CN101854904A - 化妆品组合物的稳定化 - Google Patents
化妆品组合物的稳定化 Download PDFInfo
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- CN101854904A CN101854904A CN200880105126A CN200880105126A CN101854904A CN 101854904 A CN101854904 A CN 101854904A CN 200880105126 A CN200880105126 A CN 200880105126A CN 200880105126 A CN200880105126 A CN 200880105126A CN 101854904 A CN101854904 A CN 101854904A
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- Prior art keywords
- alkyl
- formula
- acid
- ester
- purposes
- Prior art date
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- 239000002537 cosmetic Substances 0.000 title claims abstract description 44
- 230000006641 stabilisation Effects 0.000 title description 3
- 238000011105 stabilization Methods 0.000 title description 2
- -1 biphenylyl Chemical group 0.000 claims abstract description 180
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 150000001851 cinnamic acid derivatives Chemical class 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical class C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical class OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 7
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- 150000003839 salts Chemical class 0.000 description 10
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Landscapes
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- Cosmetics (AREA)
Abstract
公开了选自如下物质的的紫外吸收剂用于稳定化妆品组合物的用途:(a1)二苯基丙烯酸酯;(a2)式(1)的羟苯基三嗪,其中R1、R2和R3彼此独立地为C1-C18烷基;(a3)式(2)的苯并三唑衍生物,其中R4是至少三种异构的各自具有8至30个碳原子并具有式(2a)的支化仲烷基的无规统计混合物;E1是直链C1-C14烷基;E2是直链C4-C15烷基;其中E1与E2中的碳原子总数为7至29;且R5是C1-C5烷基;和(a4)萘二甲酸二烷基酯,所述化妆品组合物包含(b)式(3)的对称三嗪衍生物,其中A是式(3a)或(3b)的基团,R6和R10彼此独立地为氢;C1-C18烷基;或C6-C12芳基;R7、R8和R9彼此独立地为氢;或式(3c)的基团,其中,在式(3a)中,基团R7、R8和R9中的至少一个是式(3c)的基团;R11、R12、R13和R14彼此独立地为氢;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;单-或二-C1-C18烷基氨基;C1-C10酰基氨基;或-COOH;M是碱金属离子;x是1或2;且y是2至10的数;和紫外吸收剂,其选自(c1)肉桂酸衍生物;和(c2)二苯甲酰基甲烷衍生物。
Description
公知的是,紫外辐射(光)对人皮肤有害。根据波长,紫外辐射造成不同类型的皮肤损伤。UV-B辐射(大约290至大约320纳米)造成晒伤并可能造成皮肤癌。UV-A辐射(大约320至大约400纳米)在将皮肤晒黑的同时也会导致晒伤和诱发皮肤癌。此外,UV-A辐射可加剧UV-B辐射的有害作用。
因此,有效的防晒制剂优选同时包含覆盖大约290纳米至大约400纳米的全范围的至少一种UV-A和UV-B过滤剂以防止人皮肤受到日光的伤害。
UV-A的作用主要通过自由基,例如诱发细胞DNA、脂质和蛋白质的不同类型降解的反应性氧类作为媒介。可见的症状通常是长期累积作用的结果。因此皮肤光老化与UV-A光相关联。同样已知的是,正常的室外UV-A辐射就足以造成蛋白质胶原和弹性蛋白的破坏,以致皮肤的紧实度和弹性损失。因此,日常皮肤护理的UVA防护非常重要。
许多UV-B过滤剂注册用于防晒制品,它们主要是3-亚苄基樟脑、水杨酸乙基己酯和肉桂酸酯的衍生物,如对甲氧基肉桂酸2-乙基己酯。
一类新型有机紫外过滤剂是微粉化三嗪衍生物,其常与肉桂酸衍生物和/或二苯甲酰基甲烷衍生物混合使用。
不幸地,防晒组合物中所用的这种紫外过滤剂组合发生相对迅速的光降解,结果防日光伤害性损失。
本发明的一个挑战因此是提高这些特定紫外过滤剂组合的稳定性。
令人惊讶地,已经发现,二苯基丙烯酸酯和特定的三嗪衍生物的使用会提高包含特定的微粉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的紫外吸收剂的组合的化妆品和皮肤病制剂的稳定性。
因此,本发明涉及选自如下物质的紫外吸收剂用于稳定化妆品组合物的用途,
(a1)二苯基丙烯酸酯;
(a2)下式的羟苯基三嗪
R1、R2和R3彼此独立地为C1-C18烷基;
(a3)下式的苯并三唑衍生物
E1是直链C1-C14烷基;
E2是直链C4-C15烷基;其中E1与E2中的碳原子总数为7至29;且
R5是C1-C5烷基;和
(a4)萘二甲酸二烷基酯;
所述化妆品组合物包含:
(b)式(3)的对称三嗪衍生物:(3)其中
R6和R10彼此独立地为氢;C1-C18烷基;或C6-C12芳基;
其中在式(3a)中,基团R7、R8和R9中的至少一个是式(3c)的基团;
R11、R12、R13和R14彼此独立地为氢;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;单-或二-C1-C18烷基氨基;C1-C10酰基氨基;或-COOH;
M是碱金属离子;
x是1或2;且
y是2至10的数;
和紫外吸收剂,其选自
(c1)肉桂酸衍生物;和
(c2)二苯甲酰基甲烷衍生物。
根据对式(1)的化合物的基团的定义的C1-C18烷基是直链或支化烷基,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。
根据对式(1)的化合物的基团的定义的C1-C18烷基可以被如下基团取代: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。
根据对式(1)的化合物的基团的定义的C1-C18烷基是例如甲氧基、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。
根据对式(1)的化合物的基团的定义的C6-C10芳基是例如萘基和优选苯基。
本发明优选涉及选自如下物质的紫外吸收剂用于稳定化妆品组合物的用途,
(a1)二苯基丙烯酸酯;
(a2)下式的羟苯基三嗪:
(1)其中
R1、R2和R3彼此独立地为C1-C18烷基;
(a3)下式的苯并三唑衍生物:
E1是直链C1-C14烷基;
E2是直链C4-C15烷基;其中E1与E2中的碳原子总数为7至29;且
R5是C1-C5烷基;和
(a4)萘二甲酸二烷基酯;
所述化妆品组合物包含:
R6和R10彼此独立地为氢;C1-C18烷基;或C6-C12芳基;
其中,在式(3a)中,基团R7、R8和R9中的至少一个是式(3c)的基团;
R11、R12、R13、R14和R15彼此独立地为氢;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;单-或二-C1-C18烷基氨基;C1-C10酰基氨基;或-COOH;
M是碱金属离子;
x是1或2;且
y是2至10的数;和
(c1)肉桂酸衍生物。
本发明优选涉及
(a1)二苯基丙烯酸酯;
(a2)式(1)的羟苯基三嗪;
(a3)式(2)的苯并三唑衍生物;
(a4)萘二甲酸二烷基酯;
用于稳定化妆品组合物的用途,所述化妆品组合物包含
(b)式(3)的对称三嗪衍生物和选自(c2)二苯甲酰基甲烷衍生物的紫外吸收剂。
所述二苯基丙烯酸酯(a)优选选自2-氰基-3,3-二苯基丙烯酸2-乙基己酯和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-乙基己酯。
所述对称三嗪衍生物(b)优选符合下式:
其中
R6、R10、R11、R12和R13如式(1)中所定义。
更优选地,在式(1)中,R6和R10是氢和/或R11和R13是氢。
在式(3)中,优选地
R12是氢;羟基;C1-C5烷基;C1-C5烷氧基;-COOM;-COOH;或COOR15;
M是碱金属离子;且
R15是C1-C5烷基。
最优选的对称三嗪衍生物(b)对应于下式的化合物:
其中,R6、R7、R8、R14和R15如式(1)中所定义。
在式(5)中,R6、R7、R8、R14和R15优选是氢;或彼此独立地为C1-C18烷基。
最优选的对称三嗪衍生物(b)对应于下式的化合物:
本发明中优选使用的三嗪衍生物的进一步实例是下式的化合物:
符合式(3)的三嗪衍生物(组分(b))优选以微粉态使用。
没有烷基取代基或只有低碳烷基取代基的式(3)的三嗪衍生物的特点是油溶性差和熔点高。它们因此特别适合以微粉态用作紫外吸收剂。
它们可以通过适用于制备微粒的任何已知方法制备,例如湿磨、湿捏合、由合适的溶剂喷雾干燥、通过超临界流体(例如,CO2)根据RESS法(RapidExpansion of Supercritical Solutions)的膨胀、通过从合适的溶剂,包括超临界流体中再沉淀(GASR法=Gas Anti-Solvent Recrystallisation/PCA法=Precipitation with Compressed Anti-solvents)。
作为用于制备微溶的微粉化有机化合物的研磨装置,可以使用,例如,喷射磨机、球磨机、振动磨机或锤磨机,优选高速混合磨机。再更优选的磨机是现代球磨机;这些类型的磨机的制造商是例如Netzsch(LMZ磨机)、Drais(DCP-Viscoflow或Cosmo)、Bühler AG(离心磨机)或Bachhofer。
用于制备微粉化有机紫外吸收剂的捏合装置的实例是典型的sigma桨叶分批捏合机,以及分批捏合机组(IKA-Werke)或连续捏合机(来自Wernerund Pfleiderer的Continua)。
本发明中所用的微溶有机化合物的研磨优选用研磨助剂进行。
使用分散剂作为用于所有上述微粉化法的低分子量研磨助剂。
下面在题为“具体分散剂”的段落中公开了可用的阴离子型、非离子型或两性表面活性剂。
优选可用于水分散体的研磨助剂是HLB(Hydrophile-LipophileBalance(亲水-亲脂平衡))值高于8,更优选高于10的阴离子型表面活性剂。
可以使用任何常规可用的阴离子型、非离子型或两性表面活性剂作为分散剂。这类表面活性剂体系可以包含例如:羧酸及其盐:钠、钾和铵的碱性皂、钙或镁的金属皂、有机皂,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;脂肪醇聚乙二醇醚,如月桂基聚氧乙烯(n)醚、十四烷基聚氧乙烯(n)醚、十六/十八醇聚氧乙烯(n)醚、硬脂基聚氧乙烯(n)醚、油基聚氧乙烯(n)醚;脂肪酸聚乙二醇醚,如PEG-n硬脂酸酯、PEG-n油酸酯、PEG-n椰油酸酯,单酸甘油酯和多元醇酯,1至100摩尔环氧乙烷与多元醇的加成产物的C12-C22脂肪酸单-和二-酯,脂肪酸和聚甘油酯,如单硬脂酸酯甘油、聚甘油基-3-二异硬脂酸二异硬脂酰酯、聚甘油基-3-二异硬脂酸酯、二异硬脂酸三甘油酯、聚甘油基-2-倍半异硬脂酸酯或聚甘油二聚酸酯。来自多个这些物质类别的化合物的混合物也合适。脂肪酸聚乙二醇酯,如单硬脂酸二乙二醇酯,脂肪酸和聚乙二醇酯、脂肪酸和蔗糖酯,如sucro酯,甘油和蔗糖酯如sucro甘油酯。山梨糖醇和失水山梨糖醇、具有6至22个碳原子的饱和和不饱和脂肪酸和环氧乙烷加成产物的失水山梨糖醇单-和二-酯、聚山梨酯-n系列、失水山梨糖醇酯,如倍半异硬脂酸酯、失水山梨糖醇、PEG-(6)-异硬脂酸失水山梨糖醇酯、PEG-(10)-月桂酸失水山梨糖醇酯、PEG-17-二油酸失水山梨糖醇酯、葡萄糖衍生物、C8-C22烷基-单-和低聚-糖苷和乙氧基化类似物(其中葡萄糖优选作为糖组分)、O/W乳化剂如甲基gluceth-20倍半硬脂酸酯、失水山梨糖醇硬脂酸酯/蔗糖椰油酸酯、甲基葡萄糖倍半硬脂酸酯、(十六/十八)醇/(十六/十八)烷基葡糖苷、W/O乳化剂如甲基葡萄糖二油酸酯/甲基葡萄糖硬脂酸酯;硫酸盐和磺化衍生物、二烷基磺基丁二酸盐、琥珀酸二辛酯、烷基十二烷基磺酸盐、直链磺化烷烃、磺化四丙烯磺酸盐、十二烷基硫酸钠、铵和乙醇胺的十二烷基硫酸盐、十二烷基醚硫酸盐、月桂基聚氧乙烯醚硫酸钠[Texapon N70]或十四烷基聚氧乙烯醚硫酸钠[Texapon K14S]、磺基丁二酸盐、acetyl isothionates、链烷醇酰胺硫酸盐、牛磺酸、甲基牛磺酸、咪唑硫酸盐;分子中带有至少一个季铵基团和至少一个羧酸根和/或磺酸根的两性离子或两性表面活性剂。尤其合适的两性离子表面活性剂是内铵盐,如N-烷基-N,N-二甲基甘氨酸铵、椰油烷基二甲基甘氨酸铵、N-酰基氨基丙基-N,N-二甲基甘氨酸铵、椰油酰基氨基丙基二甲基甘氨酸铵和2-烷基-3-羧基甲基-3-羟基乙基咪唑啉,各自在烷基或酰基中具有8至18个碳原子,以及椰油酰基氨基乙基羟基乙基羧基甲基甘氨酸酯、N-烷基甜菜碱、N-烷基氨基甜菜碱。
适合作为分散剂的温和表面活性剂,即皮肤尤其耐受的表面活性剂的实例包括脂肪醇聚乙二醇醚硫酸盐、单酸甘油酯硫酸盐、单-和/或二-烷基磺基丁二酸盐、脂肪酸羟乙基磺酸盐、脂肪酸肌氨酸盐、脂肪酸牛磺酸盐、脂肪酸谷氨酸盐、α-烯烃磺酸盐、醚羧酸、烷基葡聚寡糖、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,后者优选基于小麦蛋白。非离子型表面活性剂,如PEG-6蜂蜡(和)PEG-6硬脂酸酯(和)聚甘油基-2-硬脂酸酯[Apifac]、硬脂酸甘油酯(和)PEG-100硬脂酸酯[Arlacel 165]、PEG-5硬脂酸甘油酯[arlatone 983 S]、失水山梨糖醇油酸酯(和)聚甘油基-3蓖麻醇酸酯[Arlacel 1689]、失水山梨糖醇硬脂酸酯和蔗糖椰油酸酯[arlatone 2121]、硬脂酸甘油酯和月桂基聚氧乙烯(23)醚[Cerasynth 945]、十六/十八醇和十六烷基聚氧乙烯(20)醚[Cetomacrogol Wax]、十六/十八醇和colysorbate 60和PEG-150和硬脂酸酯-20[Polawax GP 200,PolawaxNF]、十六/十八醇和十六/十八烷基聚葡糖苷[Emulgade PL 1618]、十六/十八醇和十六/十八醇聚氧乙烯(20)醚[Emulgade 1000NI,Cosmowax]、十六/十八醇和PEG-40蓖麻油[Emulgade F Special]、十六/十八醇和PEG-40蓖麻油和十六/十八烷基硫酸钠[Emulgade F]、十八烷醇和硬脂基聚氧乙烯(7)醚和硬脂基聚氧乙烯(10)醚[Emulgator E 2155]、十六/十八醇和硬脂基聚氧乙烯(7)醚和硬脂基聚氧乙烯(10)醚[Emulsifying wax U.S.N.F]、硬脂酸甘油酯和PEG-75硬脂酸酯[Gelot 64]、丙二醇十六烷基聚氧乙烯(3)醚乙酸酯[Hetester PCS]、丙二醇isoceth-3乙酸酯[Hetester PHA]、十六/十八醇和十六烷基聚氧乙烯(12)醚和油基聚氧乙烯(12)醚[Lanbritol Wax N 21]、PEG-6硬脂酸酯和PEG-32硬脂酸酯[Tefose 1500]、PEG-6硬脂酸酯和十六烷基聚氧乙烯(20)醚和硬脂基聚氧乙烯(20)醚[Tefose 2000]、PEG-6硬脂酸酯和十六烷基聚氧乙烯(20)醚和硬脂酸甘油酯和硬脂基聚氧乙烯(20)醚[Tefose2561]、硬脂酸甘油酯和十六/十八醇聚氧乙烯(20)醚[Teginacid H,C,X]。
阴离子型乳化剂如PEG-2硬脂酸酯SE、硬脂酸甘油酯SE[Monelgine,Cutina KD]、丙二醇硬脂酸酯[Tegin P]、十六/十八醇和十六/十八烷基硫酸钠[Lanette N,Cutina LE,Crodacol GP]、十六/十八醇和十二烷基硫酸钠[Lanette W]、trilaneth-4磷酸酯和硬脂酸乙二醇酯和PEG-2硬脂酸酯[Sedefos 75]、硬脂酸甘油酯和十二烷基硫酸钠[Teginacid Special]。阳离子酸碱,如十六/十八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,如月桂基聚氧乙烯醚硫酸钠[Texapon N70,来自Cognis]或十四烷基聚氧乙烯醚硫酸钠[TexaponK14S,来自Cognis]。
这些具体分散剂可以以该组合物总重量的例如1至30重量%,尤其是2至20重量%,优选3至10重量%的量使用。
可用的溶剂是水、盐水、(聚-)乙二醇、甘油或化妆品可用的油。其它可用的溶剂在下面标题“脂肪酸酯”、“天然和合成甘油三酯,包括甘油酯和衍生物”、“珠光蜡”、“烃油”和“硅酮或硅氧烷”的段落中公开。
如此获得的微粉化的微溶有机化合物通常具有0.02至2微米,优选0.03至1.5微米,更尤其0.05至1.0微米的平均粒度。
根据本发明的组分(b)的微粉化紫外吸收剂以水分散体形式使用,其包含:
30-60,优选35至55份根据组分(b)的微溶的有机微粉化物质;
2-20,优选2至20份分散剂;
0.1-1份,优选0.1至0.5份增稠剂(例如黄原胶);和
20-68份水。
根据组分(b)的化合物对选自乙基己基三嗪和二辛基丁酰氨基三嗪酮的紫外吸收剂也具有稳定作用。
肉桂酸衍生物(c1)优选符合下式:
其中
R16和R17彼此独立地为氢;羟基;或C1-C5烷基;或C1-C5烷氧基;且
R18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-乙基己酯。
所述二苯甲酰基甲烷衍生物(c2)优选选自4-(叔丁基)-4’-甲氧基二苯甲酰基甲烷。
本发明还涉及化妆品组合物,其包含:
0.1至10%b.w.的二苯基丙烯酸酯紫外过滤剂(a);
0.1至10.%b.w.的三嗪紫外过滤剂(b);和
0.1至10%b.w.的肉桂酸衍生物紫外过滤剂(c1)和/或二苯甲酰基甲烷衍生物(c2);
其中紫外过滤剂(a)、(b)、(c1)和(c2)如权利要求1中所定义。
优选地,化妆品组合物包含:
0.1至10%b.w.的二苯基丙烯酸酯紫外过滤剂(a);
0.1至10.%b.w.的三嗪紫外过滤剂(b);和
0.1至10%b.w.的肉桂酸衍生物紫外过滤剂(c1);
其中紫外过滤剂(a)、(b)和(c1)如权利要求1中所定义。
优选地,化妆品组合物包含:
0.1至10%b.w.的二苯基丙烯酸酯紫外过滤剂(a);
0.1至10.%b.w.的三嗪紫外过滤剂(b);和
0.1至10%b.w.的二苯甲酰基甲烷衍生物(c2);
其中紫外过滤剂(a)、(b)和(c2)如权利要求1中所定义。
本发明的化妆品制剂或药物组合物可另外含有一种或多于一种如表1和2中所列的其它紫外过滤剂。
表1.可另外与本发明的紫外吸收剂一起使用的合适的紫外过滤剂物质 |
对氨基苯甲酸衍生物,例如4-二甲基氨基苯甲酸2-乙基己酯; |
水杨酸衍生物,例如水杨酸2-乙基己酯; |
二苯甲酮衍生物,例如2-羟基-4-甲氧基二苯甲酮及其5-磺酸衍生物; |
3-咪唑-4-基丙烯酸和酯; |
苯并呋喃衍生物,尤其是EP-A-582189、US-A-5338539、US-A-5518713和EP-A-613893中所述的2-(对氨基苯基)苯并呋喃衍生物; |
聚合紫外吸收剂,例如EP-A-709080中所述的亚苄基丙二酸酯衍生物; |
樟脑衍生物,例如3-(4′-甲基)亚苄基-莰烷-2-酮、3-亚苄基莰烷-2-酮、N-[2(和4)-2-氧龙脑-3-亚基-甲基]-苄基]丙烯酰胺聚合物、3-(4′-三甲基-铵)-亚苄基-莰烷-2-酮硫酸甲酯盐、3,3′-(1,4-亚苯基二次甲基)-双(7,7-二甲基-2-氧代-双环[2.2.1]庚烷-1-甲磺酸)和盐、3-(4′-磺基)亚苄基-莰烷-2-酮和盐;樟脑烷基苄基硫酸甲酯铵; |
苯并三唑化合物,例如2,2′-亚甲基-双(6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)-苯酚; |
三苯胺基-s-三嗪衍生物,例如2,4,6-三苯胺-(对-羰-2′-乙-1′-氧基)-1,3,5-三嗪和US-A-5332568、EP-A-517104、EP-A-507691、WO 93/17002和EP-A-570838中公开的紫外吸收剂; |
2-苯基苯并咪唑-5-磺酸及其盐; |
邻氨基苯甲酸薄荷酯; |
涂布或未涂布的无机微粒防晒剂,如二氧化钛、氧化锌、铁氧化物、云母、MnO、Fe2O3、Ce2O3、Al2O3、ZrO2。(表面涂层:聚甲基丙烯酸甲酯、聚甲基硅氧烷(如CAS 9004-73-3中所述的甲基氢聚硅氧烷)、聚二甲硅氧烷、三异硬脂酸异丙基钛(如CAS 61417-49-0中所述)、金属皂如硬脂酸镁(如CAS 4086-70-8中所述)、全氟代醇磷酸盐如C9-15氟代醇磷酸盐(如CAS 74499-44-8;JP 5-86984、JP 4-330007中所述))。初级粒度为平均5纳米-35纳米,在分散体中的粒度为100纳米-300纳米。 |
DE 10011317、EP 1133980和EP 1046391中公开的氨基羟基-二苯甲酮衍生物 |
表1.可另外与本发明的紫外吸收剂一起使用的合适的紫外过滤剂物质 |
如EP 1167358中公开的苯基-苯并咪唑衍生物 |
所述化妆品或药物制品可以通过使用常规方法将紫外吸收剂(a)、(b)和(c)以及任选的其它紫外吸收剂与辅助剂物理混合,例如通过将各组分简单搅拌在一起来制备。
化妆品或药物制品含有占该组合物总重量的0.05-40重量%的本发明的紫外吸收剂混合物。
本发明的紫外吸收剂混合物可用于保护皮肤、头发和/或天然或人造发色。
所述化妆品或药物制品可以是,例如,霜、凝胶、洗液、酒精溶液和水/酒精溶液、乳液、蜡/脂肪组合物、棒状制品、粉末或油膏。除上文提到的紫外过滤剂外,化妆品或药物制品还可以含有下述其它辅助剂。
作为含水和含油的乳液(例如W/O、O/W、O/W/O和W/O/W乳液或微乳液),所述制品含有,例如,占该组合物总重量的0.1至30重量%,优选0.1至15重量%,尤其0.5至10重量%的一种或多种紫外吸收剂、占该组合物总重量的1至60重量%,尤其5至50重量%,优选10至35重量%的至少一种油组分、占该组合物总重量的0至30重量%,尤其1至30重量%,优选4至20重量%的至少一种乳化剂、占该组合物总重量的10至90重量%,尤其30至90重量%的水和0至88.9重量%,尤其1至50重量%的其它化妆品可用的辅助剂。
本发明的化妆品或药物组合物/制品还可以含有一种或多种如下所述的附加化合物。
脂肪醇
基于具有6至18个,优选8至10个碳原子的脂肪醇的Guerbet醇,包括十六烷醇、十八烷醇、十六/十八醇、油醇、辛基十二烷醇、C12-C15醇的苯甲酸酯、乙酰基化羊毛脂醇,等等。
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,尤其是2-乙基己醇的酯,羟基羧酸与直链或支化C6-C22脂肪醇的酯,尤其是苹果酸二辛酯,直链和/或支化脂肪酸与多元醇(例如丙二醇、二聚二醇或三聚二醇)和/或Guerbet醇的酯,例如己酸、辛酸、2-乙基己酸、癸酸、月桂酸、异十三烷酸、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(gadoleic acid)、山萮酸和芥酸及其工业级混合物(例如在压榨除去天然脂肪和油中、在使来自Roelen’s羰基合成的醛类还原中或在不饱和脂肪酸二聚中获得)与醇例如异丙醇、己醇、辛醇、2-乙基己醇、癸醇、月桂醇、异十三烷醇、肉豆蔻醇、鲸蜡醇、棕榈醇(palmoleyl alcohol)、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(gadoleyl alcohol)、山萮醇、瓢儿菜醇和顺芜醇(brassidyl alcohol)及其工业级混合物(例如在基于脂肪和油的工业级甲酯或来自Roelen’s羰基合成的醛的高压氢化中获得和作为不饱和脂肪醇的二聚中的单体馏分获得)的酯。
这类酯油的实例是肉豆蔻酸异丙酯、棕榈酸异丙酯、硬脂酸异丙酯、异硬脂酸异丙酯、油酸异丙酯、硬脂酸正丁酯、月桂酸正己酯、油酸正癸酯、硬脂酸异辛酯、硬脂酸异壬酯、异壬酸异壬酯、棕榈酸2-乙基己酯、月桂酸2-己酯、硬脂酸2-己基癸酯、棕榈酸2-辛基十二烷基酯、油酸油醇酯、芥酸油醇酯、瓢儿菜醇油酸酯、芥酸瓢儿菜酯、十六/十八醇辛酸酯、鲸蜡醇棕榈酸酯、鲸蜡醇硬脂酸酯、鲸蜡醇油酸酯、鲸蜡醇山萮酸酯、乙酸鲸蜡酯、肉豆蔻酸肉豆蔻酯、山萮酸肉豆蔻酯、油酸肉豆蔻酯、硬脂酸肉豆蔻酯、棕榈酸肉豆蔻酯、乳酸十四烷醇酯、丙二醇二辛酸酯/癸酸酯、庚酸硬脂基酯、苹果酸二异硬脂基酯、羟基硬脂酸辛酯,等等。
其它辅助剂
α-葡糖基芸香苷(CAS No.130603-71-3)、邻羟基苯甲酸2-丁基辛酯(CAS No.190085-41-7)、维生素E(CAS No.1406-18-4)、维生素E乙酸酯(CAS No.58-95-7)、2,6-萘二甲酸二乙基己酯、己二酸二正丁酯、己二酸二(2-乙基己基)酯、琥珀酸二(2-乙基己基)酯和乙酸二异十三烷基酯,以及二醇酯,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Guerbet醇与饱和和/或不饱和的芳族羧酸,尤其是苯甲酸的酯、C2-C12二羧酸与具有1至22个碳原子的直链或支化醇或具有2至10个碳原子和2至6个羟基的多元醇的酯,或亚氨基二琥珀酸和亚氨基二琥珀酸盐[CAS 7408-20-0]或胶乳粒子、芦荟、甘菊、银杏、人参、辅酶Q10、laminaria ochroleuca提取物、magnolia oborata提取物、Melalenca alternifolia叶油、覆盆子种子(rubus idaeus seed)油、蔓越莓种子(vaccinium macrocarpon seed)油、南瓜子提取物、南瓜子油、葡萄籽提取物、肌肽、α-熊果苷、madecassoside、termino-laside、四氢类姜黄素(THC)、来自红藻porphyra umbilicalis的mycosporines氨基酸、类mycosporine氨基酸、类mycosporines氨基酸(如WO2002039974中所述)、顺式-9-十八烯二酸、硫辛酸、laurimino dipropiomic acid生育酚磷酸酯(LDTP)、微晶纤维素(MCC)、如WO 0341676中所述的聚碳酸酯、如WO0341675中所述的甾醇(胆固醇、羊毛甾醇、植物甾醇)和如US6616935中所述的直链聚-α-葡聚糖。
天然或合成甘油三酯,包括甘油酯和衍生物
通过与其它醇反应而改性的基于C6-C18脂肪酸的二-或三-甘油酯(辛酸/癸酸甘油三酯、小麦胚芽甘油酯,等等)。聚甘油的脂肪酸酯(聚甘油基-n,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、小麦胚芽油、芝麻油、氢化棉籽油、椰子油、鳄梨油、玉米油、氢化蓖麻油、牛油树脂、可可脂、大豆油、貂油、葵花油、红花油、澳洲坚果油、橄榄油、氢化牛油、杏仁油、榛子油、琉璃苣油等等。
蜡,包括长链酸和醇的酯以及具有类似蜡的性质的化合物,例如巴西棕榈蜡、蜂蜡(白或黄)、羊毛脂蜡、小烛树蜡、地蜡、日本蜡、石蜡、微晶蜡、纯地蜡、十六/十八烷基酯蜡、合成蜂蜡等。以及亲水蜡,如十六/十八醇或偏甘油酯。
珠光蜡:
亚烷基二醇酯,尤其是乙二醇二硬脂酸酯;脂肪酸烷醇酰胺,尤其是椰油脂肪酸二乙醇酰胺;偏甘油酯,尤其是硬脂酸单甘油酯;多价、未取代或羟基取代的羧酸与具有6至22个碳原子的脂肪醇的酯,尤其是酒石酸的长链酯;脂肪物质,例如总共具有至少24个碳原子的脂肪醇、脂肪酮、脂肪醛、脂肪醚和脂肪碳酸酯,尤其是月桂酮和二硬脂醚;脂肪酸,如硬脂酸、羟基硬脂酸或山萮酸,具有12至22个碳原子的烯烃环氧化物与具有12至22个碳原子的脂肪醇和/或具有2至15个碳原子和2至10个羟基的多元醇的开环产物,及其混合物。
烃油:
矿物油(轻质或重质)、矿脂(黄色或白色)、微晶蜡、链烷烃和异链烷烃化合物、氢化异链烷烃分子,如聚癸烯和聚丁烯、氢化聚异丁烯、角鲨烷、异十六烷、异十二烷和来自植物和动物领域的其它材料。
硅酮或硅氧烷(有机取代的聚硅氧烷):
二甲基聚硅氧烷、甲基苯基聚硅氧烷、环硅酮以及氨基-、脂肪酸-、醇-、聚醚-、环氧-、氟-、糖苷-和/或烷基-改性的硅酮化合物,其在室温下可以是液体或树脂形式。直链聚硅氧烷、聚二甲基硅氧烷(Dow Corning 200fluid,Rhodia Mirasil DM)、聚二甲基硅氧烷醇、环硅酮流液、环五硅氧烷挥发物(Dow Corning 345液)、苯基三甲基硅氧烷(Dow Corning 556液)。同样合适的是simethicones,其是平均链长为200至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。另外,在Cosm.Toil.91,27(1976)中可以找到Todd等人关于合适的挥发性硅酮的详细综述。
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
任何常规可用的乳化剂都可用于该组合物。乳化剂体系可以包含例如:羧酸及其盐:钠、钾和铵的碱性皂、钙或镁的金属皂、有机皂,如月桂酸、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至22个碳原子的直链脂肪醇、用具有12至22个碳原子的脂肪酸和在烷基中具有8至15个碳原子的烷基酚支化的2至30摩尔环氧乙烷和/或0至5摩尔环氧丙烷;脂肪醇聚乙二醇醚,如月桂基聚氧乙烯(n)醚、十六/十八醇聚氧乙烯(n)醚、硬脂基聚氧乙烯(n)醚、油基聚氧乙烯(n)醚;脂肪酸聚乙二醇醚,如PEG-n硬脂酸酯、PEG-n油酸酯、PEG-n椰油酸酯;单酸甘油酯和多元醇酯;1至30摩尔环氧乙烷与多元醇的加成产物的C12-C22脂肪酸单-和二-酯;脂肪酸和聚甘油酯,如单硬脂酸甘油酯、聚甘油基-3-二异硬脂酸二异硬脂酰酯、聚甘油基-3-二异硬脂酸酯、二异硬脂酸三甘油酯、聚甘油基-2-倍半异硬脂酸酯或聚甘油二聚酸酯。来自多个这些物质类别的化合物的混合物也合适。脂肪酸聚乙二醇酯,如单硬脂酸二乙二醇酯,脂肪酸和聚乙二醇酯、脂肪酸和蔗糖酯,如sucro酯,甘油和蔗糖酯如sucro甘油酯;山梨糖醇和失水山梨糖醇、具有6至22个碳原子的饱和和不饱和脂肪酸和环氧乙烷加成产物的失水山梨糖醇单-和二-酯;聚山梨酯-n系列、失水山梨糖醇酯,如倍半异硬脂酸酯、失水山梨糖醇、PEG-(6)-异硬脂酸失水山梨糖醇酯、PEG-(10)-失水山梨糖醇月桂酸酯、PEG-17-二油酸酯失水山梨糖醇;葡萄糖衍生物、C8-C22烷基-单-和低聚-糖苷和乙氧基化类似物(其中葡萄糖优选作为糖组分);O/W乳化剂如甲基gluceth-20倍半硬脂酸酯、失水山梨糖醇硬脂酸酯/蔗糖椰油酸酯、甲基葡萄糖倍半硬脂酸酯、(十六/十八)醇/(十六/十八)烷基葡糖苷、W/O乳化剂如甲基葡萄糖二油酸酯/甲基葡萄糖异硬脂酸酯;硫酸盐和磺化衍生物、二烷基磺基丁二酸盐、琥珀酸二辛酯、烷基十二烷基磺酸盐、直链磺化烷烃、磺化四丙烯磺酸盐、月桂基硫酸钠、铵和乙醇胺的月桂基硫酸盐、月桂基醚硫酸盐、月桂基聚氧乙烯醚硫酸钠、磺基丁二酸盐、acetyl isothionates、链烷醇酰胺硫酸盐、牛磺酸、甲基牛磺酸、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,如烷基咪唑啉、吡啶衍生物、isoquinoteines、十六烷基氯化吡啶鎓、十六烷基溴化吡啶鎓、季铵,如十六烷基三甲基溴化铵(cetyltrimethylbroide ammonium bromide(CTBA))、硬脂基烷基鎓(stearylalkonium)。酰胺衍生物、烷醇酰胺,如酰基酰胺DEA、乙氧基化酰胺,如PEG-n酰基酰胺、氧基去酰胺(oxydeamide)。聚硅氧烷/聚烷基/聚醚共聚物和衍生物、聚二甲基硅氧烷、共聚醇、硅酮聚环氧乙烷共聚物、硅酮乙二醇共聚物;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);分子中带有至少一个季铵基团和至少一个羧酸根和/或磺酸根的两性离子表面活性剂。尤其合适的两性离子表面活性剂是内铵盐,如N-烷基-N,N-二甲基甘氨酸铵、椰油烷基二甲基甘氨酸铵、N-酰基氨基丙基-N,N-二甲基甘氨酸铵、椰油酰基氨基丙基二甲基甘氨酸铵和2-烷基-3-羧基甲基-3-羟基乙基咪唑啉,各自在烷基或酰基中具有8至18个碳原子,以及椰油酰基氨基乙基羟基乙基羧基甲基甘氨酸酯、N-烷基甜菜碱、N-烷基氨基甜菜碱。烷基咪唑啉、烷基肽(alkylopeptides)、脂氨基酸、自乳化碱和如K.F.DePolo,A shorttextbook of cosmetology(简明美容学),第8章,表8-7,第250-251页中所述的化合物。
非离子型乳化剂,如PEG-6蜂蜡(和)PEG-6硬脂酸酯(和)聚甘油基-2-硬脂酸酯[Apifac]、硬脂酸甘油酯(和)PEG-100硬脂酸酯[Arlacel 165]、PEG-5硬脂酸甘油酯[arlatone 983 S]、失水山梨糖醇油酸酯(和)聚甘油基-3蓖麻醇酸酯[Arlacel 1689]、失水山梨糖醇硬脂酸酯和蔗糖椰油酸酯[arlatone 2121]、硬脂酸甘油酯和月桂基聚氧乙烯(23)醚[Cerasynth 945]、十六/十八醇和十六烷基聚氧乙烯(20)醚[Cetomacrogol Wax]、十六/十八醇和colysorbate 60和PEG-150和硬脂酸酯-20[Polawax GP 200,PolawaxNF]、十六/十八醇和十六/十八烷基聚葡糖苷[Emulgade PL 1618]、十六/十八醇和十六/十八醇聚氧乙烯(20)醚[Emulgade 1000NI,Cosmowax]、十六/十八醇和PEG-40蓖麻油[Emulgade F Special]、十六/十八醇和PEG-40蓖麻油和十六/十八烷基硫酸钠[Emulgade F]、硬脂醇和硬脂基聚氧乙烯(7)醚和硬脂基聚氧乙烯(10)醚[Emulgator E 2155]、十六/十八醇和硬脂基聚氧乙烯(7)醚和硬脂基聚氧乙烯(10)醚[Emulsifying wax U.S.N.F]、硬脂酸甘油酯和PEG-75硬脂酸酯[Gelot 64]、丙二醇十六烷基聚氧乙烯(3)醚乙酸酯[Hetester PCS]、丙二醇isoceth-3乙酸酯[Hetester PHA]、十六/十八醇和十六烷基聚氧乙烯(12)醚和油基聚氧乙烯(12)醚[Lanbritol Wax N 21]、PEG-6硬脂酸酯和PEG-32硬脂酸酯[Tefose 1500]、PEG-6硬脂酸酯和十六烷基聚氧乙烯(20)醚和硬脂基聚氧乙烯(20)醚[Tefose 2000]、PEG-6硬脂酸酯和十六烷基聚氧乙烯(20)醚和硬脂酸甘油酯和硬脂基聚氧乙烯(20)醚[Tefose2561]、硬脂酸甘油酯和十六/十八醇聚氧乙烯(20)醚[Teginacid H,C,X]。
阴离子型乳化剂如PEG-2硬脂酸酯SE、硬脂酸甘油酯SE[Monelgine,Cutina KD]、丙二醇硬脂酸酯[Tegin P]、十六/十八醇和十六/十八烷基硫酸钠[Lanette N,Cutina LE,Crodacol GP]、十六/十八醇和月桂基硫酸钠[Lanette W]、trilaneth-4磷酸酯和硬脂酸乙二醇酯和PEG-2硬脂酸酯[Sedefos 75]、硬脂酸甘油酯和月桂基硫酸钠[Teginacid Special]。阳离子酸碱,如十六/十八醇和十六烷基三甲基溴化铵。
所述乳化剂可以以该组合物总重量的例如1至30重量%,尤其是4至20重量%,优选5至10重量%的量使用。
当配制在O/W乳液中时,这类乳化剂体系的优选量可以构成油相的5%至20%。
辅助剂和添加剂
所述化妆品/药物制品,例如霜、凝胶、洗液、酒精溶液和水/酒精溶液、乳液、蜡/脂肪组合物、棒状制品、粉末或油膏还可以含有温和表面活性剂、富脂剂、稠度调节剂、增稠剂、聚合物、稳定剂、生物源活性成分、除臭活性成分、抗头屑剂、成膜剂、溶胀剂、其它紫外防护因子、抗氧化剂、水溶助长剂、防腐剂、驱虫剂、自黑剂、增溶剂、香精油、着色剂、抑菌剂等作为进一步的辅助剂和添加剂。
富脂剂
适合用作富脂剂的物质是,例如,羊毛脂和卵磷脂,以及聚乙氧基化或丙烯酸化羊毛脂和卵磷脂衍生物、多元醇脂肪酸酯、单酸甘油酯和脂肪酸链烷醇酰胺,后者同时充当泡沫稳定剂。
表面活性剂
合适的温和表面活性剂,即皮肤尤其耐受的表面活性剂的实例包括脂肪醇聚乙二醇醚硫酸酯、单酸甘油酯硫酸盐、单-和/或二-烷基磺基丁二酸盐、脂肪酸羟乙基磺酸盐、脂肪酸肌氨酸盐、脂肪酸牛磺酸盐、脂肪酸谷氨酸盐、α-烯烃磺酸盐、醚羧酸、烷基葡聚寡糖、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,后者优选基于小麦蛋白。
稠度调节剂/增稠剂和流变改性剂
二氧化硅、硅酸镁、硅酸铝、聚糖或其衍生物,例如透明质酸、黄原胶、瓜尔胶、琼脂、藻酸盐、角叉菜胶、胶凝糖(gellan)、pectines或改性纤维素,如羟基纤维素、羟基丙基甲基纤维素。此外,聚丙烯酸酯或网状丙烯酸的均聚物和聚丙烯酰胺、卡波姆(carbopol型号980、981、1382、ETD 2001、ETD2020、Ultrez 10)或Salcare系列,如Salcare SC80(硬脂基聚氧乙烯(10)醚烯丙醚/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-1十三烷基聚氧乙烯(6)醚)、sepigel 305(聚丙烯酰胺/月桂基聚氧乙烯(7)醚)、Simulgel NS和Simulgel EG(丙烯酸羟乙酯/丙烯酰基二甲基牛磺酸钠共聚物)、Stabilen30(丙烯酸酯/异癸酸乙烯酯交联聚合物)、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/聚氧乙烯(25)山萮醇醚甲基丙烯酸酯共聚物)等等。
聚合物
合适的阳离子型聚合物是,例如阳离子型纤维素衍生物,例如可以以Polymer JR 400为名获自Amerchol的季铵化羟甲基纤维素、阳离子淀粉、二烯丙基铵盐和丙烯酰胺的共聚物、季铵化乙烯基吡咯烷酮/乙烯基咪唑聚合物,例如(BASF),聚乙二醇和胺的缩合产物、季铵化胶原多肽,例如例如月桂基二甲基铵羟丙基水解胶原(/Grünau),季铵化小麦多肽,聚乙烯亚胺,阳离子硅酮聚合物,例如酰氨基聚甲基硅氧烷,己二酸与二甲氨基羟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),例如在FR-A-2 252 840中描述的聚氨基聚酰胺及其交联水溶性聚合物,阳离子甲壳质衍生物,例如任选地以微晶分布的季铵化壳聚糖;二卤代烷基如二溴丁烷与双二烷基胺如双二甲氨基-1,3-丙烷的缩合产物,阳离子瓜尔胶,例如来自Celanese的Jaguar C-17、Jaguar C-16,季铵盐聚合物,例如来自Miranol的Mirapol A-15、Mirapol AD-1、Mirapol AZ-1。作为阴离子的、两性离子的、两性的和非离子的聚合物,可以考虑例如乙酸乙烯酯/巴豆酸共聚物,乙烯基吡咯烷酮/丙烯酸乙烯酯共聚物,乙酸乙烯酯/马来酸丁酯/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与多元醇交联的聚丙烯酸,丙烯酰胺基丙基-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氨基乙酯/甲基丙烯酸2-羟丙酯共聚物,聚乙烯基吡咯烷酮,乙烯基吡咯烷酮/乙酸乙烯酯共聚物,乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙酯/乙烯基己内酰胺三元共聚物,以及任选的衍生纤维素醚和硅酮。此外,可以使用在EP 1093796(第3-8页,第17-68段)中描述的聚合物。
生物源活性成分
生物源活性成分被理解为是指,例如,生育酚、生育酚乙酸酯、生育酚棕榈酸酯、抗坏血酸、脱氧核糖核酸、视黄醇、没药醇、尿囊素、植烷三醇(phytantriol)、泛醇、AHA酸、氨基酸、神经酰胺、类神经酰胺、精油、植物提取物和维生素络合物。
除臭活性成分
作为除臭活性成分,考虑例如,止汗剂,例如氯氢氧化铝(参见J.Soc.Cosm.Chem.24,281(1973))。可以以商标of Hoechst AG,Frankfurt(FRG)购得例如符合式Al2(OH)5Clx2.5H2O的氯氢氧化铝,其尤其优选使用(参见J.Pharm.Pharmacol.26,531(1975))。除该氯氢氧化铝外,还可以使用羟基乙酸铝和酸性铝/锆盐。可以加入酯酶抑制剂作为进一步的除臭活性成分。这类抑制剂优选是柠檬酸三烷基酯、如柠檬酸三甲酯、柠檬酸三丙酯、柠檬酸三异丙酯、柠檬酸三丁酯,尤其是柠檬酸三乙酯(Hydagen CAT,Henkel),它们抑制酶活性并因此减轻臭味形成。考虑作为酯酶抑制剂的其它物质是甾醇硫酸酯或磷酸酯,例如羊毛甾醇、胆固醇、菜油甾醇、豆甾醇和谷甾醇硫酸酯或磷酸酯,二羧酸及其酯,例如戊二酸、戊二酸单乙酯、戊二酸二乙酯、己二酸、己二酸单乙酯、己二酸二乙酯、丙二酸和丙二酸二乙酯和羟基羧酸及其酯,例如柠檬酸、苹果酸、酒石酸或酒石酸二乙酯。在该制品中(尤其是在棒状制品中)也可以存在影响微生物菌群和杀灭或抑制汗分解菌的生长的杀菌活性成分。实例包括壳聚糖、苯氧基乙醇和洗必泰葡糖酸盐。5-氯-2-(2,4-二氯苯氧基)-苯酚(三氯生,Irgasan,Ciba Specialty Chemicals Inc.)也经证实尤其有效。
抗头屑剂
作为抗头屑剂,可以使用,例如,氯咪巴唑(climbazole)、吡啶酮乙醇酸盐(octopirox)和吡啶硫酮锌(zinc pyrithione)。常规成膜剂包括,例如,壳聚糖、微晶壳聚糖、季铵化壳聚糖、聚乙烯基吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、含高比例的丙烯酸、胶原、透明质酸及其盐和类似化合物的季纤维素衍生物的聚合物。
抗氧化剂
除主要光防护物质外,还可以使用抗氧化剂类型的次要光防护物质,中断紫外辐射穿透皮肤或头发时引发的光化学反应链。这类抗氧化剂的典型实例是氨基酸(例如甘氨酸、组氨酸、酪氨酸、色氨酸)及其衍生物、咪唑(例如尿刊酸)及其衍生物、肽,如D,L-肌肽、D-肌肽、L-肌肽及其衍生物(例如鹅肌肽)、类胡萝卜素、胡萝卜素、番茄红素及其衍生物、绿原酸及其衍生物、硫辛酸及其衍生物(例如二氢硫辛酸)、aurothioglycose、丙基硫尿嘧啶和其它硫醇(例如硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺和它们的糖基、N-乙酰基、甲基、乙基、丙基、戊基、丁基、月桂基、棕榈酰基、油基、亚油基、胆甾醇基和甘油基酯)以及它们的盐、硫代二丙酸二月桂酯、硫代二丙酸二硬脂酯、硫代二丙酸及其衍生物(酯、醚、肽、脂质、核苷酸、核苷和盐)以及亚砜胺化合物(例如丁硫氨酸亚砜胺、高半胱氨酸亚砜胺、丁硫氨酸砜、五-、六-、七-硫堇亚砜胺)、以及(金属)螯合剂(例如羟基脂肪酸、棕榈酸植酸、乳铁蛋白)、羟基酸(例如柠檬酸、乳酸、苹果酸)、腐殖酸、胆汁酸、胆汁提取物、胆红素、胆绿素、EDTA、EDDS、EGTA及其衍生物、不饱和脂肪酸及其衍生物(例如亚麻酸、亚油酸、油酸)、叶酸及其衍生物、泛醌和泛醇及其衍生物、维生素C和衍生物(例如抗坏血酸棕榈酸酯、抗坏血酸磷酸镁、抗坏血酸乙酸酯)、生育酚和衍生物(例如维生素E乙酸酯)、维生素A和衍生物(例如维生素A棕榈酸酯)以及苯偶姻树脂的苯甲酸松柏醇酯、芸香亭酸及其衍生物、糖基芸香苷、阿魏酸、亚糠基葡萄糖醇、肌肽、丁基羟基甲苯、丁基羟基苯甲醚、去甲二氢愈创木酸、三羟基苯丁酮、尿酸及其衍生物、甘露糖及其衍生物、超氧化物岐化酶、N-[3-(3,5-二-叔丁基-4-羟基苯基)丙酰基]磺胺酸(及其盐,例如二钠盐)、锌及其衍生物(例如ZnO、ZnSO4)、硒及其衍生物(例如蛋氨酸硒)、1,2-二苯乙烯及其衍生物(例如氧化1,2-二苯乙烯、反-氧化1,2-二苯乙烯)和这些提到的活性成分的根据本发明合适的衍生物(盐、酯、醚、糖、核苷酸、核苷、肽和脂质)。也可以提到HALS(=″受阻胺光稳定剂″)化合物。
例如在WO 0025731中列出其它合成和天然抗氧化剂: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)。
所存在的抗氧化剂的量通常为式(1)的紫外吸收剂重量的0.001至30重量%,优选0.01至3重量%。
水溶助长剂
为了改进流动性能,也可以使用水溶助长剂,例如具有低碳原子数的乙氧基化或非乙氧基化单-醇、二醇或多元醇或它们的醚(例如乙醇、异丙醇、1,2-二丙二醇、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、二乙二醇单甲基醚;二乙二醇单乙基醚、二乙二醇单丁基醚和类似产品)。考虑用于此用途的多元醇优选具有2至15个碳原子和至少两个羟基。该多元醇还可以含有其它官能团,尤其是氨基,和/或可以用氮改性。典型实例如下:甘油、烷撑二醇,例如乙二醇、二乙二醇、丙二醇、丁二醇、己二醇以及平均分子量为100至1000道尔顿的聚乙二醇;特征缩合度为1.5至10的工业级低聚甘油混合物,例如具有40至50重量%的双甘油含量的工业双甘油混合物;羟甲基化合物,尤其例如三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、季戊四醇和二季戊四醇;低碳烷基-葡糖苷,尤其是在烷基中具有1至8个碳原子的那些,例如甲基和丁基葡糖苷;具有5至12个碳原子的糖醇,例如山梨糖醇或甘露醇;具有5至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,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,对羟基苯甲酸甲酯、乙酯、丙酯、丁酯、苯扎氯铵、2-溴-2-硝基-丙-1,3-二醇、脱氢乙酸、二偶氮烷基脲、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、咪唑烷基脲、三氯生和下列参考文献中列出的其它物质类别:K.F.DePolo-A short textbook of cosmetology(简明美容学),第7章,表7-2、7-3、7-4和7-5,第210-219页。
抑菌剂
抑菌剂的典型实例是对革兰氏阳性菌具有特异性作用的防腐剂,如2,4,4′-三氯-2′-羟基二苯基醚、洗必泰(1,6-二(4-氯苯基-双胍)己烷)或TCC(3,4,4′-三氯碳酰苯胺)。多种芳香物质和香精油也具有抗微生物性质。典型实例是丁香油、薄荷油和百里香油中的活性成分丁香酚、薄荷醇和百里酚。有用的天然除臭剂是椴树花油中存在的萜烯醇金合欢醇(3,7,11-三甲基-2,6,10-十二碳三烯-1-醇)。单月桂酸甘油酯也经证实是抑菌剂。所存在的附加抑菌剂的量通常为该制品固含量的0.1至2重量%。
芳香油
天然和/或合成芳香物质的混合物。来自以下的提取物:花(百合、熏衣草、玫瑰、茉莉、苦橙花、依兰),茎和叶(天竺葵、广藿香、苦橙叶),果实(茴香子、芫荽、芡蒿子(caraway)、刺柏),果皮(香柠檬、柠檬、柑橘),根(肉豆蔻、当归、芹菜、小豆蔻、木香、鸢尾、菖蒲),木(松木、檀香木、愈创木、柏木、蔷薇木),草本植物和禾本植物(龙嵩、香茅、鼠尾草、百里香),针叶植物和桠枝植物(云杉、松、欧洲赤松、山松(mountain pine)),树脂和香树脂(古篷香脂、榄香脂、安息香、没药、乳香、防风根)。也考虑动物原料,例如灵猫香和海狸香。典型的合成芳香物质为例如酯、醚、醛、酮、醇或烃类产品。酯类芳香物质化合物为例如乙酸苄酯、异丁酸苯氧基乙酯、乙酸对叔丁基环己酯、乙酸芳樟酯、乙酸二甲基苄基甲酯、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、甘氨酸乙基甲基苯酯、丙酸烯丙基环己酯、丙酸苏合香酯和水杨酸苄酯。醚包括例如苄基乙基醚;醛包括例如具有8-18个烃原子的直链烷醛、柠檬醛、香茅醛、香茅基氧基乙醛、仙客来醛、羟基香茅醛、铃兰醛和波洁红醛(bourgeonal);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(anethol)、香茅醇、丁子香酚、异丁子香酚、香叶醇、芳樟醇、苯乙醇和萜品油;以及烃主要包括萜烯和香脂。然而,优选使用一起产生吸引人气味的多种芳香物质的混合物。主要用作芳香组分的较低挥发度的香精油也适合作为芳香油,例如鼠尾草油、春黄菊油、丁子香油、蜂花油、肉桂叶油、椴树花油、刺柏油、岩兰油、乳香油、古蓬油、labolanum oil和杂薰衣草油。优选使用香柠檬油、二氢月桂烯醇、铃兰醛、新铃兰醛(lyral)、香茅醇、苯乙醇、己基肉桂醛、香叶醇、苄基丙酮、仙客来醛、芳樟醇、乙氧基甲氧基环十一烷(boisambrene forte)、龙涎呋喃(ambroxan)、吲哚、二氢茉莉酮酸甲酯(hedione)、Sandelice、柠檬皮油、红橘油、橙油、戊基甘醇酸烯丙酯、女贞醛(cyclovertal)、杂薰衣草油、香紫苏油(muscatel sage oil)、突厥酮、波旁香叶油(bourbon geranium oil)、水杨酸环己酯、甲基柏木酮、龙涎酮(iso-E-Super)、Fixolide NP、合成橡苔(evernyl)、γ-甲基紫罗兰酮(iraldeingamma)、苯乙酸、乙酸香叶酯、乙酸苄酯、玫瑰醚、romillat、irotyl和floramat单独或彼此混合。
着色剂
作为着色剂,可以使用如出版物“Kosmetische”of theFarbstoffkommission der Deutschen Forschungsgemeinschaft,VerlagChemie,Weinheim,1984,第81至106页中汇编的适合并允许用于化妆品用途的物质。该着色剂通常以总混合物的0.001至0.1重量%的浓度使用。
其它辅助剂
化妆品制品还可以含有防沫剂如硅酮、结构剂如马来酸、增溶剂如乙二醇、丙二醇、甘油或二乙二醇、遮光剂如胶乳、苯乙烯/PVP或苯乙烯/丙烯酰胺共聚物、络合剂如EDTA、NTA、丙氨酸二乙酸或膦酸、推进剂如丙烷/丁烷混合物、N2O、二甲基醚、CO2、N2或空气、所谓偶联剂和显色剂组分如氧化染料前体、还原剂如巯基乙酸及其衍生物、硫代乳酸、半胱胺、硫代苹果酸或巯基乙烷磺酸、或氧化剂如过氧化氢、溴酸钾或溴酸钠作为辅助剂。
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;合适的自黑剂是例如二羟基丙酮和/或赤藓酮糖,或二羟基丙酮和/或如WO 01/85124中所述的二羟基丙酮前体和/或赤藓酮糖。
作为SPF增强剂的聚合物珠或中空球体
上文列出的紫外吸收剂和紫外吸收剂组合与SPF增强剂,如非活性成分,如苯乙烯/丙烯酸酯共聚物、二氧化硅珠、球形硅酸镁、交联聚甲基丙烯酸甲酯(PMMA;Micopearl M305 Seppic)的组合可以更好地使防晒产品的紫外防护最大化。Holosphere添加剂(ISP,Silica ShellsKobo.)使辐射偏转,因此提高光子的有效路径长度(EP0893119)。上文提到的一些珠粒提供涂抹过程中的柔软感。此外,这类珠粒,例如MicropearlM305的光学活性可以通过消除反射现象来调节皮肤光泽,并可以间接散射紫外光。
化妆品或药物制品
化妆品或药物制剂包含在多种化妆制品中。例如,尤其考虑下列制品:
-皮肤护理制品,例如片剂或液体皂、无皂洗涤剂或洗涤膏形式的皮肤洗涤和清洁制品,
-沐浴制品,例如液体(泡沫浴、乳液、淋浴制品)或固体沐浴制品,例如洗浴香精块和浴盐;
-皮肤护理制品,例如润肤乳液、多重乳液或润肤油;
-化妆个人护理制品,例如日霜或粉霜、擦面粉(散粉或粉饼)、胭脂或粉底霜形式的面部彩妆,眼部护理制品,例如眼影制品、睫毛膏、眼线、眼霜或眼线膏;唇部护理制品,例如唇膏、唇彩、唇线笔;指甲护理制品,如指甲油、洗甲油、指甲硬化剂或去死皮剂;
-足部护理制品,例如足浴剂、足粉、护足霜或足部香膏、专用除臭剂和止汗剂或去茧制品;
-光防护制品,如防晒乳、液、霜或油、防晒隔离霜或tropicals、晒前制品或晒后制品;
-皮肤美黑制品,例如自黑霜;
-脱色素制品,例如皮肤漂白制品或皮肤增亮制品;
-驱虫剂,例如驱虫油、液、喷雾或棒;
-除臭剂,如除臭喷雾、泵作用喷雾剂、除臭凝胶、棒或滚抹装;
-止汗剂,例如止汗棒、霜或滚抹装;
-清洁和护理粉刺皮肤的制品,例如合成清洁剂(固体或液体)、去角质或磨砂制品或去角质面膜;
-化学形式的除毛制品(脱毛),例如除毛粉、液体除毛制品、霜或糊形式的除毛制品、凝胶形式或气溶胶形式的除毛制品;
-剃须制品,例如剃须皂、泡沫剃须膏、非泡沫剃须膏、泡沫和凝胶、干剃须用的须前制品、须后水或须后液;
-芳香制品,例如香水(eau de Cologne、eau de toilette、eau de perfume、perfume de toilette、perfume)、香精油或香膏;
-美容护发制品,例如香波和护发素形式的洗发制品,护发制品,例如预处理制品、生发油、造型霜、造型凝胶、润发脂、护发素(hair rinses)、发膜、强效护发品,头发定型制品,例如烫发(热烫、温和烫、冷烫)用的烫发制品、直发制品、液体头发定型制品、头发定型泡沫、头发定型喷雾、漂白制品,例如,过氧化氢溶液,增亮香波、漂白霜、漂白粉、漂白糊或油、临时、半永久或永久染发剂、含自氧化染料的制品、或天然染发剂,如指甲花或春黄菊。
呈现形式
所列最终制剂可以以多种呈现形式存在,例如:
-液体制品,如W/O、O/W、O/W/O、W/O/W或PIT乳液和所有种类的微乳液形式,
-凝胶形式,
-油、霜、乳或液形式,
-粉末、漆、片或彩妆形式,
-棒形式,
-喷雾剂(含推进剂气体的喷雾剂或泵作用喷雾剂)或气溶胶形式,
-泡沫形式,或
-糊形式。
作为皮肤化妆制品,特别重要的是光防护制品,如防晒乳、液、霜、油、防晒隔离霜或tropicals、晒前制品或晒后制品,以及皮肤美黑制品,例如自黑霜。特别有意义的是防晒霜、防晒液、防晒乳和喷雾形式的防晒制品。
作为头发化妆制品,特别重要的是上述护发制品,尤其是香波、头发调理剂形式的洗发制品,头发护理制品,例如预处理制品、生发油、造型霜、造型凝胶、润发脂、护发素、发膜、强效护发品,直发制品、液体头发定型制品、头发定型泡沫和头发定型喷雾。特别有意义的是香波形式的洗发制品。
香波具有例如下列组成:0.01至5重量%的如权利要求1所述的水分散体、12.0重量%的月桂基聚氧乙烯(2)醚-硫酸钠、4.0重量%椰油酰氨基丙基甜菜碱、3.0重量%氯化钠和加至100%的水。
例如,尤其可以使用下列头发化妆品制剂:
a1)由本发明的紫外吸收剂、PEG-6-C10羰基合成醇和失水山梨糖醇倍半油酸酯构成的自发乳化原料制剂,向其中加入水和任何所需季铵化合物,例如4%貂油酰氨基丙基二甲基-2-羟基乙基氯化铵或聚季铵盐80;
a2)由本发明的紫外吸收剂、柠檬酸三丁酯和PEG-20-失水山梨糖醇单油酸酯构成的自发乳化原料制剂,向其中加入水和任何所需季铵化合物,例如4%貂油酰氨基丙基二甲基-2-羟基乙基氯化铵或聚季铵盐80;
b)本发明的紫外吸收剂在丁基三甘醇和柠檬酸三丁酯中的四倍浓缩溶液(quat-doped solutions);
c)本发明的紫外吸收剂与n-烷基吡咯烷酮的混合物或溶液。
这类制剂中的其它典型成分是防腐剂、杀菌剂和抑菌剂、香精、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制剂的其它典型成分,如醇、聚醇、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等。
化妆品和药物制品的实例(X=优选组合)
O1/W/O2乳液 | ||||||||
成分 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
主乳液O1/W | ||||||||
PEG-60氢化蓖麻油25% | X | X | X | X |
O1/W/O2乳液 | ||||||||
硬脂基聚氧乙烯(25)醚 25% | X | X | X | X | ||||
油相 75% | ||||||||
脂肪酸酯 | X | X | ||||||
天然和合成甘油三酯 | 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 Qs 100% | X | X | X | X | X | X | X | X |
非离子型多功能W/O乳化剂2%-5% | X | X | X | X | X | X | X | X |
蜡1%-5% | X | X | X | X | X | X | X | X |
油相20%-30% | X | X | X | X | X | X | X | X |
硅油 | ||||||||
主乳液O1/W15% | X | X | X | X | X | X | X | X |
电解质(NaCl,MgSO4)0.1%-0.5% | X | X | X | X | X | X | X | X |
去离子水Qs 100% | X | X | X | X | X | X | X | X |
香精油0.1%-0.4% | X | X | X | X | X | X | X | X |
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中所述的紫外吸收剂0%-30% | X | X | X | X | X | X | X | X |
本发明的化妆品制品的显著特征是对人皮肤的优异的抵抗日光损伤的防护作用。
下列实施例具体说明本发明。
实施例1:制剂F1-F3
F1 | F2 | F3 | |
成分 INCI名 | [%b.w.] | [%b.w.] | [%b.w.] |
去离子水 | 75.80 | 73.50 | 70.50 |
EDTA二钠 | 0.20 | 0.20 | 0.20 |
甘油 | 2.00 | 2.00 | |
黄原胶 | 0.50 | 0.50 | 0.50 |
F1 | F2 | F3 | |
甲氧基肉桂酸乙基己酯 | 2.00 | 2.00 | 2.00 |
Octocrylene(2-氰基3,3-二苯基丙烯酸2-乙基己酯) | 5.00 | ||
硬脂酸甘油酯&PEG-100硬脂酸酯 | 4.00 | 4.00 | 4.00 |
十六/十八醇 | 2.500 | 2.500 | 2.50 |
苯甲酸苯乙酯 | |||
苯甲酸C12-15烷基酯 | 8.00 | 8.00 | 8.00 |
棕榈酸辛酯 | 5.00 | 5.00 | 5.00 |
三-联苯基三嗪 | 2.00 | 2.00 | |
癸基葡糖苷 | 0.3 | 0.3 | |
体外SPF | 3.8±0.4 | 8.6±0.9 | 12.8±1.3 |
UVA/UVB-比率 | 0.21 | 0.46 | 0.44 |
实施例2:紫外吸收剂组合的光降解
为了测定光降解,使用所谓的“平板试验”:
将2微升/平方厘米的制剂在石英板(2.8平方厘米的喷砂表面)上铺开并在使用Atlas CPS+太阳模拟器0、5和10MED紫外照射后冲洗掉。
包含组分(a)、(b)和(c)的受试制剂:
组分(a) | 2-氰基-3,3-二苯基丙烯酸2-乙基己酯(OCR) |
组分(b) | 1,3,5-三嗪,2,4,6-三([1,1’-联苯]-4-基)(TBT) |
组分(c) | 甲氧基肉桂酸乙基己酯(OMC) |
结果
结果列在表3中。
用星号(*)标注的物质是回收百分比所指的那些。
就标准偏差而言,实验误差在±3%的范围内。
1,3,5-三嗪,2,4,6-三([1,1’-联苯]-4-基)(TBT)(组分(b))本身在所有条件下在实验误差范围内没有表现出降解。对Octocrylene(OCR)观察到相同结果。
结果进一步表明,在甲氧基肉桂酸乙基己酯(OCR)和1,3,5-三嗪,2,4,6-三([1,1’-联苯]-4-基)(TBT)的组合中,可以通过添加Octocrylene来稳定甲氧基肉桂酸乙基己酯。
实施例3
使用所谓的“平板试验”:将2微升/平方厘米的制剂在石英板(2.8平方厘米的喷砂表面)上铺开并在使用Atlas CPS+太阳模拟器0、5和10MED紫外照射后冲洗掉。
研究单独的BMDBM(丁基甲氧基二苯甲酰基甲烷)的制剂,BMDBM及OCR(Octocrylene)组合的制剂,以及BMDBM与三-联苯基三嗪(TBT)以及与BEMT(双-乙基己氧基苯酚甲氧基苯基三嗪)或苯并三唑基十二烷基对甲酚(BDC)组合的制剂。
使1三-联苯基三嗪(TBT)的浓度保持在4%,相当于2%活性物。
结果
结果列在表4中。
百分比是指BMDBM的回收率。
就在95%显著性水平下的置信区间而言,实验误差在BMDBM的原始量的±2%的范围内(对于各条件,研究四个板)。
三-联苯基三嗪(TBT)本身的活性在所有条件下在实验误差范围内没有表现出劣化。
对BEMT、BDC和OCR观察到相同结果。
结论
数据表明,TBT的存在造成BMDBM光降解加速。当使用现实浓度时,通过添加Octocrylene以及通过BEMT或BDC,可以几乎完全逆转这种作用。
Claims (19)
1.选自如下物质的紫外吸收剂用于稳定化妆品组合物的用途,
(a1)二苯基丙烯酸酯;
(a2)下式的羟苯基三嗪:
R1、R2和R3彼此独立地为C1-C18烷基;
(a3)下式的苯并三唑衍生物:
E1是直链C1-C14烷基;
E2是直链C4-C15烷基;其中E1与E2中的碳原子总数为7至29;且
R5是C1-C5烷基;和
(a4)萘二甲酸二烷基酯;
所述化妆品组合物包含:
R6和R10彼此独立地为氢;C1-C18烷基;或C6-C12芳基;
其中,在式(3a)中,基团R7、R8和R9中的至少一个是式(3c)的基团;
R11、R12、R13和R14彼此独立地为氢;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;或-COOH;
M是碱金属离子;
x是1或2;且
y是2至10的数;
和紫外吸收剂,其选自
(c1)肉桂酸衍生物;和
(c2)二苯甲酰基甲烷衍生物。
2.根据权利要求1的用途,其包括选自如下物质的紫外吸收剂用于稳定化妆品组合物,
(a1)二苯基丙烯酸酯;
(a2)下式的羟苯基三嗪:
R1、R2和R3彼此独立地为C1-C18烷基;
(a3)下式的苯并三唑衍生物:
E1是直链C1-C14烷基;
E2是直链C4-C15烷基;其中E1与E2中的碳原子总数为7至29;且
R5是C1-C5烷基;和
(a4)萘二甲酸二烷基酯;
所述化妆品组合物包含:
R6和R10彼此独立地为氢;C1-C18烷基;或C6-C12芳基;
其中,在式(3a)中,基团R7、R8和R9中的至少一个是式(3c)的基团;
R11、R12、R13、R14和R15彼此独立地为氢;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;且
y是2至10的数;和
(c1)肉桂酸衍生物。
3.根据权利要求1或2的用途,其包括:
(a1)二苯基丙烯酸酯;
(a2)式(1)的羟苯基三嗪;
(a3)式(2)的苯并三唑衍生物;
(a4)萘二甲酸二烷基酯;
用于稳定化妆品组合物,
所述化妆品组合物包含:
(b)式(3)的对称三嗪衍生物和
选自(c2)二苯甲酰基甲烷衍生物的紫外吸收剂。
4.根据权利要求1至3任一项的用途,其中二苯基丙烯酸酯(a)选自2-氰基-3,3-二苯基丙烯酸2-乙基己酯和2-氰基丙烯酸3-(苯并呋喃基)酯。
5.根据权利要求4的用途,其中二苯基丙烯酸酯(a)选自2-氰基-3,3-二苯基丙烯酸2-乙基己酯。
7.根据权利要求1至6任一项的用途,其中R6和R10是氢。
8.根据权利要求1至7任一项的用途,其中R11和R13是氢。
9.根据权利要求1至8任一项的用途,其中
R12是氢;羟基;C1-C5烷基;C1-C5烷氧基;-COOM;-COOH;或COOR15;
M是碱金属离子;且
R15是C1-C5烷基。
12.根据权利要求11的用途,其中R6、R7、R8、R14和R15是氢;或彼此独立地为C1-C18烷基。
13.根据权利要求1至12任一项的用途,其中对称三嗪衍生物(b)以微粉化形式使用。
15.根据权利要求1至14任一项的用途,其中肉桂酸衍生物(c1)是4-甲氧基肉桂酸2-乙基己酯。
16.根据权利要求14的用途,其中二苯甲酰基甲烷衍生物(c2)选自4-(叔丁基)-4’-甲氧基二苯甲酰基甲烷。
17.化妆品组合物,其包含:
0.1至10%b.w.的二苯基丙烯酸酯紫外过滤剂(a);
0.1至10.%b.w.的三嗪紫外过滤剂(b);和
0.1至10%b.w.的肉桂酸衍生物紫外过滤剂(c1)和/或二苯甲酰基甲烷衍生物(c2);
其中紫外过滤剂(a)、(b)、(c1)和(c2)如权利要求1中所定义。
18.化妆品组合物,其包含:
0.1至10%b.w.的二苯基丙烯酸酯紫外过滤剂(a);
0.1至10.%b.w.的三嗪紫外过滤剂(b);和
0.1至10%b.w.的肉桂酸衍生物紫外过滤剂(c1);
其中紫外过滤剂(a)、(b)和(c1)如权利要求1中所定义。
19.化妆品组合物,其包含:
0.1至10%b.w.的二苯基丙烯酸酯紫外过滤剂(a);
0.1至10.%b.w.的三嗪紫外过滤剂(b);和
0.1至10%b.w.的二苯甲酰基甲烷衍生物(c2);
其中紫外过滤剂(a)、(b)和(c2)如权利要求1中所定义。
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WO2009027390A2 (en) * | 2007-08-30 | 2009-03-05 | Basf Se | Stabilization of cosmetic compositions |
KR101872446B1 (ko) * | 2013-07-25 | 2018-06-28 | 에이엠지 컴퍼니 리미티드 | 화장료 용기 |
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2008
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- 2008-08-26 BR BRPI0815768A patent/BRPI0815768B1/pt active IP Right Grant
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- 2008-08-26 KR KR1020207004217A patent/KR102345271B1/ko active IP Right Grant
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Cited By (5)
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CN104093395A (zh) * | 2012-01-31 | 2014-10-08 | 皮埃尔·法布尔皮肤化妆品公司 | 新型光保护系统 |
CN104093395B (zh) * | 2012-01-31 | 2018-05-25 | 皮埃尔·法布尔皮肤化妆品公司 | 光保护系统 |
CN108464951A (zh) * | 2012-01-31 | 2018-08-31 | 皮埃尔·法布尔皮肤化妆品公司 | 光保护系统 |
TWI640325B (zh) * | 2012-01-31 | 2018-11-11 | 法商皮爾法伯皮膚化妝品公司 | 新穎光防護系統 |
CN115835855A (zh) * | 2020-06-24 | 2023-03-21 | 莱雅公司 | 脂肪介质中包含接枝聚羟基烷酸酯共聚物的化妆品组合物 |
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KR20180120787A (ko) | 2018-11-06 |
KR20160093089A (ko) | 2016-08-05 |
KR20200019262A (ko) | 2020-02-21 |
US20150250695A1 (en) | 2015-09-10 |
MX2010001762A (es) | 2010-03-10 |
AU2008292235A1 (en) | 2009-03-05 |
US9066872B2 (en) | 2015-06-30 |
BRPI0815768B1 (pt) | 2016-10-11 |
JP2016166227A (ja) | 2016-09-15 |
WO2009027390A3 (en) | 2010-06-24 |
EP2180878A2 (en) | 2010-05-05 |
CN101854904B (zh) | 2012-08-15 |
KR20100063096A (ko) | 2010-06-10 |
KR102127963B1 (ko) | 2020-06-29 |
EP2180878B1 (en) | 2019-01-16 |
EP3492144A1 (en) | 2019-06-05 |
WO2009027390A2 (en) | 2009-03-05 |
ES2720328T3 (es) | 2019-07-19 |
JP2010536924A (ja) | 2010-12-02 |
JP6612672B2 (ja) | 2019-11-27 |
BRPI0815768A2 (pt) | 2014-09-30 |
US20110104088A1 (en) | 2011-05-05 |
KR102345271B1 (ko) | 2021-12-31 |
AU2008292235B2 (en) | 2013-08-22 |
JP2014148532A (ja) | 2014-08-21 |
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