烯酸2-乙基己基酯和2-氰基丙烯酸3-(苯并呋喃基)酯,更优选选自2-氰基-3,3-二苯基丙烯酸2-乙基己基酯。
优选的羟基苯基三嗪对应于下式:
R5、R8和R11彼此独立地是C1-C18烷基。
最优选的根据式(1a)的羟基苯基三嗪衍生物是二-乙基己氧基苯酚甲氧基苯基三嗪。
其它优选的羟基苯基三嗪对应于下式
R1是-COOR6或-CO-NHR7;
R2是-COOR9或-CO-NHR10;和
R3是-COOR12或-CO-NHR13;其中
R6、R7、R9、R10、R12和R13彼此独立地是C1-C12烷基,优选2-乙基己基。
最优选的根据式(1a)的羟基苯基三嗪衍生物是乙基己基三嗪酮和二辛基丁酰氨基三嗪酮。
如果在式(2)中(对于二苯酮衍生物(b1))的n1优选定义为数字2,则:
R16是C1-C12亚烷基;和
R14、R15和A如式(2)中所定义。
优选二苯酮衍生物(b1)对应于下式
R14和R15是氢或C1-C5烷基。
最优选,二苯酮衍生物(b1)对应于下式:
最优选的根据组分(b2)的苯并三唑衍生物是2,2′-甲烷二基二[6-(2H-苯并三唑-2-基)-4-(2,4,4-三甲基戊烷-2-基)苯酚](Bisotrizole),其对应于下式的化合物:
根据式(2)-(4)的二苯酮衍生物(b)优选以微粒状态使用。
优选的根据组分(b3)的化合物对应于下式
R17、R21、R22、R23和R24如在式(4)中所定义。
最优选的是式(4)的化合物,其中R17和R21是氢。
最优选的是下式的化合物:
这些有机UV吸收剂(b1)、(b2)和(b3)的特征在于油溶性差并且熔点高。所以,它们尤其适合以微粒状态用做UV吸收剂。
它们可以通过任何适合于制备微粒的公知方法制备,例如湿研磨、湿捏合、从合适的溶剂喷雾干燥、通过超临界流体(例如CO2)根据RESS方法膨胀(超临界溶液的快速膨胀),通过从合适的溶剂再沉淀,包括超临界流体(GASR方法=气体抗溶剂重结晶/PCA方法=用压缩抗溶剂沉淀)。
作为用于制备微溶性微粒有机化合物的研磨设备,可以使用例如喷射磨机、球磨机、震动磨机或锤磨机,优选高速混合磨机。更优选的磨机是现代球磨机;这些类型的磨机的生产者是例如Netzsch(LMZ mill)、Drais(DCP-Viscoflow或Cosmo)、Bühler AG(离心磨)或Bachhofer。
用于制备微粒有机UV吸收剂的捏合设备的例子是典型的曲拐式间歇捏合机,以及系列间歇捏合机(IKA-Werke)或连续捏合机(Continua,来自Werner und Pfleiderer)。
用于本发明中的微溶性有机化合物的研磨操作是优选用研磨助剂进行。
分散剂是用做用于所有上述微粒化工艺的低分子量研磨助剂。
有用的阴离子、非离子或两性表面活性剂是在下面的标题“特定的分散剂”中公开。
优选的用于水分散液的研磨助剂是HLB(亲水亲油平衡)值高于8、更优选高于10的阴离子表面活性剂。
特定的分散剂
任何常规使用的阴离子、非离子或两性表面活性剂可以用做分散剂。这些表面活性剂体系可以含有例如:羧酸和它们的盐:钠、钾和铵的碱性皂,钙或镁的金属皂,有机基础皂例如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸和油酸等,烷基磷酸酯或磷酸酯,酸式磷酸盐,二乙醇胺磷酸盐,十六烷基磷酸钾,乙氧基化羧酸或聚乙二醇酯,PEG-n丙烯酸酯。脂肪醇聚二醇醚,例如月桂基醇聚醚-n、肉豆蔻醇聚醚-n、鲸蜡硬脂醇聚醚-n、硬脂醇聚醚-n、油醇聚醚-n。脂肪酸聚二醇醚,例如PEG-n硬脂酸酯、PEG-n油酸酯、PEG-n椰油酸酯、单甘油酯和多元醇酯,1-100摩尔氧化乙烯与多元醇的加合产物的C12-C22脂肪酸单酯和二酯,脂肪酸和聚甘油的酯例如单硬脂酸酯甘油、二异硬脂酰基聚甘油基-3-二异硬脂酸酯,聚甘油基-3-二异硬脂酸酯,三甘油基二异硬脂酸酯,聚甘油基-2-倍半异硬脂酸酯,或聚甘油基二聚体(dimerate)。来自多种这些物质的化合物的混合物也是合适的。脂肪酸聚二醇酯例如单硬脂酸酯二甘醇,脂肪酸和聚乙二醇的酯,脂肪酸和蔗糖的酯例如蔗糖酯,甘油和蔗糖的酯例如蔗糖甘油酯。山梨醇和脱水山梨醇,具有6-22个碳原子的饱和和不饱和脂肪酸与环氧乙烷加合产物的脱水山梨醇单酯和二酯,聚山梨酯-n系列,脱水山梨醇酯例如倍半异硬脂酸酯,脱水山梨醇,PEG-(6)-异硬脂酸脱水山梨醇酯,PEG-(10)-脱水山梨醇月桂酸酯,PEG-17-二油酸脱水山梨醇酯,葡萄糖衍生物,C8-C22烷基-单和低聚-苷以及其中葡萄糖优选用做糖组分的乙氧基化类似物,O/W乳化剂例如甲基葡萄糖苷聚醚-20倍半硬脂酸酯,脱水山梨醇硬脂酸酯/蔗糖椰油酸酯,甲基葡萄糖倍半硬脂酸酯,十六/十八烷基醇/十六/十八烷基葡萄糖苷,W/O乳化剂例如甲基葡萄糖二油酸酯/甲基葡萄糖异硬脂酸酯。硫酸盐和磺酸化衍生物,二烷基磺基琥珀酸盐,二辛基琥珀酸盐,烷基月桂基磺酸盐,直链磺化链烷烃,磺酸化四亚丙基磺酸盐,月桂基硫酸钠,月桂基硫酸铵和乙醇胺月桂基硫酸盐,月桂基醚硫酸盐,月桂醇聚氧乙烯醚硫酸钠[Texapon N70]或肉豆蔻醇聚醚硫酸钠[Texapon K14S],磺基琥珀酸盐,乙酰基羟乙基磺酸盐,链烷醇酰胺硫酸盐,牛磺酸盐,甲基牛磺酸盐,咪唑硫酸盐。两性离子或两性表面活性剂在分子中带有至少一个季铵基团和至少一个羧酸酯和/或磺酸酯基团。尤其合适的两性离子表面活性剂是甜菜碱,例如N-烷基N,N-二甲基氨基乙酸铵,椰油烷基二甲基氨基乙酸铵,N-酰基氨基丙基-N,N-二甲基氨基乙酸铵,椰油酰基氨基丙基二甲基氨基乙酸铵,以及2-烷基-3-羧基甲基-3-羟基乙基咪唑啉,其在烷基或酰基中各自具有8-18个碳原子,以及椰油酰基氨基乙基羟基乙基羧基甲基氨基乙酸盐,N-烷基甜菜碱,N-烷基氨基甜菜碱。
适合作为分散剂的合适的温和表面活性剂的例子,也就是说皮肤能很好接受的表面活性剂,包括脂肪醇聚二醇醚硫酸盐,单甘油酯硫酸盐,单-和/或二-烷基磺基琥珀酸盐,脂肪酸羟乙基磺酸盐,脂肪酸肌氨酸盐,脂肪酸氨基乙磺酸盐,脂肪酸谷氨酸盐,α-烯烃磺酸盐,醚羧酸,烷基低聚葡糖苷,脂肪酸葡糖酰胺,烷基酰氨基甜菜碱,和/或蛋白质脂肪酸缩合产物,后者优选是基于小麦蛋白。
非离子表面活性剂PEG-6蜂蜡(和)PEG-6硬脂酸酯(和)聚甘油基–2-异硬脂酸酯[Apifac],甘油基硬脂酸酯(和)PEG-100硬脂酸酯[Arlacel 165],PEG-5甘油基硬脂酸酯[arlatone 983 S],脱水山梨醇油酸酯(和)聚甘油基-3蓖麻醇酸酯[Arlacel 1689],脱水山梨醇硬脂酸酯和蔗糖椰油酸酯[arlatone 2121],甘油基硬脂酸酯和月桂醇聚氧乙烯醚-23[Cerasynth 945],十六/十八烷基醇和鲸蜡硬脂醇聚醚-20[Cetomacrogol Wax],十六/十八烷基醇和聚山梨酯-60和PEG-150和硬脂酸酯-20[Pola蜡GP 200,Pola蜡NF],十六/十八烷基醇和十六/十八烷基聚葡糖苷[Emulgade PL 1618],十六/十八烷基醇和鲸蜡硬脂醇聚醚-20[Emulgade 1000NI,Cosmowax],十六/十八烷基醇和PEG-40蓖麻油[Emulgade FSpecial],十六/十八烷基醇和PEG-40蓖麻油和十六/十八烷基硫酸钠[Emulgade F],硬脂醇和硬脂醇聚醚-7和硬脂醇聚醚-10[Emulgator E 2155],十六/十八烷基醇和硬脂醇聚醚-7和硬脂醇聚醚-10[乳化蜡U.S.N.F],甘油基硬脂酸酯和PEG-75硬脂酸酯[Gelot 64],丙二醇鲸蜡硬脂醇聚醚-3乙酸酯[Hetester PCS],丙二醇异鲸蜡醇聚醚-3乙酸酯[Hetester PHA],十六/十八烷基醇和鲸蜡硬脂醇聚醚-12和油醇聚醚-12[Lanbritol WaxN 21],PEG–6硬脂酸酯和PEG-32硬脂酸酯[Tefose 1500],PEG-6硬脂酸酯和鲸蜡硬脂醇聚醚-20和硬脂醇聚醚-20[Tefose 2000],PEG-6硬脂酸酯和鲸蜡硬脂醇聚醚-20和甘油基硬脂酸酯和硬脂醇聚醚-20[Tefose 2561],甘油基硬脂酸酯和鲸蜡硬脂醇聚醚-20[Teginacid H,C,X]。
阴离子乳化剂,例如PEG-2硬脂酸酯SE,甘油基硬脂酸酯SE[Monelgine,CutinaKD],丙二醇硬脂酸酯[Tegin P],十六/十八烷基醇和十六/十八烷基硫酸钠[Lanette N,Cutina LE,Crodacol GP],十六/十八烷基醇和月桂基硫酸钠[Lanette W],三(羊毛脂醇聚醚-4)磷酸酯和乙二醇硬脂酸酯和PEG-2硬脂酸酯[Sedefos 75],甘油基硬脂酸酯和月桂基硫酸钠[Teginacid Special]。阳离子酸碱,例如十六/十八烷基醇和十六烷基三甲基溴化铵。
最优选的分散剂是烷基硫酸钠或烷基醚硫酸钠,例如月桂醇聚氧乙烯醚硫酸钠[Texapon N70,来自Cognis]或肉豆蔻醇聚醚硫酸钠[Texapon K14 S,来自Cognis]。
特定的分散剂的用量可以例如是1-30重量%,尤其是2-20重量%,优选3-10重量%,基于组合物的总重量计。
有用的溶剂是水、盐水、(聚)乙二醇、甘油或化妆品可接受的油。其它有用的溶剂公开在下面的标题“脂肪酸的酯”、“天然和合成的甘油三酯,包括甘油酯和衍生物”、“珠光蜡”、“烃油”和“有机硅或硅氧烷”中。
如此获得的微溶性有机化合物微粒通常具有0.2-2微米的平均粒径,优选0.03-1.5微米,更尤其是0.05-1.0微米。
根据本发明组分(b1)、(b2)和(b3)的微粒UV吸收剂作为水分散体使用,其含有:
30-60份、优选35-55份的分别根据组分(b1)、(b2)或(b3)的微溶性有机微粒物质;
2-20份、优选2-20份的分散剂;
0.1-1份、优选0.1-0.5份的增稠剂(例如黄原酸胶);和
20-68份的水。
根据组分(b1)、(b2)或(b3)的化合物也对选自乙基己基三嗪和二辛基丁酰氨基三嗪酮的UV吸收剂具有稳定作用。
肉桂酸衍生物(c1)优选对应于下式:
R27和R28各自独立地是氢;羟基;C1-C5烷基;或C1-C5烷氧基;和
R29是C1-C5烷基。
最优选的肉桂酸衍生物(c1)是4-甲氧基肉桂酸2-乙基己基酯。
二苯甲酰基甲烷衍生物(c2)是优选选自4-叔丁基-4’-甲氧基二苯甲酰基甲烷。
最优选,本发明涉及选自以下(a1)和(a2)的UV吸收剂用于稳定化妆品组合物的用途:
(a1)二苯基丙烯酸酯;和
(a2)式(1)的羟基苯基三嗪,
所述化妆品组合物含有:
(b)式(2)的二苯酮衍生物;和选自以下的UV滤光剂:
(c1)肉桂酸衍生物;和
(c2)二苯甲酰基甲烷衍生物。
最优选,本发明涉及选自以下(a1)和(a2)的UV吸收剂用于稳定化妆品组合物的用途:
(a1)二苯基丙烯酸酯;和
(a2)式(1)的羟基苯基三嗪,
所述化妆品组合物含有:
(b)式(2b)的二苯酮衍生物;和
(c1)肉桂酸衍生物。
最优选,本发明涉及选自以下(a1)和(a2)的UV吸收剂用于稳定化妆品组合物的用途:
(a1)二苯基丙烯酸酯;和
(a2)式(1)的羟基苯基三嗪,
所述化妆品组合物含有:
(b)式(2b)的二苯酮衍生物;和
(c2)二苯甲酰基甲烷衍生物。
本发明还涉及一种化妆品组合物,其含有:
0.1-10重量%的二苯基丙烯酸酯(a1)和/或羟基苯基三嗪(a2);
0.1-10重量%的选自二苯酮衍生物(b1)、苯并三唑衍生物(b2)和三嗪衍生物(b3)的有机UV吸收剂;和
0.1-10重量%的肉桂酸衍生物(c1)和/或二苯甲酰基甲烷衍生物(c2);
其中UV滤光剂(a1)、(a2)、(b1)、(b2)、(b3)、(c1)和(c2)如权利要求1中所定义。
也优选这样的化妆品组合物,其含有:
0.1-10重量%的二苯基丙烯酸酯(a1)和/或羟基苯基三嗪(a2);
0.1-10重量%的选自二苯酮衍生物(b1);和
0.1-10重量%的肉桂酸衍生物(c1)和/或二苯甲酰基甲烷衍生物(c2);
其中UV滤光剂(a1)、(a2)、(b1)、(c1)和(c2)如权利要求1中所定义。
本发明还涉及选自以下的UV吸收剂用于稳定化妆品组合物的用途:
(b1)式(2)的二苯酮衍生物;
(b2)式(3)的苯并三唑衍生物;和
(b3)式(4)的三嗪衍生物,
所述化妆品组合物含有:
(a2)式(1)的羟基苯基三嗪,其中
式(1)、(2)、(3)和(4)的化合物如权利要求1中所定义。
根据本发明的化妆品配料或药物组合物可以另外含有一种或多于一种的列在下表1和2中的其它UV滤光剂。
化妆品或药物制剂可以通过将UV吸收剂(a1)(a2)、(b1)(b2)、(b3)和(c1)和(c2)和任选的其它UV吸收剂与助剂使用常规方法通过物理混合制备,例如通过将各组分简单地一起搅拌。
化妆品或药物制剂含有0.05-40重量%的本发明的UV吸收剂混合物,基于组合物的总重量计。
本发明的UV吸收剂混合物用于保护皮肤、头发和/或天然或人工发色。
化妆品或药物制剂可以例如是乳霜、凝胶、洗剂、醇溶液和水/醇溶液、乳液、蜡/脂肪组合物、棒状制剂、粉末或软膏。除了上述UV滤光剂之外,化妆品或药物制剂可以含有下述的其它助剂。
作为含有水和油的乳液(例如W/O、O/W、O/W/O和W/O/W乳液或微乳液),所述制剂含有例如基于组合物总重量计的0.1-30重量%、优选0.1-15重量%和尤其0.5-10重量%的一种或多种UV吸收剂,基于组合物总重量计的1-60重量%、尤其5-50重量%和优选10-35重量%的至少一种油组分,基于组合物总重量计的0-30重量%、尤其1-30重量%和优选4-20重量%的至少一种乳化剂,基于组合物总重量计的10-90重量%、尤其30-90重量%的水,以及0-88.9重量%、尤其1-50重量%的其它化妆品可接受的助剂。
本发明的化妆品或药物组合物/制剂可以还含有一种或多种下述额外化合物。
脂肪醇
基于具有6-18、优选8-10个碳原子的脂肪醇的格尔伯特醇,包括十六醇、硬脂醇、十六/十八醇、油基醇、辛基十二烷醇,C12-C15醇的苯甲酸酯,乙酰化羊毛脂醇等。
脂肪酸的酯
直链C6-C24脂肪酸与直链C3-C24醇的酯,支化C6-C13羧酸与直链C6-C24脂肪醇的酯,直链C6-C24脂肪酸与支化醇的酯,尤其2-乙基己醇,羟基羧酸与直链或支化C6-C22脂肪醇的酯,尤其马来酸二辛酯,直链和/或支化脂肪酸与多元醇的酯(例如丙二醇、二聚体二醇或三聚体三醇)和/或格尔伯特醇,例如己酸、辛酸、2-乙基己酸、癸酸、月桂酸、异十三酸、肉豆蔻酸、棕榈酸、棕榈油酸、硬脂酸、异硬脂酸、油酸、反油酸,岩芹酸,亚油酸,亚麻酸,桐酸,花生酸,鳕烯酸,山嵛酸和芥酸,和它们与醇的工业级混合物(例如在压力去除天然脂肪和油中,在来自Roelen羰基合成的还原醛中,或在不饱和脂肪酸的二聚中),醇例如是异丙醇、己醇,辛醇,2-乙基己基醇,癸醇,月桂醇,异十三醇,肉豆蔻醇,十六醇,棕榈醇,硬脂醇,异硬脂醇,油醇,反油醇,岩芹醇,亚油醇,亚麻醇,桐醇,花生醇,鳕烯醇,山嵛醇,芥醇和巴惟醇,以及它们的工业级混合物(例如在基于脂肪和油的工业级甲基酯的高压氢化中或来自Roelen羰基合成的醛和作为在不饱和脂肪醇的二聚中的单体级分获得)。
这些酯油的例子是肉豆蔻酸异丙基酯,棕榈酸异丙基酯,硬脂酸异丙基酯,异硬脂酸异丙基酯,油酸异丙基酯,硬脂酸正丁基酯,月桂酸正己基酯,油酸正癸基酯,硬脂酸异辛基酯,硬脂酸异壬基酯,异壬酸异丙基酯,棕榈酸2-乙基己基酯,月桂酸2-己基酯,硬脂酸2-己基癸基酯,棕榈酸2-辛基十二烷基酯,油酸油基酯,芥酸油基酯,瓢儿菜醇油酸酯,瓢儿菜醇芥酸酯,辛酸十六/十八烷基酯,棕榈酸十六烷基酯,硬脂酸十六烷基酯,油酸十六烷基酯,山嵛酸十六烷基酯,乙酸十六烷基酯,肉豆蔻酸肉豆蔻基酯,山嵛酸肉豆蔻基酯,油酸肉豆蔻基酯,硬脂酸肉豆蔻基酯,棕榈酸肉豆蔻基酯,乳酸肉豆蔻基酯,丙二醇二辛酸酯/癸酸酯,庚酸硬脂基酯,二异硬脂基马来酸酯,羟基硬脂酸辛基酯等。
其它助剂
α-葡糖基芦丁(CAS No.130603-71-3),o-羟基苯甲酸2-丁基辛基酯(CASNo.190085-41-7),维生素E(CAS No.1406-18-4),维生素E乙酸酯(CAS No.58-95-7),二乙基己基2,6-萘酸酯,二正丁基己二酸酯,二(2-乙基己基)-己二酸酯,二(2-乙基己基)-琥珀酸酯和二异十三烷基乙酸酯,以及二醇酯,例如乙二醇二油酸酯,乙二醇二异十三烷酸酯,丙二醇二(2-乙基己酸酯),丙二醇二异硬脂酸酯,丙二醇二壬酸酯,丁二醇二异硬脂酸酯和新戊二醇二辛酸酯。C6-C24脂肪醇和/或格尔伯特醇与芳族羧酸的酯,其中芳族羧酸是饱和和/或不饱和的,尤其是苯甲酸,C2-C12二羧酸与直链或支化的具有1-22个碳原子的醇或具有2-10个碳原子和2-6个羟基的多元醇形成的酯,或亚氨基二琥珀酸和亚氨基二琥珀酸盐[CAS 7408-20-0]或乳胶粒子,芦荟,黄春菊,银杏叶,人参,辅酶Q10,楔基海带提取物,日本厚朴提取物,互生叶白千层叶油,覆盆子油,蔓越莓子油,南瓜子提取物,南瓜子油,葡萄子油,肌肽,α-熊果苷,羟基积雪草苷,Termino-Laside,四氢化姜黄素(THC),类孢菌素,类孢菌素例如来自红藻脐形紫菜(porphyra umbilicalis)的氨基酸,类孢菌素类氨基酸(如WO2002039974所述),顺-9-十八碳烯二酸,硫辛酸,月桂亚氨基二丙酸生育酚基磷酸酯(LDTP),微晶纤维素(MCC),如WO 0341676所述的聚碳酸酯,如WO0341675所述的甾醇(胆甾醇,羊毛甾醇,植物甾醇),以及如US6616935所述的直链聚-α-葡聚糖。
天然或合成的甘油三酯、包括甘油酯和衍生物
二或三甘油酯,其是基于C6-C18脂肪酸,通过与其它醇反应改性(辛酸/癸酸三甘油酯,麦芽甘油酯等)。聚甘油的脂肪酸酯(聚甘油基-n例如聚甘油基-4癸酸酯,聚甘油基-2异硬脂酸酯等,或蓖麻油,氢化植物油,甜杏仁油,麦芽油,芝麻油,氢化棉子油,椰子油,鳄梨油,玉米油,氢化蓖麻油,牛油树脂,可可脂,豆油,貂油,向日葵油,红花油,澳洲坚果油,橄榄油,氢化牛油,杏仁壳油,榛子油,琉璃苣油等。
蜡包括长链酸和醇的酯,以及具有蜡状性质的化合物,例如巴西棕榈蜡,蜂蜡(白色或黄色),羊毛脂蜡,小烛树蜡,地蜡,日本蜡,石蜡,微晶蜡,白蜡,十六/十八酯蜡,合成蜂蜡等。以及亲水性蜡,例如十六/十八醇或偏甘油酯。
珠光蜡
亚烷基二醇酯,特别是乙二醇二硬脂酸酯;脂肪酸链烷醇酰胺,特别是椰油脂肪酸二乙醇酰胺;偏甘油酯,特别是硬脂酸单甘油酯;多价的、未取代或被羟基取代的羧酸与具有6-22个碳原子的脂肪醇形成的酯,特别是酒石酸的长链酯;脂肪物质,例如脂肪醇、脂肪酮、脂肪醛、脂肪醚和脂肪碳酸酯,其具有总共至少24个碳原子,特别是月桂酮和二硬脂基醚;脂肪酸,例如硬脂酸,羟基硬脂酸或山嵛酸,具有12-22个碳原子的烯烃环氧化物与具有12-22个碳原子的脂肪醇和/或具有2-15个碳原子和2-10个羟基的多元醇形成的开环产物,以及它们的混合物。
烃油:
矿物油(轻质或重质),凡士林(黄色或白色),微晶蜡,链烷和异链烷化合物,氢化异链烷分子例如聚癸烯和聚丁烯,氢化聚异丁烯,角鲨烷,异十六烷,异十二烷,以及来自植物和动物领域的其它化合物。
有机硅或硅氧烷(有机取代的聚硅氧烷)
二甲基聚硅氧烷,甲基苯基聚硅氧烷,环硅氧烷,以及氨基-、脂肪酸-、醇-、聚醚-、环氧基-、氟-、苷-和/或烷基-改性的硅化合物,它们在室温下可以是液体或树脂形式。线性聚硅氧烷,聚二甲基硅氧烷(Dow Corning 200流体,Rhodia Mirasil DM),聚二甲基硅氧烷共聚醇,环状硅氧烷流体,环五硅氧烷挥发物质(Dow Corning 345流体),苯基聚三甲基硅氧烷(Dow Corning 556流体)。也合适的是硅酸盐聚甲基硅氧烷,它们是平均链长度为200-300个二甲基硅氧烷单元的聚二甲基硅氧烷与氢化硅酸盐的混合物。关于合适的挥发性硅氧烷的详细信息,可以参见Todd等,Cosm.Toil.91,27(1976)。
氟化或全氟化油
全氟己烷、二甲基环己烷、乙基环戊烷、聚全氟甲基异丙基醚。
乳化剂
任何常规的乳化剂可以用于本发明组合物。乳化剂体系可以含有例如:羧酸和它们的盐:钠、钾和铵的碱性皂,钙或镁的金属皂,有机基础皂例如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸和油酸等。烷基磷酸盐或磷酸酯,酸式磷酸盐,二乙醇胺磷酸盐,十六烷基磷酸钾。乙氧基化羧酸或聚乙二醇酯,PEG-n丙烯酸酯。具有8-22个碳原子的直链脂肪醇,从2-30摩尔环氧乙烷和/或从0-5摩尔环氧丙烷与具有12-22个碳原子的脂肪酸和在烷基中具有8-15个碳原子的烷级酚支化。脂肪醇聚二醇醚,例如月桂醇聚醚-n、鲸蜡硬脂醇聚醚-n、硬脂醇聚醚-n、油醇聚醚-n。脂肪酸聚二醇醚,例如PEG-n硬脂酸酯、PEG-n油酸酯、PEG-n椰油酸酯。单甘油酯和多元醇酯。1-30摩尔氧化乙烯与多元醇的加合产物的C12-C22脂肪酸单酯和二酯。脂肪酸和聚甘油酯,例如单硬脂酸酯甘油、二异硬脂酰基聚甘油基-3-二异硬脂酸酯,聚甘油基-3-二异硬脂酸酯,三甘油基二异硬脂酸酯,聚甘油基-2-倍半异硬脂酸酯,或聚甘油基二聚酸酯。来自多种这些物质的化合物的混合物也是合适的。脂肪酸聚二醇酯,例如单硬脂酸酯二甘醇,脂肪酸和聚乙二醇酯,脂肪酸和蔗糖的酯例如蔗糖酯,甘油和蔗糖的酯例如蔗糖甘油酯。山梨醇和脱水山梨醇,具有6-22个碳原子的饱和和不饱和脂肪酸与环氧乙烷加合产物的脱水山梨醇单酯和二酯。聚山梨酯-n系列,脱水山梨醇酯例如倍半异硬脂酸酯,脱水山梨醇,PEG-(6)-异硬脂酸脱水山梨醇酯,PEG-(10)-脱水山梨醇月桂酸酯,PEG-17-二油酸脱水山梨醇酯,葡萄糖衍生物,C8-C22烷基-单和低聚-苷以及其中葡萄糖优选用做糖组分的乙氧基化类似物。O/W乳化剂例如甲基葡糖苷聚醚-20倍半硬脂酸酯,脱水山梨醇硬脂酸酯/蔗糖椰油酸酯,甲基葡萄糖倍半硬脂酸酯,十六/十八烷基醇/十六/十八烷基苷。W/O乳化剂例如甲基葡萄糖二油酸酯/甲基葡萄糖异硬脂酸酯。硫酸盐和磺酸化衍生物,二烷基磺基琥珀酸盐,二辛基琥珀酸盐,烷基月桂基磺酸盐,直链磺化链烷烃,磺酸化四亚丙基磺酸盐,月桂基硫酸钠,月桂基硫酸铵和乙醇胺月桂基硫酸盐,月桂基醚硫酸盐,月桂醇聚氧乙烯醚硫酸钠,磺基琥珀酸盐,乙酰基羟乙基磺酸盐,链烷醇酰胺硫酸盐,牛磺酸盐,甲基牛磺酸盐,咪唑硫酸盐。胺衍生物,胺盐,乙氧基化胺,具有含杂环的链的氧化物胺例如烷基咪唑啉,吡啶衍生物,异喹啉,十六烷基氯化吡啶翁,十六烷基溴化吡啶翁,季铵例如十六烷基三甲基硼化溴化铵(CTBA),司拉氯铵。酰胺衍生物,链烷醇酰胺例如酰基酰胺DEA,乙氧基化酰胺例如PEG-n酰基酰胺,氧化酰胺。聚硅氧烷/聚烷基/聚醚共聚物和它们的衍生物,聚二甲基硅氧烷,共聚多元醇,有机硅聚氧化乙烯共聚物,有机硅二醇共聚物。丙氧基化或POE-n醚(Meroxapols),Polaxamers或聚(氧乙烯)m-嵌段-聚(氧丙烯)n-嵌段(氧乙烯)。两性离子表面活性剂在分子中带有至少一个季铵基团和至少一个羧酸酯和/或磺酸酯基团。尤其合适的两性离子表面活性剂是甜菜碱,例如N-烷基N,N-二甲基氨基乙酸铵,椰油烷基二甲基氨基乙酸铵,N-酰基氨基丙基-N,N-二甲基氨基乙酸铵,椰油酰基氨基丙基二甲基氨基乙酸铵,以及2-烷基-3-羧基甲基-3-羟基乙基咪唑啉,其在烷基或酰基中各自具有8-18个碳原子,以及椰油酰基氨基乙基羟基乙基羧基甲基氨基乙酸盐,N-烷基甜菜碱,N-烷基氨基甜菜碱。烷基咪唑啉,烷基肽,脂酰氨基酸,自乳化碱,以及如K.F.DePolo,化妆学简要教材,第8章,表8-7,p250-251所述的化合物。
非离子乳化剂PEG-6蜂蜡(和)PEG-6硬脂酸酯(和)聚甘油基–2-异硬脂酸酯[Apifac],甘油基硬脂酸酯(和)PEG-100硬脂酸酯[Arlacel 165],PEG-5甘油基硬脂酸酯[arlatone 983 S],脱水山梨醇油酸酯(和)聚甘油基-3蓖麻醇酸酯[Arlacel 1689],脱水山梨醇硬脂酸酯和蔗糖椰油酸酯[arlatone 2121],甘油基硬脂酸酯和月桂醇聚氧乙烯醚-23[Cerasynth 945],十六/十八烷基醇和鲸蜡硬脂醇聚醚-20[Cetomacrogol wax],十六/十八烷基醇和聚山梨酯-60和PEG-150和硬脂酸酯-20[Polawax GP 200,Polawax NF],十六/十八烷基醇和十六/十八烷基聚葡糖苷[Emulgade PL 1618],十六/十八烷基醇和鲸蜡硬脂醇聚醚-20[Emulgade 1000NI,Cosmowax],十六/十八烷基醇和PEG-40蓖麻油[Emulgade F Special],十六/十八烷基醇和PEG-40蓖麻油和十六/十八烷基硫酸钠[Emulgade F],硬脂醇和硬脂醇聚醚-7和硬脂醇聚醚-10[Emulgator E 2155],十六/十八烷基醇和硬脂醇聚醚-7和硬脂醇聚醚-10[乳化蜡U.S.N.F],甘油基硬脂酸酯和PEG-75硬脂酸酯[Gelot 64],丙二醇鲸蜡硬脂醇聚醚-3乙酸酯[Hetester PCS],丙二醇异鲸蜡醇聚醚-3乙酸酯[Hetester PHA],十六/十八烷基醇和鲸蜡硬脂醇聚醚-12和油醇聚醚-12[Lanbritol Wax N 21],PEG–6硬脂酸酯和PEG-32硬脂酸酯[Tefose 1500],PEG-6硬脂酸酯和鲸蜡硬脂醇聚醚-20和硬脂醇聚醚-20[Tefose 2000],PEG-6硬脂酸酯和鲸蜡硬脂醇聚醚-20和甘油基硬脂酸酯和硬脂醇聚醚-20[Tefose 2561],甘油基硬脂酸酯和鲸蜡硬脂醇聚醚-20[Teginacid H,C,X]。
阴离子乳化剂,例如PEG-2硬脂酸酯SE,甘油基硬脂酸酯SE[Monelgine,CutinaKD],丙二醇硬脂酸酯[Tegin P],十六/十八烷基醇和十六/十八烷基硫酸钠[Lanette N,Cutina LE,Crodacol GP],十六/十八烷基醇和月桂基硫酸钠[Lanette W],三(羊毛脂醇聚醚-4)磷酸酯和乙二醇硬脂酸酯和PEG-2硬脂酸酯[Sedefos 75],甘油基硬脂酸酯和月桂基硫酸钠[Teginacid Special]。阳离子酸碱,例如十六/十八烷基醇和十六烷基三甲基溴化铵。
乳化剂的用量可以例如是1-30重量%,尤其是4-20重量%,优选5-10重量%,基于组合物的总重量计。
当在O/W乳液中配制时,这些乳化剂体系的优选用量可以占油相的5-20%。
助剂和添加剂
化妆品/药物制剂,例如乳霜、凝胶、洗剂、醇溶液和水/醇溶液、乳液、蜡/脂肪组合物、棒状制剂、粉末或软膏,可以另外含有以下物质作为助剂和添加剂:温和表面活性剂,超加脂剂,稠度调节剂,增稠剂,聚合物,稳定剂,生物源活性成分,去味活性成分,去头皮屑剂,成膜剂,溶胀剂,其它UV光保护因素,抗氧化剂,水溶助长剂,防腐剂,昆虫驱除剂,自晒黑剂,增溶剂,芳香油,着色剂,细菌抑制剂等。
超加脂剂
适合用做超加脂剂的物质是例如羊毛脂、卵磷脂,和聚乙氧基化或丙烯酰基化的羊毛脂和卵磷脂衍生物,多元醇脂肪酸酯,单甘油酯和脂肪酸链烷醇酰胺,后者也同时用作泡沫稳定剂。
表面活性剂
合适的温和表面活性剂的例子,也就是说尤其皮肤能良好接受的表面活性剂,包括脂肪醇聚二醇醚硫酸盐,单甘油酯硫酸盐,单-和/或二-烷基磺基琥珀酸盐,脂肪酸羟乙基磺酸盐,脂肪酸肌氨酸盐,脂肪酸氨基乙磺酸盐,脂肪酸谷氨酸盐,α-烯烃磺酸盐,醚羧酸,烷基低聚葡糖苷,脂肪酸葡糖酰胺,烷基酰氨基甜菜碱,和/或蛋白质脂肪酸缩合产物,后者优选是基于小麦蛋白。
稠度调节剂/增稠剂和流变改进剂
二氧化硅,硅酸镁,硅酸铝,多糖或其衍生物,例如透明质酸,黄原酸胶,瓜尔胶,藻酸,藻酸盐,角叉菜胶,结冷胶,果胶或改性纤维素,例如羟基纤维素、羟基丙基甲基纤维素。另外,聚丙烯酸酯或网状丙烯酸的均聚物和聚丙烯酰胺,卡波姆(Carbomer)(carbopol类型980,981,1382,ETD 2001,ETD2020,Ultrez 10)或Salcare系列例如Salcare SC80(硬脂醇聚醚-10烯丙基醚/丙烯酸酯共聚物)、Salcare SC81(丙烯酸酯共聚物)、Salcare SC91和Salcare AST(丙烯酸钠共聚物/PPG-1十三烷醇聚醚-6),Sepigel 305(聚丙烯酰胺/月桂醇聚氧乙烯醚-7),Simulgel NS和Simulgel EG(丙烯酸羟基乙基酯/丙烯酰基二甲基酒石酸钠共聚物),Stabilen 30(丙烯酸酯/异癸酸乙烯基酯交联聚合物),Pemulen TR-1(丙烯酸酯/丙烯酸C10-30烷基酯交联聚合物),Luvigel EM(丙烯酸钠共聚物),Aculyn 28(丙烯酸酯/山嵛醇聚醚-25甲基丙烯酸酯共聚物)等。
聚合物
合适的阳离子聚合物是例如阳离子纤维素衍生物,例如季化羟基甲基纤维素,可以以商品名JR 400从Amerchol获得;阳离子淀粉,二烯丙基铵盐和丙烯酰胺的共聚物,季化乙烯基吡咯烷酮/乙烯基咪唑聚合物,例如(BASF),聚二醇和胺的缩合产物,季化胶原多肽,例如月桂基二甲基铵羟基丙基水解胶原(L/Grünau),季化小麦多肽,聚乙烯亚胺,阳离子有机硅聚合物,例如酰胺基聚甲基硅氧烷,己二酸和二甲基氨基羟基丙基二亚乙基三胺的共聚物(Cartaretin/Sandoz),丙烯酸与二甲基二烯丙基氯化铵的共聚物(Merquat 550/Chemviron),聚氨基聚酰胺,例如参见FR-A-2 252 840,以及它们的交联的水溶性聚合物,阳离子壳多糖衍生物,例如季化脱乙酰壳多糖,任选作为微晶分布;二卤代烷基化物的缩合产物,例如二溴丁烷,以及二烷基胺,例如双二甲基氨基-1,3-丙烷,阳离子瓜尔胶,例如来自Celanese公司的Jaguar C-17、Jaguar C-16,季铵盐聚合物,例如来自Miranol公司的Mirapol A-15、Mirapol AD-1、Mirapol AZ-1。作为阴离子、两性离子、两性和非离子性聚合物,可以考虑例如乙酸乙烯基酯/巴豆酸共聚物,乙烯基吡咯烷酮/丙烯酸乙烯基酯共聚物,乙酸乙烯基酯/马来酸丁基酯/丙烯酸异冰片酯共聚物,甲基乙烯基醚/马来酸酐共聚物及其酯,未交联的聚丙烯酸和用多元醇交联的聚丙烯酸,丙烯酰氨基丙基-三甲基氯化铵/丙烯酸酯共聚物,辛基丙烯酰胺/甲基丙烯酸甲酯/甲基丙烯酸叔丁基氨基乙基酯/甲基丙烯酸2-羟基丙基酯共聚物,聚乙烯基吡咯烷酮,乙烯基吡咯烷酮/乙酸乙烯基酯共聚物,乙烯基吡咯烷酮/甲基丙烯酸二甲基氨基乙基酯/乙烯基己内酰胺三元共聚物以及任选衍生化的纤维素醚和有机硅。此外,可以使用如EP 1093796(第3-8页第17-68段)所述的聚合物。
生物源活性成分
生物源活性成分理解为表示例如生育酚、乙酸生育酚、棕榈酸生育酚、抗坏血酸、脱氧核糖核酸、视黄醇、红没药醇、尿囊素、植三醇、泛醇、AHA酸、氨基酸、神经酰胺、假神经酰胺、精油、植物提取物和维生素复合物。
去味活性成分
作为去味活性成分,可以考虑例如防汗剂,例如氯代水合铝(参见J.Soc.Cosm.Chem.24,281(1973))。以商品名例如Hoechst AG的Frankfurt(FRG),可以例如对应于式Al2(OH)5Cl x 2.5H2O的氯代水合铝,尤其优选使用它们(参见J.Pharm.Pharmacol.26,531(1975))。除了氯代水合物之外,也可以使用羟基乙酸铝和酸性铝/锆盐。酯酶抑制剂可以作为其它去味活性成分。这些抑制剂优选是柠檬酸三烷基酯,例如柠檬酸三甲基酯、柠檬酸三丙基酯、柠檬酸三异丙基酯、柠檬酸三丁基酯,特别是柠檬酸三乙基酯这些物质抑制酶的活性,从而减少气味的形成。其它适合作为酯酶抑制剂的物质是胆固醇硫酸酯或磷酸酯,例如羊毛甾醇,胆固醇,菜油甾醇,豆甾醇和谷甾醇的硫酸酯或磷酸酯;二羧酸和其酯,例如戊二酸、戊二酸单乙基酯、戊二酸二乙基酯、己二酸、己二酸单乙基酯、己二酸二乙基酯、丙二酸、丙二酸二乙基酯;羟基羧酸和其酯,例如柠檬酸、苹果酸、酒石酸或酒石酸二乙基酯。在制剂中(尤其在棒状制剂中)也可以存在抗菌活性成分,其影响菌落并杀死或抑制分解汗液的细菌的生长。例子包括脱乙酰壳多糖、苯氧基乙醇和氯己定葡糖酸盐。已经证明尤其有效的是5-氯-2-(2,4-二氯苯氧基乙醇)-苯酚(三氯生,Irgasan,Ciba Specialty Chemicals Inc.)。
抗头皮屑剂
作为抗头皮屑剂,可以提到甘宝素、吡啶酮乙醇胺盐(Octopirox)和2-巯基吡啶氧化锌。常规的成膜剂包括例如脱乙酰壳多糖,微晶脱乙酰壳多糖,季化脱乙酰壳多糖,聚乙烯基吡咯烷酮,乙烯基吡咯烷酮/乙酸乙烯酯共聚物,含高比例丙烯酸的季化纤维素衍生物的聚合物,胶原,透明质酸和其盐,以及相似的化合物。
抗氧化剂
除了主要的光防护物质之外,也可以使用辅助光防护物质,其当UV辐射穿透皮肤或头发时能干扰引起的光化学反应链。这些抗氧化剂的典型例子是:氨基酸(例如甘氨酸、组氨酸、酪氨酸、色氨酸)以及它们的衍生物,咪唑(例如咪唑丙烯酸)以及它们的衍生物,肽,例如D,L-肌肽、D-肌肽、L-肌肽和它们的衍生物(例如鹅肌肽),类胡萝卜素,胡萝卜素,番茄红素和它们的衍生物,绿原酸和它们的衍生物,硫辛酸和它们的衍生物(例如二氢硫辛酸),金硫葡糖,丙基硫尿和它们的硫醇(例如硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺和它们的葡糖基酯、N-乙酰基酯、甲酯、乙酯、丙酯、戊酯、丁基和月桂基酯、棕榈酰酯、油基酯、γ-亚油基酯、胆固醇酯和甘油酯),以及它们的盐,硫代二丙酸二月桂基酯,硫代二丙酸二硬脂基酯,硫代二丙酸和它们的衍生物(酯、醚、肽、类脂、核苷酸、核苷和盐),以及磺基肟化合物(例如丁基硫堇亚胺、同型半胱氨酸硫堇亚胺、丁硫氨酸砜、五-、六-和七硫堇亚胺),以及(金属)螯合剂(例如羟基脂肪酸、棕榈酸、肌醇六磷酸、乳铁蛋白)、羟基酸(例如柠檬酸、乳酸、苹果酸)、腐殖酸、胆酸、胆酸提取物、胆红素、胆绿素、EDTA、EDDS、EGTA和它们的衍生物,不饱和脂肪酸以及它们的衍生物(例如亚麻酸、亚油酸、油酸),叶酸和它们的衍生物,泛醌和泛醌醇以及它们的衍生物,维生素C和衍生物(例如棕榈酸抗坏血酸基酯、抗坏血酸基磷酸镁、乙酸抗坏血酸基酯),生育酚和衍生物(例如维生素E乙酸酯),维生素A和衍生物(维生素A棕榈酸酯),以及苯偶姻树脂的苯甲酸酯,芸香亭酸和它们的衍生物,α-葡糖基芦丁,阿魏酸,亚呋喃基山梨醇,肌钛,丁基羟基甲苯,丁基羟基甲苯茴香醚,去甲二氢愈创木酸,三羟基丁酰苯,尿酸及其衍生物,甘露糖及其衍生物,超氧化物歧化酶,N-[3-(3.5-二叔丁基-4-羟基苯基)丙酰基]丙氨酸(及其盐,例如二钠盐),锌及其衍生物(例如ZnO,ZnSO4),硒及其衍生物(例如硒代甲硫酸氨),1,2-二苯乙烯及其衍生物(例如1,2-二苯乙烯氧化物,反式1,2-二苯乙烯氧化物),以及根据本发明合适的这些活性成分的衍生物(盐、酯、醚、糖、核苷酸、肽和类脂)。也可以提到HALS(=“位阻胺光稳定剂”)化合物。
其它合成和天然抗氧化剂列在例如WO 0025731中:结构1-3(第2页)、结构4(第6页)、结构5-6(第7页)和化合物7-33(第8-14页)。
抗氧化剂的存在量通常是0.001-30重量%,优选0.01-3重量%,基于式(1)的UV吸收剂的重量计。
水溶助长剂
为了改进流动行为,也可以使用水溶助长剂,例如乙氧基化或非乙氧基化的具有低碳原子数目的一元醇、二醇或多元醇或它们的醚(例如乙醇、异丙醇、1,2-丙二醇,丙二醇,甘油,乙二醇,乙二醇单乙基醚,乙二醇单丁基醚,丙二醇单甲基醚,丙二醇单乙基醚,丙二醇单丁基醚,二甘醇单甲基醚;二甘醇单乙基醚,二甘醇单丁基醚和相似产物)。考虑用于此目的的多元醇优选具有2-15个碳原子和至少两个羟基。多元醇也可以含有其它官能团,尤其是氨基,和/或可以用氮改性。典型的例子如下:甘油,亚烷基二醇,例如乙二醇、二甘醇、丙二醇、丁二醇、己二醇以及平均分子量为100-1000道尔顿的聚乙二醇;固有缩合度为1.5-10的工业低聚甘油混合物,例如双甘油含量为40-50重量%的工业双甘油混合物;羟甲基化合物,例如尤其是三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、季戊四醇和二季戊四醇;低级烷基葡糖苷,尤其是在烷基中具有1-8个个碳原子的那些,例如甲基和丁基葡糖苷;具有5-12个碳原子的糖醇,例如山梨醇或甘露醇;具有5-12个碳原子的糖,例如葡萄糖或蔗糖;氨基糖,例如葡糖胺;二醇胺,例如二乙醇胺或2-氨基-1,3-丙二醇。
防腐剂
合适的防腐剂包括例如甲基-、乙基-、丙基-、丁基-对羟基苯甲酸酯,苯扎氯铵,2-溴-2-硝基丙烷-1,3-二醇,脱氢乙酸,二恶唑烷基脲,2-二氯苄基醇,DMDM乙内酰脲,甲醛溶液,甲基二溴戊二腈,苯氧基乙醇,羟基甲基甘氨酸钠,咪唑烷二基脲,三氯生和在以下文献中列出的其它物质:K.F.DePolo–化妆学的简易教材(A short textbook ofcosmetology),第7章,表7-2、7-3、7-4和7-5,第210-219页。
细菌抑制剂
细菌抑制剂的典型例子是能抵抗格兰氏阳性菌的物质,例如2,4,4'-三氯-2'-羟基二苯基醚,氯己定(1.6-二(4-氯苯基-双胍基)己烷)或TCC(3,4,4'-三氯-N-碳酰苯胺)。许多芳族物质和醚合物油也具有抗菌性能。典型的例子是活性成分丁香油,薄荷醇和丁香油中的百里酚,薄荷油和百里香油。感兴趣的天然去味剂是萜烯醇金合欢醇(3,7,11-三甲基-2,6,10-十二碳三烯-1-醇),其存在于莱姆花油中。甘油单月桂酸酯也用做抗菌剂。额外抗菌剂的存在量一般是0.1-2重量%,基于制剂的固含量计。
芳香油
作为芳香油,可以提到天然和/或合成的芳族物质的混合物。天然的芳族物质是例如来自以下的提取物:花(百合,薰衣草,玫瑰,茉莉,橙花,依兰),根和叶子(天竺葵,广藿香,苦橙叶),果实(八角,香菜,百里香,杜松),果皮(佛手柑,柠檬,橙子),根(肉豆蔻,当归,芹菜,豆蔻,广木香,鹫尾,菖蒲),木材(松木,檀香,愈创木,雪松,红木),草本植物和草(茵陈篙,柠檬草,鼠尾草,麝香草),来自枝叶(云杉,松,苏格兰松,山松),来自树脂和香脂(白松香,榄香,茴香醚,没药,乳香,红没药)。也可以考虑动物原料,例如果子狸和海狸香。典型的合成芳族物质是例如酯、醚、醛、酮、醇或烃类型的的产物。酯类型的芳族物质是例如乙酸苄基酯,异丁酸苯氧基乙基酯,对乙酸叔丁基环己基酯,乙酸里哪基酯,乙酸二甲基苄基甲基酯,乙酸苯基乙基酯,苯甲酸里哪基酯,甲酸苄基酯,乙基甲基苯基甘氨酸酯,丙酸烯丙基环己基酯,丙酸苯乙烯基酯和水杨酸苄基酯。醚包括例如苄基乙基醚;醛包括例如具有8-18个烃原子的直链醛,柠檬醛,香茅醛,香茅基氧基乙醛,仙客来醛,羟基香茅醛,铃兰醛和波吉洪醛;酮包括例如紫罗兰酮、异甲基紫罗兰酮和甲基柏木酮;醇包括例如茴香脑,香茅醇,丁香油,异丁香油,香叶醇,里哪醇,苯基乙基醇和萜品醇;烃主要包括萜烯和香脂。但是优选使用各种芳族物质的混合物,它们一起产生吸引人的气味。具有较低挥发性的醚合物油也适合作为芳香油,它们主要用做芳香组分,例如鼠尾草油,甘菊油,丁香油,柠檬草油,肉桂叶油,莱姆花油,杜松子油,香根草油,乳香油,白松香油,岩蔷薇油和薰衣草油。优选使用佛手柑油,二氢月桂烯醇,铃兰醛,新铃兰醛,香茅醇,苯基乙基醇,己基肉桂醛,香叶醇,苄基丙酮,仙客来醛,里哪醇,乙氧基甲氧基环十一烷,龙延呋喃,吲哚,二氢茉莉酮酸甲酯,三得利则,柠檬油,红橘油,橙油,烯丙基戊基乙二醇酯,硬脂酸钙,薰衣草油,香紫苏油,突厥酮,香叶油,环己基水杨酸酯,甲基柏木烯酮,异-E-Super,Fixolide NP,橡苔,甲基α-紫罗兰酮(iraldein gamma),苯基乙酸,乙酸香叶酯,乙酸苄基酯,玫瑰醚,罗米亚(romillat),2-乙基己酸乙基酯(Irotyl)和2-叔丁基环己基乙基碳酸酯(Floramat),它们单独使用或作为彼此的混合物使用。
着色剂
可以用作着色剂的并且适合用于化妆品目的的物质例如汇总在出版物"Kosmetische,Farbstoffkommission der DeutschenForschungsgemeinschaft,Verlag Chemie,Weinheim,1984,第81-106页中。着色剂的浓度通常是0.001-0.1重量%,基于全部混合物计。
其它助剂
化妆品制剂还可以含有以下物质作为助剂:消泡剂,例如有机硅;结构剂,例如马来酸;增溶剂,例如乙二醇、丙二醇、甘油或二甘醇;不透明剂,例如乳胶、苯乙烯/PVP或苯乙烯/丙烯酰胺共聚物;配合剂,例如EDTA、NTA、苯胺二乙酸或膦酸;推进剂,例如丙烷/丁烷混合物、N2O、二甲基醚、CO2、N2或空气;所谓的偶合剂和显影剂组分作为氧化染料前体;还原剂,例如硫代乙醇酸及其衍生物,硫代乳酸,半胱胺,硫代苹果酸或巯基乙磺酸;或氧化剂,例如过氧化氢、溴化钾或溴化钠。
合适的驱虫剂是例如N,N-二乙基-间-甲苯酰胺、1,2-戊二醇或驱虫剂3535;合适的自晒黑剂是例如二羟基丙酮和/或赤藓酮糖或如WO 01/85124所述的二羟基丙酮和/或二羟基丙酮前体,和/或赤藓酮糖。
作为SPF改进剂的聚合物珠或中空球
UV-吸收剂的组合以及上述UV-吸收剂与SPF改进剂的组合物,例如非活性成分,例如苯乙烯/丙烯酸酯共聚物,二氧化硅珠,球形硅酸镁,交联的聚甲基丙烯酸甲基酯(PMMA;Micopearl M305 Seppic),能最优化防晒产品的UV保护作用。极限球面添加剂(ISP,Silica Shells Kobo.)偏转了辐射,所以增加了光子的有效路径长度(EP0893119)。一些上述的珠提供了在分布期间的柔软感觉。此外,这些珠例如MicropearlM305的光活性能通过清除反射现象调节皮肤光泽,并可以间接地散射UV光。
化妆品或药物制剂
在许多化妆品制剂中含有化妆品或药物配料。可以例如考虑尤其以下制剂:
-皮肤护理制剂,例如皮肤洗涤和清洁制剂,是片剂或液体皂、无皂洗涤剂或洗涤浆料的形式,
-洗浴制剂,例如液体(泡泡浴、乳剂、淋浴制剂)或固体洗浴制剂,例如洗浴块料和浴盐;
-皮肤护理制剂,例如护肤乳液、多重乳液或润肤油;
-化妆品个人护理制剂,例如日霜或粉霜形式的面部粉底,粉底(松散或压紧形式),胭脂或霜剂粉底,眼部护理制剂,例如眼影制剂,腮红,眼线笔、眼霜或眼部定妆剂;唇部护理制剂,例如唇膏、唇彩、唇线笔,指甲护理制剂,例如指甲油、指甲油去除剂、指甲硬化剂或角质去除剂;
-足部护理制剂,例如足部洗浴用品、足粉、护足霜或护足膏,特殊除味剂和防汗剂或去足底老茧制剂;
-光防护制剂,例如防晒乳、防晒液、防晒霜或油,防晒隔离剂或局部用品,预晒黑制剂或晒后制剂;
-皮肤晒黑制剂,例如自晒黑乳剂;
-脱色制剂,例如用于漂白皮肤的制剂或皮肤光亮制剂;
-驱虫剂,例如驱虫油、洗剂、喷雾或棒;
-去味剂,例如去味喷雾、泵式作用喷雾、去味凝胶、棒或走珠;
-防汗剂,例如防汗棒、乳霜或走珠;
-用于清洁和护理粗糙皮肤的制剂,例如合成洗涤剂(固体或液体),剥离式或洗涤式制剂,或剥离式面膜;
-化学形式的头发去除制剂(脱发),例如去发粉、液体脱发制剂,乳霜或糊料形式的去发制剂,凝胶或气溶胶泡沫形式的去发制剂;
-剃须制剂,例如剃须皂、发泡剃须乳、非发泡剃须乳、泡沫和凝胶,剃须钱用于干燥剃须的制剂,剃须后制剂或须后水;
-芳香制剂,例如香料(古龙水,香氛,淡香精,盥用水,香水),芳香油或香料乳;
-化妆用头发处理制剂,例如洗发剂和调理剂形式的洗发制剂,头发护理制剂,例如预处理制剂,头发强壮剂,定型乳,定型凝胶,发油,洗发剂,处理小包,深层头发处理,头发结构化制剂,例如用于永久卷曲的烫发制剂(热烫,温和烫,冷烫),头发拉直制剂,液体头发定型制剂,头发泡沫,头发喷雾剂,漂白制剂,例如过氧化氢溶液,增白洗发剂,漂白乳剂,漂白粉,漂白浆料或油;临时、半永久或永久头发着色剂,含有自氧化染料的制剂,或天然头发着色剂,例如指甲花或甘菊。
存在形式
所列出的最终配料可以以各种存在形式存在,例如:
-液体制剂的形式,作为W/O、O/W、O/W/O、W/O/W或PIT乳液和所有种类的微乳液,
-凝胶的形式,
-油、乳剂、奶或洗剂的形式,
-粉末、清漆、片剂或粉底的形式,
-棒状物的形式,
-喷雾(带有推进剂气体或起泵作用的喷雾)或气溶胶的形式,
-泡沫的形式,或
-糊料的形式。
特别重要作为用于皮肤的化妆品制剂是光防护制剂,例如防晒奶、洗剂、乳剂、油,日晒隔离或局部用品,预晒黑制剂或晒后制剂,以及皮肤晒黑制剂,例如自晒黑乳。特别感兴趣的是防晒乳、防晒液、防晒奶和喷雾形式的防晒制剂。
特别重要的用于头发的化妆品制剂是上述用于头发处理的制剂,尤其是洗发剂形式的头发洗涤制剂,头发调理剂,头发护理制剂例如预处理制剂,头发强壮剂,定型乳,定型凝胶,发油,头发清洗剂,处理小包,深层头发处理剂,头发拉直制剂,液体头发定型制剂,头发泡沫和头发喷雾剂。特别感兴趣的是洗发剂形式的头发洗涤制剂。
洗发剂具有例如以下组成:0.01-5重量%的如权利要求1所定义的水分散体,12.0重量%的月桂醇聚醚-2-硫酸钠,4.0重量%的椰油酰胺基丙基甜菜碱,3.0重量%的氯化钠,以及加到100%的水。
例如,尤其可以使用以下头发化妆品配料:
a1)自发乳化原料配料,包含根据本发明的UV吸收剂、PEG-6-C10羰基合成醇和脱水山梨醇倍半油酸酯,其中加入水和任何所需的季铵化合物,例如4%酰胺基丙基二甲基-2-羟基乙基氯化铵或季铵盐(Quaternium)-80;
a2)自发乳化原料配料,包含根据本发明的UV吸收剂、三丁基柠檬酸酯和PEG-20-脱水山梨醇单油酸酯,其中加入水和任何所需的季铵化合物,例如4%酰胺基丙基二甲基-2-羟基乙基氯化铵或季铵盐-80;
b)根据本发明的UV吸收剂在丁基三乙二醇和三丁基柠檬酸酯中的四份掺杂的溶液;
c)根据本发明的UV吸收剂与N-烷基吡咯烷酮的混合物或溶液。
在这些配料中的其它典型成分是防腐剂、杀菌剂和抗菌剂、香料、染料、颜料、增稠剂、保湿剂、润湿剂、脂肪、油、蜡或化妆品和个人护理配料中的其它典型成分,例如醇、多元醇、聚合物、电解质、有机溶剂、硅衍生物、软化剂、乳化剂或乳化表面活性剂、表面活性剂、分散剂、抗氧化剂、抗刺激剂和抗炎剂等。
化妆品和药物制剂的实施例(X=优选的组合)
<u>O1/W/O2乳液</u> | ||||||||
<u>成分</u> | <u>1</u> | <u>2</u> | <u>3</u> | <u>4</u> | <u>5</u> | <u>6</u> | <u>7</u> | <u>8</u> |
初级乳液 O1/W | ||||||||
PEG-60氢化蓖麻油 25% | X | X | X | X | ||||
硬脂醇聚醚-25 25% | X | X | X | X | ||||
油相 75% | ||||||||
脂肪酸酯s | X | X | ||||||
天然和合成的三甘油酯s | X | X | ||||||
烃油 | X | X | ||||||
硅油 | X | X | ||||||
防腐剂 0.3%-0.8% | X | X | X | X | X | X | X | X |
去离子水 适量100% | X | X | X | X | X | X | X | X |
非离子性多官能W/O乳化剂 2%-5% | X | X | X | X | X | X | X | X |
蜡es 1%-5% | X | X | X | X | X | X | X | X |
油相 20%-30% | X | X | X | X | X | X | X | X |
硅油 | ||||||||
初级乳液O1/W 15% | X | X | X | X | X | X | X | X |
电解质(NaCl,MgSO<sub>4</sub>)0.1%-0.5% | X | X | X | X | X | X | X | X |
去离子水 适量100% | X | X | X | X | X | X | X | X |
芳香油 0.1%-0.4% | X | X | X | X | X | X | X | X |
根据本发明的化妆品组合物 0.1%-20% | X | X | X | X | X | X | X | X |
如表1和2所述的UV吸收剂 0%-30% | X | X | X | X | X | X | X | X |
备注:
*颗粒有机填料50-200nm,水分散体,活性成分w/w%
**颗粒有机填料50-200nm,包封的活性成分w/w%
***颗粒有机填料10-200nm,活性成分w/w%
方法:
评价体外防晒因子检测(SPF)的方法
其中El=红斑作用谱;Sl=太阳光谱辐射,Tl=样品的光谱透射率。
评价体外UVA保护因子(UVA PF)的方法
经由太阳模拟器进行预辐射步骤(考虑到防晒产品的光稳定性),例如AtlasSuntest CPS+,
其中Tl=防晒产品在波长l下的透射率,Tm=在UVA范围内的透射率数据的数学平均值。
本发明的化妆品制剂具有优异的保护人皮肤免受阳光损害作用的性能。
以下实施例解释本发明。
实施例1:UV吸收剂组合物的光降解
为了检测光降解,使用所谓的“片材实验”:
将2μl/cm2的配料分布在石英片材(磨砂表面为2.8cm2)上,并在使用Atlas CPS+太阳模拟器进行0、5、10、20和50MED的UV辐射后清洗这些片材。
结果
组分(a)、(b)和(c)的组合物的结果列在表3中。
用星号(*)标记的物质是回收的百分比。组分(a)的百分比表示活性百分比。
用标准偏差表示的实验误差在±3%范围内。
表3的结果显示在甲氧基肉桂酸乙基己基酯和哌嗪二-氨基二苯酮的组合中,可以通过加入奥克立林来稳定甲氧基肉桂酸乙基己基酯。
组分(a)、(b)和(d)的组合物的结果列在表4中。
用星号(*)标记的物质是回收的百分比。组分(a)的百分比表示活性百分比。
用标准偏差表示的实验误差在±3%范围内。
表4的结果显示在甲氧基肉桂酸乙基己基酯和哌嗪二-氨基二苯酮的组合中,可以通过加入二-乙基己氧基苯酚甲氧基苯基三嗪来稳定甲氧基肉桂酸乙基己基酯。
组分(a)、(b)和(d)的组合物的结果列在表5中。
用星号(*)标记的物质是回收的百分比。组分(a)的百分比表示活性百分比。
用标准偏差表示的实验误差在±3%范围内。
表5的结果显示乙基己基三嗪酮和二辛基丁酰氨基三嗪酮都能在哌嗪二-氨基二苯酮的存在下光稳定。
Claims (8)
2.权利要求1的用途,其中二苯基丙烯酸酯(a1)是选自2-氰基-3,3-二苯基丙烯酸2-乙基己基酯和2-氰基丙烯酸3-(苯并呋喃基)酯。
3.权利要求1或2的用途,其中二苯基丙烯酸酯(a1)是选自2-氰基-3,3-二苯基丙烯酸2-乙基己基酯。
5.权利要求1或2的用途,其中有机UV吸收剂(b2)以微粒化形式使用。
7.权利要求1或2的用途,其中肉桂酸衍生物(c1)是4-甲氧基肉桂酸2-乙基己基酯。
8.一种化妆品组合物,其含有:
0.1-10重量%的二苯基丙烯酸酯(a1)和/或羟基苯基三嗪(a2);
0.1-10重量%的选自苯并三唑衍生物(b2)的有机UV吸收剂;和
0.1-10重量%的肉桂酸衍生物(c1);
其中UV滤光剂(a1)、(a2)、(b2)和(c1)如权利要求1中所定义。
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EP2561853A1 (de) * | 2011-08-24 | 2013-02-27 | PM-International AG | Sonnenschutzspray mit Sonnenschutzfaktor SPF 20 bis SPF 30 |
JP5965619B2 (ja) * | 2011-11-18 | 2016-08-10 | 株式会社ミルボン | スプレー |
EP3546025A3 (en) * | 2011-11-23 | 2021-09-15 | Basf Se | Use of oleogels in uv absorber compositions |
ES2700951T3 (es) * | 2012-05-14 | 2019-02-20 | Johnson & Johnson Consumer Inc | Composiciones de brillo y métodos de uso |
EP3128993B1 (en) | 2014-04-11 | 2020-08-26 | Basf Se | Mixtures of cosmetic uv absorbers |
CN107072902B (zh) * | 2014-10-17 | 2021-01-19 | 帝斯曼知识产权资产管理有限公司 | 包含10-羟基硬脂酸的美容组合物的用途 |
ES2735405T3 (es) * | 2014-12-18 | 2019-12-18 | Oreal | Composición que comprende partículas de polímero, un aceite a base de hidrocarburos y un copolímero de bloque a base de hidrocarburos, y procedimiento de uso de la misma |
JP6097417B1 (ja) * | 2016-01-16 | 2017-03-15 | ジェイオーコスメティックス株式会社 | 油性睫毛用化粧料および化粧方法 |
KR20190008337A (ko) * | 2016-05-19 | 2019-01-23 | 바스프 에스이 | 마이크로-미립자 유기 uv 흡수제 조성물 |
DE102017201947A1 (de) * | 2017-02-08 | 2018-08-09 | Beiersdorf Ag | Kosmetischer Sonnenschutzstift |
BR112020004375B1 (pt) * | 2017-09-05 | 2022-09-06 | Vizor, Llc | Composição protetora solar contra radiação ultravioleta e produto cosmético |
US11679068B2 (en) | 2017-09-05 | 2023-06-20 | Vizor, Llc | Hydroxy cinnamate and silanol adduct coated inorganic sunscreen agents |
US11266579B2 (en) * | 2017-10-31 | 2022-03-08 | Shiseido Company, Ltd. | Oil-in-water type emulsion solid cosmetic |
JP6845510B2 (ja) * | 2018-12-27 | 2021-03-17 | 株式会社佐野商会 | 化粧料 |
CN111557864B (zh) * | 2020-05-18 | 2023-03-31 | 珠海市嘉琪精细化工有限公司 | 一种持妆且滋润的口红及其制备方法 |
EP4233832A1 (de) * | 2022-02-24 | 2023-08-30 | Dermcos GmbH | Transparentes sonnenschutzmittel mit hohem uva schutz |
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US9283160B2 (en) | 2016-03-15 |
EP2391334A2 (en) | 2011-12-07 |
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CN102791248B (zh) | 2016-01-06 |
WO2010091963A2 (en) | 2010-08-19 |
BRPI1006974A2 (pt) | 2017-05-30 |
CN102791248A (zh) | 2012-11-21 |
KR101669663B1 (ko) | 2016-10-26 |
WO2010091963A3 (en) | 2013-05-02 |
JP2012518601A (ja) | 2012-08-16 |
US20160158132A1 (en) | 2016-06-09 |
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