CN115227593A - 优化形成维生素d的防晒配制剂 - Google Patents
优化形成维生素d的防晒配制剂 Download PDFInfo
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- CN115227593A CN115227593A CN202210350723.9A CN202210350723A CN115227593A CN 115227593 A CN115227593 A CN 115227593A CN 202210350723 A CN202210350723 A CN 202210350723A CN 115227593 A CN115227593 A CN 115227593A
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Abstract
本发明涉及防晒配制剂,其包含特定的UV过滤剂,其中‑前维生素D3形成的有效辐照度Epvd与皮肤上红斑形成的有效辐照度Eer之比R为至少1.8,其用于提高UV辐射在人体皮肤上的透射率以产生胆钙化醇(前维生素D3),同时用于在暴露于太阳时保护人体皮肤以防UV辐射的方法中,所述方法包括将所述防晒配制剂应用于皮肤。
Description
本申请是申请号为201580041053.0的专利申请的分案申请,原申请的申请日为2015年7月24日,发明名称为“优化形成维生素D的防晒配制剂”。
本发明涉及提高UV辐射在人体皮肤上的透射率以产生胆钙化醇(维生素D3),同时在暴露于太阳时保护人体皮肤以防所述UV辐射的方法。
熟知对日光的长期暴露可能对人体皮肤具有损坏效应。取决于波长, UV辐射导致不同类型的皮肤损坏。UV-B辐射(约290至约320nm)造成晒斑并且可导致皮肤癌。UV-A辐射(约320至约400nm)在产生皮肤晒黑的同时还贡献于晒斑和引发皮肤癌。
目前熟知合适的太阳保护应包括宽带保护,这意指,即防晒霜应当保护以防UVA和UVB辐射。自2006年起,the European Recommendation 要求设计UVB保护等级的最小UVA保护,其暗示UVA-PF(UVA保护因子)为SPF(防晒因子)的至少1/3。
除UV辐射的已知损害效应外,需要一定量的UVB辐射以在皮肤中形成维生素D3及其前体。
通过用防晒霜降低红斑有效辐照度(=Er)以防止晒斑,造成维生素D3形成的有效辐照度(=EpvD)也降低。因此,防晒霜可降低或者甚至防止皮肤中的维生素D3产生。这不是令人惊讶的,因为造成导致晒斑(红斑)和皮肤损坏的辐射在也造成表皮维生素D3合成的相同辐射范围内。显示出局部应用具有8的防晒因子的防晒霜在整体暴露于会导致温和晒斑的模拟日光以后防止维生素D3循环浓度的任何提高。因此,防晒霜的使用可减少身体自身的维生素D3产生且长期防晒霜使用可导致血液中不想要的较低维生素 D3水平。
本发明下面的问题是找到抵消太阳暴露期间对维生素D3形成的抑制的防晒霜。
令人惊讶的是,发现包含至少一种特殊UV过滤剂的防晒霜符合这些要求。
因此,本发明提及防晒配制剂,其包含至少一种选自如下的UV过滤剂(A):
(a)三嗪衍生物;
(b)肉桂酸衍生物;
(c)双间苯二酚基三嗪;
(f)苯并咪唑衍生物;
(i5)4-甲基亚苄基樟脑;
(h)苯甲酰哌嗪衍生物;
(k)二芳基丁二烯衍生物;
(l)苯基苯并三唑衍生物;
(n)亚苄基丙二酸酯;
(o3)水杨酸三乙醇胺;
(r)咪唑啉衍生物;
(u)选自金属氧化物的无机UV过滤剂;
(v)萘二甲酸酯;和
(w)部花青衍生物;且
任选包含至少一种选自如下的UV过滤剂(B):
(d)氨基二苯甲酮衍生物;
(e)二苯甲酰甲烷衍生物;
(g)β,β-二苯基丙烯酸酯衍生物;
(i)不同于(i5)的樟脑衍生物;
(o)不同于(o3)的水杨酸酯衍生物;
(p)邻氨基苯甲酸酯衍生物;和
(s)亚苄基丙二酸酯衍生物;其中:
-维生素D3形成的有效辐照度Epvd与皮肤上红斑形成的有效辐照度Eer之比为至少1.8,
其用于提高UV辐射在人体皮肤上的透射率以产生维生素D3,同时用于在暴露于太阳时保护人体皮肤以防UV辐射的方法中,所述方法包括将所述防晒配制剂应用于皮肤。
附图说明:
图1:自然日光下维生素D3形成的有效辐照度与红斑形成的有效辐照度之比R=EpvD/Eer。
图2:具有强UVA(A1.3)和维生素D3最佳化(A1.4)保护性能的四种SPF 6防晒霜(表1中的组成)的模拟UV透射率的光谱。
图3:具有强UVA(A2.3)和维生素D3最佳化(A2.4)保护性能的四种SPF 15防晒霜(表2中的组成)的模拟UV透射率的光谱。
图4:具有强UVA(A3.3)和维生素D3最佳化(A3.4)保护性能的四种SPF 30防晒霜(表3中的组成)的模拟UV透射率的光谱。
有效辐照度
有效辐照度Eer可根据下式通过光源的辐射度(=标准太阳辐射S(λ))与分别在光谱范围内的任何波长下的红斑形成的各自作用光谱ser(λ)和维生素D3产生的spvD(λ)相乘而计算:
(EIer):红斑形成的有效辐照度Eer:Eer=∫S(λ)ser(λ)dλ
(EIpvD):维生素D3形成的有效辐照度EpvD:EpvD=∫S(λ)sVD(λ)dλ
自然日光下维生素D3形成的有效辐照度与红斑形成的有效辐照度之比R=EpvD/Eer近似地为:
这可通过图1演示。
如权利要求1中所定义的UV过滤剂类别包含不同种类的UV过滤剂,即UV-B过滤剂(290-320nm)、UV-AII过滤剂(320-340nm)以及宽谱和 UV-AI过滤剂(340-400nm)。
在下文中,列举常用UV过滤剂类别的代表。
合适的三嗪衍生物(a)选自:
(a1)乙基己基三嗪酮;
(a2)三-联苯三嗪;
(a3)二乙基己基丁酰氨基三嗪酮,
(a4)亚苯基双-联苯三嗪;
(a5)对应于下式的5,6,5',6'-四苯基-3,3'-(1,4-亚苯基)双(1,2,4-三嗪):
(a6)下式的苯甲酸,4,4'-[[6-[[3-[1,3,3,3-四甲基-1-[(三甲基甲硅烷基)氧基]-1-二硅氧烷基]丙基]氨基]-1,3,5-三嗪-2,4-二基]二亚氨基]双-,二丁基酯:
合适的肉桂酸衍生物(b)选自:
(b1)甲氧基肉桂酸乙基己酯;
(b2)甲氧基肉桂酸异丙酯;
(b3)甲氧基肉桂酸异戊酯;
(b4)甲基肉桂酸二异丙酯;
(b5)西诺沙酯(Cinnoxate);
(b6)乙基己酸甘油酯;
(b7)下式的2-丙烯酸,3-(4-乙氧基苯基)-,2-甲基苯基酯:
(b8)下式的2-丙烯酸,3-(4-甲氧基苯基)-,2-甲基苯基酯:
(b9)下式的丙二酸,2-[(4-甲氧基苯基)亚甲基]-,1,3-双(2-甲基丁基)酯:
(b10)下式的丙二酸,2-[(4-甲氧基苯基)亚甲基]-,1,3-双(2-乙基己基)酯:
合适的双间苯二酚基三嗪(c)选自:
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;和
(c2)双-乙基己氧基苯酚甲氧基苯基三嗪/聚甲基丙烯酸甲酯的水分散体。
合适的氨基二苯甲酮衍生物(d)选自:
(d1)二乙氨基羟苯甲酰基苯甲酸己酯。
合适的二苯甲酰甲烷衍生物(e)选自:
(e1)丁基甲氧基二苯甲酰甲烷;和
(e2)异丙基二苯甲酰甲烷。
合适的苯并咪唑衍生物(f)选自:
(f1)苯基苯并咪唑磺酸;和
(f2)苯基二苯并咪唑四磺酸二钠。
合适的β,β-二苯基丙烯酸酯衍生物(g)选自:
(g1)奥克立林;和
(g2)依托立林。
合适的苯甲酰哌嗪衍生物(h)选自:
(h1)1,4-(2-(4-二乙基氨基-2-羟基苯甲酰)苯甲酰)哌嗪。
合适的樟脑衍生物(i)选自:
(i1)对苯二亚甲基二樟脑磺酸;
(i2)亚苄基樟脑磺酸;
(i3)樟脑苯扎铵甲基硫酸盐;
(i4)3-亚苄基樟脑;
(i5)甲基亚苄基樟脑;和
(i6)聚丙烯酰氨基甲基亚苄基樟脑。
合适的二芳基丁二烯衍生物(k)选自:
(k1)1,1-二羧基(2,2′-二甲基-丙基)-4,4-二苯基丁二烯。
合适的苯基苯并三唑衍生物(l)选自:
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(l2)甲酚曲唑三硅氧烷;
(l3)下式的苯酚,2-(2H-苯并三唑-2-基)-6-[[(2-乙基己基)氧基]甲基]-4-甲基-
(l4)苯并三唑基十二烷基对甲酚;
(l5)如US 20110195036、WO 2011097555所述的聚合苯并三唑类UV过滤剂;例如由二聚物二醇(C36H72O)、二-三羟基丙烷、己二酸二甲酯、己二酸甲酯和3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羟基苯丙酸甲酯制备的聚合物;和
(l6)对应于下式的2-(2H-苯并三唑-2-基)-6-(2-乙基己氧基甲基)-4-甲基-苯酚:
合适的丙二酸衍生物(n)选自:
(n1)下式的亚苄基丙二酸酯:
其中:
R1为甲基;乙基;丙基;或正丁基;
如果R1为甲基,则
R2和R3相互独立地为氢;或甲基;
R4为甲基;乙基;或正丙基;
R5和R6相互独立地为氢;或C1-C3烷基;
如果R1为乙基;丙基;或正丁基,则
R为异丙基。
优选,在式(BM)中:
R1为甲基。
最优选下式的化合物:
式(BM)化合物的实例列于下表中:
其它合适的丙二酸酯(n)指:
(n2)对应于下式的亚丁香基丙二酸二乙基己酯:
合适的水杨酸酯衍生物选自:
(o1)水杨酸乙基己酯;
(o2)二丙二醇水杨酸酯;
(o3)TEA水杨酸酯;和
(o4)胡莫柳酯。
合适的邻氨基苯甲酸酯衍生物(p)指:
(p1)邻氨基苯甲酸薄荷酯。
合适的咪唑啉衍生物(r)选自:
(r1)乙基己基二甲氧基亚苄基;和
(r2)二氧代咪唑啉丙酸酯。
合适的亚苄基丙二酸酯衍生物选自:
(s1)聚硅氧烷-15。
合适的无机UV过滤剂(u)选自:
(u1)氧化锌;
(u2)Fe2O3;和
(u3)二氧化钛。
合适的萘二甲酸酯(v)选自:
(v1)2,6-萘二甲酸二乙基己酯。
优选,本发明防晒配制剂具有至少2的SPF。
更优选,本发明防晒配制剂具有至少6的SPF。
本发明防晒配制剂包含一种或者多于一种UV过滤剂。
例如,本发明防晒配制剂可包含1、2、3、4、5或6种选自如权利要求1中所定义的UV过滤剂类别的UV过滤剂。
优选,本发明防晒配制剂包含选自如下的UV过滤剂:
(a1)乙基己基三嗪酮.
(a2)三-联苯三嗪;
(a3)二乙基己基丁酰氨基三嗪酮;
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(c2)双-乙基己氧基苯酚甲氧基苯基三嗪/聚甲基丙烯酸甲酯的水分散体; (d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(e1)丁基甲氧基二苯甲酰甲烷;
(f1)苯基苯并咪唑磺酸;
(f2)苯基二苯并咪唑四磺酸二钠;
(g1)奥克立林;
(h1)1,4-(2-(4-二乙基氨基-2-羟基苯甲酰)苯甲酰)哌嗪;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(l2)甲酚曲唑三硅氧烷;
(l6)2-(2H-苯并三唑-2-基)-6-(2-乙基己氧基甲基)-4-甲基-苯酚;
(i1)对苯二亚甲基二樟脑磺酸;
(n1)式(BM9)的化合物;
(o1)水杨酸乙基己酯;
(o4)胡莫柳酯;
(p1)邻氨基苯甲酸薄荷酯;
(s1)聚硅氧烷-15;
(u1)氧化锌;和
(u3)二氧化钛;
更优选,本发明防晒配制剂包含选自如下的UV过滤剂:
(a1)乙基己基三嗪酮;
(b1)甲氧基肉桂酸乙基己酯;
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(e1)丁基甲氧基二苯甲酰甲烷;
(f1)苯基苯并咪唑磺酸;
(g1)奥克立林;和
(u3)二氧化钛。
优选,该防晒配制剂具有至少6的SPF。
甚至更优选,本发明防晒配制剂包含选自如下的UV过滤剂:
(b1)甲氧基肉桂酸乙基己酯;
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(e1)丁基甲氧基二苯甲酰甲烷;
(f1)苯基苯并咪唑磺酸;和
(g1)奥克立林。
优选,该防晒配制剂具有至少6的SPF。
此外,本发明防晒配制剂优选包含选自如下的UV过滤剂:
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;和
(e1)丁基甲氧基二苯甲酰甲烷。
优选,该防晒配制剂具有至少6的SPF。
优选,本发明防晒配制剂包含选自如下的UV过滤剂浓缩物:
(a)0.1-40%b.w.三嗪衍生物;
(b)0.1-30%b.w.肉桂酸衍生物;
(c)0.1-10%b.w.双间苯二酚基三嗪;
(f)0.1-10%b.w.苯并咪唑衍生物;
(i5)0.1-10%b.w.4-甲基亚苄基樟脑;
(h)0.1-10%b.w.苯甲酰哌嗪衍生物;
(k)0.1-20%b.w.二芳基丁二烯衍生物;
(l)0.1-30%b.w.苯基苯并三唑衍生物;
(n)0.1-20%b.w.亚苄基丙二酸酯;
(o3)0.1-15%b.w.水杨酸三乙醇胺;
(r)0.1-10%b.w.咪唑啉衍生物;
(u)0.1-50%b.w.选自金属氧化物的无机UV过滤剂;
(v)0.1-20%b.w.萘二甲酸酯;和
(w)0.1-20%b.w.部花青衍生物;且
任选包含至少一种选自如下的UV过滤剂(B):
(d)0.1-20%b.w.氨基二苯甲酮衍生物;
(e)0.1-5%b.w.二苯甲酰甲烷衍生物;
(g)0.1-1%b.w.β,β-二苯基丙烯酸酯衍生物;
(i)0.1-10%b.w.不同于(i5)的樟脑衍生物;
(o)0.1-35%b.w.不同于(o3)的水杨酸酯衍生物;
(p)0.1-10%b.w.邻氨基苯甲酸酯衍生物;和
(s)0.1-10%b.w.亚苄基丙二酸酯衍生物。
更优选,本发明防晒配制剂包含选自如下的UV过滤剂浓缩物:
(a1)1-3%b.w.乙基己基三嗪酮;
(b1)1-3.5%b.w.甲氧基肉桂酸乙基己酯;
(c1)0.6-10%b.w.双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)0.8-10%b.w.二乙氨基羟苯甲酰基苯甲酸己酯;
(e1)2-3%b.w.丁基甲氧基二苯甲酰甲烷;
(f1)2-3%b.w.苯基苯并咪唑磺酸;
(g1)2.0-2.5%b.w.奥克立林;
(l1)2-7.5%b.w.亚甲基双-苯并三唑基四甲基丁基苯酚;和
(u3)3.0-3.5%b.w.二氧化钛。
本发明防晒配制剂通过使用以下UV过滤剂组合而实现>15的SPF:
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;和
(e1)丁基甲氧基二苯甲酰甲烷;最优选
(d1)9.0-11.0%b.w.二乙氨基羟苯甲酰基苯甲酸己酯;
(l1)2.5-3.5%b.w.亚甲基双-苯并三唑基四甲基丁基苯酚;和
(e1)2.5-3.5%b.w丁基甲氧基二苯甲酰甲烷。
本发明防晒配制剂通过使用以下UV过滤剂组合而实现>30的SPF:
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;和
(e1)丁基甲氧基二苯甲酰甲烷;
最优选
(c1)1.5-2.5%b.w.双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)9.5-10.5%b.w.二乙氨基羟苯甲酰基苯甲酸己酯;
(l1)7-8%b.w.亚甲基双-苯并三唑基四甲基丁基苯酚;和
(e1)2.5-3.5%b.w.丁基甲氧基二苯甲酰甲烷。
优选,使用本发明防晒配制剂,其中UV过滤剂选自宽带(340-400nm 的光谱)UV过滤剂:
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(c2)双-乙基己氧基苯酚甲氧基苯基三嗪/聚甲基丙烯酸甲酯的水分散体;
(f2)苯基二苯并咪唑四磺酸二钠;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(l2)甲酚曲唑三硅氧烷;
(u1)氧化锌;和任选
(e1)丁基甲氧基二苯甲酰甲烷;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(i1)对苯二亚甲基二樟脑磺酸;和
(p1)邻氨基苯甲酸薄荷酯。
此外,本发明提及防晒配制剂,其包含选自如下的UV过滤剂:
(a)三嗪衍生物
(b)肉桂酸衍生物;
(c)双间苯二酚基三嗪;
(f)苯并咪唑衍生物;
(h)苯甲酰哌嗪衍生物;
(i5)4-甲基亚苄基樟脑;
(l)苯基苯并三唑衍生物;
(n)亚苄基丙二酸酯;
(o3)水杨酸三乙醇胺;
(r)咪唑啉衍生物;
(u)选自金属氧化物的无机UV过滤剂;
(v)萘二甲酸酯;和
(w)部花青衍生物;
其中防晒配制剂仅包含所选择的UV过滤剂中的一种。
优选,使用防晒配制剂,其中UV过滤剂选自宽带(340-400nm的光谱)UV过滤剂:
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(c2)双-乙基己氧基苯酚甲氧基苯基三嗪/聚甲基丙烯酸甲酯的水分散体;
(f2)苯基二苯并咪唑四磺酸二钠;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(i1)对苯二亚甲基二樟脑磺酸;和
(u1)氧化锌;
其中防晒配制剂仅包含所选择的UV过滤剂中的一种。
此外,优选防晒配制剂,其包含选自如下的颗粒UV过滤剂:
(a2)三-联苯三嗪;
(c2)双-乙基己氧基苯酚甲氧基苯基三嗪/聚甲基丙烯酸甲酯的水分散体;
(h1)1,4-(2-(4-二乙基氨基-2-羟基苯甲酰)苯甲酰)哌嗪;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(u1)氧化锌;和
(u3)二氧化钛。
此外,优选防晒配制剂,其包含选自如下的非颗粒UV过滤剂:
(a1)乙基己基三嗪酮.
(a3)二乙基己基丁酰氨基三嗪酮;
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(e1)丁基甲氧基二苯甲酰甲烷;
(f1)苯基苯并咪唑磺酸;
(f2)苯基二苯并咪唑四磺酸二钠;
(g1)奥克立林;
(h1)1,4-(2-(4-二乙基氨基-2-羟基苯甲酰)苯甲酰)哌嗪;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(l2)甲酚曲唑三硅氧烷;
(l6)2-(2H-苯并三唑-2-基)-6-(2-乙基己氧基甲基)-4-甲基-苯酚;
(i1)对苯二亚甲基二樟脑磺酸;
(n1)式(BM9)的化合物;
(o1)水杨酸乙基己酯;
(o4)胡莫柳酯;
(p1)邻氨基苯甲酸薄荷酯;和
(s1)聚硅氧烷-15。
本发明防晒配制剂的优选的维生素D3形成的有效辐照度Epvd与皮肤上红斑形成的有效辐照度Eer之比为至少1.8,优选至少1,85,更优选至少 1,90,甚至更优选>1,95,最优选至少2,0,最优选至少2,1。
优选其中维生素D3形成的有效辐照度Epvd与皮肤上红斑形成的有效辐照度Eer之比为至少1.8;且包含表1的UV过滤剂组合CSF 1-CSF 32 的其它本发明防晒配制剂。
根据本发明,可提供在达>SPF60的巨大SPF范围内具有对改进的维生素D3产生而言最佳化的透明度的防晒组合物,其包括但不限于the European CommissionRecommendation建议的防晒因子(缩写为SPF):SPF 6、15、30、50和50+(>60)。根据the ECRecommendation,6的SPF 属于“低保护”类别,SPF 15属于“中等保护”,SPF 30和50属于“高保护”,SPF 50+(要求SPF min 60)属于“非常高保护”类别。
关于宽带保护,the EC recommendation称UVA-PF/SPF比应当至少为1/3,且临界波长(CW)为至少370nm。对于低UVA保护,UVA-PF/SPF 比明显更低,对于高UVA保护,它远高于1/3。
防晒霜需要降低皮肤上的Eer和Epvd。比R=Epvd/Eer可通过选择合适的UV过滤剂组合而最佳化。对于以防Eer的给定保护,所述比R越高,防晒霜在维生素D3产生方面执行越好。
本发明防晒配制剂尤其用于保护对紫外线敏感的有机材料,尤其是人和动物皮肤和毛发以防UV辐射的作用,同时用于提高UV辐射的透射率以在人体皮肤上产生维生素D3。因此,这类UV过滤剂组合适用作化妆品和药物制剂中的光保护剂。
本发明防晒配制剂包含基于配制剂的总重量1-50重量%,优选1-20 重量%,优选3-15重量%的如权利要求1中所定义的UV过滤剂组合和化妆品耐受辅助剂。
本发明防晒配制剂可通过使用常规方法,例如通过将各组分简单地搅拌在一起,尤其是通过使用已知化妆品UV吸收剂,例如甲氧基肉桂酸乙基己酯(UV过滤剂组分(b1))的溶解性能将如权利要求1中所定义的UV过滤剂与辅助剂物理混合而制备。如权利要求1中所定义的UV过滤剂可例如不经进一步处理而用于防晒配制剂中。
用于本发明防晒霜中的一些UV过滤剂,例如(l1)亚甲基双-苯并三唑基四甲基丁基苯酚、(a2)三-联苯三嗪或者(h1)1,4-(2-(4-二乙基氨基-2-羟基苯甲酰)苯甲酰)哌嗪可以以其微粉化状态使用(纳米级有机过滤剂、颗粒有机过滤剂、UV吸收剂颜料)。
适于制备微粒的任何已知方法可用于制备微粉化UV过滤剂,例如在球磨机中用硬研磨介质如硅酸锆球和在水中或者在合适有机溶剂中的保护性表面活性剂或保护性聚合物湿研磨(用于可泵送分散体的低粘性微粉化方法),使用连续或不连续(分批)捏合机湿捏合(不可泵送糊的高粘性微粉化方法),从合适的溶剂中喷雾干燥,通过超临界流体(例如CO2)根据RESS 方法(超临界溶液的快速膨胀)膨胀或者通过从合适溶剂,包括超临界流体中沉淀。
用于制备微粉化有机UV过滤剂的合适研磨设备为例如喷射磨、球磨机、振动磨或锤磨机,优选高速混合磨或球磨机。研磨优选用研磨助剂进行。
所得微粉化UV过滤剂通常具有0.02-2μm,优选0.05-1.5μm,更尤其是0.1-1.0μm的平均粒度。
本发明中所用微粉化UV过滤剂优选作为水分散体存在。本发明中所用略溶性有机化合物的研磨优选用研磨助剂进行。分散剂作为低分子量研磨助剂用于所有以上微粉化方法。用于水分散体的优选有用研磨助剂为具有高于8,更优选高于10的HLB值的阴离子表面活性剂。任何常用阴离子、非离子或两性表面活性剂可用作分散剂(组分(b))。这类表面活性剂体系可包含例如:羧酸及其盐:钠、钾和铵的碱性皂,钙或镁的金属皂,有机基皂,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,酸性磷酸酯,二乙醇胺磷酸盐,鲸蜡基磷酸钾。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,例如月桂醇聚醚-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。脂肪酸聚乙二醇醚,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成产物的C12-C22 脂肪酸单酯和二酯。脂肪酸和聚甘油酯,例如甘油单硬脂酸酯、二异硬脂酰聚甘油基-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。来自多个那些物质类别的化合物的混合物也是合适的。脂肪酸聚乙二醇酯,例如二甘醇单硬脂酸酯,脂肪酸和聚乙二醇酯,脂肪酸和蔗糖酯,例如脂肪酸蔗糖酯,甘油和蔗糖酯,例如脂肪酸甘油酯。山梨糖醇和脱水山梨糖醇,具有6-22 个碳原子的饱和和不饱和脂肪酸的脱水山梨糖醇单酯和二酯,和氧化乙烯加成产物。聚山梨酸酯-n系列,脱水山梨糖醇酯,例如脱水山梨糖醇倍半硬脂酸酯、PEG-(6)脱水山梨糖醇异硬脂酸酯、PEG-(10)脱水山梨糖醇月桂酸酯、PEG-17脱水山梨糖醇二油酸酯。葡萄糖衍生物,C8-C22烷基单糖和低聚糖和乙氧基化类似物,其中葡萄糖优选作为糖组分。O/W乳化剂,例如甲基葡萄糖醇聚醚-倍半硬脂酸酯、脱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、鲸蜡硬脂醇/鲸蜡硬脂基葡糖苷。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、线性磺化石蜡、磺化四丙炔磺酸盐、月桂基硫酸钠、铵和乙醇胺月桂基硫酸盐、月桂醚硫酸盐、月桂醇聚醚硫酸钠或肉豆蔻醇聚醚硫酸钠、磺基琥珀酸盐、酰基羟乙磺酸盐、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/或磺酸根基团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为甜菜碱,例如 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、椰油酰氨基丙基二甲基甘氨酸铵和2-烷基-3-羧甲基 -3-羟乙基咪唑啉,其各自在烷基或酰基中具有8-18个碳原子,以及椰油酰氨基乙基羟乙基羧甲基甘氨酸盐、N-烷基甜菜碱、N-烷基氨基甜菜碱。作为分散剂的合适温和表面活性剂,即皮肤尤其好地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、脂肪酸牛磺酸盐、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。非离子表面活性剂,例如PEG-6蜂蜡(和)PEG-6硬脂酸酯(和)聚甘油基-2- 异硬脂酸酯[Apifac]、甘油硬脂酸酯(和)PEG-100硬脂酸酯[Arlacel 165]、 PEG-5甘油硬脂酸酯(arlatone 983S]、脱水山梨糖醇油酸酯(和)聚甘油基-3 蓖麻醇酸酯[Arlacel1689)、脱水山梨糖醇硬脂酸酯和蔗糖椰油酸酯 [arlatone 2121]、甘油硬脂酸酯和月桂醇聚醚-23[Cerasynth 945]、鲸蜡硬脂醇和鲸蜡醇聚醚-20[Cetomacrogol Wax]、鲸蜡硬脂醇和聚山梨酸酯60 和PEG-150和硬脂酸酯-20[Polawax GP 200,Polawax NF]、鲸蜡硬脂醇和鲸蜡硬脂基聚葡糖苷[Emulgade PL 1618]、鲸蜡硬脂醇和鲸蜡硬脂醇聚醚 -20[Emulgade1OOONI,Cosmowax]、鲸蜡硬脂醇和PEG-40蓖麻油[Emulgade F Special]、鲸蜡硬脂醇和PEG-40蓖麻油和鲸蜡硬脂基硫酸钠 [Emulgade F]、硬脂醇和硬脂醇聚醚7和硬脂醇聚醚10[Emulgator E 2155]、鲸蜡硬脂醇和硬脂醇聚醚-7和硬脂醇聚醚10[Emulsifying waxU.S.N.F]、甘油硬脂酸酯和PEG-75硬脂酸酯[Gelot 64]、丙二醇鲸蜡醇聚醚-3乙酸酯[Hetester PCS)、丙二醇-8-异鲸蜡醇聚醚-3乙酸酯[Hetester PHA]、鲸蜡硬脂醇和鲸蜡醇聚醚和油醇聚醚-12[Lanbritol Wax N 21]、 PEG-6硬脂酸酯和PEG-32硬脂酸酯[Tefose1500]、PEG-6硬脂酸酯和鲸蜡醇聚醚-20和硬脂醇聚醚20[Tefose 2000]、PEG-6硬脂酸酯和鲸蜡醇聚醚-20和甘油硬脂酸酯和硬脂醇聚醚20[Tefose 2561]、甘油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、甘油硬脂酸酯SE[Monelgine,Cutina KD]、丙二醇硬脂酸酯[Tegin P]、鲸蜡硬脂醇和鲸蜡硬脂基硫酸钠[Lanette N,Cutina LE,Crodacol GP]、鲸蜡硬脂醇和月桂基硫酸钠[Lanette W]、三羊毛醇聚醚-4磷酸盐和乙二醇硬脂酸酯和PEG-2硬脂酸酯[Sedefos 75]、甘油硬脂酸酯和月桂基硫酸钠 [Teginacid Special]。阳离子酸基础物,例如鲸蜡硬脂醇和西曲溴铵。最优选的分散剂(b)为烷基硫酸钠或烷基醚硫酸钠,例如月桂醇聚醚硫酸钠[来自 Cognis的TexaponN70]或肉豆蔻醇聚醚硫酸钠[来自Cognis的Texapon K14 S]。具体的分散剂可以以基于组合物的总重量例如1-30重量%,尤其是2-20重量%,优选3-10重量%的量使用。有用的溶剂为水、盐水、(聚 -)乙二醇、甘油或化妆品可接受油。其它有用的溶剂在下面公开于标题为“脂肪酸的酯”、“天然和合成甘油三酯,包括甘油酯和衍生物”、“珠光蜡”、“烃油”和“聚硅氧烷或硅氧烷”的部分中。
如果本发明配制剂呈现含水和含油乳液(例如W/O、O/W、O/W/O和 W/O/W乳液或微乳液),则它们包含例如基于组合物的总重量0.1-30重量%,优选0.1-15重量%,尤其是0.5-10重量%的选自(a)-(x)的UV过滤剂,基于组合物的总重量1-60重量%,尤其是5-50重量%,优选10-35重量%至少一种油组分,基于组合物的总重量0-30重量%,尤其是1-30重量%,优选4-20重量%至少一种乳化剂,基于组合物的总重量10-90重量%,尤其是30-90重量%水,和0-88.9重量%,尤其是1-50重量%其它化妆品耐受辅助剂。
含油组合物(例如油、W/O、O/W、O/W/O和W/O/W乳液或微乳液) 的合适油组分为例如基于具有6-18,优选8-10个碳原子的脂肪醇的格尔伯特醇,线性C6-C24脂肪酸与线性C3-C24醇的酯,支化C6-C13羧酸与线性 C6-C24脂肪醇的酯,线性C6-C24脂肪酸与支化醇,尤其是2-乙基己醇的酯,羟基羧酸与线性或支化C6-C22脂肪醇的酯,尤其是苹果酸二辛酯,线性和 /或支化脂肪酸与多元醇(例如丙二醇、二聚物二醇或三聚物三醇)和/或格尔伯特醇的酯,基于C6-C10脂肪酸的甘油三酯、基于C6-C18脂肪酸的液体单 -/二-/三甘油酯混合物,C6-C24脂肪醇和/或格尔伯特醇与芳族羧酸,尤其是苯甲酸的酯,C2-C12二羧酸与具有1-22个碳原子的线性或支化醇或者具有 2-10个碳原子和2-6个羟基的多元醇的酯,植物油(例如向日葵油、橄榄油、大豆油、菜子油、杏仁油、霍霍巴油、橙油、小麦胚芽油、桃仁油和椰子油的液体组分),支化伯醇,取代环己烷,线性和支化C6-C22脂肪醇碳酸酯、格尔伯特醇碳酸酯,苯甲酸与线性和/或支化C6-C22醇的酯(例如 TN),具有12-36个碳原子,尤其是12-24个碳原子的线性或支化、对称或不对称二烷基醚,例如二-正辛基醚、二-正癸基醚、二-正壬基醚、二-正十一烷基醚、二-正十二烷基醚、正己基正辛基醚、正辛基正癸基醚、正癸基正十一烷基醚、正十一烷基正十二烷基醚、正己基正十一烷基醚、二-叔丁基醚、二异戊基醚、二-3-乙基癸基醚、叔丁基正辛基醚、异戊基正辛基醚和2-甲基戊基-正辛基醚;环氧化脂肪酸酯与多元醇的开环产物、硅油和/ 或脂族烃或环烷烃。重要的还有脂肪酸与具有3-24个碳原子的醇的单酯。该组物质包含具有8-24个碳原子的脂肪酸,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、鳕油酸、山萮酸和芥酸及其工业级混合物(例如在天然脂肪和油的压力脱除中,在来自Roelen羰基合成的醛的还原中,或者在不饱和脂肪酸的二聚中得到的),与醇,例如异丙醇、己醇、辛醇、2-乙基己醇、癸醇、月桂醇、异十三醇、肉豆蔻醇、鲸蜡醇、棕榈油醇、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、鳕油醇、山萮醇、瓢儿菜醇和巴惟醇及其工业级混合物(例如在基于脂肪和油的工业级甲基酯或来自 Roelen羰基合成的醛的高压氢化中得到以及作为不饱和脂肪醇二聚中的单体馏分得到)的酯化产物。尤其重要的是肉豆蔻酸异丙酯、异壬酸C16-C18烷基酯、硬脂酸2-乙基己酯、油酸鲸蜡酯、三辛酸甘油酯、椰油脂肪酸癸酸/辛酸酯和硬脂酸正丁酯。可使用的其它油组分为二羧酸酯,例如己二酸二正丁酯、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,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。优选的单醇或多元醇为乙醇、异丙醇、丙二醇、己二醇、甘油和山梨糖醇。还可使用一种或多种烷基羧酸的二价和/或三价金属盐(碱土金属,尤其是Al3+)。
油组分可以以基于组合物的总重量例如1-60重量%,尤其是5-50重量%,优选10-35重量%的量使用。
任何常用乳化剂可用于本发明化妆品组合物。
合适的乳化剂为例如来自以下组的非离子表面活性剂:
-2-30摩尔氧化乙烯和/或0-5摩尔氧化丙烯与具有8-22个碳原子的线性脂肪醇,与具有12-22个碳原子的脂肪酸以及与烷基中具有8-15个碳原子的烷基苯酚的加成产物,例如鲸蜡硬脂醇聚醚-20或鲸蜡硬脂醇聚醚-12;
-1-30摩尔氧化乙烯与具有3-6个碳原子的多元醇,尤其是与甘油的加成产物的C12-C22脂肪酸单酯或二酯;
-具有6-22个碳原子的饱和和不饱和脂肪酸及其氧化乙烯加成产物的甘油单酯或二酯和脱水山梨糖醇单酯和二酯,例如甘油硬脂酸酯、甘油异硬脂酸酯、甘油油酸酯、脱水山梨糖醇油酸酯或脱水山梨糖醇倍半油酸酯;
-C8-C22烷基单-和-低聚-糖苷及其乙氧基化类似物,优选1.1-5,尤其是 1.2-1.4的低聚度,且葡萄糖优选作为糖组分;
-2-60摩尔,尤其是15-60摩尔氧化乙烯与蓖麻油和/或氢化蓖麻油的加成产物;
-多元醇酯,尤其是聚甘油酯,例如二异硬脂酰聚甘油基-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。来自多个那些物质类别的化合物的混合物也是合适的;
-基于线性、支化、不饱和或饱和C6-C22脂肪酸、蓖麻油酸以及12-羟基硬脂酸以及基于甘油、聚甘油、季戊四醇、二季戊四醇、糖醇(例如山梨糖醇)、烷基葡糖苷(例如甲基葡糖苷、丁基葡糖苷、月桂基葡糖苷)以及聚葡糖苷(例如纤维素)的偏酯,例如聚甘油基-2-二羟基硬脂酸酯或聚甘油基-2-蓖麻油酸酯;
-单-、二-和三-烷基磷酸酯以及单-、二-和/或三-PEG-烷基磷酸酯及其盐;
-羊毛蜡醇;
-天然衍生物的一种或多种乙氧基化酯,例如氢化蓖麻油的聚乙氧基化酯;
-硅油乳化剂,例如聚硅氧烷多元醇;
-聚硅氧烷/聚烷基/聚醚共聚物和相应的衍生物,例如鲸蜡基二甲基聚硅氧烷共聚醇;
-季戊四醇、脂肪酸、柠檬酸和脂肪醇的混合酯(参见DE-A-1 165 574)和/ 或具有6-22个碳原子的脂肪酸、甲基葡萄糖和多元醇,优选甘油或聚甘油的混合酯,例如聚甘油基-3-葡萄糖二硬脂酸酯、聚甘油基-3-葡萄糖二油酸酯、甲基葡萄糖二油酸酯或二椰油酰季戊四醇二硬脂基柠檬酸酯;以及
-聚亚烷基二醇。
氧化乙烯和/或氧化丙烯与脂肪醇、脂肪酸、烷基苯酚、甘油单酯或二酯以及脂肪酸的脱水山梨糖醇单酯和二酯,或者与蓖麻油的加成产物是已知的市售产品。它们通常为同系物混合物,其平均烷氧基化度对应于氧化乙烯和/或氧化丙烯与进行加成反应的基质的量之比。氧化乙烯与甘油的加成产物的C12-C18脂肪酸单酯或二酯例如作为用于化妆品配制剂的脂肪修复物质由DE-A-2 024 051已知。
C8-C18烷基单-和-低聚糖苷、其制备及其用途由现有技术已知。它们尤其通过葡萄糖或低聚糖与具有8-18个碳原子的伯醇反应而制备。合适的配糖基包括其中环状糖基与脂肪酸配糖键合的单糖苷,以及具有至多优选约 8的低聚度的低聚糖苷。低聚度为基于该工业级产品常见的同系物分布的统计平均值。
也可使用两性离子表面活性剂作为乳化剂。术语“两性表面活性剂”尤其表示分子中带有至少一个季铵基团和至少一个羧酸根和/或磺酸根的表面活性化合物。尤其合适的两性离子表面活性剂为所谓的甜菜碱,例如 N-烷基-N,N-二甲基甘氨酸铵,例如椰油烷基二甲基甘氨酸铵、N-酰氨基丙基-N,N-二甲基甘氨酸铵,例如椰油酰氨基丙基二甲基甘氨酸铵,和2-烷基 -3-羧甲基-3-羟乙基咪唑啉,其各自在烷基或酰基中具有8-18个碳原子,以及椰油酰氨基乙基羟乙基羧甲基甘氨酸盐。尤其优选通过CTFA名椰油酰氨基丙基甜菜碱已知的脂肪酸酰胺衍生物。适用作乳化剂的还有两性表面活性剂。两性表面活性剂应当理解尤其意指除包含C8-C18烷基或酰基外,分子中包含至少一个游离氨基和至少一个-COOH或-SO3H基团并且能够形成内盐的那些。合适的两性表面活性剂的实例包括N-烷基甘氨酸、N-烷基丙酸、N-烷基氨基丁酸、N-烷基亚氨基丙酸、N-羟乙基-N-烷基酰氨基丙基甘氨酸、N-烷基牛磺酸、N-烷基肌氨酸、2-烷基氨基丙酸和烷基氨基乙酸,其各自在烷基中具有约8-18个碳原子。
尤其优选的两性表面活性剂为N-椰油烷基氨基丙酸酯、椰油酰氨基乙基氨基丙酸酯和C12-C18酰基肌氨酸。除两性乳化剂外,还考虑季铵乳化剂,尤其优选酯季铵盐类型的那些,优选甲基-季铵化二脂肪酸三乙醇胺酯盐。
优选非离子乳化剂,优选具有8-22个碳原子和4-30个EO单元的乙氧基化脂肪醇。
乳化剂可以以基于组合物的总重量例如1-30重量%,尤其是4-20重量%,优选5-10重量%的量使用。然而,原则上也可省去乳化剂的使用。
本发明组合物,例如霜、凝胶、洗液、醇和水/醇溶液、乳液、蜡/脂肪组合物、棒制剂、粉末或软膏还可包含温和表面活性剂、富脂剂、珠光蜡、稠度调节剂、增稠剂、聚合物、聚硅氧烷化合物、脂肪、蜡、稳定剂、生物源性活性成分、除臭活性成分、去头屑剂、成膜剂、溶胀剂、抗氧化剂、水溶助长剂、防腐剂、昆虫驱避剂、自美黑剂、增溶剂、芳香油、着色剂、抑菌剂等作为其它辅助剂和添加剂。
适用作富脂剂的物质为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、甘油一酸酯和脂肪酸链烷醇酰胺,后者同时充当泡沫稳定剂。
合适的温和表面活性剂,即皮肤尤其好地耐受的表面活性剂的实例包括脂肪醇聚乙二醇醚硫酸盐、甘油一酸酯硫酸盐、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、脂肪酸牛磺酸盐、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物,后者优选基于小麦蛋白。
合适的珠光剂为例如:亚烷基二醇酯,尤其是乙二醇二硬脂酸酯;脂肪酸链烷醇酰胺,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羧酸与具有6-22个碳原子的脂肪醇的酯,尤其是酒石酸的长链酯;脂肪物质,例如脂肪醇、脂肪酮、脂肪醛、脂肪醚和脂肪碳酸酯,其总计具有至少24个碳原子,尤其是月桂酮和二硬脂基醚;脂肪酸,例如硬脂酸、羟基硬脂酸或山萮酸、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个羟基的多元醇的开环产物,及其混合物。
合适的稠度调节剂尤其是具有12-22个碳原子,优选16-18个碳原子的脂肪醇或脂肪醇,以及另外偏甘油酯、脂肪酸和羟基脂肪酸。优选这类物质与烷基低聚葡糖苷和/或相同链长的脂肪酸N-甲基葡糖酰胺和/或聚甘油聚-12羟基硬脂酸酯的组合。合适的增稠剂包括例如Aerosil类型(亲水性硅酸),多糖,尤其是黄原酸胶、瓜尔胶、琼脂、藻酸盐和甲基纤维素、羧甲基纤维素和羟甲基纤维素,以及脂肪酸的相对高分子量聚乙二醇单酯或二酯、聚丙烯酸酯(例如来自Goodrich的或来自Sigma的)、聚丙烯酰胺、聚乙烯催化和聚乙烯基吡咯烷酮,表面活性剂,例如乙氧基化脂肪酸甘油酯、脂肪酸与多元醇,例如季戊四醇或三甲基丙烷的酯、具有有限同系物分布的脂肪醇乙氧基化物和烷基低聚葡糖苷以及电解质,例如氯化钠或氯化铵。
合适的阳离子聚合物为例如阳离子纤维素衍生物,例如可以以名称JR 由Amerchol得到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,例如月桂基二胺羟丙基水解胶原(L/Grünau),季铵化小麦多肽,聚乙烯亚胺,阳离子聚硅氧烷聚合物,例如酰氨基聚二甲基硅氧烷,己二酸和二甲基氨基羟丙基二亚乙基三胺的共聚物(/Sandoz),丙烯酸与二甲基二烯丙基氯化铵的共聚物(550/Chemviron),聚氨基聚酰胺,如例如FR-A-2 252 840所述,及其交联水溶性聚合物,阳离子几丁质衍生物,例如任选作为微晶分布的季铵化脱乙酰壳多糖;二卤代烷基如二溴丁烷与双二烷基胺如双二甲基氨基-1,3-丙烷的缩合产物,阳离子瓜尔胶,例如来自Celanese的C-17、C-16,季铵化铵盐聚合物,例如来自Miranol的A-15、AD-1、AZ-1。
合适的阴离子、两性离子、两性和非离子聚合物为例如乙酸乙烯酯/ 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/丙烯酸异冰片基酯共聚物、甲基乙烯基醚/马来酸酐共聚物及其酯、未交联聚丙烯酸和与多元醇交联的聚丙烯酸、丙烯酰氨丙基三甲基氯化铵/ 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酯/甲基丙烯酸2-羟基丙酯共聚物、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/甲基丙烯酸二甲基氨基乙酯/乙烯基己内酰胺三元共聚物以及任选盐化的纤维素醚和聚硅氧烷。
合适的聚硅氧烷化合物为例如二甲基聚硅氧烷、甲基苯基聚硅氧烷、环状聚硅氧烷,以及氨基-、脂肪酸-、醇-、聚醚-、环氧基-、氟-、糖-和/ 或烷基改性聚硅氧烷化合物,其在室温下可以为液体或树脂形式。合适的还有有机硅树脂,其为具有200-300个二甲基硅氧烷单元的平均链长的聚二甲基硅氧烷与氢化硅酸盐的混合物。Todd等人给出的合适挥发性聚硅氧烷的详细调查还可在Cosm.Toil.91,27(1976)中找到。
脂肪的典型实例为甘油酯,并且作为蜡,尤其考虑蜂蜡、巴西棕榈蜡、褐煤蜡、石蜡、氢化蓖麻油和在室温下为固体的脂肪酸酯或微蜡,其任选与亲水性蜡,例如鲸蜡基硬脂醇或偏甘油酯组合。脂肪酸的金属盐,例如镁、铝和/或锌硬脂酸盐或蓖麻油酸盐可用作稳定剂。
生物源性活性成分应当理解意指例如生育酚、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、红没药醇、尿囊素、植烷三醇、泛酰醇、AHA酸、氨基酸、神经酰胺、假神经酰胺、精油、植物提取物和纤维素络合物。
合适的除臭活性成分为例如止汗药,例如水合氯化铝(参见J.Soc.Cosm.Chem.24,281(1973))。尤其优选对应于式Al2(OH)5Cl x 2.5H2O、已知并且以HoechstAG,Frankfurt(FRG)的商标市购的水合氯化铝(参见J.Pharm.Pharmacol.26,531(1975))。除水合氯化物外,也可使用羟基乙酸铝和酸性铝/锆盐。酯酶抑制剂可作为其它除臭活性成分加入。这类抑制剂优选为柠檬酸三烷基酯,例如柠檬酸三甲酯、柠檬酸三丙酯、柠檬酸三异丙基酯、柠檬酸三丁酯,尤其是柠檬酸三乙酯(CAT, Henkel KGaA,Düsseldorf/FRG),其抑制酶活性,因此降低气味形成。其它合适的酯酶抑制剂为甾醇硫酸酯或磷酸酯,例如羊毛甾醇、胆甾醇、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以及羟基羧酸及其酯,例如柠檬酸、苹果酸、酒石酸或酒石酸二乙酯。影响微生物菌丛并杀灭或抑制汗分解细菌生长的抗菌活性成分也可存在于制剂中(尤其是棒制剂中)。实例包括脱乙酰壳多糖、苯氧基乙醇和葡萄糖酸洗必泰。5-氯-2-(2,4-二氯苯氧基)-苯酚( BASF)也证明是尤其有效的。
常规成膜剂包括例如脱乙酰壳多糖、微晶脱乙酰壳多糖、季铵化脱乙酰壳多糖、聚乙烯基吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、包含高含量丙烯酸的季铵化纤维素衍生物的聚合物、胶原、透明质酸及其盐和类似的化合物。用于水相的合适溶胀剂为蒙脱石、粘土矿物质、Pemulen 以及烷基改性类型的Carbopol(Goodrich)。其它合适的聚合物和溶胀剂可由R.Lochhead汇总于Cosm.Toil.108,95(1993)中。
为改进流动行为,也可使用水溶助长剂,例如乙醇、异丙醇或多元醇。用于该目的的合适多元醇优选包含2-15个碳原子和至少2个羟基。
多元醇还可包含其它官能团,尤其是氨基,和/或可用氮改性。典型的实例如下:
-甘油;
-亚烷基二醇,例如乙二醇、二甘醇、丙二醇、丁二醇、己二醇以及具有 100-1000道尔顿的平均分子量的聚乙二醇;
-具有1.5-10的本征缩合度的工业级低聚甘油混合物,例如具有40-50重量%的双甘油含量的工业级双甘油混合物;
-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,尤其是烷基中具有1-8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,例如山梨糖醇或甘露糖醇;
-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。
合适的防腐剂包括例如苯氧基乙醇、甲醛溶液、羟苯酯、戊二醇或山梨酸和theCosmetics Regulations的Schedule 6,Parts A和B中列出的其它物质类别。
合适的芳香油为天然和/或合成芳族物质的混合物。天然芳族物质的代表为例如来自花(百合、熏衣草、玫瑰、茉莉、橙花、依兰)、叶(天竺葵、广藿香、橙叶)、果实(大茴香、胡荽、Carraway、刺柏)、果皮(香柠檬、柠檬、橙)、根(肉豆蔻、当归、芹菜、小豆蔻、闭鞘姜、鸢尾、Calmus)、木(松木、白檀、愈创木、柏木、蔷薇木)、药草和禾草(龙嵩、柠檬草、鼠尾草、百里香)、针状物和嫩枝(云杉、松树、欧洲赤松、山松)、树脂和香液(白松香、榄香、安息香、没药树、乳香、红没药)的提取物。还考虑动物原料,例如麝猫香或海狸香。典型的合成芳族物质为例如酯、醚、醛、酮、醇或烃类型的产物。
酯类型的芳族物质化合物为例如乙酸苄基酯、异丁酸苯氧基乙酯、乙酸对-叔丁基环己基酯、乙酸里哪酯、乙酸二甲基-苄基原酯、乙酸苯基乙酯、苯甲酸里哪酯、甲酸苄基酯、甘氨酸乙基甲基苯基酯、丙酸烯丙基环己基酯、丙酸苏合香酯和水杨酸苄基酯。醚包括例如苄基乙基醚;醛包括例如具有8-18个烃原子的线性醛、柠檬醛、香茅醛、香茅氧基乙醛、兔耳草醛、羟基香茅醛、铃兰醛和对叔丁基苯丙醛(bourgeonal);酮包括例如紫罗酮、α-异甲基紫罗酮和甲基柏木酮;醇包括例如乙醇、茴香脑、香茅醇、丁子香酚、异丁子香酚、香叶醇、里哪醇、苯乙醇和萜品醇;烃主要包括萜烯和香液。然而,优选使用一起产生迷人气味的各种芳族物质的混合物。主要用作芳香组分的较低挥发度的醚醛油也适用作芳香油,例如鼠尾草油、春黄菊油、丁香油、蜂花油、肉桂叶的油、莱姆花油、杜松子油、岩兰油、乳香油、格蓬油、Labolanum oil和杂薰衣草油。优选使用单独或相互的混合物的香柠檬油、二氢月桂烯醇、铃兰醛、新铃兰醛、香茅醇、苯乙醇、α- 己基肉桂醛、香叶醇、苄基丙酮、兔耳草醛、里哪醇、龙涎木香、龙涎呋喃、吲哚、二氢茉莉酮酸甲酯、Sandelice、柠檬油、红桔油、橙油、羟乙酸烯丙基戊基酯、Cyclovertal、杂薰衣草油、紫鼠尾草油、β-大马酮、波旁天竺葵精油、水杨酸环己基酯、vertofix coeur、iso-E-Super、Fixolide NP、 evernyl、iraldein gamma、苯乙酸、乙酸香叶酯、乙酸苄酯、氧化玫瑰、 romillat、irotyl和floramat。
容许用于化妆品目的的合适着色剂例如公开于the Farbstoffkom- mission derDeutschen Forschungsgemeinschaft的“Kosmetische”,Verlag Chemie,Weinheim,1984,第81-106页。着色剂通常以基于总混合物0.001-0.1重量%的浓度使用。
抑菌剂的典型实例为对革兰氏阳性菌具有特殊作用的防腐剂,例如 2,4,4'-三氯-2'-羟基二苯醚、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)。
大量芳族物质和醚醛油也具有抗菌性能。典型的实例为丁香油、薄荷油和百里香油中的活性成分丁子香酚、薄荷醇和麝香草酚。有意义的天然除臭剂为萜烯醇法呢醇(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。甘油单月桂酸酯也证明是抗菌剂。存在的其它抑菌剂的量基于本发明化妆品组合物的固体含量通常为0.1-2重量%。
此外,本发明化妆品组合物可包含消泡剂,例如聚硅氧烷,表面活性剂,例如马来酸,增溶剂,例如乙二醇、丙二醇、甘油或二甘醇,遮光剂,例如胶乳、苯乙烯/PVP或苯乙烯/丙烯酰胺共聚物,络合剂,例如EDTA、 NTA、β-丙二酸二乙酸或膦酸,推进剂,例如丙烷/丁烷混合物、N2O、二甲醚、CO2、N2或空气,所谓的耦合剂和显影剂组分,例如氧化染料前体、硫代羟基乙酸及其衍生物、硫代乳酸、半胱胺、硫代苹果酸或作为还原剂的α-巯基乙烷磺酸或过氧化氢、作为氧化剂的溴酸钾或溴酸钠作为辅助剂。
昆虫驱避剂为例如N,N-二乙基-间-甲苯酰胺、1,2-戊二醇或昆虫驱避剂 3535。
合适的自美黑剂为二羟基丙酮、赤藓酮糖或者二羟基丙酮和赤藓酮糖的混合物。
本发明化妆品配制剂包含在多种化妆品制剂,尤其是以下制剂中:
-皮肤护理制剂,例如护肤乳液、多重乳液或护肤油;
-化妆品个人护理制剂,例如日霜或粉霜形式的面部粉底,扑面粉(疏松或压实的)、口红或粉底霜,眼部护理制剂,例如眼影制剂、睫毛膏、眼线笔、眼霜或眼部精华霜;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、指甲硬化剂或去指皮水;
-光保护制剂,例如防晒乳、洗液、霜或油、防晒霜或tropicals、美黑前制剂或晒后制剂;
-皮肤美黑制剂,例如自美黑霜;
-脱色制剂,例如用于漂白皮肤的制剂或皮肤增亮制剂;
-昆虫驱避剂,例如驱虫油、洗液、喷剂或棒。
最终配制剂可以以多种呈现形式存在,例如:
-液体制剂的形式,如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、双、乳或洗液的形式,
-粉、清漆、片剂或粉底的形式,
-棒的形式,
-喷剂(具有推进剂气体的喷剂或泵作用喷剂)或气溶胶的形式,
-泡沫的形式,或者
-糊的形式。
重要的皮肤用化妆品组合物为光保护制剂,例如防晒乳、洗液、霜、油、防晒霜或Tropicals、美黑前制剂或晒后制剂,以及皮肤美黑制剂,例如自美黑霜。特别有意义的是防晒霜、防晒露、防晒油、防晒乳和喷剂形式的防晒制剂。
A.本发明UV过滤剂和UV过滤剂组合的实施例
方法
防晒霜的光谱透射率T(λ)的计算
为计算具有给定过滤剂组合物的防晒霜的光谱透射率T(λ),使用模拟工具。该工具基于以下元件:具有相关UV过滤剂的UV光谱的数据库(作为十摩尔消光系数给出),皮肤上的防晒霜膜的不规则性轮廓的数学描述,考虑由于光不稳定性导致的UV过滤剂浓度的变化,和考虑配制影响如乳液的油和水相中的UV过滤剂分布。
SPF(红斑衰减)和前维生素D形成的衰减因数AFvd的测定
从科学文献中已知整体暴露于1MED红斑辐射暴露(最小红斑剂量,这是24小时暴露以后UV-B辐射的最小量)=250J/m2红斑辐射暴露等于约 10,000IU维生素D3的口服吸收。对于最大太阳输入(根据COLIPA,无云天空最高点的太阳),接收1MED耗费约20分钟。推荐的维生素D3吸收量为1,000-4,000IU/天。DGE(Deutsche Gesellschaft für2011) 推荐2000IU/天的日常供应。该推荐涉及例如由于不暴露于UV辐射导致的内生/表皮维生素D3产量缺乏。该量的维生素D3可在未保护皮肤暴露于上述最大太阳输入的条件下f20/5=4分钟以后在皮肤中产生。防晒霜削弱了红斑辐射和维生素D3-有效辐射。
MED=最小红斑剂量=在暴露以后24小时在皮肤上产生首次泛红的 UVB辐射的最小量[J/m2]=250J/m2红斑辐射(标准值)1IU=25ng Vit D3。
SPF根据下式计算:
类似于SPF,维生素D3-有效辐射的衰减因数AFPVD定义为:
Eλ(λ)光谱太阳辐射,
T(λ)给定防晒霜的光谱透射率,且二者:
ser(λ)红斑的作用光谱
spvd(λ)皮肤中维生素D3形成的作用光谱。
使用BASF Sunscreen Simulator计算Eer、EVD、EVD/Eer、SPF、AFVD: (www.basf.com/ sunscreensimulator;Herzog,B.;Osterwalder,U.In Silico Determination of TopicalSun Protection.Cosm Sci Tech.2011;62:1-8。
当受保护的皮肤暴露于上述最大太阳输入时,用或不用防晒霜产生相同量的2,000IU推荐维生素D3吸收量的暴露时间tPVD为:
关于一些防晒霜实施例的衰减因数AFPVD和暴露时间tPVD在表4中给出。
选择过滤剂组合物的实例以实现6、15和30的防晒因子(缩写为SPF)。结果:
实施例A1:SPF 6防晒霜
表1显示如上文所解释的4种SPF 6防晒霜的组成以及SPF计算值、 Epvd/Eer比、UVA-PF、UVA-PF/SPF比和临界波长CW。
图2显示涉及导致SPF 6的四种不同类型的UV过滤剂组合物的防晒膜的光谱透射率。
实施例A2:SPF 15防晒霜
表2显示4种SPF 15防晒霜的组成以及SPF计算值、Epvd/Eer比、 UVA-PF、UVA-PF/SPF比和临界波长CW。
在图3中,描述了涉及导致SPF 15的四种不同类型的UV过滤剂组合物的防晒霜膜的模拟光谱透射率。
实施例A3:SPF 30防晒霜
表3显示4种SPF 30防晒霜的组成以及SPF计算值、Epvd/Eer比、 UVA-PF、UVA-PF/SPF比和临界波长CW。
图4显示涉及导致SPF 30的四种不同类型的UV过滤剂组合物的防晒霜膜的模拟光谱透射率。
实施例A3.3和A3.4证明可使防晒霜关于维生素D3-有效辐射的透射率最佳化,即使SPF是相同的。
实施例A4:维生素D/天的推荐量的测定
当受保护的皮肤暴露于上述最大太阳输入时,获得2000IU/天的推荐维生素D吸收量的暴露时间tPVD为:
tPVD=4×AFPVD分钟
关于4个防晒霜实施例的衰减因数AFPVD和暴露时间tPVD在表4中给出。
用例如具有SPF=30的防晒霜的日光暴露的暴露时间tPVD为在日光浴者的通常时帧内约2小时。因此,它实际上对使防晒霜在低衰减因数AFPVD方面最佳化而言是有意义的。
B.化妆品配制剂的实施例
配制剂如下制备:制备部分A和B并分别加热至80℃。然后在搅拌下将部分A加入部分B中。在短暂均化以后,在搅拌下加入部分C。在冷却至室温以后,将部分D的成分以所列顺序加入。
配制剂如下制备:将部分A加热至80℃,冷却至室温并在搅拌下结合到部分B中。在均化(用ultra-turrax型装置)以后,加入部分C,其后再次均化。最后加入部分D的成分并将配制剂再次均化。
配制剂如下制备:制备部分A和B并分别加热至80℃。然后在搅拌下将部分A加入部分B中。在短暂均化以后,在搅拌下加入部分C。在冷却至室温以后,将部分D的成分以所列顺序加入。
配制剂如下制备:制备部分A和B并分别加热至80℃。然后在搅拌下将部分A加入部分B中。在短暂均化以后,在搅拌下加入部分C。在冷却至室温以后,将部分D的成分以所列顺序加入。
配制剂如下制备:制备部分A和B并分别加热至80℃。然后在搅拌下将部分A加入部分B中。在短暂均化以后,在搅拌下加入部分C。在冷却至室温以后,将部分D的成分以所列顺序加入。
配制剂如下制备:制备部分A和B并分别加热至80℃。然后在搅拌下将部分A加入部分B中。在短暂均化以后,在搅拌下加入部分C。在冷却至室温以后,将部分D的成分以所列顺序加入。
Claims (18)
1.防晒配制剂,其包含至少一种选自如下的UV过滤剂(A):
(a)三嗪衍生物;
(b)肉桂酸衍生物;
(c)双间苯二酚基三嗪;
(f)苯并咪唑衍生物;
(i5)4-甲基亚苄基樟脑;
(h)苯甲酰哌嗪衍生物;
(k)二芳基丁二烯衍生物;
(l)苯基苯并三唑衍生物;
(n)亚苄基丙二酸酯;
(o3)水杨酸三乙醇胺;
(r)咪唑啉衍生物;
(u)选自金属氧化物的无机UV过滤剂;
(v)萘二甲酸酯;和
(w)部花青衍生物;且
任选包含至少一种选自如下的UV过滤剂(B):
(d)氨基二苯甲酮衍生物;
(e)二苯甲酰甲烷衍生物;
(g)β,β-二苯基丙烯酸酯衍生物;
(i5)不同于的樟脑衍生物;
(o3)不同于的水杨酸酯衍生物;
(p)邻氨基苯甲酸酯衍生物;和
(s)亚苄基丙二酸酯衍生物;
其中:
-前维生素D3形成的有效辐照度Epvd与皮肤上红斑形成的有效辐照度Eer之比R为至少1.8,
其用于提高UV辐射在人体皮肤上的透射率以产生胆钙化醇(前维生素D3),同时用于在暴露于太阳时保护人体皮肤以防UV辐射的方法中,所述方法包括将所述防晒配制剂应用于皮肤。
2.根据权利要求1的防晒配制剂,其中防晒配制剂具有至少2的SPF。
3.根据权利要求1的防晒配制剂,其中防晒配制剂具有至少6的SPF。
4.根据权利要求1-3中任一项的防晒配制剂,其中UV过滤剂选自:
(a1)乙基己基三嗪酮;
(a2)三-联苯三嗪;
(a3)二乙基己基丁酰氨基三嗪酮;
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(c2)双-乙基己氧基苯酚甲氧基苯基三嗪/聚甲基丙烯酸甲酯的水分散体;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(e1)丁基甲氧基二苯甲酰甲烷;
(f1)苯基苯并咪唑磺酸;
(f2)苯基二苯并咪唑四磺酸二钠;
(g1)奥克立林;
(h1)1,4-(2-(4-二乙基氨基-2-羟基苯甲酰)苯甲酰)哌嗪;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(l2)甲酚曲唑三硅氧烷;
(l6)2-(2H-苯并三唑-2-基)-6-(2-乙基己氧基甲基)-4-甲基-苯酚;
(i1)对苯二亚甲基二樟脑磺酸;
(n1)式(BM9)的化合物;
(o1)水杨酸乙基己酯;
(o4)胡莫柳酯;
(p1)邻氨基苯甲酸薄荷酯;
(s1)聚硅氧烷-15;
(u1)氧化锌;和
(u3)二氧化钛。
5.根据权利要求1-4中任一项的防晒配制剂,其中UV过滤剂选自:
(a1)乙基己基三嗪酮;
(b1)甲氧基肉桂酸乙基己酯;
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(e1)丁基甲氧基二苯甲酰甲烷;
(f1)苯基苯并咪唑磺酸;
(g1)奥克立林;和
(u3)二氧化钛。
6.根据权利要求1-5中任一项的防晒配制剂,其中UV过滤剂选自:
(b1)甲氧基肉桂酸乙基己酯;
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯,
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚,
(e1)丁基甲氧基二苯甲酰甲烷;
(f1)苯基苯并咪唑磺酸;和
(g1)奥克立林。
7.根据权利要求1-6中任一项的防晒配制剂,其中UV过滤剂选自:
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;和
(e1)丁基甲氧基二苯甲酰甲烷。
8.根据权利要求5-7中任一项的防晒配制剂,其中防晒配制剂具有至少6的SPF。
9.根据权利要求1-8中任一项的防晒配制剂,其中UV过滤剂选自:
(a)0.1-40%b.w.三嗪衍生物;
(b)0.1-30%b.w.肉桂酸衍生物;
(c)0.1-10%b.w.双间苯二酚基三嗪;
(f)0.1-10%b.w.苯并咪唑衍生物;
(i5)0.1-10%b.w.4-甲基亚苄基樟脑;
(h)0.1-10%b.w.苯甲酰哌嗪衍生物;
(k)0.1-20%b.w.二芳基丁二烯衍生物;
(l)0.1-30%b.w.苯基苯并三唑衍生物;
(n)0.1-20%b.w.亚苄基丙二酸酯;
(o3)0.1-15%b.w.水杨酸三乙醇胺;
(r)0.1-10%b.w.咪唑啉衍生物;
(u)0.1-50%b.w.选自金属氧化物的无机UV过滤剂;
(v)0.1-20%b.w.萘二甲酸酯;和
(w)0.1-20%b.w.部花青衍生物;且
任选包含至少一种选自如下的UV过滤剂(B):
(d)0.1-20%b.w.氨基二苯甲酮衍生物;
(e)0.1-5%b.w.二苯甲酰甲烷衍生物;
(g)0.1-1%b.w.β,β-二苯基丙烯酸酯衍生物;
(i)0.1-10%b.w.不同于(i5)的樟脑衍生物;
(o)0.1-35%b.w.不同于(o3)的水杨酸酯衍生物;
(p)0.1-10%b.w.邻氨基苯甲酸酯衍生物;和
(s)0.1-10%b.w.亚苄基丙二酸酯衍生物。
10.根据权利要求1-9中任一项的防晒配制剂,其中防晒配制剂包含选自如下的UV过滤剂:
(a1)1-3%b.w.乙基己基三嗪酮;
(b1)1-3.5%b.w.甲氧基肉桂酸乙基己酯;
(c1)0.6-10%b.w.双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)0.8-10%b.w.二乙氨基羟苯甲酰基苯甲酸己酯;
(e1)2-3%b.w.丁基甲氧基二苯甲酰甲烷;
(f1)2-3%b.w.苯基苯并咪唑磺酸;
(g1)2.0-2.5%b.w.奥克立林;
(l1)2-7.5%b.w.亚甲基双-苯并三唑基四甲基丁基苯酚;和
(u3)3.0-3.5%b.w.二氧化钛。
11.根据权利要求1-10中任一项的防晒配制剂,其中防晒配制剂包含如下的UV过滤剂组合:
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;和
(e1)丁基甲氧基二苯甲酰甲烷;
其中防晒配制剂具有>15的SPF。
12.根据权利要求1-10中任一项的防晒配制剂,其中防晒配制剂包含如下的UV过滤剂组合:
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;和
(e1)丁基甲氧基二苯甲酰甲烷;
其中防晒配制剂具有>30的SPF。
13.根据权利要求1-12中任一项的防晒配制剂,其中UV过滤剂选自宽带(340-400nm的光谱)UV过滤剂:
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(c2)双-乙基己氧基苯酚甲氧基苯基三嗪/聚甲基丙烯酸甲酯的水分散体;
(f2)苯基二苯并咪唑四磺酸二钠;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(l2)甲酚曲唑三硅氧烷;
(u1)氧化锌;和任选
(e1)丁基甲氧基二苯甲酰甲烷;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(i1)对苯二亚甲基二樟脑磺酸;和
(p1)邻氨基苯甲酸薄荷酯。
14.根据权利要求1-13中任一项的防晒配制剂,其包含选自如下的UV过滤剂:
(a)三嗪衍生物;
(b)肉桂酸衍生物;
(c)双间苯二酚基三嗪;
(f)苯并咪唑衍生物;
(h)苯甲酰哌嗪衍生物;
(i5)4-甲基亚苄基樟脑;
(l)苯基苯并三唑衍生物;
(n)亚苄基丙二酸酯;
(o3)水杨酸三乙醇胺;
(r)咪唑啉衍生物;
(u)选自金属氧化物的无机UV过滤剂;
(v)萘二甲酸酯;和
(w)部花青衍生物;
其中防晒配制剂仅包含所选择的UV过滤剂中的一种。
15.根据权利要求14的防晒配制剂,其中UV过滤剂选自宽带(340-400nm的光谱)UV过滤剂:
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(c2)双-乙基己氧基苯酚甲氧基苯基三嗪/聚甲基丙烯酸甲酯的水分散体;
(f2)苯基二苯并咪唑四磺酸二钠;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(i1)对苯二亚甲基二樟脑磺酸;和
(u1)氧化锌;
其中防晒配制剂仅包含所选择的UV过滤剂中的一种。
16.根据权利要求1-15中任一项的防晒配制剂,其中UV过滤剂选自颗粒UV过滤剂,所述颗粒UV过滤剂选自:
(a2)三-联苯三嗪;
(c2)双-乙基己氧基苯酚甲氧基苯基三嗪/聚甲基丙烯酸甲酯的水分散体;
(h1)1,4-(2-(4-二乙基氨基-2-羟基苯甲酰)苯甲酰)哌嗪;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(u1)氧化锌;和
(u3)二氧化钛。
17.根据权利要求1-15中任一项的防晒配制剂,其中UV过滤剂选自非颗粒UV过滤剂,所述非颗粒UV过滤剂选自:
(a1)乙基己基三嗪酮;
(a3)二乙基己基丁酰氨基三嗪酮;
(c1)双-乙基己氧基苯酚甲氧基苯基三嗪;
(d1)二乙氨基羟苯甲酰基苯甲酸己酯;
(e1)丁基甲氧基二苯甲酰甲烷;
(f1)苯基苯并咪唑磺酸;
(f2)苯基二苯并咪唑四磺酸二钠;
(g1)奥克立林;
(h1)1,4-(2-(4-二乙基氨基-2-羟基苯甲酰)苯甲酰)哌嗪;
(l1)亚甲基双-苯并三唑基四甲基丁基苯酚;
(l2)甲酚曲唑三硅氧烷;
(l6)2-(2H-苯并三唑-2-基)-6-(2-乙基己氧基甲基)-4-甲基-苯酚;
(i1)对苯二亚甲基二樟脑磺酸;
(n1)式(BM9)的化合物;
(o1)水杨酸乙基己酯;
(o4)胡莫柳酯;
(p1)邻氨基苯甲酸薄荷酯;和
(s1)聚硅氧烷-15。
18.根据权利要求1-17中任一项的防晒配制剂,其中维生素D形成的有效辐照度Epvd与皮肤上红斑形成的有效辐照度Eer之比为>2.0。
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PCT/EP2015/066985 WO2016012586A1 (en) | 2014-07-25 | 2015-07-24 | Sunscreen formulations optimized for the formation of vitamin d |
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WO2016037942A1 (en) * | 2014-09-09 | 2016-03-17 | Basf Se | Mixtures of cosmetic uv absorbers |
EP3458162B1 (en) * | 2016-05-19 | 2024-07-10 | Basf Se | Micro-particulate organic uv absorber composition |
DE102017213219A1 (de) * | 2017-08-01 | 2019-02-07 | Beiersdorf Ag | Sonnenschutzmittel mit geringen Augenreizungspotential |
CN108186389A (zh) * | 2018-03-01 | 2018-06-22 | 花安堂生物科技集团有限公司 | 一种复合防晒剂和由其组成的防晒组合物及其制备方法 |
JP7556850B2 (ja) * | 2018-10-05 | 2024-09-26 | ベーアーエスエフ・エスエー | 布帛汚れを低減するためのメチレンビス-ベンゾトリアゾリルテトラメチルブチルフェノール |
KR20210138668A (ko) | 2019-03-15 | 2021-11-19 | 바스프 에스이 | 디에틸아미노 히드록시벤조일 헥실 벤조에이트, 부틸 메톡시디벤조일메탄 및 유기 미립자 uv 필터를 갖는 효율적인 선스크린 조성물 |
US20220151896A1 (en) * | 2019-03-15 | 2022-05-19 | Basf Se | Efficient sunscreen compositions with diethylamino hydroxybenzoyl hexyl benzoate and organic particulate uv filter |
WO2020187762A1 (en) * | 2019-03-15 | 2020-09-24 | Basf Se | Efficient sunscreen compositions with diethylamino hydroxybenzoyl hexyl benzoate and butyl methoxydibenzoylmethane |
CN114746070A (zh) * | 2019-11-20 | 2022-07-12 | 科蒂公司 | 具有多种光防护uv滤光剂的防晒霜组合物 |
BR102021002817A2 (pt) * | 2020-02-21 | 2021-09-08 | Nouryon Chemicals International B.V. | Formulação anidra, formulação anidra de proteção solar, método de proteção de um usuário a ser exposto ou já exposto à luz solar dos efeitos prejudiciais da exposição à luz solar e método para impermeabilização de uma formulação anidra de proteção solar compreendendo pelo menos um agente ativo de proteção solar |
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