CN1110302C - 治疗皮肤病况的含氧酸及相关化合物 - Google Patents
治疗皮肤病况的含氧酸及相关化合物 Download PDFInfo
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- CN1110302C CN1110302C CN97195278A CN97195278A CN1110302C CN 1110302 C CN1110302 C CN 1110302C CN 97195278 A CN97195278 A CN 97195278A CN 97195278 A CN97195278 A CN 97195278A CN 1110302 C CN1110302 C CN 1110302C
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Abstract
本发明系关于使用下式(I)化合物作为活性成分来治疗皮肤病况的用途;含此类化合物的组合物;及使用此类化合物及组合物治疗皮肤病况的方法。其中,R4为(CR5R6-CR7R8-X1)n-CR9R10R11;n可为1至18的整数;R1、R2、R3、R5、R6、R7、R8、R9、R10及R11各自为氢或非氢的取代基;而X、X1、Y及Z各自为O。
Description
相关的申请
此申请为申请号N0.08/658,089(申请日期1996年6月4日)的部份接续申请。
发明背景
I.发明领域
本发明系关于一种可作为局部治疗皮肤病况的活性成分的新颖化合物、含此类化合物的组合物及用此类化合物和组合物治疗皮肤病况的方法。此类的化合物包括式(I):
其中,R4为(CR5R6-CR7R8-X1)n-CR9R10R11;n是1至18的整数;R1、R2、R3、R5、R6、R7、R8、R9、R10及R11各自为氢或非氢的取代基,其中优选的非氢的取代基包括:烷基、烯基、氧杂-烷基、芳烷基及芳基;而X、X1、Y及Z各自为O、NH或S,其中优选的化合物包括X、X1、Y及Z各为氧及R1、R2、R3、R5、R6、R7、R8、R9、R10及R11各自为氢的化合物。
II.现有技术的描述
使用于皮肤的α羟基酸(全部具碳原子骨架)已描述于U.S.专利No.5,091,171。使用于化妆品的2-羟基烯酸组合物也经揭示、例如U.S.专利No.5,108,751。此化合物在碳原子骨架上必须具有未取代的α羟基,并且可能对皮肤有益。但是使用此α羟基酸的趋势逐渐变弱,因为它们需要低的操作pH范围,对于最常见的化合物(即乙醇酸及乳酸)来说,这会引起皮肤疼痛。
因此曾提出过以含全部碳原子的直链二羧酸取代α羟基酸作为局部配方的建议。例如:U.S.专利Nos.4,292,326、4,386,104及5,385,943描述使用7至13个碳原子的二羧酸来治疗各种皮肤病症。U.S.专利No.4,885,282也曾类似地描述用4至18个碳原子的二羧酸化合物来治疗皮肤病症。
使用此类二羧酸的问题是其不溶于水溶液。而化妆用的传递系统是以水溶液为主。同时,全部含碳原子的二羧酸在常温下为固体,极难操作;若配制成溶液,以审美学上的观点而言此混合物也不适于化妆的用途。
因此需要一种化合物或一种类型的化合物进行温和的剥落活化,以便能局部的治疗皮肤。
也需要一种温和剥落的局部组合物,该组合物含水溶性化合物,能应用于制造审美学上可接受的化妆用的或皮肤学的产品。
发明概要
本发明的目的是提供一种水溶性化合物或一种类型的此类化合物,能用于生产审美学上可接受的温和剥落的组合物,以作为局部的使用。
本发明的另一目的是提供含此水溶性化合物的局部用组合物,具有多重护肤功能。
本发明进一步的目的是对于含氧酸来说提供一种新的,皮肤学及化妆用途。
此类及其他的目的将会在以下的揭示中一一证实。
发明的详细描述
本发明的基本化合物是以下式(I)的化合物:其中,R4为(CR5R6-CR7R8-X1)n-CR9R10R11;n是1至18的整数;R1、R2、R3、R5、R6、R7、R8、R9、R10及R11各自为氢或非氢的取代基。
X、X1、Y及Z各自为O、NH或S。优选的此类化合物:其X、X1、Y及Z全为氧。最优选的此类化合物:其X、X1、Y及Z各为氧,且R1、R2、R3、R5、R6、R7、R8、R9、R10及R11各为氢。
优选的非氢取代基包括:烷基、烯基、氧杂烷基、芳烷基及芳基。非氢的取代基的实例包括:甲基、乙基、丙基、异丙基、丁基、异丁基、己基、庚基、辛基、壬基、十二基、甲氧基、乙氧基、丙氧基、丁氧基、环己烯基、羟甲基、羟乙基、羟丙基、环丁基及环己基。
式(I)化合物的实例包括:3,6-二氧杂庚酸(CH3-O-CH2-CH2-O-CH2-COOH);7,7-二甲基-3,6-二氧杂庚酸((CH3)2CH-O-CH2-CH2-O-CH2-COOH);3,6-二氧杂庚酸乙基酯(CH3-O-CH2-CH2-O-CH2-COOC2H5);3,6-二氧杂庚酰胺(CH3-O-CH2-CH2-O-CH2-CONH2);3,6-二氧杂庚酸十二碳烷基酯(CH3-O-CH2-CH2-O-CH2-COOC12H25);2-苯基-3,6-二氧杂庚酸(CH3-O-CH2-CH2-O-CH(Phe)-COOH);2-苄基-3,6-二氧杂庚酸(CH3-O-CH2-CH2-O-CH(CH2Phe)-COOH);2-甲基-3,6-二氧杂庚酸(CH3-O-CH2-CH2-O-CH(CH3)-COOH);3-氨基-6-氧杂庚酸(CH3-O-CH2-CH2-NH-CH2-COOH);3,6,9-三氧杂癸酸(CH3-O-CH2-CH2-OCH2-CH2-O-CH2-COOH);2-苯基-3,6,9-三氧杂癸酸(CH3-O-CH2CH2-O-CH2-CH2-O-CH(Phe)-COOH);2-苄基-3,6,9-三氧杂癸酸(CH3-O-CH2-CH2-O-CH2-CH2-O-CH(CH2-Phe)-COOH);2-癸基-3,6,9-三氧杂癸酸(CH3-O-CH2-CH2-O-CH2-CH2-O-CH(C10H21)-COOH);3,6,9,12-四氧杂十三碳烷酸(CH3-O-CH2-CH2-O-CH2-CH2-O-CH2CH2-O-CH2-COOH);3,6,9,12,15-五氧杂十六酸(CH3-O-CH2-CH2-O-CH2-CH2-O-CH2-CH2-O-CH2-CH2-O-CH2-COOH);2-甲基-3,6,9-三氧杂癸酸(CH3-O-CH2-CH2-O-CH2-CH2-O-CH(CH3)-COOH);10,10-二甲基-3,6,9-三氧杂癸酸((CH3)2CH-O-CH2-CH2-O-CH2-CH2-O-CH2-COOH);2-乙基-3,6,9,12-四氧杂十三碳烷酸(CH3-O-CH2-CH2-O-CH2-CH2-O-CH2-CH2-O-CH(C2H5)-COOH);10-苯基-3,6,9-三氧杂癸酸(Phe-CH2-O-CH2-CH2-O-CH2-CH2-O-CH2-COOH);3,6,9-三氧杂癸酸乙基酯(CH3-O-CH2-CH2-O-CH2-CH2-O-CH2-COOC2H5);3,6,9-三氨基癸酸(CH3-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-COOH);3,6,9,12-四氨基十三碳烷酸(CH3-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-COOH);9-氨基-3,6-二氧杂癸酸(CH3-NH-CH2-CH2-O-CH2-CH2-O-CH2-COOH);6,9-二氨基-3-氧杂癸酸(CH3-NH-CH2-CH2-NH-CH2-CH2-O-CH2-COOH);3,6,9-三硫代癸酸(CH3-S-CH2-CH2-S-CH2-CH2-S-CH2-COOH);9,12-二硫代-3,6-二氧杂十三碳烷酸(CH3-S-CH2-CH2-S-CH2-CH2-O-CH2-CH2O-CH2-COOH);9-氨基-3,6-二氧杂癸酸单酰胺(CH3-NHCH2-CH2-O-CH2-CH2-O-CH2-CONH2);3,6,9-三氧杂癸酸单酰胺(CH3-O-CH2-CH2-O-CH2-CH2-O-CH2-CONH2);10,10-二甲基3,6,9-三氧杂癸酰胺((CH3)2CH-O-CH2-CH2-O-CH2-CH2-O-CH2CONH2);10,10-二甲基-3,6,9-三氧杂癸酸乙基酯((CH3)2CH-O-CH2-CH2-O-CH2-CH2-O-CH2-COOC2H5);10,10-二甲基-3,6,9-三氧杂癸酸十七烷基酯((CH3)2CH-O-CH2-CH2-O-CH2-CH2-O-CH2-COOC17H35);及10,10-二甲基-3,6,9-三氧杂癸酸((CH3)2-CH-O-CH2-CH2-O-CH2-CH2-O-CH(CH3)-COOH)。
式(I)化合物是制作环氧树脂固化剂及硬化剂时的中间物,参见U.S.专利N0s.5,017,675及5,319,004,以上二专利转让给Hoechst AG.。德国专利申请公开N0.DE-A-2936123描述了制备此环氧树脂的中间化合物。此化合物也可购自Hoechst AG。
式I化合物可用市售的聚胺、聚醇及聚硫醇通过本领域熟练技术人员熟知的常规化学反应制备,例如:酰胺化反应、催化氧化反应、酯化反应及其他已知的有机化学合成方法,如描述于有机化学教科书,包括:March,高等有机化学:反应、机理及结构(
Advanced Organic Chemistry:Reactions,Mechanisms and Structure),3rd.,ed.,JohnWiley Interscience(1985)及Carey等高等有机化学(
Advanced Organic Chemistry),3rd ed.,Parts A和B,Plenum Press,New York(1990)。
可用于局部的本发明组合物的含氧酸化合物也可为衍生物的形式,该形式的衍生物可经皮肤上的水解酶(例如糖苷酶、磷酸酯酶、酯酶及酰胺酶)的作用转变回酸性的形式。适用的衍生物的实例包括:式I化合物与脂族醇的酯类、碳水化合物、酰胺、内酯及酐。
本文中式(I)化合物及其衍生物,统称为“含氧酸”及/或“氧杂化合物”及/或“含氧酸化合物”。
“局部施用”指直接涂敷或涂抹在皮肤表面。“局部用组合物”指意欲直接涂敷或涂抹在皮肤表面上的组合物。“有效量”指足以使被治疗皮肤病况(例如:归因于、伴随着异常的脱皮或由异常脱皮引起恶化的病况)起正性变化(例如:脱皮正常化)的化合物或组合物的含量。“生理学上可接受的载体”或“适当的局部用载体”指药品、化妆用品、药剂、或惰性成分,它们适于直接与人类的组织接触而不致引起不希望的毒性。所有的百分比指占有局部用组合物总重量的重量百分比。
根据本发明,将氧杂化合物作为活性成分而施用在局部治疗各种归因于、伴随异常脱皮或由异常脱皮引起恶化的皮肤病况。此病症包括(但非限于)皮肤干燥、鱼鳞癣、手掌及足底的皮肤角化过度、头皮屑、单纯慢性苔藓、毛囊角化病、角化病、雀斑、老人斑、黑斑病、瘢点的皮肤、粉刺、牛皮癣、湿疹、瘙痒、发炎性皮肤病、膨胀性萎缩纹(Striae distensae)(即扩张斑纹)、疣及老茧(calluses)。
出乎预料和令人惊奇地发现此化合物可作为活性剂用于局部用制剂中以治疗皮肤老化(光老化及内生性老化)的前兆包括:皮肤皱纹例如眼部细纹或“鱼尾纹”或嘴部细纹、不规则的色素沉淀、皮肤灰黄、皮肤失去弹性及张力。
含氧杂化合物及含其的局部用组合物也可用于治疗与指甲、表皮及毛发相关的病症,例如向内生长毛发、毛囊炎及假性毛囊炎。本化合物也可软化毛发以及加速消除毛发的向内生长,因此式(I)化合物也可作为刮胡子用组合物。
此氧杂化合物能以自由酸的形式或以与有机或无机碱(例如:三乙醇胺、精氨酸、赖氨酸、氢氧化钾、氢氧化钠、氢氧化锂及氢氧化铵)中和而形成相应盐的形式加入组合物。
在与生理学上可接受的载体组合而形成局部用组合物时,含氧酸化合物的有效量介于大约0.1%至大约95%之间。有效量及施用频率随受治疗的特定肤病况、患者年龄及身体状况、、病症的严重性、治疗时间、其他共同治疗的特性、所使用的特定化合物或组合物、运送化合物或组合物的特定载体、及其他本领域熟练技术人员所知的类似因素而异。
含氧酸化合物治疗皮肤病况的药效会受组合物pH影响。因此据信需要将组合物的pH维持在酸性范围pH<7.0,优选pH<5.0,最优选pH介于3.5及4.0之间。组合物的pH可用由强碱(例如:KOH、NaOH、NHOH)及弱酸(例如:磷酸、乙酸、乳酸、碳酸)所形成的水溶性盐来调节。此盐的实例包括:磷酸氢钾、磷酸钠、乙酸钠、乳酸钠等。其他用于调整局部组合物pH的方法也为本领域熟练技术人员所熟知。
本发明的组合物与α羟基酸配方相比具有明显优点,其中包括温和性优异。含有α羟基的配方(例如:乙醇酸及乳酸)在施用于颜面时会引起某些人不适及在其他人的皮肤上严重刺激。与乙醇酸配方比较,本发明的含氧酸组合物对皮肤非常温和,但是对上层角质层脱皮的正常化非常有效。比正常化是减轻上述的皮肤病况所必需的。
本发明的局部组合物优于含二羧酸组合物之处包括:优选的水溶性及优异的角质层脱皮活性。含氧酸可以至少为重量的20至30%的浓度轻易溶于水。因此含氧酸在组合物中的含量较具弹性。二羧酸为中至长链的直链全碳骨架,因此几近于不溶于水及其他审美学上可接受的载体。此特性严重限制了二羧酸运送载体的选择。二羧酸的脱皮活性也值得怀疑。例如,测试含5%及10%十二烷二酸的配方表明,对角质层脱皮的正常化效用与单独使用载体差不多。
能适当与含氧酸共同使用的某些特定载体的实例包括:
(1)(a)大约2重量%至大约10重量%甘油,(b)大约1重量%至大约10重量%丙二醇,(c)大约0.1重量%至大约2重量%羟乙基纤维素,(d)大约0.1重量%至大约1重量%咪唑烷基脲,及(e)大约0.01重量%至大约2重量%EDTA二钠;
(2)(a)大约1重量%至大约10重量%甘油,(b)大约1重量%至大约10重量%丙二醇,(c)大约1重量%至大约10重量%棕榈酸辛基酯,(d)大约1重量%至大约10重量%肉豆蔻酸肉豆蔻基酯,(e)大约1重量%至大约6重量%鲸蜡硬脂醇(cetearyl alcohol/西塔瑞(Ceteareth)-20,(f)大约0.5重量%至大约6重量%单硬脂酸甘油酯,(g)大约0.1重量%至大约2重量%羟乙基纤维素,(h)大约0.1重量%至大约1重量%咪唑烷基脲,(i)大约0.05重量%至大约0.5重量%对羟基苯甲酸甲酯(methylparaben),及(i)大约0.01重量%至大约2重量%EDTA二钠;及
(3)(a)大约2重量%至大约10重量%甘油,(b)大约1重量%至大约10重量%棕榈酸辛基酯,(c)大约1重量%至大约10重量%肉豆蔻酸肉豆蔻基酯,(d)大约1重量%至大约7重量%鲸蜡硬脂醇(cetearylalcohol)/西塔瑞(Ceteareth)-20,(e)大约1重量%至大约10重量%丙二醇,(f)大约1重量%至大约6重量%单硬脂酸甘油基酯,(g)大约0.1重量%至大约2重量%羟乙基纤维素,(h)大约0.1重量%至大约1重量%咪唑烷基脲,(i)大约0.05重量%至大约0.5重量%对羟基苯甲酸甲酯,及(i)大约0.01重量%至大约2重量%EDTA二钠。
本发明的局部用组合物可作成洗液。一种第一或较基本的的洗液含有的含氧酸大约在0.1重量%至大约90重量%,优选大约1重量%至大约50重量%,而最优选大约5重量%至大约20重量%;其余的部分是水。一种第二洗液含有的含氧酸大约在0.1重量%至大约90重量%,优选大约1重量%至大约50重量%,而最优选大约5重量%至大约20重量%;含有润肤剂大约0.5重量%至大约50重量%;乳化剂大约0.1重量%至大约30重量%;而其余的部分是水。第二洗液也可含保存剂多至大约10重量%;芳香剂大约0.1重量%至大约3重量%;及染料或颜料多至大约5重量%。
本发明的局部用组合物也可配制成乳膏。一种第一或较基本的乳膏所含的含氧酸大约0.1重量%至大约95重量%,优选大约1重量%至大约50重量%,而最优选大约5重量%至大约20重量%;所含的润肤剂大约0.5重量%至大约50重量%;所含的增稠剂大约0.1重量%至大约6重量%;而其余的部分是水。一种第二的较佳乳膏所含的含氧酸大约0.1重量%至大约90重量%,优选大约1重量%至大约50重量%,而最优选大约5重量%至大约20重量%;所含的润肤剂大约0.5重量%至大约50重量%;所含的乳化剂大约0.1重量%至大约30重量%;所含的增稠剂大约0.1重量%至大约6重量%;而其余的部分是水。
此含氧酸可与传统的润肤剂组合,该润肤剂包括:矿油、矿脂、石蜡、纯地蜡、天然地蜡、微晶蜡、全氢角鲨烯、二甲基聚硅氧烷、甲基苯基聚硅氧烷、硅氧烷-二醇共聚物、三酸甘油酯、乙酰化的单甘油酯、乙氧基化的甘油酯、脂肪酸的烷基酯、脂肪酸及醇类、羊毛脂及羊毛脂衍生物、多元醇酯、类固醇、蜜蜡衍生物、多元醇及聚醚、及脂肪酸酰胺。其他适当的润肤剂可参见Sagarin,化妆品科学与技术(
Cosmetics. Science and Technology),2nd Ed.,vol.PP.32-43)1972),全文在此并入作为参考文献。
乳化剂可为阳离子性、阴离子性、非离子性、两性或其组合。其中以非离子性乳化剂较佳。非离子性乳化剂的实例有市售的脱水山梨醇、烷氧基化的脂肪醇及烷基聚糖苷。阴离子性乳化剂包括:肥皂、烷基硫酸盐、单烷基及二烷基磷酸盐、烷基磺酸盐及酰基异硫代硫酸盐(acylisothionates)。其他适当的乳化剂可参见McCutcheon,洗涤剂和乳化剂(
Detergents and Emulsifiers),North American Edition,317-324页(1986),全文在此并入作为参考文献。
本组合物中使用的适当保存剂包括:链烷醇,尤其是乙醇及苄基醇、对羟基苯甲酸酯(parabens)、山梨酸盐、尿素衍生物、及异噻唑啉酮。
此洗液或乳膏可用本领域熟练技术人员所熟知的传统均质化方法制备,也可用微流化方法,包括在高压均质器中共同混合这种乳膏及洗液的液相及油相,以便将未经高压处理的乳膏及洗液的乳状液颗粒大小显著地降低至大约它的1/400之一。微流化法可制备含有效量含氧酸的优异稳定的乳膏及洗液,而无须使用传统的乳化剂及表面活性剂。
本发明的局部用组合物也可配制成微乳状液。一种第一基本的微乳状液系统所含的含氧酸大约0.1重量%至大约50重量%,优选大约1重量%至大约30重量%,而最优选大约5重量%至大约20重量%;所含的碳氢化合物大约0.5重量%至大约20重量%;所含的油大约0.5重量%至大约20重量%;而其余的部分是水。第二种更佳的微乳状液系统所合的含氧酸大约1重量%至大约20重量%;所含的碳氢化合物大约0.5重量%至大约15重量%;所含的油大约1重量%至大约15重量%;所含的脂肪醇大约0.1重量%至大约10重量%;所含的非离子的表面活性剂至多30重量%;而其余的部分是水。
本发明的局部用组合物可配制成水包油或油包水的乳状液、凝胶、洗液、软膏、棒状物、喷雾液、胶布、贴片。本发明的组合物也可配制成多相的乳状液,例如水包油包水型的乳状液,揭示于U.S.专利No.4,254,105,全文在此并入作为参考文献。本发明的组合物也可配制成三重乳化液水包油-聚硅氧烷液体的形式,揭示于U.S.专利No.4,960,764,全文在此并入作为参考文献。
本发明的组合物也可作成脂质体的配方,例如:依据描述于Mezei,药物药理学杂志(
J.Pharmaceut.Pharmacol.),34卷,473-474页(1982)的方法或其改良的方法。在此组合物中,含氧酸溶液小滴可包埋于脂质体的载体内,脂质体外壳可为磷脂或其他适当的脂质(例如:皮肤脂质)。为形成局部用组合物,此脂质体可被加入上述任何的载体系统,例如根据局部用脂质体的制备方法、使用及组合物,参见Mezei,药物科学概论(
Topics in Pharmaceutical Sciences),Breimer等编,345-358页,ElsevierScience Publishers BV,New York(1985),全文在此并入作为参考文献,或根据逆相挥发方法,参见Szoka等。,国家科学院院报(
Proc.Nat.Acad. Sciences),vol.75,4194-4198页(1978)及Diploses等,化妆品化学家协会杂志(
J.Soc.Cosmetic Chemists).vol 43,93-100页(1992),全文在此并入作为参考文献。含氧酸溶液也可包埋于聚合的载体,其外壳由适当的聚合物组成,例如:凝胶、交联的凝胶、聚酰胺、聚丙烯酸酯等,以形成并入局部组合物的载体。
本发明的组合物可包括含氧酸化合物作为仅有的活性成分,或此含氧酸化合物可与其他化妆用的及医药学上的活性成分及赋形剂共同使用。其他适当的化妆用的及医药学上的活性剂包括(但非限于):抗真菌剂、维生素、防晒剂、类维生素A、抗过敏剂、脱色剂、抗炎剂、麻醉剂、表面活性剂、湿润剂、剥落剂、稳定剂、保存剂、抗菌剂、增稠剂、润滑剂、致湿剂、螯合剂及皮肤穿透增进剂,及上述的乳化剂、润肤剂、芳香剂及着色剂。
适当的增稠剂的实例包括:黄原胶(xanthan gum)、耐浓盐水的黄原胶、羟丙基纤维素、羟乙基纤维素、carbopol及金合欢树胶、Sepigel305(购自Seppic Co.,France)、V型树胶(vee-gum)或硅铝酸镁。
局部用组合物中,含氧酸也可与湿润剂,例如脲、PCA、氨基酸、某些聚醇类及其他吸湿性的化合物共同使用以增强其功效。
局部用组合物也可含大约0.1重量%至大约90重量%,优选大约1重量%至大约50重量%,而最优选大约5重量%至大约20重量%的含氧酸,及角质层分离剂,例如:水杨酸及苄酰基过氧化物、及皮肤光亮剂,例如:曲酸苯醌、甘草衍生物、抗坏血酸及其衍生物(例如抗坏血基磷酸镁)、及甘油赫提酸(glycerhetinic acid)及其衍生物。
大约0.1重量%至大约90重量%,优选大约1重量%至大约50重量%,而最优选大约5重量%至大约20重量%的含氧酸可与有机的及无机的防晒剂,例如:二氧化钛、氧化锌、亚苄基樟脑、邻氨基苯甲酸酯、丁基甲氧基二苄酰基甲烷、萘酚磺酸酯及肉桂酸衍生物形成局部用配方。其中,丁基甲氧基二苄酰基甲烷及肉桂酸衍生物较佳。
本发明的局部用组合物也可含大约0.1重量%至大约90重量%,优选大约1重量%至大约50重量%,最优选大约5重量%至大约20重量%的含氧酸,其与以下各化合物共同配制:
(i)类维生素A,例如:视黄醇、视黄酸、棕榈酸视黄基酯、丙酸视黄基酯、乙酸视黄基酯、异维生素A酸(isotretinoin)及合成的类维生素A类似物;(ii)荷尔蒙化合物,例如:雌三醇、雌二醇、雌酮或共轭的雌激素;(iii)α-羟基酸或多羟基α-羟基酸,例如:乙醇酸、乳酸、酒石酸、古洛糖酸及其他羧酸以及其单体的、聚合的、环形的或非环形的衍生物;(iv)α-酮酸,例如:丙酮酸、2-氧代丙酸、2-氧代丁酸、2-氧代戊酸等。
大约0.1重量%至大约90重量%,优选大约1重量%至大约50重量%,而最优选大约5重量%至大约20重量%的含氧酸可用于含有一种或多种以下的化合物的局部用配方以获得进一步优点:
(i)维生素包括:酶辅助因子,例如:维生素B6、维生素B12、维生素D3,1,25-二羟基维生素D3、维生素B1、维生素B2、维生素K、维生素E、生育三烯酚及其衍生物、烟酸及其酯类、泛酸及其酯类、泛酰醇、叶酸及其衍生物、胆碱、肉碱及非正式的维生素或“假维生素”(例如:维生素F或顺、顺-亚油酸)、维生素M或叶酰谷氨酸、维生素B10及B11、芝麻籽因子、特尼丁(termitin)、6-氨基青霉烷酸、因赛丁(insectine)、海波微素(hypomycin)及枝霉菌素、维生素L或邻氨基苯甲酸、维生素L2或腺苷酰硫甲基-戊糖(adenylthiomethyl-pentose)、肌醇或顺1,2,3,5-反-4-6-环己烷己醇及其酯类,尤其是费丝(phytic)酸、杏素(laetrile)或1-扁桃腈-β-葡糖醛酸、苦杏仁苷、维生素B15或潘氨酸、维生素B13或乳清酸、维生素H3或普鲁卡因盐酸盐、维生素U或甲硫氨酸的甲基-锍盐、及吡咯并喹啉醌;
(ii)抗真菌剂包括:例如:克利氮杂茂环(clotrimazole)、酮康氮杂茂环(ketoconazole)、微氮杂茂环(miconazole)、那非得(naftifine)、多那得(tolnaftate)、amphotericin B、制霉菌素、5-氟胞嘧啶、几富灵(griseofulvin)、卤博精(haloprogin),其中多那得(tolnaftate)。卤博精(haloprogin)及微氮杂茂环(miconazole)最佳;
(iii)棕色剂包括:例如二羟基丙酮及2-羟基-1,4-萘醌,其中二羟基-丙酮最佳;
(iv)抗分支杆菌剂:例如红霉素、四环素及相关的化合物,尤其是去氧环素(doxycyclin)及甲环素(methacyclin)、头孢菌素、青霉素、大环内酯物、肽化合物,例如:诺凡辛素(novobiocin)、万古霉素、夹竹桃霉素、派蒙素(paromomycin)、露可素(leucomycine)、含大环内酯分子的安逢素(amphomycin)、喹诺酮衍生物及其他干扰细菌细胞壁合成,细胞膜功能,RNA代谢、嘌呤、嘧啶及蛋白质合成、呼吸作用或磷酸化作用的化合物;
(v)局部用止痛剂,例如:利多卡因、苯佐卡因、丁卡因(butacaine)、四卡因(tetracaine)、丁子香油及丁子香酚,其中苯佐卡因及利多卡因最佳;
(vi)皮肤障蔽功能所需的脂质化合物包括,例如:西酰胺(ceramide)、必需的脂肪酸及其酯类(尤其是甘油酯)、ω-羟基脂肪酸或其以羧酸羟基而与链烷醇衍生而来的酯类化合物、或与其他脂肪酸在ω-羟基上衍生的酯类化合物(以后者最佳)、磷脂、胆固醇及其酯类,例如:胆固醇半琥珀酸酯及胆固醇磷酸酯,其中胆固醇磷酸酯及必须的脂肪酸最佳、植物性甾醇、胆甾烷醇及其衍生物。可加入局部用组合物的脂质化合物可为单一的分子或来自合成、动物或植物来源的脂质复合混合物;
(vii)抗过敏剂及H1及/或H2抗组胺药,例如:二苯基羟基胺、克米坐(clemizole)、安他坐林(antazoline)、噻哌苯胺(thenaldine)、苯基多罗西安(phenyltoloxamine)柠檬酸盐、三环抗过敏剂,例如:酮体分(ketotifene)、二噻定(dithiadene)及噻定(thiadene)的3-噻吩基硫化物、H2-受体阻断剂,尤其是百里酰胺(burimamide)、马太酰胺(metiamide)及西太定(cimetidien)、可未立酸(cromolic acid)及其盐类;
(viii)含氧酸可与局部用抗炎剂共同使用以减轻发炎现象。
此类抗炎剂的浓度大约为0.025重量%至10重量%,优选0.5重量%至1重量%,抗炎剂的浓度可视所使用的药剂药效而作上下的调整。可与含氧酸共同使用的类固醇抗炎剂的实例包括:氢化可的松、羟基三安西酮(hydroxytriamcilone)、α-甲基地塞米松、磷酸地塞米松、二丙酸贝卡美松(beclamethasone)、戊酸氢化可的松、环戊基丙酸氢化可的松、强体松同(prednisolone)、及其混合物,其中强体松同(prednisolone)及氢化可的松最佳;及
(ix)也可使用非类固醇抗炎剂,例如参见Rainsford,抗炎及抗风湿药物(
Antiinflammatory and Anti-Rheumatic Drugs),VolS.I-III,CRCPress,Boca,Raton,Florida(1985),而具体NSAID的适当的实例包括:奥西甘(oxicams)(例如:比罗西甘(piroxicam)、异西甘(isoxicam))、分那密酸(fenamic acid)衍生物、美克分那密酸(meclofenamic acid)衍生物(例如;美克分那密酸钠(sodium meclofenamate))、富分那密酸(flufenamic acid)衍生物、美分那密酸(mefenamic acid)衍生物、丙酸酯、例如:布洛芬、那波生(naproxen)、本未西波分(benoxaprofen)、富比波分(flubiprofen)、同波分(ketoprofen)、速波分(suprofen),其中以布洛芬最佳;吡唑烷二酮,其中以保泰松最佳;乙酸衍生物,例如:二克分那(diclofenac)、分克分那(fenclofenac)、引朵美西辛(indomethacin)、速林达(sulindac),其中以引朵美西辛(indomethacin)最佳;水杨酸衍生物,例如:阿司匹林(aspirin)、戴沙酸(disalacid)、及本诺利(benorylate),其中阿司匹林(aspirin)及戴沙酸(disalacid)最佳。
本发明的组合物也可包括具抗炎活性的安全天然抗炎产品,例如:芦荟萃取物、茜草属茜草萃取物、没药属穆库尔没药萃取物、柳树皮、母菊花、山金车花、紫草根、葫芦巴种子等本领域熟练技术人员熟知的天然物。
本发明的局部用组合物可含大约0.1重量%至大约90重量%,优选大约1重量%至大约50重量%,而最优选大约5重量%至大约20重量%的含氧酸与具有酚羟基抗氧化剂的组合。该类的抗氧化剂包括:棓酸衍生物(例如:没食子酸丙基酯)、生物类黄酮(例如:昆西丁(quercetin)、鲁丁(rutin)、戴辛(daidzein)、杰尼丁(genistein))、阿魏酸(Ferrulic acid)衍生物(例如:阿魏酸乙酯、阿魏酸钠)、6-羟基-2,5,7-四甲基苯并二氢吡喃-2-羧酸。组合物也可含有效浓度的水溶性抗氧化剂、例如:尿酸、还原酸、单宁酸、罗马尼酸(rosmarinic acid)及卡代因(catechins)。
有益的共同配方含大约0.1重量%至大约90重量%,优选大约1重量%至大约50重量%,及最优选大约5重量%至大约20重量%的含氧酸与氧化氮合成酶抑制剂以减轻皮肤红肿、血管扩张及发炎反应,对电磁及离子辐射或化学或生化攻击性化合物的作用特别有效。此氧化氮合成酶抑制剂的浓度为大约0.05重量%至10重量%,最优选1重量%至3重量%,并系由下列化合物中选出:胍衍生物(尤其是单氨基胍及甲基胍)、L-精氨酸衍生物(尤其是NG-硝基-L-精氨酸及其酯类)、NG-单甲基-L-精氨酸、2-亚氨基哌啶(2-imino pipperidines)及其他2-亚氨基氮杂杂环化合物。
组合物可能包含的其它抗氧化剂是具有一个或多个硫氢基(-SH)的还原或非还原形式的抗氧化剂,例如:谷胱甘肽、硫辛酸、硫代乙醇酸、及其他硫氢基化合物。化妆用的组合物的硫氢基抗氧化剂的含量不该超过0.5重量%,但药用考虑其药效则可酌量提高其浓度。组合物还可包括无机抗氧化剂,例如:亚硫酸盐、亚硫酸氢盐、偏亚硫酸氢盐、或其他无机盐及含四价氧化态硫的酸。含硫无机酸的较佳抗氧化剂含量大约为0.01重量%至大约0.5重量%,最优选的含量介于大约0.1重量%至大约0.4重量%。
本发明的组合物也可含:大约0.1重量%至大约90重量%,优选大约1重量%至大约50重量%,而最优选大约5重量%至大约20重量%的含氧酸与大约0.025重量%至大约5重量%(0.5重量%至2重量%较佳,而0.5重量%至1重量%最佳)的所谓的电子自旋阱(electron spin-traps)化合物,例如:硝酮(nitrones)、N-叔丁基-硝酮及α-(4-吡啶基-1-氧化物)-N-叔丁基-硝酮或其他化合物(能形成半衰期大于一分钟的自由基)共同配制。
大约0.1重量%至大约90重量%,优选大约1重量%至大约50重量%,及最优选大约5重量%至大约20重量%的含氧酸也可用于包含驱虫剂例如:脂族的、环(状)的或芳香族的酰胺、香茅油、松油醇、辛欧(cineole)、逆油(neem oil)及对苯二甲酸及其酯类的组合物。其他适当的驱虫剂参见美国农业部技术公报第1549号(Technical Bulletin No.1549from the U.S.Department of Agriculture)或其农业手册(AgriculturalHandbook)Nos.69,340及461。
本发明含含氧酸的局部用组合物也可含冷却皮肤的化合物,例如:薄荷醇、基甘油、不对称的碳酸酯、硫代碳酸酯及氨基甲酸酯、N-取代的甲酰胺、脲或膦氧化物,例如描述于化妆品化学杂志(J.Cosmet.Chem.),vol.29,p.185(1978),乳酸盖基酯、及薄荷酮甘油缩醛。
本发明局部用组合物对皮肤的一般活性及温和性可通过中和至pH3.5-7.0而强化(最优选在pH3.7-5.6),可用一种或多种两性及假两性的化合物,例如:甘氨酸、丙氨酸、缬氨酸、丝氨酸、硫堇、甲硫氨酸、白氨酸、天冬酰胺、组氨酸、谷氨酸、谷氨酰胺、赖氨酸、胱氨酸、半胱氨酸、色氨酸、丝氨酸、苯基丙氨酸、瓜氨酸、肌酸、脯氨酸、3-或4-羟基脯氨酸、5-羟基赖氨酸、乌氨酸及其衍生物、3-氨基丙酸及其他氨基羧酸、刀豆氨酸、副刀豆氨酸、高精氨酸、牛磺酸、氨基醛糖酸及氨基糖、氨基糖醛酸、氨基醛糖二酸(aminoaIdaric acid)、去乙酰化的透明质酸、玻璃样生物醛酸(hyalobiuronic acid)、软骨生、去硫的肝素、神经氨酸或唾液酸、甲硫氨酸砜、甘氨酰基甘氨酸、软骨素、D,L-鞘氨醇、鞘磷酯、蛇肉肽、胰高血糖素、高肌肽、磷脂酰基丝氨酸、可可双甘氨酸(cocoamphoglycine)、磷脂酰基乙醇胺、半胱氨酸亚磺酸、谷胱甘肽、两性的无机氧化物、聚酰氨基胺、以聚酰氨基胺为基础的树状体、羟甲基甘氨酸钠及聚乙烯胺。
本发明局部用组合物的药效及其温和性可因在组合物中加入某些螯合剂而强化,螯合剂的加入量大约0.01重量%至大约25重量%、更优选大约0.5重量%至大约10重量%,而最优选大约1重量%至大约5重量%。螯合剂的适当实例包括:对锌、钙、镁、铁及/或铜离子具高亲和力的化合物,例如:乙二胺四乙酸、(亚乙基二氧基)-二亚乙基-二次氮基-四乙酸、水杨醛肟、羟基喹啉、二氨基环己烷四乙酸、二亚乙基-三氨基-五-乙酸、二甲基乙二肟、苯偶姻肟、三亚乙基四胺、低弗利沙密(desferrioxamine)或其混合物。
本发明也包括用此类化合物治疗上述皮肤病况的方法。此方法包括在局部施用有效剂量的一种或多种式(I)化合物至皮肤患部,正常情况下一天一次或两次。此方法也包括:局部施用有效量于生理学上可接受的载体内含一种或多种式(I)化合物的组合物至皮肤患部,正常情况下一天一次或两次。本发明的方法包括局部施用浓度多至100%的式(I)化合物,当该化合物在室温下为液态时(例如:3,6,9-三氧杂十一烷二酸),以及当例如用此氧杂化合物剥落皮肤或软化毛发。
以下的实施例是用以说明本发明而非限制本发明的范围。
实施例
本发明的组合物一般制作成局部施用的洗液、乳膏或凝胶。
实施例1 含氧酸局部用组合物的制备
于适当的容器中,将水、甘油、丙二醇、Na2EDTA及3,6,9三氧杂癸酸相互混合。容器中加入氢氧化铵,将pH调整至适当的范围。将此pH-调整过的溶液加热至170-175°F。搅拌加入羟乙基纤维素至形成均匀的相A为止。
至于洗液及乳膏,将相B加至适当的第二个容器中混合加热至170-175°F。将相B加至相A,并在170-175°F下充分混合。将此批产品冷却至120°F。加入相C并混合至均匀。
相
凝胶
洗液
乳膏(A)水 Q.S Q.S. Q.S甘油 5.00 3.00 5.00丙二醇 3.00 3.00 3.00EDTA二钠 0.10 0.10 0.103,6,9-三氧杂癸酸 10.00 10.00 10.00羟乙基纤维素 0.50 0.30 0.500氢氧化铵(30%) 至pH3.7-3.9 至pH3.7-3.9 至pH3.7-3.9
相
凝胶
洗液
乳膏(B)棕榈酸辛基酯 - 3.00 5.00肉豆蔻酸肉豆蔻基酯 - 3.00 5.00单硬脂酸甘油酯 - 1.50 3.00鲸蜡硬脂醇&Ceteareth-20 - 3.00 5.00对羟基苯甲酸甲酯 - 0.20 0.20(methyl paraben)(C)咪唑烷基脲 0.30 0.30 0.30
除了pH范围及用水平衡Q.S.外,所有的数目代表总组合物重量的百分比。
本领域熟练技术人员参考此公开后可轻易地发觉除洗液、乳膏或凝胶外的载体。
本发明的含氧酸化合物及组合物是要减轻皮肤病况,而为此目的,必需具备使微观的角质层脱皮或巨观的上皮剥落正常化的作用。本发明含氧酸组合物以下的实施例能提供卓越的角质层剥离活性。
实施例2 治疗色素过度沉淀的斑点的乳膏
此实施例描述一种乳膏,该乳膏可用于降低手上皮肤色素过度沉淀的斑点的出现。
重量%肉豆蔻酸异丙基酯 3.0聚乙二醇(1000)单硬脂酸酯 5.0十六酸 10.03,6,9-三氧杂癸酸 10.0甘油 3.0聚乙二醇(300)单硬脂酸酯 5.0对羟基苯甲酸甲酯(methyl paraben) 0.2抗坏血基(ascorbyl)磷酸镁 2.0水 60.0芳香剂&着色剂 至100.0三乙醇胺 至pH4.0
除了pH外,所有的数目代表总组合物重量的百分比。
实施例3 治疗皮肤干燥,鱼鳞癣及过度角化病的乳膏
此实施例描述一种根据本发明的聚硅氧烷乳膏,该乳膏可用于治疗皮肤干燥,鱼鳞癣及过度角化病。
重量%相A月桂基美西孔(Laurylmethicone)共聚醇 2.0矿油 1.0羊毛脂 1.5向日葵或大豆油 10.0环美西孔(cyclomethicone) 6.0油溶性罗美利(rosmary)萃取物 2.0相B碘化钠 2.03,6,9-三氧杂癸酸 9.03-氨基-6-氧杂庚酸 1.0羟甲基甘氨酸钠 0.5去离子水 至100.0磷酸氢钠 至pH3.8
除了pH外,所有的数目代表总组合物重量的百分比。
实施例4 聚硅氧烷凝胶
本实施例说明一种聚硅氧烷凝胶包水的组合物
重量%相A二美西孔醇(dimethiconol) 10.0二美西孔(dimethicone)共聚醇 10.0环美西孔(cyclomethicone) 5.0相B3,6-二氧杂 庚酸 8.0甘油 20.0去离子水 至100.0三乙醇胺 至pH4.0
除了pH外,所有的数目代表总组合物重量的百分比。
实施例5
治疗粉刺、皮肤瘢点及老人斑的乳膏
本实施例说明一种用于治疗粉刺、皮肤瘢点及老人斑的颜面乳膏。
重量%相A油酸 1.0硬脂酸 17.0聚氧乙烯(20丙二醇单硬脂酸酯) 10.0视黄醇 0.1相B甘油 5.02-吡咯烷酮-5-羧酸 5.03,6,9-三氧杂癸酸 7.53,6-二氧杂庚酰胺 2.5乳酸 3.0去离子水 至100.0氢氧化铵 至pH4.2
除了pH之外所有的数目代表总组合物的百分比。
基于本公开可对本发明作出各种改良及变化。此类的改变及改良也包含于本发明以下定义的权利要求的精神与范围之内。
Claims (43)
2.如权利要求1的组合物,其中该组合物含0.1重量%至95重量%的该式(I)化合物。
3.如权利要求2的组合物,其中该组合物含1重量%至50重量%的该式(I)化合物。
4.如权利要求3的组合物,其中该组合物含5重量%至20重量%的该式(I)化合物。
5.如权利要求1的组合物,其中n是2至12的整数。
6.如权利要求1的组合物,其中该组合物进一步包含至少两种不同的式(I)化合物的混合物。
7.如权利要求1的组合物,其中所述的烷基、烯基、氧杂烷基、芳烷基和芳基选自:甲基、乙基、丙基、异丙基、丁基、异丁基、己基、庚基、辛基、壬基、十二碳烷基、甲氧基、乙氧基、丙氧基、丁氧基、环己烯基、羟甲基、羟乙基、羟丙基、环丁基及环己基。
8.如权利要求1的组合物,其中R1、R2、R3、R5、R6、R7、R8、R9、R10及R11各为氢。
9.如权利要求1的组合物,其中该化合物选自:3,6-二氧杂庚酸、7,7-二甲基-3,6-二氧杂庚酸、3,6-二氧杂庚酸乙酯、3,6-二氧杂庚酰胺、3,6-二氧杂庚酸十二碳烷基酯、2-苯基-3,6-二氧杂庚酸、2-苄基-3,6-二氧杂庚酸、2-甲基-3,6-二氧杂庚酸、3-氨基-6-氧杂庚酸、3,6,9-三氧杂癸酸、2-苯基-3,6,9-三氧杂癸酸、2-苄基-3,6,9-三氧杂癸酸、2-癸基-3,6,9-三氧杂癸酸、3,6,9,12-四氧杂十三碳烷酸、3,6,9,12,15-五氧杂十六碳烷酸、2-甲基-3,6,9-三氧杂癸酸、10,10-二甲基-3,6,9-三氧杂癸酸、2-乙基-3,6,9,12-四氧杂十三碳烷酸、10-苯基-3,6,9-三氧杂癸酸、3,6,9-三氧杂癸酸乙酯、3,6,9-三氨基癸酸、3,6,9,12-四氨基十三碳烷酸、9-氨基-3,6-二氧杂癸酸、6,9-二氨基-3-氧杂癸酸、3,6,9-三硫代癸酸、9,12-二硫代-3,6-二氧杂十三碳烷酸、9-氨基-3,6-二氧杂癸酸单酰胺、3,6,9-三氧杂癸酸单酰胺、10,10-二甲基-3,6,9-三氧杂癸酸酰胺、10,10-二甲基-3,6,9-三氧杂癸酸乙酯、10,10-二甲基-3,6,9-三氧杂癸酸十七碳烷基酯、10,10-二甲基-3,6,9-三氧杂癸酸及其混合物。
10.如权利要求1的组合物,其中该载体选自洗液、乳膏及凝胶。
11.如权利要求1的组合物,其进一步包括至少一种活性化合物,该化合物选自:抗真菌剂、维生素、防晒剂、类维生素A、抗过敏剂、脱色剂、消炎剂、麻醉剂、表面活性剂、湿润剂、剥落剂、乳化剂、稳定剂、保存剂、抗菌剂、润肤剂、增稠剂、润滑剂、致湿剂、螯合剂、芳香剂、着色剂及皮肤穿透增进剂。
12.如权利要求1的组合物,其中该组合物的pH小于7.0。
13.如权利要求12的组合物,其中该pH为3.5至7.0。
14.如权利要求13的组合物,其中该pH为3.5至4.0。
15.如权利要求2的组合物,其中该组合物含1重量%至50重量%的该式(I)化合物,且pH小于7.0。
16.如权利要求12的组合物,其中该局部用载体包含0.1重量%至95重量%的该式(I)化合物:0.5重量%至50重量%的润肤剂;及0.1重量%至30重量%的乳化剂。
17.如权利要求16的组合物,其中该化合物选自:3,6-二氧杂庚酸、3,6,9-三氧杂癸酸、3,6,9,12-四氧杂十三碳烷酸及3,6,9,12,15-五氧杂十六碳烷酸;而其中该润肤剂选自:矿油、矿脂、石蜡、纯地蜡、天然地蜡、微晶蜡、全氢角鲨烯、二甲基聚硅氧烷、甲基苯基聚硅氧烷、硅氧烷二醇共聚物、三酸甘油酯、乙酰化单甘油酯、乙氧基化甘油酯、脂肪酸烷基酯、脂肪酸及醇类、羊毛脂及羊毛脂衍生物、多元醇酯、固醇、蜜蜡衍生物、多元醇及聚醚、及脂肪酸酰胺;且其中该乳化剂选自:脱水山梨糖醇、烷氧基化脂肪醇、烷基聚糖苷、肥皂、烷基硫酸盐、磷酸单烷基酯及二烷基酯、烷基磺酸盐、及酰基异硫代硫酸盐。
18.如权利要求2的组合物,其中该组合物选自:水包油乳液、油包水乳液、水包油包水乳液及硅氧烷液体包水包油乳液的形式。
19.如权利要求10的组合物,其中该局部用载体包含选自下列的组分:氢氧化铵、鲸蜡硬脂醇(cetearyl alcohol)/西塔瑞(Ceteareth)-20、EDTA、甘油、单硬脂酸甘油酯、羟乙基纤维素、咪唑烷基脲、对羟基苯甲酸甲酯、肉豆蔻酸肉豆蔻基酯、棕榈酸辛酯及丙二醇及其混合物。
20.如权利要求10的组合物,其中含0.1重量%至20重量%3,6,9-三氧杂癸酸及载体。
21.如权利要求18的组合物,其中该载体含:
(a)2重量%至10重量%的甘油;及
(b)1重量%至10重量%的丙二醇;且该组合物的pH为7.0或更低。
22.如权利要求21的组合物,其中该载体进一步包含0.1重量%至2重量%的羟乙基纤维素。
23.如权利要求22的组合物,其中该载体进一步含0.1重量%至1重量%的咪唑烷基脲;及0.01重量%至2重量%的EDTA-二钠。
24.如权利要求20的组合物,其中该载体含:
(a)1重量%至10重量%甘油;
(b)1重量%至10重量%丙二醇;
(c)1重量%至10重量%棕榈酸辛酯;
(d)1重量%至10重量%肉豆蔻酸肉豆蔻基酯;
(e)1重量%至6重量%鲸蜡硬脂醇/西塔瑞(Ceteareth)-20;及
(f)0.5重量%至6重量%单硬脂酸甘油酯;且该组合物的pH为7.0或更低。
25.如权利要求24的组合物,其中该载体另含0.1重量%至2重量%羟乙基纤维素。
26.如权利要求25的组合物,其中该载体另含0.1重量%至1重量%咪唑烷基脲;0.05重量%至0.5重量%对羟基苯甲酸甲酯;及0.01重量%至2重量%EDTA二钠。
27.如权利要求20的组合物,其中该载体含:
(a)2重量%至10重量%甘油;
(b)1重量%至10重量%棕榈酸辛酯;
(c)1重量%至10重量%肉豆蔻酸肉豆蔻基酯;
(d)1重量%至7重量%鲸蜡硬脂醇/西塔瑞(Ceteareth)-20;
(e)1重量%至10重量%丙二醇;
(f)1重量%至6重量%单硬脂酸甘油酯;且该组合物的pH为7.0或更低。
28.如权利要求27的组合物,其中该载体另含0.1重量%至2重量%羟乙基纤维素。
29.如权利要求28的组合物,其中该载体另含0.1重量%至1重量%咪唑烷基脲;0.05重量%至0.5重量%对羟基苯甲酸甲酯;及0.01重量%至2重量%EDTA二钠。
30.式(I)化合物在制备用于治疗起因于、伴随异常脱皮或由异常脱皮引起恶化的皮肤病况的局部用组合物中的用途:
其中R4为(CR5R6-CR7R8-X1)n-CR9R10R11,n是1至18的整数;R1、R2、R3、R5、R6、R7、R8、R9、R10及R11各自为氢、烷基、烯基、氧杂烷基、芳烷基或芳基;而X、X1、Y及Z各自为O。
31.如权利要求30的用途,其中该化合物与适当的局部用载体混合成局部用组合物。
32.如权利要求30的用途,其中使用二种或多种式(I)化合物的混合物。
33.如权利要求31的用途,其中该组合物含0.1重量%至95重量%的式(I)化合物。
34.如权利要求33的用途,其中该组合物含1重量%至50重量%的该式(I)化合物。
35.如权利要求33的用途,其中n是2至12的整数。
36.如权利要求30的用途,其中所述烷基、烯基、氧杂烷基、芳烷基或芳基选自:甲基、乙基、丙基、异丙基、丁基、异丁基、己基、庚基、辛基、壬基、十二碳烷基、甲氧基、乙氧基、丙氧基、丁氧基、环己烯基、羟甲基、羟乙基、羟丙基、环丁基及环己基。
37.如权利要求30的用途,其中R1、R2、R3、R5、R6、R7、R8、R9、R10及R11各为氢。
38.如权利要求30的用途,其中该化合物选自:3,6-二氧杂庚酸、7,7-二甲基-3,6-二氧杂庚酸、3,6-二氧杂庚酸乙酯、3,6-二氧杂庚酰胺、3,6-二氧杂庚酸十二碳烷基酯、2-苯基-3,6-二氧杂庚酸、2-苄基-3,6-二氧杂庚酸、2-甲基-3,6-二氧杂庚酸、3-氨基-6-氧杂庚酸、3,6,9-三氧杂癸酸、2-苯基-3,6,9-三氧杂癸酸、2-苄基-3,6,9-三氧杂癸酸、2-癸基-3,6,9-三氧杂癸酸、3,6,9,12-四氧杂十三碳烷酸、3,6,9,12,15-五氧杂十六碳烷酸、2-甲基-3,6,9-三氧杂癸酸、10,10-二甲基-3,6,9-三氧杂癸酸、2-乙基-3,6,9,12-四氧杂十三碳烷酸、10-苯基-3,6,9-三氧杂癸酸、3,6,9-三氧杂癸酸乙酯、3,6,9-三氨基癸酸、3,6,9,12-四氨基十三碳烷酸、9-氨基-3,6-二氧杂癸酸、6,9-二氨基-3-氧杂癸酸、3,6,9-三硫代癸酸、9,12-二硫代-3,6-二氧杂十三碳烷酸、9-氨基-3,6-二氧杂癸酸单酰胺、3,6,9-三氧杂癸酸单酰胺、10,10-二甲基-3,6,9-三氧杂癸酸酰胺、10,10-二甲基-3,6,9-三氧杂癸酸乙酯、10,10-二甲基-3,6,9-三氧杂癸酸十七碳烷基酯、10,10-二甲基-3,6,9-三氧杂癸酸及其混合物。
39.如权利要求38的用途,其中该化合物是3,6,9-三氧杂癸酸。
40.如权利要求30的用途,其中该皮肤病况选自:皮肤干燥、鱼鳞癣、手掌及足底的皮肤角化过度、头皮屑、单纯慢性苔藓、毛囊角化病、角化病、雀斑、老人斑、黑斑病、瘢点的皮肤、粉刺、牛皮癣、湿疹、瘙痒、发炎性皮肤病、膨胀性萎缩纹、疣、老茧、皮肤老化的前兆、皮肤皱纹、口部周围的细纹、不规则的色素沉淀、皮肤灰黄、皮肤失去弹性及张力、及与指甲、表皮及毛发相关的病症。
41.如权利要求31的用途,其中该组合物另包括至少一种活性成分,该活性成分选自:抗真菌剂、维生素、防晒剂、类维生素A、抗过敏剂、脱色剂、消炎剂、麻醉剂、表面活性剂、湿润剂、剥落剂、乳化剂、稳定剂、保存剂、抗菌剂、润肤剂、增稠剂、润滑剂、致湿剂、螯合剂、芳香剂、着色剂及皮肤穿透增进剂。
42.式(I)化合物在制备用于剥落皮肤的局部用组合物中的用途:
其中R4为(CR5R6-CR7R8-X1)n-CR9R10R11,n是1至18的整数;R1、R2、R3、R5、R6、R7、R8、R9、R10及R11各自为氢、烷基、烯基、氧杂烷基、芳烷基或芳基;而X、X1、Y及Z各自为O。
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- 1997-06-02 BR BRPI9709427-7A patent/BR9709427B1/pt not_active IP Right Cessation
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- 1997-06-02 US US08/863,502 patent/US6069169A/en not_active Expired - Lifetime
- 1997-06-02 JP JP10500710A patent/JP2000511900A/ja active Pending
- 1997-06-02 WO PCT/US1997/009281 patent/WO1997046231A1/en active IP Right Grant
- 1997-06-02 CA CA002256582A patent/CA2256582C/en not_active Expired - Lifetime
- 1997-06-02 CN CN97195278A patent/CN1110302C/zh not_active Expired - Lifetime
- 1997-06-02 AT AT97927863T patent/ATE280577T1/de not_active IP Right Cessation
- 1997-06-02 EP EP97927863A patent/EP0910362B1/en not_active Expired - Lifetime
- 1997-06-03 AR ARP970102399A patent/AR008384A1/es active IP Right Grant
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1998
- 1998-09-14 US US09/152,574 patent/US6071962A/en not_active Expired - Lifetime
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1999
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2000
- 2000-05-08 US US09/566,556 patent/US6333356B1/en not_active Expired - Lifetime
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2001
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WO1997046231A1 (en) | 1997-12-11 |
HK1020167A1 (en) | 2000-03-31 |
US6069169A (en) | 2000-05-30 |
AR008384A1 (es) | 2000-01-19 |
JP2000511900A (ja) | 2000-09-12 |
EP0910362B1 (en) | 2004-10-27 |
CN1221342A (zh) | 1999-06-30 |
US20020040056A1 (en) | 2002-04-04 |
EP0910362A4 (en) | 1999-12-22 |
ATE280577T1 (de) | 2004-11-15 |
JPH1072334A (ja) | 1998-03-17 |
EP0910362A1 (en) | 1999-04-28 |
US6333356B1 (en) | 2001-12-25 |
US6534543B2 (en) | 2003-03-18 |
BR9709427B1 (pt) | 2009-05-05 |
CA2256582C (en) | 2008-08-12 |
DE69731385T2 (de) | 2006-02-02 |
CA2256582A1 (en) | 1997-12-11 |
US6071962A (en) | 2000-06-06 |
DE69731385D1 (de) | 2004-12-02 |
BR9709427A (pt) | 2000-01-11 |
US5847003A (en) | 1998-12-08 |
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