CN1406576A - 含有稳定剂和氨基取代的羟基二苯甲酮的水包油型的低乳化剂或无乳化剂体系 - Google Patents
含有稳定剂和氨基取代的羟基二苯甲酮的水包油型的低乳化剂或无乳化剂体系 Download PDFInfo
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- CN1406576A CN1406576A CN02141655.9A CN02141655A CN1406576A CN 1406576 A CN1406576 A CN 1406576A CN 02141655 A CN02141655 A CN 02141655A CN 1406576 A CN1406576 A CN 1406576A
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- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
Abstract
属于水包油型细分散体的化妆品或皮肤用制剂,包含a)油相,b)水相,c)一种或多种稳定剂,d)至多2.00wt%的一种或多种乳化剂,和e)通式I的氨基取代的羟基二苯甲酮。
Description
本发明涉及水包油型的无乳化剂或低乳化剂细分散体系,优选作为化妆品或皮肤用(dermatological)制剂。
乳液通常被理解为由彼此不混溶或仅仅有限地混溶并且常常称作相的两种液体组成的非均相体系。在乳液中,两种液体中的一种以非常细微液滴形式分散在另一种液体中。
如果两种液体是水和油而且油滴精细地分散在水中,则它是水包油型乳状液(O/W乳液,例如奶状液)。O/W乳液的基本特性由水确定。对于油包水型乳液(W/O乳液,例如奶油状),原理是相反的,而且基本特性由油确定。
为了获得一种液体在另一种中的永久分散体,对于传统意义上的乳液来说需要添加界面活性物质(乳化剂)。乳化剂具有由在空间上彼此分开的极性(亲水性)和非极性(亲脂性)分子结构部分组成的两亲性分子结构。对于简单的乳液,被乳化剂壳包围的一种相(W/O乳液中的水滴或O/W乳液中的脂质囊)的精细分散液滴存在于第二相中。乳化剂通过让自身处于两种液体之间的界面中来减少各相之间的界面张力。在油/水相界上它们形成界面薄膜,防止液滴的不可逆聚结。乳液常常用乳化剂混合物来稳定化。
传统的乳化剂能够被分成离子型(阴离子型,阳离子型和两性)和非离子型,这取决于它们的亲水性分子结构部分:
·阴离子乳化剂的最著名的实例是皂,通常用于指饱和的或不饱和的高级脂肪酸的水溶性钠或钾盐。
·阳离子乳化剂的重要代表是季铵化合物。
·非离子乳化剂的亲水性分子结构部分常常由甘油,聚甘油,脱水山梨糖醇,碳水化合物或聚氧化乙烯二醇组成和通常经酯和醚键连接于亲脂性的分子结构部分。该亲脂性的分子结构部分通常由脂肪族醇,脂肪酸或异脂肪酸组成。
通过改变极性和非极性分子结构部分的结构和尺寸,乳化剂的亲油性和亲水性能够在大范围内变化。
乳液的稳定性的决定因素是乳化剂的正确选择。就此而论,在体系中存在的全部物质的特征需要考虑。如果考虑例如皮肤护理乳液,则极性的油组分和例如UV过滤剂将导致不稳定性。因此与乳化剂一样,通常还使用其它稳定剂,它们例如用于提高乳液的粘度和/或用作保护胶体。
乳液代表了在化妆品和/或皮肤用制剂领域中重要的产品类型。
化妆品制剂基本上用于皮肤护理。在化妆意义上的皮肤护理主要是皮肤作为抵抗环境影响(例如油、化学品、微生物)和防止内源性物质(例如水,天然脂肪,电解质)的损失的一种阻隔结构的自然功能得到加强或恢复。这一功能的损坏可导致毒性或变应原性物质的吸收增加或微生物的侵袭,并因此导致毒性或变应性皮肤反应。
皮肤护理的另一目的是补偿每天清洗所引起的皮肤的类脂和水的损失。当自然再生能力不够时这是特别重要的。此外,皮肤护理产品应该能够防止环境影响,尤其防止太阳和风的影响,并延迟皮肤老化。
化妆品制剂也用作除臭药。此类配制剂用于除去体臭,它在新的汗(它本身是无臭的)由微生物分解时所产生。
医用局部组合物一般包含有效浓度的一种或多种药物。为简单起见,为了在化妆品和医用以及相应产品之间进行清楚的区分,参见德意志联邦共和国的法律条文(例如Cosmetics Directive,Foods and Drugs Act)。
本身来说,常规乳化剂在化妆品或皮肤用制剂中的使用是安全的。然而,乳化剂,最终与任何化学物质一样,在各种情况下引起变应性反应或以使用者的过度敏感性为基础的各种反应。
因此例如已知某些光致皮肤病通过某些乳化剂触发,而且通过各种脂肪和同时暴露于日光所触发。此类光致皮肤病也称作“马洛尔卡(Mallorca)粉刺”。因此人们曾尝试将常规乳化剂的量减少至最低,在理想情况下甚至完全不用。
与所述乳液一样,现有技术认识到其它无乳化剂、精细分散的化妆品或皮肤用制剂,它们通常被称为水分散体。水分散体属于液体、半固体或固体内部(不连续的)脂相在外部水(连续)相中的分散体。
对于液体脂相在外部水相中的水分散体,例如通过在水相中构建凝胶结构(其中类脂小滴稳定地悬浮)来确保稳定性。德国专利申请公开说明书44 25 268描述了水包油型的稳定的、精细分散的、无乳化剂的化妆品或皮肤用制剂,除了油相和水相之外还包含选自丙烯酸聚合物、多糖及其烷基醚中的一种或多种增稠剂,虽然对于这些增稠剂来说不一定测量到界面张力的减少。
基于类似的水分散体,德国申请公开说明书43 03 983公开了基本上无乳化剂的化妆品或皮肤用光保护配制剂,用作UV过滤物质的无机微细颜料被引入到水分散体的脂相中。
虽然一方面很有可能设计出完全无乳化剂的制剂,但是另一方面,一定的低乳化剂含量有时候不是完全所不希望的,因为乳化剂的不存在将使得许多原料的引入在技术上变得困难。
本发明的目的是用化妆品或皮肤用制剂来丰富现有技术,获得了可以容忍低乳化剂含量的在皮肤上有良好感觉的稳定制剂。
我们已经发现这一目的可通过属于水包油型细分散体系的化妆品或皮肤用制剂来实现,包含
a)油相,
b)水相,
c)一种或多种稳定剂,
d)至多2.00wt%的一种或多种乳化剂,和
e)通式I的氨基取代的羟基二苯甲酮和任选的其它化妆品或药物助剂,添加剂和/或活性成分。根据本发明,如果制剂无乳化剂则是特别理想的,但是至多包含0.1-2.00wt%,优选0.5-1.5wt%(基于制剂的总重量)的一种或多种乳化剂。
在本发明的制剂中使用的稳定剂优选是水胶体这一物质类的代表。
“水胶体”是更准确名称“亲水胶体”的技术性缩写。水胶体是具有较大线性结构和具有相互作用的分子间力的大分子,其允许在各分子之间有次价键和主价键并因此形成网状结构。一些是水溶性的天然或合成聚合物,其在含水体系中形成了凝胶或粘稠溶液。它们通过结合水分子(水合)而提高了水的粘度或将水吸收和包封到它们的交织大分子中,同时限制水的活动性。此类水溶性聚合物代表了一大组化学上非常不同的天然和合成聚合物,它们的共同特征是它们在水或含水介质中的溶解度。其先决条件是这些聚合物具有许多亲水基团以足以溶于水中并且没有太多的交联。
这一组化妆和皮肤学领域上相关的水胶体能够按如下分成:
·有机,天然的化合物如琼脂,角叉菜,黄耆胶,阿拉伯树胶,藻酸盐,果胶,多糖,瓜耳树胶粉,角豆粉,淀粉,糊精,明胶,酪蛋白;
·有机,改性的天然物质例如羧甲基纤维素及其它纤维素醚,羟乙基纤维素和羟基丙基纤维素和微晶纤维素;
·有机,完全合成的化合物例如聚丙烯酸和聚甲基丙烯酸化合物,乙烯基聚合物,聚羧酸,聚醚,聚亚胺,聚酰胺,聚氨酯类;
这里,R能够是乙基或氢原子。
乙基纤维素的乙基化度理想的是2.0-3.0,对应于40-55%,优选48.0-49.5%乙基化。平均分子量优选在选择后应使得在80份甲苯和20份乙醇的混合物中的5%强度溶液在25℃下的粘度是3-110mPas,优选9-11mPas。平均分子量特别理想地是100,000-400,000g/mol。
在本发明制剂中乙基纤维素的含量优选是0.1-10wt%,基于该制剂的总重量。此类产物例如以商品名ETHOCELStandard 10 Premium(DowChemicals)获得。
微晶纤维素是本发明的理想水胶体。它例如从“FMC CorporationFood and Pharmaceutical Products”以商品名Avicel获得。本发明特别理想的产物是品级AvicelRC-591,它是由89%微晶纤维素和11%羧甲基纤维素钠组成的改性微晶纤维素。这类原料的其它商购产品是AvicelRC/CL,AvicelCE-15,Avicel500。
理想使用的其它水胶体是例如甲基纤维素,它是纤维素的甲基醚的名称。它们通过下列结构式来表征其中R能够是氢或甲基。
对本发明来说特别理想的是纤维素混合醚,其通常同样称作甲基纤维素,除了含有主要量的甲基外,还含有2-羟乙基,2-羟丙基或2-羟基丁基。特别优选的是(羟丙基)甲基-纤维素,例如以商品名MethocelE4M从DowChemical Comp获得的那些。
根据本发明也理想的是羧甲基纤维素钠,纤维素的乙二醇醚的钠盐,在以上结构式中的R可以是氢和/或CH2-COONa。特别优选的是以商品名称NatrosolPlus 330 CS从Aqualon获得而且也称为纤维素胶的羧甲基纤维素钠。
对于本发明来说也优选的是汉生胶(CAS No.11138-66-2),也称作黄原胶,它是一般通过发酵从玉米糖中形成并以钾盐分离出来的阴离子杂多糖。它是在需氧条件下通过黄单胞菌(Xanthomonas campestris)和一些其它种类产生的并具有2×106到24×106的分子量。汉生胶是从带侧链的具有β-1,4-键合的葡萄糖(纤维素)的链形成的。亚组的结构是由葡萄糖,甘露糖,葡糖醛酸,乙酸盐和丙酮酸盐组成。丙酮酸盐单元的数目决定了汉生胶的粘度。
本发明的其它理想的凝胶前体还可以是角叉菜,具有与琼脂类似结构的凝胶形成提取物,属于真红藻亚纲(Florideae)的North Atlantic红藻(鹿角菜和Gigartina stellata)。
该术语角叉菜常常用于表示干燥的藻类产物和角叉菜胶用于表示其提取物。从藻类的热水提取物沉淀的角叉菜是从无色至沙色的粉末,它具有100,000到800,000的分子量和大约25%的硫酸酯含量。角叉菜非常容易溶于温水中,在冷却后形成了触变凝胶,即使水含量是95-98%。凝胶的刚度受到角叉菜的双螺旋结构的影响。
对于角叉菜胶而言,区分出三种主要成分:凝胶形成性κ级分由D-半乳糖4-硫酸酯和3,6-脱水-α-D-半乳糖组成,它在1,3-和1,4-位上具有交替的糖苷键(相反,琼脂含有3,6-脱水-α-L-半乳糖)。非胶凝性λ级分由1,3-糖苷键连接的D-半乳糖2-硫酸酯和1,4-键合的D-半乳糖-2,6-二硫酸酯基团组成,并且容易溶于冷水中。ι-角叉菜胶由在1,3键的D-半乳糖4-硫酸酯和在1,4键的3,6-脱水-α-D-半乳糖2-硫酸酯组成,既是水溶性的又是凝胶形成性的。所存在的阳离子(K+、NH4 +、Na+、Mg2+、Ca2+)的性质还影响角叉菜的溶解性。
聚丙烯酸酯类是同样为本发明所优选使用的胶凝剂。对本发明来说理想的聚丙烯酸酯类是丙烯酸酯-丙烯酸烷基酯共聚物,尤其选自卡波姆(carbomers)或卡波波尔(carbopols)的那些(Carbopol实际上是B.F.Goodrich Company的注册商标)。尤其,对本发明来说理想的丙烯酸酯-丙烯酸烷基酯共聚物由下面的结构表征:其中R’是长链烷基,x和y表示数字,其使每一种共聚用单体的各自化学计算比例用符号表示。
根据本发明,特别优选的是以商品名Carbopol1382、Carbopol981和Carbopol5984从B.F.Goodrich Company商购的丙烯酸酯共聚物和/或丙烯酸酯-丙烯酸烷基酯共聚物,非常特别优选的是选自Carbopol品级980,981,1382,2984,5984和Carbomer 2001的聚丙烯酸酯类。
也理想的是丙烯酸C10-30-烷基酯和选自丙烯酸、甲基丙烯酸或其酯类中的一种或多种单体的共聚物,其可用蔗糖的烯丙基醚或季戊四醇的烯丙基醚加以交联。
带有INCI名称“丙烯酸酯/丙烯酸C10-30烷基酯交互聚合物(crosspolymer)”的化合物同样是理想的。特别理想的是能够以商品名PemulenTR1和PemulenTR2从B.F.Goodrich Company获得的那些聚合物。
带有INCI名称丙烯酰基二甲基牛磺酸铵/乙烯基吡咯烷酮共聚物的化合物是适宜的。
根据本发明,丙烯酰基二甲基牛磺酸铵/乙烯基吡咯烷酮共聚物具有经验式[C7H16N2SO4]n[C6H9NO]m,它对应于下面的统计结构
本发明的优选物质种类以登记号58374-69-9,13162-05-5和88-12-0列在化学文摘中并且以商品名AristoflexAVC从Clariant GmbH获得。
也理想的是包括丙烯酰基二甲基牛磺酸盐的共聚物/交互共聚物,例如从Seppic S.A获得的SimugelEG或SimugelEG。
本发明所使用的其它完全合成的水胶体是:
A.阴离子聚氨酯类,其可溶于或可分散于水中和理想地可从下面化合物获得
Aa)至少一种每分子含有两个或更多个活性氢原子的化合物,
Ab)至少一种含酸或盐基团的二醇,和
Ac)至少一种二异氰酸酯。
该组分Aa)尤其是在每种情况下具有至多3000的数均分子量的二醇,氨基醇,二胺,聚酯醇,聚醚醇,或其混合物,其中至多3mol%的该化合物可被三醇或三胺代替。优选的是二醇类和聚酯二醇类。尤其,该组分Aa)包括至少50wt%的聚酯二醇,基于组分Aa)的总重量。合适的聚酯二醇是常用于制备聚氨酯的所有那些化合物,尤其是邻苯二甲酸和二甘醇,间苯二酸和1,4-丁二醇,间苯二甲酸/己二酸和1,6-己二醇,以及己二酸和乙二醇或5-NaSO3-间苯二酸,邻苯二甲酸,己二酸和1,6-己二醇的反应产物。
可以使用的二醇类的例子是乙二醇,丙二醇,丁二醇,新戊二醇,聚醚醇,如分子量至多3000的聚乙二醇,数均分子量至多3000的环氧乙烷和环氧丙烷的嵌段共聚物或含有无规分布方式或嵌段形式的共聚合烯化氧单元的环氧乙烷、环氧丙烷和环氧丁烷的嵌段共聚物。优选乙二醇,新戊二醇,二-,三-,四-,五-或六甘醇。可使用的其它二醇是聚(α-羟基羧酸)二醇类。
合适的氨基醇是例如2-氨基乙醇,2-(N-甲基氨基)乙醇,3-氨基丙醇或4-氨基丁醇。
合适二胺类的例子是乙二胺,丙二胺,1,4-二氨基丁烷和1,6-二氨基己烷以及可通过聚烯化氧与氨的胺化作用制备的α,ω-二胺类。
组分Ac)尤其是六亚甲基二异氰酸酯,异佛尔酮二异氰酸酯,甲基二苯基异氰酸酯(MDI)和/或甲苯二异氰酸酯。
该聚氨酯类可通过Aa)组和Ab)组的化合物在惰性溶剂中在70-130℃的温度下在惰性气体氛围中与Ac)组的化合物反应来获得。如果合适的话,这一反应能够在链增长剂存在下进行,以便制备具有较高分子量的聚氨酯类。在聚氨酯类的制备中常见的是,组分[(Aa)+(Ab)]∶Ac理想地以0.8-1.1∶1的摩尔比使用。聚氨酯类的酸值是由该组成以及组分(Ab)的化合物在组分(Aa)和(Ab)的混合物中的浓度决定的。
该聚氨酯类具有根据H.Fikentscher的K值(利用在N-甲基吡咯烷酮中0.1wt%强度溶液在25℃和pH7下测定)为15-100,优选25-50。
该K值,也称作特性粘度,是利用聚合物溶液的粘度测量法容易测定的参数和因此常常用于表征聚合物的工业领域中。
含酸基团的聚氨酯在中和(部分或完全)后是水可溶的或可分散的,无需借助于乳化剂。聚氨酯的盐通常比未中和的聚氨酯类具有更好的在水中的溶解性或分散性。用于中和聚氨酯类的碱是碱金属碱,如氢氧化钠溶液,氢氧化钾溶液,苏打,碳酸氢钠,碳酸钾或碳酸氢钾和碱土金属碱类,如氢氧化钙,氧化钙,氢氧化镁或碳酸镁,以及氨和胺类。2-氨基-2-甲基丙醇,二乙氨基丙基胺和三异丙醇胺已经被证明特别可用于含有酸基的聚氨酯类的中和。含有酸基的聚氨酯类的中和也能够通过使用两种或多种碱的混合物,例如氢氧化钠溶液和三异丙醇胺的混合物来进行。取决于预定的用途,中和可以是部分的,例如20-40%,或完全的,即100%。
这些聚合物及其制备更详细地描述在DE-A-42 25 045中,其整个范围被引入这里供参考。
B.以下组分形成的水溶性或水可分散的阳离子聚氨酯类和聚脲类
Ba)至少一种二异氰酸酯,其还可早已预先与一种或多种每分子含有两个或多个活性氢原子的化合物反应,和
Bb)至少一种二醇,具有一个或多个叔、季或质子化叔氨基氮原子的伯或仲氨基醇,伯或仲二胺或伯或仲三胺。
优选的二异氰酸酯是以上在A)下给出的那些。具有两个或多个活性氢原子的化合物是二醇类,氨基醇类,二胺类,聚酯醇类,聚酰胺二胺和聚醚醇。这一类型的合适化合物是以上在A)下给出的那些。
该聚氨酯类是按照以上在A)下所述制备的。带电荷的阳离子基团能够通过质子化(例如用羧酸如乳酸)或通过季铵化(例如用烷基化剂如C1-C4烷基卤化物或硫酸酯),在聚脲类中从所存在的叔氨基氮原子产生。此类烷基化剂的例子是乙基氯,乙基溴,甲基氯,甲基溴,硫酸二甲酯和硫酸二乙酯。
这些聚合物及其制备更详细地描述在DE-A-42 41 118中,其整个范围被引入这里供参考。
C.由以下组分形成的具有羧酸酯基团的线性聚氨酯类:
Ca)具有下式的2,2-羟甲基取代的羧酸其中RR’是氢原子或C1-C20-烷基,其用量足以使得在聚氨酯中存在0.35-2.25毫当量的羧基/1g的聚氨酯,
Cb)10-90wt%(基于聚氨酯的重量)的一种或多种具有不超过两个活性氢原子的有机化合物,和
Cc)一种或多种有机二异氰酸酯。
在聚氨酯中存在的羧基最后用合适的碱至少部分地中和。这些聚合物及其制备更详细地描述在EP-A-619 111中,其整个范围被引入这里供参考。
D.三或四羧酸的酸酐和二醇类,二胺类或氨基醇类的含羧基缩聚产物(聚酯,聚酰胺或聚酯酰胺)。这些聚合物及其制备更详细地描述在DE-A-4224 761中,其整个范围被引入这里供参考。
E.聚丙烯酸酯类和聚甲基丙烯酸酯,更详细地描述在DE-A-43 14305,36 27 970和29 17 504中。在此这些出版物以其全部内容引入供参考。
根据本发明使用的聚合物优选具有15-100,优选25-50的K值。该聚合物通常以0.2-20wt%的量存在于本发明的组合物中,基于组合物的总重量。该盐以有效改进聚合物的可交换性的量使用。该盐通常以0.02-10wt%,优选0.05-5wt%和尤其0.1-3wt%的量使用,基于组合物的总重量。
作为无机增稠剂,例如有可能从改性或未改性的、天然或合成的层状硅酸盐中选择代表物。
虽然完全有利的是使用纯的组分,但是也理想的是不同的改性和/或未改性层状硅酸盐的混合物存在于本发明的组合物中。
对本申请而言,层状硅酸盐被理解为指硅酸盐和硅铝酸盐,其中硅酸盐或铝酸盐单元经三个Si-O-或Al-O-键连接在一起并形成波浪状的片或层状结构。第四个Si-O-或Al-O-价通过阳离子来饱和。在各层之间存在较弱的静电相互作用,例如氢键。同时,该层状结构基本上由强共价键来确定。
层状硅酸盐的化学计算法,对于纯硅酸盐结构是(Si2O5 2-)和对于硅铝酸盐是(AlmSi2- mO5 (2+m)-)。
m是大于零和低于2的数。
如果纯的硅酸盐不存在,而是存在硅铝酸盐,则需要考虑被Al3+置换的每一个Si4+基团需要另一个单电荷的阳离子来中和电荷的情况。
电荷平衡优选通过H+,碱金属离子或碱土金属离子来调整。铝作为平衡离子也是已知的和有利的。与硅铝酸盐相反,这些化合物被称作硅酸铝。“硅铝酸铝盐”,其中铝同时存在于硅酸盐网络中并且作为平衡离子,是已知的和有时候对于本发明是有利的。
层状硅酸盐已经在文献中充分描述过,例如“Lehrbuch derAnorganischen Chemie”[无机化学教科书],A.F.Hollemann,E.Wiberg和N.Wiberg,第91-100版,Walter de Gruyter-Verlag 1985,passim,和“Lehrbuch der Anorganischen Chemie”,H.Remy,第12版,AkademischeVerlagsgeseuschaft,Leipzig 1965,passim。蒙脱土的层状结构见于RmppsChemie-Lexikon,Franckh’sche Verlagshandlung W.Keller & Co.,Stuttgart,第8版,1985,p.2668f。
层状硅酸盐的例子是:
蒙脱土 Na0.33((Al1.67Mg0.33)(OH)2(Si4O10))
常见的简化形式: Al2O3*4SiO2*H2O*nH2O或
Al2[(OH)2/Si4O10]·nH2O
高岭石 Al2(OH)4(Si2O5)
伊利石 (K,H3O)y(Mg3(OH)2(Si4-yAlyO10))或
(K,H3O)y(Al2(OH)2(Si4-yAlyO10))
其中y=0.7-0.9
贝得石 (Ca,Na)0.3(Al2(OH)2(Al0.5Si3.5O10))
囊脱石 Na0.33(Fe2(OH)2(Al0.33Si3.67O10))
滑石 (Ca,Na)0.33((Mg,Fe)3(OH)2(Al0.33Si3.67O10))
锂蒙脱石 Na0.33((Mg,Li)3(OH,F)2(Si4O10))
蒙脱土是天然膨润土的主要矿物。
本发明非常理想的无机凝胶前体是硅酸铝,如蒙脱土(膨润土,锂蒙脱石及其衍生物,如季铵盐(quaternium)-18膨润土,季铵盐-18锂蒙脱石,硬脂基二甲基苄铵(stearalkonium)膨润土和硬脂基二甲基苄铵锂蒙脱石),以及硅酸镁铝(Veegum品级),和硅酸钠镁(Laponite品级)。
蒙脱土代表了属于双八面体绿土类型的粘土矿物,并且是块状物,在水中溶胀但不变成塑性。在蒙脱土的三层结构中层包覆体也会由于水(2-7倍量)和其它物质,例如醇类,二醇类,吡啶,α-甲基吡啶,铵化合物,羟基-硅铝酸盐离子等的可逆引入而溶胀。
以上给出的化学式仅是近似的:因为蒙脱土具有大容量供离子交换用,Al能够被Mg、Fe2+、Fe3+、Zn、Pb(例如来自废水中的有害物质),Cr,和铜等置换。八面体层的负电荷由在层间位置中的阳离子补偿,尤其Na+(钠蒙脱石)和Ca2+(钙蒙脱石仅仅在非常小的程度上溶胀)。
对本发明有利的合成硅酸镁和/或膨润土例如由Süd-Chemie以商品名Optigel销售。
本发明适宜的硅酸铝例如由R.T.Vanderbilt Comp.,Inc.以商品名Veegum销售。各种Veegum品级,根据本发明来说它们全部是理想的,通过以下组成来表征
(正规品级) HV K HS S-728
SiO2 55.5 56.9 64.7 69.0 65.3
MgO 13.0 13.0 5.4 2.9 3.3
Al2O3 8.9 10.3 14.8 14.7 17.0
Fe2O3 1.0 0.8 1.5 1.8 0.7
CaO 2.0 2.0 1.1 1.3 1.3
Na2O 2.1 2.8 2.2 2.2 3.8
K2O 1.3 1.3 1.9 0.4 0.2
灰化损失 11.1 12.6 7.6 5.5 7.5
这些产物在水中溶胀形成粘性凝胶,具有碱性反应。蒙脱土或膨润土的亲有机化(层间阳离子交换为烷基季铵离子)得到的产物(有机皂土)优选在有机溶剂和油,脂肪,软膏,油墨,表面涂料中和在洗涤剂中用于分散作用。
Bentone是各种中性和化学惰性胶凝剂的商品名,它们由长链有机铵盐和特定类型的蒙脱土构成。有机皂土溶胀在有机介质中并引起后者溶胀。该凝胶在稀酸和稀碱中有耐受性,虽然它们在与强酸和碱长时间接触时部分地损失它们的胶凝性质。因为它们的亲有机性质,有机皂土仅能被水艰难地润湿。
下列Bentone品级例如由Kronos Titan销售:Bentone27,一种有机改性的蒙脱土,Bentone34(二甲基二辛基铵膨润土),它根据US2,531,427制备且因为它的亲脂性基团,在亲脂性介质中比在水中更容易溶胀,Bentone38,一种有机改性的蒙脱土,乳白色到白色粉末,BentoneLT,提纯的粘土矿物,BentoneGel MIO,一种有机改性的蒙脱土,它以在矿物油(SUS-71)中非常细微的悬浮液来提供(10%膨润土,86.7%矿物油和3.3%润湿剂),BentoneGel IPM,一种有机改性的膨润土,它悬浮于十四烷酸异丙酯(10%膨润土,86.7%肉豆蔻酸异丙基酯,3.3%润湿剂),BentoneGel CAO,有机改性的蒙脱土,它调和在蓖麻油中(10%膨润土,86.7%蓖麻油和3.3%润湿剂),BentoneGel Lantrol,一种有机改性的蒙脱土,它以浆料形式用于进一步的处理,尤其用于化妆品组合物的制备中;10%膨润土,64.9 Lantrol(羊毛蜡油),22.0十四烷酸异丙酯,3.0润湿剂和0.1对羟基苯甲酸丙酯,BentoneGel Lan I,一种在羊毛蜡USP和棕榈酸异丙酯的混合物中的10%强度Bentone27糊,BentoneGel Lan II,一种在纯液体羊毛蜡中的膨润土糊,BentoneGel NV,一种在邻苯二甲酸二丁酯中15%强度Bentone27糊,BentoneGel OMS,一种在ShellsolT.中的膨润土糊,BentoneGel OMS 25,一种在异链烷烃类中的膨润土糊(IdoparH),BentoneGel IPP,在棕榈酸异丙酯中的膨润土糊。
优选用作稳定剂的一种或多种水胶体在成品化妆品或皮肤用制剂中的总量理想地选择为低于5wt%,优选在0.05-3.0wt%之间,特别优选在0.1-1.0wt%之间,基于制剂的总重量。
根据本发明的制剂包含作为组分e)的通式I的氨基取代的羟基二苯甲酮:
这类物质尤其描述在DE-A-199 17 906中。化合物I尤其以它在油中的良好溶解度,它加工到化妆品制剂中的良好加工性和在皮肤上的良好感觉为特征。
通式I化合物在成品化妆品或皮肤用制剂中的用量有利地为0.01wt%-20wt%,优选0.1wt%-10wt%,特别优选1wt%-7wt%,基于制剂的总重量。
可使用的本发明制剂的基本成分是:
·水或水溶液
·乙醇水溶液
·天然油和/或化学改性的天然油和/或合成油;
·脂肪、蜡和其它天然和合成的脂肪物质,优选脂肪酸与低碳数的醇如异丙醇、丙二醇或甘油的酯,或脂肪醇与低碳数的链烷酸或与脂肪酸的酯;
·低碳数的醇类、二醇类或多元醇,及其醚类,优选乙醇,异丙醇,丙二醇,甘油,乙二醇,乙二醇单乙基或单丁基醚,丙二醇单甲基、单乙基或单丁基醚,二甘醇单甲基或单乙基醚和类似产物。
尤其使用上述溶剂的混合物。
对于本公开物而言,表达语“类脂”有时用作脂肪、油、蜡等的通用术语,该表达语对于所属技术领域的专业人员来说完全是寻常的。术语“油相”和“脂相”也可同义地使用。
油和脂肪在它们的极性上彼此不同,但是难以定义。早已建议采用对水的界面张力作为油或油相的极性指数的量度。在该油相和水之间的界面张力越低,所述油相的极性越大。根据本发明,该界面张力被认为是给定的油组分的极性的可能量度。
界面张力是作用于两个相之间的界面中一米长度的假想线上的力。这一界面张力的物理单位通常从力/长度关系计算并且通常以mN/m(毫牛顿除以米)表达。如果它力图减少界面,则它具有正号。在相反的情况下,它具有负号。对于本发明,如果类脂对水的界面张力低于30mN/m,则它们被认为是极性的。
极性的油例如是卵磷脂和脂肪酸甘油三酯中的那些,即具有8-24个、尤其12-18个碳原子的链长度的饱和的和/或不饱和的,支化和/或未支化的链烷羧酸的甘油三酯。该脂肪酸甘油三酯例如理想地选自合成、半合成和天然油如橄榄油,向日葵油,大豆油,花生油,菜子油,杏仁油,棕榈油,椰子油,蓖麻油,小麦胚芽油,葡萄子油,蓟油,月见草油,昆士兰果油等,只要观察到在主权利要求中要求的状态就行。
其它极性的油组分能够选自具有3-30个碳原子的链长的饱和的和/或不饱和的,支化和/或未支化的链烷羧酸以及具有3-30个碳原子的链长的饱和的和/或不饱和的,支化和/或未支化的醇类的酯类,和选自芳族羧酸和具有3-30个碳原子的链长的饱和的和/或不饱和的,支化和/或未支化的醇类的酯类。此类酯油理想地选自十四烷酸异丙酯,棕榈酸异丙酯,硬脂酸异丙基酯,油酸异丙酯,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,异壬酸异壬基酯,棕榈酸2-乙基己基酯,月桂酸2-乙基己基酯,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,油酸瓢儿菜基酯,芥酸瓢儿菜基酯和此类酯的合成、半合成和天然混合物,例如霍霍巴油。
另外,该油相能够理想地选自二烷基醚,饱和的或不饱和的、支化或未支化的醇类。如果本发明制剂的油相含有苯甲酸C12-15烷基酯或全部由后者组成,则是特别理想的。
另外,该油相理想地选自格尔伯特(Guerbet)醇类。格尔伯特醇类是以第一次描述了它们的制备方法的Marcel Guerbet来命名的。它们根据以下反应式通过如下方式形成通过醇氧化成醛,醛的醛醇缩合,从醛醇中除去水以及烯丙醛的氢化。格尔伯特醇类甚至在室温下是液体并且几乎没有皮肤刺激性。它们能够理想地在皮肤护理和头发护理组合物中用作加脂(fatting)、过分加脂以及再加脂的组分。
格尔伯特醇类在化妆品中的应用本身是已知的。此类物质在大多数场合下以如下结构来表征:
在这里,R1和R2通常是未支化的烷基。
根据本发明,格尔伯特醇理想地选自满足以下条件的那些:
R1是丙基,丁基,戊基,己基,庚基或辛基和
R2是己基,庚基,辛基,壬基,癸基,十一烷基,十二烷基,十三烷基或十四烷基。
根据本发明优选的格尔伯特醇类是具有以下化学结构的2-丁基辛醇:例如以商品名Isofol12从Condea Chemie GmbH获得,和具有以下化学结构的2-己基癸醇例如以商品名Isofol16从Condea Chemie GmbH获得。
根据本发明的格尔伯特醇类的混合物也能够理想地根据本发明来使用。2-丁基辛醇和2-己基癸醇的混合物例如能够以商品名Isofol14从Condea Chemie GmbH获得。
格尔伯特醇类在成品化妆品或皮肤用制剂中的总量理想地选自至多25.0wt%,优选在0.5-15.0wt%范围内,基于制剂的总重量。
对于本发明,此类油和蜡组分的任何混合物也能够理想地使用。也理想的是使用蜡,例如棕榈酸鲸蜡酯,作为油相的唯一类脂组分。
非极性的油例如是选自以下的那些:支化和未支化的烃和烃蜡,尤其凡士林(矿脂),石蜡油,角鲨烷和角鲨烯,聚烯烃类和氢化聚异丁烯。在聚烯烃类当中,聚癸烯是优选的物质。
根据本发明可以理想地使用的脂肪和/或蜡组分能够选自植物蜡,动物蜡,矿物蜡和石化蜡。根据本发明来说有利的例子是小烛树蜡,巴西棕榈蜡,日本蜡,西班牙草蜡,软木(cork)蜡,guaruma蜡,米胚芽油蜡,甘蔗蜡,浆果(berry)蜡,小冠巴西棕蜡,褐煤蜡,霍霍巴蜡,牛油树脂,蜂蜡,紫胶蜡,鲸蜡,羊毛脂(羊毛蜡),油脂(uropygial)润滑脂,纯地蜡,地蜡,石蜡和微晶蜡,只要观察到在主权利要求中要求的状态就行。
其它有益的脂肪和/或蜡组分是化学改性的蜡和合成蜡,例如以商品名SyncrowaxHRC(甘油三(二十二烷酸酯))和SyncrowaxAW 1C(C18-C36脂肪酸)从CRODA GmbH获得的那些,褐煤酯蜡类,Sasol蜡,氢化霍霍巴蜡,合成或改性的蜂蜡(例如二甲基聚硅氧烷共聚醇(copolyol)蜂蜡和/或C30-50烷基蜂蜡),聚烯烃蜡,聚乙二醇蜡,以及化学改性的脂肪,例如氢化植物油(例如氢化蓖麻油和/或氢化椰子脂肪酸甘油酯),甘油三酯如三羟基硬脂精,脂肪酸,脂肪酸酯,和二醇酯类,例如硬脂酸C20-C40烷基酯,羟基硬脂酰基硬脂酸C20-C40烷基酯和/或乙二醇褐煤酸酯。也理想的是某些有机硅化合物,其具有与指定的脂肪和/或蜡组分类似的物理性能,例如硬脂酰氧基(stearoxy)三甲基硅烷,只要观察到在主权利要求中要求的状态就行。
根据本发明,脂肪和/或蜡组分能够单独或以混合物存在。
对于本发明,此类油和蜡组分的任何所需混合物也能够理想地使用。
该油相理想地选自异硬脂酸2-乙基己基酯,辛基十二烷醇,异壬酸异十三烷基酯,异二十烷,椰子酸(cocoate)2-乙基己基酯,苯甲酸C12-C15烷基酯,辛酸/癸酸甘油三酯,二辛基醚(dicaprylyl ether),只要观察到在主权利要求中要求的状态就行。
特别理想的混合物是辛基十二烷醇,辛酸/癸酸甘油三酯,二辛基醚的混合物,或苯甲酸C12-C15烷基酯和异硬脂酸2-乙基己基酯的混合物,苯甲酸C12-C15烷基酯和异壬酸异十三烷基酯的混合物,以及苯甲酸C12-C15烷基酯,异硬脂酸2-乙基己基酯和异壬酸异十三烷基酯的混合物,只要观察到在主权利要求中要求的状态就行。
下面的表1列出了根据本发明来说理想的类脂类,呈单种物质和彼此的混合物。对水的相应界面张力在最后一栏中给出。然而,也理想的是使用更大或更小极性组分等的混合物。
商品名 | INCI名称 | (m/Nm) |
Isofol14T | 丁基癸醇+己基癸醇+己基辛醇+丁基辛醇 | 27.6 |
Isofol16 | 己基癸醇 | 24.3 |
EutanolG | 辛基十二烷醇 | 24.8 |
CetiolOE | 二辛基醚 | 22.1 |
Miglyol812 | 辛酸/癸酸甘油三酯 | 21.3 |
CegesoftC24 | 棕榈酸辛基酯 | 23.1 |
硬脂酸异丙基酯 | 硬脂酸异丙基酯 | 21.9 |
Estol1540 EHC | 辛酸辛基酯 | 30.0 |
FinsolvTN | 苯甲酸C12-C15烷基酯 | 21.8 |
CetiolSN | 异壬酸十六烷基十八烷基(cetearyl)酯 | 28.6 |
DermofeelBGC | 丁二醇二辛酸酯/二癸酸酯 | 21.5 |
TriventOCG | 三辛酸甘油酯 | 20.2 |
MOD | 肉豆蔻酸辛基十二烷基酯 | 22.1 |
CosmacolETI | 酒石酸二-C12-C13烷基酯 | 29.4 |
Miglyol829 | 辛酸/癸酸二甘油基琥珀酸酯 | 29.5 |
Prisorine2036 | 异硬脂酸辛基酯 | 29.7 |
TegosoftSH | 庚酸硬脂基酯 | 28.7 |
AbilWax 9840 | 鲸蜡基二甲基聚硅氧烷(Cetyl Dimethicone) | 25.1 |
CetiolLC | 椰油-辛酸酯/癸酸酯(Coco-Caprylate/Caprate) | 24.8 |
IPP | 棕榈酸异丙酯 | 22.5 |
LuvitolEHO | 辛酸十六烷基/十八烷基酯 | 28.6 |
Cetiol868 | 硬脂酸辛基酯 | 28.4 |
根据本发明可以理想地使用的具有两个或更多个甲硅烷氧基的聚硅氧烷一般以下面结构单元为特征:其中硅原子可被相同或不同的烷基和/或芳基取代,这些基团一般由基团R1-R4表示,其中不同基团的数目不必限于4。m可以是2到200,000的值。
根据本发明可以理想地使用的环状聚硅氧烷一般以下面的结构单元为特征:其中硅原子可被相同或不同的烷基和/或芳基取代,这些基团在这里一般由基团R1-R4表示,其中不同基团的数目不必限于4。n能够是3/2到20的值。对于n的分数值可以考虑到在环中存在奇数的甲硅烷氧基。
苯基三甲基硅氧烷(Phenyltrimethicone)理想地选择为硅油。对于本发明,也可以理想地使用其它硅油,例如二甲基聚硅氧烷,苯基二甲基硅氧烷,环甲基聚硅氧烷(八甲基环四硅氧烷),例如六甲基环三硅氧烷,聚二甲基硅氧烷,聚(甲基苯基硅氧烷),十六烷基二甲基硅氧烷,二十二烷氧基二甲基硅氧烷。
环甲基聚硅氧烷和异壬酸异十三烷基酯的混合物以及环甲基聚硅氧烷和异硬脂酸2-乙基己基酯的那些混合物也是理想的。
然而,也理想的是选择具有类似构成的硅油,如以上所述的有机侧链已经衍生化(例如聚乙氧基化和/或聚丙氧基化)的那些化合物。这些包括例如聚硅氧烷-聚烷基-聚醚共聚物,如十六烷基二甲基硅氧烷共聚醇,(十六烷基二甲基硅氧烷共聚醇(和)聚甘油基-4异硬脂酸酯(和)月桂酸己酯)。
如果使用少量的乳化剂,则能够使用W/O乳化剂和/或O/W乳化剂,例如适宜选自一般用作W/O乳化剂的下列物质:
卵磷脂,羊毛脂,微晶蜡(Cera microcristallina)与石蜡油(Paraffinumliquidum)的混合物,地蜡,氢化蓖麻油,聚甘油基-3油酸酯,羊毛蜡酸混合物,羊毛蜡醇混合物,异硬脂酸季戊四醇基酯,聚甘油基-3二异硬脂酸酯,蜂蜡(Cera alba)和硬脂酸,二羟基十六烷基磷酸钠与异丙基羟基十六烷基醚的混合物,甲基葡萄糖二油酸酯,甲基葡萄糖二油酸酯与羟基硬脂酸酯和蜂蜡的混合物,矿物油与矿脂和地蜡以及油酸甘油酯和羊毛脂醇的混合物,矿脂与地蜡和氢化蓖麻油以及异硬脂酸甘油酯和聚甘油基-3油酸酯的混合物,PEG-7氢化蓖麻油,地蜡和氢化蓖麻油,聚甘油基-4异硬脂酸酯,聚甘油基-4异硬脂酸酯与十六烷基二甲基硅氧烷共聚醇和月桂酸己基酯的混合物,月桂基甲基硅氧烷共聚醇,十六烷基二甲基硅氧烷共聚醇,丙烯酸酯/丙烯酸C10-C30-烷基酯交互聚合物(crosspolymer),Poloxamer101,聚甘油基-2二聚羟基硬脂酸酯,聚甘油基-3二异硬脂酸酯,聚甘油基-4二聚羟基硬脂酸酯,PEG-30二聚羟基硬脂酸酯,二异硬脂酰基聚甘油基-3二异硬脂酸酯,聚甘油基-2二聚羟基硬脂酸酯,聚甘油基-3二聚羟基硬脂酸酯,聚甘油基-4二聚羟基硬脂酸酯,聚甘油基-3二油酸酯。
如果需要,能够使用一种或多种乳化剂,选自一般用作O/W乳化剂的下列物质:
硬脂酸甘油基酯与十六烷基十八烷基醚(ceteareth)-20的混合物,ceteareth-25,ceteareth-6与十八烷醇的混合物,十六烷基硬脂醇与PEG-40蓖麻油和十六烷基硬脂基硫酸钠的混合物,triceteareth-4磷酸酯,十六烷基硬脂基硫酸钠,卵磷脂trilaureth-4磷酸酯,laureth-4磷酸酯,硬脂酸,丙二醇硬脂酸酯SE,PEG-25氢化蓖麻油,PEG-54氢化蓖麻油,PEG-6辛酸/癸酸甘油酯,油酸甘油酯与丙二醇的混合物,ceteth-2,ceteth-20,聚山梨酸酯60,硬脂酸甘油酯与PEG-100硬脂酸酯的混合物,laureth-4,ceteareth-3,异硬脂基甘油基醚,十六烷基硬脂醇与十六烷基硬脂基硫酸钠的混合物,laureth-23,steareth-2,硬脂酸甘油酯与PEG-30硬脂酸酯的混合物,PEG-40硬脂酸酯,乙二醇二硬脂酸酯,PEG-22十二烷基乙二醇共聚物,聚甘油基-2 PEG-4硬脂酸酯,ceteareth-20,甲基葡萄糖倍半硬脂酸酯,steareth-10,PEG-20硬脂酸酯,steareth-2与PEG-8二硬脂酸酯的混合物,steareth-21,steareth-20,isosteareth-20,PEG-45/十二烷基乙二醇共聚物,甲氧基-PEG-22/十二烷基乙二醇共聚物,PEG-20甘油基硬脂酸酯,PEG-8蜂蜡,聚甘油基-2月桂酸酯,异硬脂基二甘油基琥珀酸酯,硬脂酰胺基丙基PG二铵(dimonium)氯化物磷酸盐,硬脂酸甘油酯SE,ceteth-20,柠檬酸三乙酯,PEG-20甲基葡萄糖倍半硬脂酸酯,ceteareth-12,甘油硬脂酸酯柠檬酸酯,磷酸鲸蜡基酯,triceteareth-4磷酸酯,trilaureth-4磷酸酯,甲基葡萄糖二硬脂酸聚甘油基酯,鲸蜡基磷酸钾,isosteareth-10,聚甘油基-2倍半异硬脂酸酯,ceteth-10,oleth-20,isoceteth-20,硬脂酸甘油酯与ceteareth-20的混合物,ceteareth-12,十六烷基硬脂醇和棕榈酸十六烷基酯,十六烷基硬脂醇与PEG-20硬脂酸酯的混合物,PEG-30硬脂酸酯,PEG-40硬脂酸酯,PEG-100硬脂酸酯。
对于本发明来说也比较理想的是,尤其当制剂的油相至少部分地由硅油组成时,使用聚硅氧烷乳化剂。该聚硅氧烷乳化剂可以理想地选自界面活性物质,选自烷基甲基硅氧烷共聚醇和/或烷基二甲聚硅氧烷共聚醇,特别选自以下面的化学结构为特征的化合物:其中X和Y彼此独立地选自基团H、支化和未支化的烷基、具有1-24个碳原子的酰基和烷氧基,p是0-200的数,q是1-40的数,和r是1-100的数。
对本发明来说特别理想使用的聚硅氧烷乳化剂的例子是二甲基聚硅氧烷共聚醇,它们由Th.Goldschmidt AG以商品名ABILB 8842,ABILB 8843,ABILB 8847,ABILB 8851,ABILB 8852,ABILB 8863,ABILB 8873和ABILB 88183销售。
对本发明来说特别理想使用的界面活性物质的另一例子是十六烷基二甲基硅氧烷共聚醇,它由Th.Goldschmidt AG以商品名ABILEM 90销售。
对本发明来说特别理想使用的界面活性物质的另一例子是环甲基硅氧烷二甲基硅氧烷共聚醇,它由Th.Goldschmidt AG以商品名ABILEM97销售。
另外,已被证明尤为理想的乳化剂是月桂基甲基硅氧烷共聚醇,它以商品名Dow Corning5200 Formulation Aid从Dow Corning Ltd商购。
若使用少量聚硅氧烷乳化剂,则它们在本发明的化妆品或皮肤用制剂中的总量理想地选自0.1-2.0wt%,优选0.5-1.5wt%,基于制剂的总重量。
对本发明而言,本发明的制剂,例如呈皮肤防护霜剂,皮肤洗液,化妆奶状液形式,例如呈防晒霜或太阳防护奶状液形式,是理想的并包括例如脂肪,油,蜡和/或其它脂肪物质,而水和如果需要,一种或多种乳化剂常常用于此类配制剂。
如同液体和固体稠度的制剂用作化妆清洁洗液或清洁霜一样,根据本发明的制剂也代表可喷雾的清洁制剂(“清洗喷雾剂”),其例如用于卸妆或用作温和的洗涤液体-任选也用于弄脏的皮肤。此类清洁制剂能够理想地进一步用作“漂洗制剂”,其可在施用之后从皮肤上漂洗掉。
所属技术领域的专业人员自然知道,若没有常规助剂和添加剂,所要求的化妆品组合物在大多数情况下是不可想象的。这些包括例如基础剂,填料,香料,染料,乳化剂,附加的活性成分如维生素类和蛋白质,光保护剂,稳定剂,驱昆虫剂,醇,水,盐,抗微生物、蛋白质水解或角蛋白水解活性物质等等。
相应的要求对于药用制剂的配方加以必要的变更。
因此,本发明的化妆或局部皮肤用制剂能够依据组成例如用作皮肤防护霜剂,清洁奶状物,防晒洗液,营养霜,日霜或晚霜等。在一些情况下有可能和理想地使用本发明的组合物作为药物配制剂的基础。
同样理想地使用本发明的制剂用于装饰性的化妆品(化妆配制剂)。
也有利的是防晒形式的那些化妆品和皮肤用制剂。除了本发明使用的活性成分之外,这些优选另外包括至少一种宽带过滤剂和/或至少一种UVA过滤物质和/或至少一种UVB过滤物质和/或至少一种无机颜料。
然而,对于本发明来说也理想的是生产这样的化妆品和皮肤用制剂,其主要目的不是防护日光,但仍然含有UV保护物质。因此例如UV-A和/或UV-B过滤物质常常被引入到日霜中。
理想的宽带过滤剂,UV-A或UV-B过滤物质是例如是具有下面结构的双间苯二酚基三嗪衍生物:其中R1,R2和R3彼此独立地选自具有1-10个碳原子的支化和未支化烷基或表示单个氢原子。特别优选的是2,4-双{[4-(2-乙基己基氧基)-2-羟基]苯基}-6-(4-甲氧基-苯基)-1,3,5-三嗪(INCI:Aniso Triazine),它以商品名称TinosorbS从CIBA-Chemikalien GmbH获得。
其中
R是支化或未支化的C1-C18-烷基,C5-C12-环烷基,任选被一个或多个C1-C4-烷基所取代,
X是氧原子或NH基团,
R1是支化或未支化的C1-C18-烷基,C5-C12-环烷基,任选被一个或多个C1-C4-烷基所取代,或氢原子,碱金属原子,铵基团或下式的基团
其中
A是支化或未支化的C1-C18-烷基,C5-C12-环烷基或芳基,任选被一个或多个C1-C4-烷基所取代,
R3是氢原子或甲基,
n是1到10的数,
R2是支化或未支化的C1-C18-烷基,C5-C12-环烷基,任选被一个或多个C1-C4-烷基取代,如果X是NH基团的话,和支化或未支化的C1-C18-烷基,C5-C12-环烷基,任选被一个或多个C1-C4-烷基取代,或氢原子,碱金属原子,铵基团或下式的基团
其中
A是支化或未支化的C1-C18-烷基,C5-C12-环烷基或芳基,任选被一个或多个C1-C4-烷基所取代,
R3是氢原子或甲基,
n是1到10的数,
如果X是氧原子的话。
本发明特别优选的UV过滤物质也是不对称地取代的s-三嗪,它的化学结构由下式给出它也在下面被称作二辛基丁基酰胺基三嗪酮(INCI:二乙基己基丁酰胺基三嗪酮)和以商品名称UVASORBHEB从Sigma 3V获得。
对于本发明来说也理想的是对称取代的s-三嗪,4,4’,4”-(1,3,5-三嗪-2,4,6-三基三亚氨基)三苯甲酸三(2-乙基己基)酯,同义词:2,4,6-三[苯胺基(对-羰-2’-乙基-1’-己氧基)]-1,3,5-三嗪(INCI:乙基己基三嗪酮),它由BASFAktiengesellschaft以商品名称UVINULT 150销售。
对于本发明也合适的是2,4-双{[4-(3-磺酸根)-2-羟基丙氧基]-2-羟基}苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪钠盐,2,4-双{[4-(3-(2-丙氧基)-2-羟基丙氧基)-2-羟基]苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪,2,4-双{[4-(2-乙基己氧基)-2-羟基]苯基}-6-[4-(2-甲氧基-乙基羧基)苯基氨基]-1,3,5-三嗪,2,4-双{[4-(3-(2-丙氧基)-2-羟基丙氧基)-2-羟基]苯基}-6-[4-(2-乙基羧基)苯基氨基]-1,3,5-三嗪,2,4-双{[4-(2-乙基己氧基)-2-羟基]苯基}-6-(1-甲基吡咯-2-基)-1,3,5-三嗪,2,4-双{[4-三(三甲基-甲硅烷氧基甲硅烷基丙氧基)-2-羟基]苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪,2,4-双{[4-(2”-甲基丙烯基氧基)-2-羟基]苯基}-6-(4-甲氧基-苯基)-1,3,5-三嗪和2,4-双{[4-(1’,1’,1’,3’,5’,5’,5’-七甲基甲硅烷氧基-2”-甲基-丙氧基)-2-羟基]苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪。
任选用于成品化妆品或皮肤用制剂中的一种或多种三嗪衍生物的总量理想地选自0.01wt%-15wt%,优选0.1wt%-10wt%的范围,在每种情况下基于制剂的总重量。
对于本发明来说理想的磺化水溶性UV过滤剂是:
亚苯基-1,4-双(2-苯并咪唑基)-3,3'-5,5'-四磺酸,它以下面的结构为特征:及其盐,特别是相应的钠,钾或三乙醇铵盐,尤其亚苯基-1,4-双(2-苯并咪唑基)-3,3'-5,5'-四磺酸双钠盐具有INCI名称bisimidazylate(CAS No.:180898-37-7),它例如以商品名Neo HeliopanAP从Haarmann & Reimer获得。
对于本发明来说其它理想的磺化UV过滤剂是2-苯基苯并咪唑-5-磺酸的盐,及其钠、钾或三乙醇铵盐,和该磺酸本身:具有INCI名称苯基苯并咪唑磺酸(CAS No.27503-81-7),它例如以商品名Eusolex232从Merck获得或以Neo HeliopanHydro从Haarmann &Reimer获得。
其它理想的磺化UV过滤剂是3,3'-(1,4-亚苯基二亚甲基)双(7,7-二甲基-2-氧代-双环[2.2.1]庚-1-基甲烷磺酸,及其钠、钾或三乙醇铵盐,和该磺酸本身:具有INCI名称Terephthalidene Dicamphor Sulfonic Acid(对苯二亚甲基二樟脑磺酸)(CAS No.:90457-82-2),它例如以商品名Mexoryl SX从Chimex获得。
其它理想的水溶性UV-B和/或宽带过滤物质是,例如:
3-亚苄基樟脑的磺酸衍生物例如4-(2-氧代-3-亚冰片基甲基)苯磺酸,2-甲基-5-(2-氧代-3-亚冰片基甲基)磺酸及其盐。
任选用于成品化妆品或皮肤用制剂中的一种或多种磺化UV过滤剂物质的总量理想地选自0.01wt%-20wt%,优选0.1wt%-10wt%的范围,在每种情况下基于制剂的总重量。
该UV-B和/或宽带过滤剂可以是油溶性的或水溶性的。理想的油溶性UV-B和/或宽带过滤物质是例如:
3-亚苄基樟脑衍生物,优选3-(4-甲基亚苄基)樟脑,3-亚苄基樟脑;
4-氨基苯甲酸衍生物,优选4-(二甲基氨基)苯甲酸2-乙基己基酯,4-(二甲基氨基)苯甲酸戊基酯,4-双(聚乙氧基)氨基苯甲酸聚乙氧基乙基酯(以商品名UvinulP25从BASF获得);
二苯甲酮的衍生物,优选2-羟基-4-甲氧基二苯甲酮(以商品名UvinulM40从BASF获得),2-羟基-4-甲氧基-4’-甲基二苯甲酮,2,2’-二羟基-4-甲氧基二苯甲酮,2-羟基-4-甲氧基二苯甲酮-5-磺酸(以商品名UvinulMS40从BASF获得);
和键合到聚合物上的UV过滤剂。
本发明的在室温下是液体的特别理想的UV过滤物质是水杨酸高基酯,2-氰基-3,3-二苯基丙烯酸2-乙基己基酯,2-羟基苯甲酸2-乙基己基酯和肉桂酸的酯,优选4-甲氧基肉桂酸2-乙基己基酯和4-甲氧基肉桂酸异戊基酯。
水杨酸高基酯(INCI:Homosalate)以下面的结构为特征:
4-甲氧基肉桂酸2-乙基己基酯(INCI:甲氧基肉桂酸乙基己基酯)例如从BASF以商品名UvinulMC 80获得并以下面的结构为特征:
4-甲氧基肉桂酸异戊基酯(INCI:对-甲氧基肉桂酸异戊基酯)例如从Haarmann & Reimer以商品名Neo HeliopanE 1000获得并以下面的结构为特征:
本发明的在室温下为液体的另一理想的UV过滤物质是(3-(4-(2,2-双乙氧基羰基乙烯基)苯氧基)丙烯基)甲基-硅氧烷/二甲基硅氧烷共聚物,它例如从Hoffmann-La Roche以商品名ParsolSLX获得。
任选用于成品化妆品或皮肤用制剂中的在室温下为液体的一种或多种UV过滤物质的总量理想地选自0.1wt%-30wt%,优选0.5wt%-20wt%的范围,在每种情况下基于制剂的总重量。
本发明的理想的二苯甲酰基甲烷衍生物尤其是4-(叔丁基)-4’-甲氧基苯甲酰基甲烷(CAS No.70356-09-1),它由BASF以商品名UvinulBMBM销售和由Merck以商品名Eusolex9020销售并且以下面的结构为特征:
其它理想的二苯甲酰基甲烷衍生物是4-异丙基二苯甲酰基甲烷(CASNo.63250-25-9),它由Merck以商品名Eusolex8020销售。Eusolex 8020以下面的结构为特征:苯并三唑以下列结构式为特征:
其中
R1和R2彼此独立地是具有1-18个碳原子的直链或支化的,饱和的或不饱和的,取代的(例如被苯基取代)或未被取代的烷基和/或本身不吸收UV射线的聚合物基团(例如,聚硅氧烷基团,丙烯酸酯基团等),和R3选自基团H或具有1-18个碳原子的烷基。
本发明的理想苯并三唑是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),它是一种以下面的化学结构式为特征的宽带滤光剂并且以商品名TinosorbM从CIBA-Chemikalien GmbH获得。
本发明的理想的苯并三唑也可以是2-(2H-苯并三唑-2-基)-4-甲基-6-[2-甲基-3-[1,3,3,3-四甲基-1-[(三甲基甲硅烷基)氧基]二硅氧烷基]丙基]苯酚(CAS No.:155633-54-8),具有INCI名称Drometrizole Trisiloxane,它由Chimex以商品名MexorylXL销售并且以下面的化学结构式为特征
本发明的其它理想的苯并三唑是[2,4’-二羟基-3-(2H-苯并三唑-2-基)-5-(1,1,3,3-四甲基丁基)-2’-正辛氧基-5’-苯甲酰基]二苯甲烷,2,2’-亚甲基双[6-(2H-苯并三唑-2-基)-4-(甲基)苯酚],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],2-(2’-羟基-5’-辛基苯基)苯并三唑,2-(2’-羟基-3’,5’-二-叔戊基苯基)苯并三唑和2-(2’-羟基-5’-甲基苯基)苯并三唑。
任选用于成品化妆品或皮肤用制剂中的一种或多种苯并三唑的总量理想地选自0.1wt%-20wt%,优选0.5wt%-15wt%,特别优选0.5wt%-10wt%,在每种情况下基于制剂的总重量。
根据本发明的化妆品和皮肤用制剂还理想地,但并非强制性地,包括基于不溶于或几乎不溶于水中的金属氧化物和/或其它金属化合物的无机颜料,尤其钛(TiO2),锌(ZnO),铁(例如Fe2O3),锆(ZrO2),硅(SiO2),锰(例如MnO),铝(Al2O3),铈(例如Ce2O3)的氧化物,相应金属的混合氧化物和此类氧化物的混合物。这些颜料是X射线无定形的或非X射线无定形的。该颜料特别优选基于TiO2。
X射线无定形的氧化物颜料是在X射线衍射实验中显示没有或没有可识别的晶体结构的金属氧化物或半金属氧化物。此类颜料常常可通过火焰反应来获得,例如由金属或半金属卤化物与氢气和空气(或纯氧)在火焰中反应。
在化妆品,皮肤用或药物配制剂中,X射线无定形的氧化物颜料用作增稠剂和触变剂,流动助剂,用于乳液和分散体稳定化和用作载体物质(例如增加细碎粉末的体积)。
已知的和常常用于化妆品或皮肤学技术中的X射线无定形的氧化物颜料是Aerosil型的二氧化硅(CAS No.7631-86-9)。可从DEGUSSA获得的Aerosil以低粒度(例如在5-40nm之间)为特征,其中该颗粒被认为是具有非常均匀的尺寸的球状颗粒。利用显微镜观察,Aerosile可辨认为疏松、白色的粉末。在本发明的意义中,X射线无定形二氧化硅颜料是特别有利的且其中,准确地说,Aerosil品级的那些是优选的。
有利的Aerosil品级是例如AerosilOX50,Aerosil130,Aerosil150,Aerosil200,Aerosil300,Aerosil380,AerosilMOX 80,AerosilMOX 170,AerosilCOK 84,AerosilR 202,AerosilR 805,AerosilR 812,AerosilR 972,AerosilR 974,AerosilR 976。
任选用于成品化妆品或皮肤用制剂中的一种或多种X射线无定形的氧化物颜料的总量理想地选自0.1wt%-20wt%,优选0.5wt%-10wt%,特别优选1wt%-5wt%,在每种情况下基于制剂的总重量。
根据本发明,非X射线无定形的无机颜料理想地呈疏水性形式,即它们已进行了表面处理赋予拒水性。该表面处理可以包括由本身已知的方法提供具有薄的疏水性层的颜料。
此类方法例如包括根据以下所示的反应产生疏水性表面层:
在这里,n和m是根据需要使用的化学计量参数,以及R和R’是所希望的有机基团。按照在DE-A 33 14 742中制备的疏水化颜料例如是理想的。
本发明的有机表面涂层可由植物或动物硬脂酸铝,植物或动物硬脂酸,月桂酸,二甲基聚硅氧烷(又名:dimethicone),甲基聚硅氧烷(methicone),simethicone(平均链长200-350个二甲基硅氧烷单元的二甲聚硅氧烷和硅胶的混合物),辛基三甲氧基硅烷或藻酸组成。这些有机表面涂层可以单独存在,共同存在和/或与无机涂料相结合存在。
根据本发明来说合适的氧化锌颗粒和氧化锌颗粒的预分散体以下面的商品名从下面列出的公司获得:
商品名称 | 涂层 | 制造商 |
Z-CoteHP1 | 2%二甲基聚硅氧烷 | BASF |
Z-Cote | - | BASF |
ZnO NDM | 5%二甲基聚硅氧烷 | H&R |
MZ-505 S | 5%甲基聚硅氧烷 | Tayca Corp. |
合适的二氧化钛颗粒和二氧化钛颗粒的预分散体以下面的商品名从下面列出的公司获得:
商品名称 | 涂层 | 制造商 |
MT-100TV | 氢氧化铝/硬脂酸 | Tayca Corporation |
MT-100Z | 氢氧化铝/硬脂酸 | Tayca Corporation |
EusolexT-2000 | 氧化铝/simethicone | Merck KgaA |
二氧化钛T805(UvinulTiO2) | 辛基三甲氧基硅烷 | Degussa,BASF |
理想的TiO2颜料例如以商品名称Uvinul TiO2获得,和理想的TiO2/Fe2O3混合氧化物是以商品名称UvinulTiO2 A从BASF获得。
任选用于成品化妆品或皮肤用制剂中的无机颜料(尤其疏水性无机微细颜料)的总量理想地选自0.1-30wt%,优选0.1-10.0wt%,尤其0.5-6.0wt%,基于该制剂的总重量。
除了早已描述过的本发明的各种成分,根据本发明的化妆品和皮肤用制剂能够进一步包括通常在此类制剂中使用的化妆用活性成分,助剂和/或添加剂,例如抗氧化剂,防腐剂,杀菌剂,香料,防沫剂,染料,具有着色作用的颜料,润肤剂,加湿剂和/或湿润剂,脂肪,油,蜡或化妆品或皮肤用配制剂的其它常用成分,如泡沫稳定剂,电解质,有机溶剂或聚硅氧烷衍生物。
在食品技术中许可的防腐剂,它们在下面以它们的E数列出,根据本发明是理想使用的。
E 200 | 山梨酸 | E 227 | 亚硫酸氢钙 |
E 201 | 山梨酸钠 | E 228 | 亚硫酸氢钾 |
E 202 | 山梨酸钾 | E 230 | 联苯(Diphenyl) |
E 203 | 山梨酸钙 | E 231 | 邻苯基苯酚 |
E 210 | 苯甲酸 | E 232 | 邻苯基苯酚钠 |
E 211 | 苯甲酸钠 | E 233 | 噻苯咪唑 |
E 212 | 苯甲酸钾 | E 235 | 游霉素 |
E 213 | 苯甲酸钙 | E 236 | 甲酸 |
E 214 | 对羟基苯甲酸乙酯 | E 237 | 甲酸钠 |
E 215 | 对-羟基苯甲酸乙酯Na盐 | E 238 | 甲酸钙 |
E 216 | 对-羟基苯甲酸正丙基酯 | E 239 | 六亚甲基四胺 |
E 217 | 对-羟基苯甲酸正丙基酯Na盐 | E 249 | 亚硝酸钾 |
E 218 | 对羟基苯甲酸甲酯 | E 250 | 亚硝酸钠 |
E 219 | 对-羟基苯甲酸甲酯Na盐 | E 251 | 硝酸钠 |
E 220 | 二氧化硫 | E 252 | 硝酸钾 |
E 221 | 亚硫酸钠 | E 280 | 丙酸 |
E 222 | 亚硫酸氢钠 | E 281 | 丙酸钠 |
E 223 | 焦亚硫酸钠(sodium disulfite) | E 282 | 丙酸钙 |
E 224 | 焦亚硫酸钾 | E 283 | 丙酸钾 |
E 226 | 亚硫酸钙 | E 290 | 二氧化碳 |
也合适的是在化妆品中常用的防腐剂或防腐助剂:二溴二氰基丁烷(2-溴-2-溴甲基戊二腈),氨基甲酸3-碘-2-丙炔基丁基酯,2-溴-2-硝基丙烷-1,3-二醇,咪唑烷基脲,5-氯-2-甲基-4-异噻唑啉-3-酮,2-氯乙酰胺,洁尔灭,苄醇+甲醛给体。
也适合作为防腐剂的是苯基羟烷基醚,尤其以名称苯氧基乙醇公知的化合物,因为它们对许多微生物的杀菌和杀真菌效果。
其它抗微生物剂同样地适合引入到根据本发明的制剂中。理想的物质是例如2,4,4’-三氯-2’-羟基二苯基醚(Irgasan),1,6-二(4-氯苯基双胍基)己烷(Chlorhexidin),3,4,4’-三氯碳酰苯胺,季铵化合物,丁香油,薄荷油,麝香草油,柠檬酸三乙酯,金合欢醇(3,7,11-三甲基-2,6,10-十二碳三烯-1-醇)以及在专利申请公开说明书DE-37 40 186,DE-39 38 140,DE-42 04 321,DE-42 29 707,DE-43 09 372,DE-44 11 664,DE-195 41 967,DE-195 43695,DE-195 43 696,DE-195 47 160,DE-196 02 108,DE-196 02 110,DE-196 02 111,DE-196 31 003,DE-196 31 004和DE-196 34 019和专利说明书DE-42 29 737,DE-42 37 081,DE-43 24 219,DE-44 29 467,DE-44 23 410和DE-195 16 705中描述的活性成分或活性成分结合物。碳酸氢钠也可理想地使用。
然而,对于本发明,理想的是将其它抗刺激性的或抗炎的活性成分加入到该制剂中,尤其鲨肝醇(α-十八烷基甘油基醚),鲨油醇(α-9-十八碳烯基甘油基醚),银鲛肝醇(α-十六烷基甘油基醚),红没药醇和/或泛醇。
同样理想的是将普通的抗氧化剂加入到本发明的制剂中。根据本发明,合适的抗氧化剂能够是适合于或常用于化妆和/或皮肤学应用的任何抗氧化剂。
该抗氧化剂理想地选自氨基酸(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),类葫萝卜素,叶红素(例如α-叶红素,β-叶红素,φ-番茄红素)及其衍生物,绿原酸及其衍生物,硫金代葡萄糖(aurothioglucose),丙基硫尿嘧啶和其它硫醇类(例如硫氧还蛋白,谷胱甘肽,半胱氨酸,胱氨酸,胱胺及其糖基,N-乙酰基,甲基,乙基,丙基,戊基,丁基和月桂基,棕榈酰基,油基,γ-亚油基,胆甾烯基和甘油基酯)及其盐,硫代二丙酸二月桂基酯,硫代二丙酸二硬脂基酯,硫代二丙酸及其衍生物(酯类,醚类,肽,类脂,核苷酸,核苷和盐)和磺酰亚胺(Sulfoximine)化合物(例如丁基硫氧硫堇胺(buthionine)磺酰亚胺,同型半胱氨酸磺酰亚胺,丁基硫氧硫堇胺砜类,五-、六-、七硫堇磺酰亚胺),都以非常少的允许剂量(例如pmol至μmol/kg),以及(金属)螯合剂(例如α-羟基脂肪酸,棕榈酸,植酸,乳铁传递蛋白),α-羟基酸(例如柠檬酸,乳酸,苹果酸),腐殖酸,胆汁酸,胆汁萃取物,胆红素,胆绿素,EDTA,EGTA及其衍生物,不饱和脂肪酸及其衍生物(例如γ-亚麻酸,亚油酸,油酸),叶酸及其衍生物,呋喃亚甲基山梨糖醇及其衍生物,泛醌和泛醌醇及其衍生物,维生素C和衍生物(例如抗坏血酰棕榈酸酯,抗坏血酰磷酸镁,抗坏血酰乙酸酯),生育酚和衍生物(例如维生素E乙酸酯),和苯偶姻树脂的苯甲酸松柏酯,阿魏酸,呋喃亚甲基山梨醇,肌肽,丁基羟基甲苯,丁基羟基茴香醚,去甲二氢愈创木脂酸,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,锌及其衍生物(例如氧化锌,硫酸锌),硒及其衍生物(例如硒蛋氨酸,均二苯代乙烯及其衍生物(例如均二苯代乙烯氧化物,反式均二苯代乙烯氧化物)以及对本发明来说合适的活性成分的衍生物(盐类,酯类,醚类,糖类,核苷酸类,核苷类,肽类和类脂类)。
抗氧化剂(一种或多种化合物)在制剂中的量优选是0.001-30wt%,特别优选0.05-20wt%,尤其1-10wt%,基于制剂的总重量。
如果维生素E和/或它的衍生物用作抗氧化剂,理想的是将其各自的浓度选择在0.001-10wt%范围内,基于配制剂的总重量。、
根据本发明的制剂也能够用作化妆品或皮肤用除臭药或止汗药的基础料。除臭药或止汗药常用的全部活性成分能够理想地使用,例如臭味遮盖剂如常规的香料成分,气味吸收剂,例如在专利申请公开说明书DE-P 40 09347中描述的层状硅酸盐,其中尤其优选蒙脱土,高岭石,伊利石,贝得石,囊脱石,滑石,锂蒙脱石,膨润土,绿土以及例如蓖麻醇酸的锌盐。
此类活性成分(一种或多种化合物)在本发明制剂中的量优选是0.001-30wt%,特别优选0.05-20wt%,尤其1-10wt%,基于制剂的总重量。
其它的添加剂尤其是季铵盐表面活性剂。这些化合物含有以共价键键合于4个烷基或芳基上的至少一个N原子。与pH无关,这导致带正电荷。适宜的化合物是烷基甜菜碱,烷基酰胺基丙基甜菜碱和烷基酰胺基丙基羟基磺基甜菜碱。根据本发明使用的阳离子表面活性剂也优选地选自季铵化合物,尤其苄基三烷基铵氯化物或溴化物例如苄基二甲基硬脂基氯化铵,烷基三烷基铵盐,例如十六烷基三甲基铵氯化物或溴化物,烷基二甲基羟基乙基铵氯化物或溴化物,二烷基二甲基铵氯化物或溴化物,烷基酰胺基乙基三甲基铵醚硫酸盐,烷基吡啶鎓盐,例如月桂基-或十六烷基-嘧啶鎓氯化物,咪唑啉衍生物和具有阳离子性质的化合物,如氧化胺,例如烷基二甲胺氧化物或烷基胺基乙基二甲基胺氧化物。尤其,十六烷基三甲基铵盐是理想使用的。
另外,“金属皂”(即高级脂肪酸的盐,碱金属盐除外)也是本发明可用的理想油增稠剂,例如硬脂酸铝,硬脂酸锌和/或硬脂酸镁。
同样理想的是将两亲性或两性离子表面活性剂(例如椰油酰胺基丙基甜菜碱)和保湿剂(例如甜菜碱)加入到本发明的制剂中。理想使用的两性表面活性剂的例子是酰基/二烷基乙二胺,例如酰基两性基乙酸钠(sodiumacylamphoacetate),酰基两性基二丙酸二钠(disodium acylamphodi-propionate),烷基两性基二乙酸二钠(disodium alkylamphodiacetate),酰基两性基羟丙基磺酸钠(sodium acylamphohydroxypropylsulfonate),酰基两性基二乙酸二钠(disodium acylamphodiacetate)和酰基两性基丙酸钠(sodium acylamphopropionate),N-烷基氨基酸,例如氨丙基烷基谷氨酰胺,烷氨基丙酸,烷基酰亚胺基二丙酸钠(sodium alkylimidodipropionate)和月桂基两性基羧基甘氨酸盐(lauroamphocarboxyglycinate)。
本发明制剂的惊人性质是它们是化妆品或皮肤用的活性成分进入皮肤的非常良好的媒介物,优选的活性成分是上述抗氧化剂,它能够保护皮肤不受氧化作用。
根据本发明,该活性成分(一种或多种化合物)也非常理想地选自亲脂性活性成分,尤其选自以下:
乙酰基水杨酸,颠茄碱,甘菊环,皮质甾醇及其衍生物,例如皮质甾醇-17-戊酸盐,B和D系列的维生素类,非常适宜的是维生素B1,维生素B12,维生素D1,以及红没药醇,不饱和脂肪酸,即必需的脂肪酸(常常也称作维生素F),尤其γ-亚麻酸,油酸,二十碳五烯酸,二十二碳六烯酸和它的衍生物,氯霉素,咖啡因,前列腺素,麝香草酚,樟脑,植物和动物来源的提取物或其它产物,例如月见草油,玻璃苣油(borrage oil)或茶麋子果实(currant)种子油,鱼油,鳕鱼肝油以及神经酰胺和神经酰胺状化合物等。
也理想的是从再加脂物质中选择活性成分,例如purcellin油,Eucerit和Neocerit。
该活性成分特别理想地选自NO合酶(synthesase)抑制剂,尤其如果本发明的制剂用于内部的和/或外部的皮肤老化的症状的治疗和预防和用于紫外线辐射在皮肤上的有害影响的治疗和预防的话。
优选的NO合酶抑制剂是硝基精氨酸。
该活性成分进一步理想地选自包括以下物质的一组:儿茶素和儿茶素的胆汁酯类和从含有儿茶素或儿茶素的胆汁酯类的植物或植物部分(例如茶科植物家族,尤其Camellia sinensis属(绿茶)的叶子)中获取的水性或有机提取物。它们的典型成分(例如,多酚或儿茶素,咖啡因,维生素类,糖,矿物,氨基酸,类脂)是特别理想的。
儿茶素是一组化合物,它们被认为是氢化的黄酮或花色素且是“儿茶素”的衍生物(儿茶酚,3,3’,4’,5,7-flavanpentol,2-(3,4-二羟苯基)苯并二氢吡喃-3,5,7-三醇)。表儿茶素((2R,3R)-3,3’,4’,5,7-flavanpentol)也是本发明的理想活性成分。
优选的活性成分也可是选自以下的多酚和儿茶素:(-)-儿茶素,(+)-儿茶素,(-)-茶素没食子酸酯,(-)-棓儿茶酸没食子酸酯,(+)-表儿茶素,(-)-表儿茶素,(-)-表儿茶素没食子酸酯,(-)-表棓儿茶素,(-)-表棓儿茶素没食子酸酯。
黄酮及其衍生物(还常常一起被叫作“黄酮”)也是本发明的有利活性成分。它们通过下列基本结构来表征(显示了取代位置):
也优选用于本发明制剂中的更重要黄酮类中的一些在下面表2中给出:
OH取代位置 | ||||||||
3 | 5 | 7 | 8 | 2’ | 3’ | 4’ | 5’ | |
黄酮 | - | - | - | - | - | - | - | - |
黄酮醇 | + | - | - | - | - | - | - | - |
柯因 | - | + | + | - | - | - | - | - |
高良姜精 | + | + | + | - | - | - | - | - |
高粱黄酮 | - | + | + | - | - | - | + | - |
漆树黄酮 | + | - | + | - | - | + | + | - |
木犀草素 | - | + | + | - | - | + | + | - |
莰非醇 | + | + | + | - | - | - | + | - |
五羟黄酮 | + | + | + | - | - | + | + | - |
桑色素 | + | + | + | - | + | - | + | - |
刺槐亭 | + | - | + | - | - | + | + | + |
棉花素 | + | + | + | + | - | + | + | - |
杨梅黄酮 | + | + | + | - | - | + | + | + |
实际上,黄酮通常呈现糖基化形式。
根据本发明,类黄酮优选选自以下通用结构式的物质其中Z1-Z7彼此独立地选自H,OH,烷氧基和羟基烷氧基,其中烷氧基和羟基烷氧基能够是支化或未支化的且具有1-18个碳原子,和其中Gly选自单-和低聚糖苷基。
然而根据本发明,类黄酮也理想地选自具有以下通用结构式的物质:其中Z1-Z6彼此独立地选自H,OH,烷氧基和羟基烷氧基,其中烷氧基和羟基烷氧基可以是支化或未支化的且具有1-18个碳原子,其中Gly选自单和低聚糖苷基。
优选地,Gly1,Gly2和Gly3彼此独立地选自己糖基,尤其鼠李糖基和葡糖基。然而,在一些情况下己糖基,例如阿洛糖基,阿卓糖基,半乳糖基,古洛糖基,艾杜糖基,甘露糖基和塔罗糖基,也可理想地使用。对本发明来说也理想的是使用戊糖基。
Z1-Z5彼此独立地选自H,OH,甲氧基,乙氧基和2-羟基乙氧基,该黄酮糖苷具有以下该结构
优选地,Gly1,Gly2和Gly3彼此独立地选自己糖基,尤其鼠李糖基和葡糖基。然而,在一些情况下其它己糖基,例如阿洛糖基,阿卓糖基,半乳糖基,古洛糖基,艾杜糖基,甘露糖基和塔罗糖基,也可理想地使用。对本发明来说也理想的是使用戊糖基。
对于本发明,特别理想地从α-葡糖基芸香苷,α-葡糖基杨梅黄酮,α-葡糖基异栎素,α-葡糖基异五羟黄酮和α-葡糖基栎素中选择黄酮糖苷。
本发明特别优选的是α-葡糖基芸香苷。
根据本发明也理想的是柚皮苷(橙苷,柚苷配基-7-鼠李葡糖苷),橙皮苷3’,5,7-三羟基-4’-甲氧基黄烷酮-7-芸香糖苷,桔皮糖苷(hesperidoside),橙皮素-7-O-芸香糖苷),芸香苷(3,3’,4’,5,7-五羟基黄酮-3-芸香糖苷,栎精-3-芸香糖苷,槐苷,芦丁(birutan),rutabion,taurutin,芸香素,云香苷(melin)),三羟乙基芦丁(3,5-二羟基-3’,4’,7-三(2-羟基乙氧基)黄酮-3-(6-O-(6-脱氧-α-L-吡喃甘露糖基)-β-D-吡喃葡萄糖苷)),羟乙基芦丁(monoxerutin)(3,3’,4’,5-四羟基-7-(2-羟基乙氧基)黄酮-3-(6-O-(6-脱氧-α-L-吡喃甘露糖基)-β-D-吡喃葡萄糖苷)),双氢刺槐亭(3,3’,4’,5’,7-五羟基黄烷酮),紫杉叶素(3,3’,4’,5,7-五羟基黄烷酮),圣草酚-7-葡糖苷(3’,4’,5,7-四羟基黄烷酮-7葡糖苷),flavanomarein(3’,4’,7,8-四羟基黄烷酮-7葡糖苷)和异栎精(3,3’,4’,5,7-五羟基黄烷酮-3-(β-D-吡喃葡萄糖苷)。
也理想的是从泛醌和塑体醌中选择活性成分。
泛醌由下列结构式表征并且是最广泛的和因此是人们研究最多的生物醌类。取决于在侧链中连接的异戊二烯单元的数目,泛醌可以称作Q-1,Q-2,Q-3等,或根据碳原子数目,称作U-5,U-10,U-15等。它们优选形成一定的链长度,例如在一些微生物和酵母中,其中n=6。在大多数哺乳动物包括人在内,Q10占优势。
辅酶Q10是特别理想的且以下列结构式表征:
各种塑体醌在异戊二烯基团的数目n上不同和因此称作例如PQ-9(n=9)。另外,在醌环上具有不同取代基的其它塑体醌也存在。
优选的衍生物是肌酸磷酸酯和肌酸硫酸酯,肌酸乙酸酯,肌酸抗坏血酸酯和在羧基上被单-或多官能醇酯化的衍生物。
其它理想的活性成分是L-肉碱[3-羟基-4-(三甲基铵)丁酰甜菜碱]。从具有下面结构通式的物质中选择的酰基肉碱其中R选自具有至多10个碳原子的支化和未支化的烷基,是本发明的理想活性成分。优选的是丙酰基肉碱和尤其乙酰肉碱。两对映异构体(D和L形式)是本发明所理想使用的。也理想的是使用任何对映异构体混合物,例如D和L形式的外消旋物。
其它理想的活性成分是sericoside,吡哆醇,维生素K以及生物素和芳香物质。
可在本发明的制剂中使用的活性成分和活性成分组合的列出当然不希望有限制意义。该活性成分能够单种使用或以彼此的任何组合使用。
此类活性成分(一种或多种化合物)在本发明制剂中的量优选是0.001-30wt%,特别优选0.05-20wt%,尤其0.1-10wt%,基于制剂的总重量。
在一些情况下,对于本发明来说也理想的是将染料和/或彩色颜料引入到本发明制剂中。
该染料和彩色颜料能够选自Cosmetics Directive的相应批准清单或化妆品着色剂的EC目录。在大多数场合下它们与食品领域所批准的染料相同。理想的彩色颜料是例如二氧化钛,云母,铁氧化物(例如Fe2O3,Fe3O4,FeO(OH))和/或氧化锡。适宜的染料是例如胭脂红,普鲁士蓝,氧化铬绿,群青色和/或锰紫。特别理想地从下面的列表中选择染料和/或彩色颜料。该色素索引指数(CIN)取自Rowe Colour Index,第三版,英国染色工作者学会(Society of Dyers and Colourists),Bradford,英格兰,1971。化学或其它名称 CIN 颜色颜料绿 10006 绿色酸性绿1 10020 绿色2,4-二硝基羟基萘-7-磺酸 10316 黄色颜料黄1 11680 黄色颜料黄3 11710 黄色颜料橙1 11725 橙色2,4-二羟基偶氮苯 11920 橙色溶剂红3 12010 红色1-(2’-氯-4’-硝基-1’-苯基偶氮)-2-羟基萘 12085 红色颜料红3 12120 红色Ceres红;苏丹红;油溶红G 12150 红色颜料红112 12370 红色颜料红7 12420 红色颜料棕1 12480 棕色4-(2’-甲氧基-5’-磺基二乙基酰胺基-1’-苯基偶 12490 红色氮)-3-羟基-5”-氯-2”,4”-一甲氧基-2-萘甲酰苯胺分散黄16 12700 黄色1-(4-磺基-1-苯基偶氮)-4-氨基苯-5磺酸 13015 黄色2,4-二羟基偶氮苯-4’-磺酸 14270 橙色2-(2,4-二甲基苯基偶氮-5-磺基)-1-羟基萘-4-磺酸 14700 红色2-(4-磺基-1-萘基偶氮)-1-萘酚-4-磺酸 14720 红色2-(6-磺基-2,4--二甲苯基偶氮)-1-萘酚-5-磺酸 14815 红色1-(4’-磺基苯基偶氮)-2-羟基萘 15510 橙色1-(2-磺基-4-氯-5-羧基-1-苯基偶氮)-2-羟基萘 15525 红色1-(3-甲基苯基偶氮-4-磺基)-2-羟基萘 15580 红色1-(4’,(8’)-磺基萘基偶氮)-2-羟基萘 15620 红色2-羟基-1,2’-偶氮萘-1’-磺酸 15630 红色3-羟基-4-苯基偶氮-2-萘基羧酸 15800 红色1-(2-磺基-4-甲基-1-苯基偶氮)-2-萘基-羧酸 15850 红色1-(2-磺基-4-甲基-5-氯-1-苯基偶氮)-2-羟基萘-3- 15865 红色羧酸1-(2-磺基-1-萘基偶氮)-2-羟基萘-3-羧酸 15880 红色1-(3-磺基-1-苯基偶氮)-2-萘酚-6-磺酸 15980 橙色1-(4-磺基-1-苯基偶氮)-2-萘酚-6-磺酸 15985 黄色Allura红 16035 红色1-(4-磺基-1-萘基偶氮)-2-萘酚-3,6-二磺酸 16185 红色酸性橙10 16230 橙色1-(4-磺基-1-萘基偶氮)-2-萘酚-6,8-二磺酸 16255 红色1-(4-磺基-1-萘基偶氮-2-萘酚-3,6,8-三磺酸 16290 红色8-氨基-2-苯基偶氮-1-萘酚-3,6-二磺酸 17200 红色酸性红1 18050 红色酸性红155 18130 红色酸性黄121 18690 黄色酸性红180 18736 红色酸性黄11 18820 黄色酸性黄17 18965 黄色4-(4-磺基-1-苯基偶氮)-1-(4-磺基苯基)-5-羟基-比 19140 黄色唑啉酮-3-羧酸颜料黄16 20040 黄色2,6-(4’-磺基-2”,4”-二甲基)双苯基偶氮)-1,3-二羟20170 橙色基苯酸性黑1 20470 黑色颜料黄13 21100 黄色颜料黄83 21108 黄色溶剂黄 21230 黄色酸性红163 24790 红色酸性红73 27290 红色2-[4’-(4”-磺基-1”-苯基偶氮)-7’-磺基-1’-萘基偶 27755 黑色氮]-1-羟基-7-氨基萘3,6-二磺酸4’-[(4”-磺基-1”-苯基偶氮)-7’-磺基-1’-萘基偶 28440 黑色氮]-1-羟基-8-乙酰基氨基萘3,5-二磺酸直接橙34,39,44,46,60 40215 橙色食用黄 40800 橙色反式-β-阿朴-8’-胡萝卜醛(C30) 40820 橙色反式-阿朴-8’-胡萝卜酸(C30)-乙酯 40825 橙色鸡油菌素 40850 橙色酸性蓝1 42045 蓝色2,4-二磺基-5-羟基-4’-4”-双(二乙基氨基)三苯基 42051 蓝色甲醇4-[(4-N-乙基-p-磺基苄基氨基)苯基(4-羟基-2-磺 42053 绿色基苯基)(亚甲基)-1-(N-乙基-N-p-磺基苄基)-2,5-环己二烯亚胺]酸性蓝7 42080 蓝色(N-乙基-p-磺基苄基氨基)苯基(2-磺基苯基)亚甲 42090 蓝色基-(N-乙基-N-p-磺基苄基)△2,5-环己二烯亚胺酸性绿9 42100 绿色二乙基二磺基苄基二-4-氨基-2-氯-二-2-甲基 42170 绿色-fuchsonimmonium碱性紫14 42510 紫色碱性紫2 42520 紫色2’-甲基-4’-(N-乙基-N-m-磺基苄基)氨基4”-(N- 42735 蓝色二乙基)氨基-2-甲基-N-乙基-N-m-磺基苄基fuchsonimmonium4’-(N-二甲基)氨基-4”-(N-苯基)氨基萘并-N-二甲 44045 蓝色基-fuchsonimmonium2-羟基-3,6-二磺基-4,4’-双二甲基氨基萘并 44090 绿色-fuchsonimmonium酸性红52 45100 红色3-(2’-甲基苯基氨基)-6-(2’-甲基-4’-磺基苯基氨 45190 紫色基)-9-(2”-羧基苯基)xanthenium盐酸性红50 45220 红色苯基-2-氧基荧光酮-2-羧酸 45350 黄色4,5-二溴荧光素 45370 橙色2,4,5,7-四溴荧光素 45380 红色溶剂染料 45396 橙色酸性红98 45405 红色3’,4’,5’,6’-四氯-2,4,5,7-四溴荧光素 45410 红色4,5-二碘荧光素 45425 红色2,4,5,7-四碘荧光素 45430 红色Quinophthalone 47000 黄色Quinophthalone二磺酸 47005 黄色酸性紫50 50325 紫色酸性黑2 50420 黑色颜料紫23 51319 紫色1,2-二羟基蒽醌,钙-铝复合物 58000 红色3-羟基芘-5,8,10-磺酸 59040 绿色1-羟基-4-N-苯基氨基蒽 60724 紫色1-羟基-4-(4’-甲基苯基氨基)蒽 60725 紫色酸性紫23 60730 紫色1,4-二(4’-甲基苯基氨基)蒽醌 61565 绿色1,4-双(邻-磺基-对-甲苯氨基)蒽 61570 绿色酸性蓝80 61585 蓝色酸性蓝62 62045 蓝色N,N’-二氢-1,2,1’,2’-蒽醌吖嗪 69800 蓝色瓮蓝6;颜料蓝64 69825 蓝色瓮橙7 71105 橙色靛蓝 73000 蓝色靛蓝-二磺酸 73015 蓝色4,4’-二甲基-6,6’-二氯硫靛 73360 红色5,5’-二氯-7,7’-二甲基硫靛 73385 紫色喹吖啶酮紫19 73900 紫色颜料红122 73915 红色颜料蓝16 74100 蓝色酞菁 74160 蓝色直接蓝86 74180 蓝色氯化酞菁 74260 绿色自然黄6,19;自然红1 75100 黄色胭脂树橙,降胭脂树素 75120 橙色番茄红素 75125 黄色反式-α-,β-和γ-胡萝卜素 75130 橙色胡萝卜素的酮和/或羟基衍生物 75135 黄色鸟嘌呤或珠光剂 75170 白色1,7-双(4-羟基-3-甲氧基苯基)-1,6-庚二烯-3,5-二酮 75300 黄色胭脂红酸的络合盐(Na,Al,Ca) 75470 红色叶绿素a和b;叶绿素和叶绿酸的铜化合物 75810 绿色铝 77000 白色水合氧化铝 77002 白色含水的硅酸铝 77004 白色佛青 77007 蓝色颜料红101和102 77015 红色硫酸钡 77120 白色氯氧化铋及其与云母的混合物 77163 白色碳酸钙 77220 白色硫酸钙 77231 白色碳 77266 黑色颜料黑9 77267 黑色植物来源的药用炭(Carbo medicinalis 77268 黑色vegetabilis)氧化铬 77288 绿色含水氧化铬 77289 绿色颜料蓝28,颜料绿14 77346 绿色颜料金属2 77400 棕色黄金 77480 棕色铁氧化物和氢氧化物 77489 橙色氧化铁 77491 红色水合氧化铁 77492 黄色氧化铁 77499 黑色六氰基高铁酸铁(II)和铁(III)的混合物 77510 蓝色颜料白18 77713 白色二磷酸锰铵盐 77742 紫色磷酸锰;Mn3(PO4)2·7H2O 77745 红色银 77820 白色二氧化钛及其与云母的混合物 77891 白色氧化锌 77947 白色6,7-二甲基-9-(1’-D-核糖基)-异咯嗪,核黄素黄色糖着色剂 棕色辣椒红,辣椒玉红素 橙色甜菜苷 红色苯并吡喃鎓盐,花色素 红色铝,锌,镁和钙的硬脂酸盐 白色溴百里酚蓝 蓝色溴甲酚绿 绿色酸性红195 红色
也理想的是油溶性天然染料例如辣椒抽提物,β-胡萝卜素或胭脂红。
对本发明也是理想的是含有珠光颜料的凝胶霜剂。尤其优选以下列出的那些类型的珠光颜料:
自然珠光颜料,例如
“珠光粉”(从鱼鳞获得的鸟嘌呤/次黄嘌呤混合晶体),“珍珠母”(磨细的贻贝壳)和单晶珠光颜料例如氯氧化铋(BiOCl)
层状基底颜料:例如云母/金属氧化物
珠光颜料的基料是例如氯氧化铋和/或二氧化钛,以及包覆在云母上的氯氧化铋和/或二氧化钛的粉状颜料或蓖麻油分散体。在CIN 77163下列出的光泽颜料是特别理想的。
也适宜的是例如基于云母/金属氧化物的下列各类型的珠光颜料:
组 | 涂层/层厚度 | 颜色 |
银白色的珠光颜料 | TiO2:40-60nm | 银 |
干涉颜料 | TiO2:60-80nm | 黄色 |
TiO2:80-100nm | 红色 | |
TiO2:100-140nm | 蓝色 | |
TiO2:120-160nm | 绿色 | |
彩色光泽颜料 | Fe2O3 | 青铜色 |
Fe2O3 | 铜色 | |
Fe2O3 | 红色 | |
Fe2O3 | 红紫色 | |
Fe2O3 | 红绿色 | |
Fe2O3 | 黑色 | |
结合颜料 | TiO2/Fe2O3 | 金色调 |
TiO2/Cr2O3 | 绿色 | |
TiO2/普鲁士蓝 | 深蓝 | |
TiO2/胭脂红 | 红色 |
特别优选的是例如从Merck以商品名Timiron,Colorona或Dichrona商购的珠光颜料。
所给出的珠光颜料的列表当然没有限制意义。对于本发明来说理想的珠光颜料可通过本身已知的许多方式获得。例如,除云母外的其它基底物能够涂敷其它的金属氧化物例如硅石等。涂有例如TiO2和Fe2O3的SiO2颗粒(“ronaspheres”)由Merck销售且特别适合于细线的光学减少,因此是理想的。
此外,理想的是完全弃用基底物如云母。特别优选的是使用SiO2制备的珠光颜料。另外还具有随角异色效果的此类颜料例如能够以商品名Sicopearl Fantastico从BASF获得。
以涂有二氧化钛的硼硅酸钙钠盐为基础的Engelhard/Mearl的颜料也可理想地使用。这些是以商品名Reflecks获得。除颜色之外,由于它们的粒度为40纳米-180微米,它们具有闪光效应。
另外,也特别理想的是可以从Flora Tech以商品名MetasomesStandard/Glitter分各种颜色(黄,红,绿,蓝)获得的随角异色效应颜料。闪光颗粒与各种助剂和染料(例如,具有色素索引(CI)值19140,77007,77289,77491的染料)相混合存在。
该染料和颜料能够单独或混合存在,并能够彼此涂敷,不同的涂层厚度通常导致不同的彩色效应。染料和颜色赋予性颜料的总量理想地选自例如0.1wt%-30wt%,优选0.5-15wt%,尤其1.0-10wt%的范围,在所有情况下基于制剂的总重量。
根据本发明的制剂是在所属技术领域的专业人员熟悉的条件下制备的。通常油相或水相分别的各种成分被混合在一起并加热,然后在搅拌下将它们两种掺混,理想的是在均化下,非常理想的是在用中至高能量输入加以搅拌下,适宜的是使用采用至多10000rpm,优选2500-7700rpm转数的齿轮圈分散机。
本发明将参考下面的实施例(配制剂配方)更详细地说明。
实施例1-5
实施例6-10
实施例11-16
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | |
钠Carbomer | 0.2 | ||||
丙烯酸酯/丙烯酸C10-C30烷基酯交互聚合物 | 0.3 | 0.2 | 0.6 | ||
羟基丙基纤维素 | 1.0 | 1.50 | |||
黄原胶 | 0.6 | 0.2 | 1.0 | 1.0 | |
化合物I | 3.5 | 3.5 | 1.5 | 6.0 | 5.0 |
二辛基丁酰胺基三嗪酮 | 2.0 | 2.0 | 1.0 | ||
乙基己基三嗪酮 | 4.0 | 4.0 | 5.0 | ||
Anisotriazine | 1.0 | 0.5 | 2.0 | 2.5 | |
双辛基三唑 | 6.0 | ||||
Drometrizole三硅氧烷 | |||||
苯基苯并咪唑-磺酸 | 2.0 | 1.0 | |||
Bisimidazylate | 1.0 | ||||
对苯二亚甲基二樟脑磺酸 | 0.2 | ||||
甲氧基肉桂酸乙基己基酯 | 7.5 | 10.0 | 5.0 |
Octocrylene | 5.0 | ||||
二甲基聚硅氧烷亚苄基丙二酸二乙酯 | 4.0 | ||||
水杨酸乙基己基酯 | |||||
Homosalate | |||||
丁基甲氧基二苯甲酰基甲烷 | 1.0 | 1.0 | 4.0 | ||
二氧化钛 | 1.0 | 4.0 | |||
氧化锌 | 4.0 | ||||
辛酸/癸酸甘油三酯 | 2.0 | ||||
氢化椰子甘油酯 | 3.0 | ||||
苯甲酸C12-C15-烷基酯 | 2.0 | 2.5 | 3.0 | ||
二辛基醚 | 4.0 | ||||
丁二醇二辛酸酯/二癸酸酯 | 4.0 | 2.0 | 6.0 | ||
碳酸二辛基酯 | 2.0 | ||||
十六烷基二甲基硅氧烷 | 2.0 | 0.5 | 1.0 | ||
牛油树脂 | 2.0 | ||||
PVP/十六碳烯共聚物 | 0.5 | 0.05 | 0.5 | ||
甘油 | 3.0 | 7.5 | 7.5 | 2.5 | |
生育酚 | 0.5 | 0.75 | 0.2 | ||
EDTA三钠 | 1.0 | 0.5 | 0.5 | 1.0 | 1.5 |
柠檬酸钠 | 0.2 | ||||
柠檬酸 | 0.1 | 0.1 | 0.1 | ||
DMDM乙内酰脲 | 0.6 | 0.2 | |||
对羟基苯甲酸甲酯 | 0.5 | 0.3 | 0.15 | ||
苯氧基乙醇 | 0.5 | 0.4 | 0.4 | 1.0 | 0.60 |
乙醇 | 3.0 | 2.0 | 3.0 | 1.0 | |
香料 | 0.2 | 0.2 | 0.2 | ||
水 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 |
实施例6 | 实施例7 | 实施例8 | 实施例9 | 实施例10 | |
钠Carbomer | 0.5 | 1.5 | |||
丙烯酸酯/丙烯酸C10-C30烷基酯交互聚合物 | 0.4 | 0.1 | 0.75 |
羟基丙基纤维素 | 0.5 | 0.25 | |||
黄原胶 | 0.2 | 0.4 | |||
化合物I | 0.5 | 2.5 | 1.0 | 2.0 | 6.0 |
二辛基丁酰胺基三嗪酮 | 1.0 | 2.0 | |||
乙基己基三嗪酮 | 2.0 | 2.0 | |||
Anisotriazine | 1.0 | 0.2 | 3.0 | 1.0 | |
双辛基三唑 | 8.0 | ||||
Drometrizole三硅氧烷 | 4.0 | ||||
苯基苯并咪唑磺酸 | 1.5 | ||||
Bisimidazylate | 1.5 | ||||
对苯二亚甲基二樟脑磺酸 | 0.5 | ||||
甲氧基肉桂酸乙基己基酯 | 7.5 | 5.0 | 10.0 | ||
Octocrylene | 10.0 | 5.0 | 5.0 | ||
二甲基聚硅氧烷亚苄基丙二酸二乙酯 | 2.5 | ||||
水杨酸乙基己基酯 | 3.5 | 5.0 | |||
Homosalate | 4.0 | ||||
丁基甲氧基二苯甲酰基甲烷 | 0.5 | ||||
二氧化钛 | 1.5 | 2.0 | 1.0 | 2.5 | |
氧化锌 | 1.0 | 0.5 | |||
辛酸/癸酸甘油三酯 | |||||
氢化椰子甘油酯 | |||||
苯甲酸C12-C15-烷基酯 | 5.0 | ||||
二辛基醚 | 7.5 | ||||
丁二醇二辛酸酯/二癸酸酯 | |||||
碳酸二辛基酯 | 7.5 | ||||
十六烷基二甲基硅氧烷 | |||||
牛油树脂 | 3.0 | ||||
PVP/十六碳烯共聚物 | 0.5 | 0.75 | 1.0 | ||
甘油 | 5.0 | 10.0 | |||
生育酚 | 0.3 | 1.5 | 1.0 | ||
EDTA三钠 | 0.5 | 0.1 | 0.5 | ||
柠檬酸钠 | 0.3 | ||||
柠檬酸 | 0.15 | ||||
DMDM乙内酰脲 | 0.3 | 0.15 |
对羟基苯甲酸甲酯 | 0.4 | ||||
苯氧基乙醇 | 1.0 | ||||
乙醇 | 7.5 | 5.0 | 7.0 | ||
香料 | 0.25 | 0.2 | |||
水 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 |
实施例11 | 实施例12 | 实施例13 | 实施例14 | 实施例15 | 实施例16 | |
钠Carbomer | 0.5 | 1.5 | 1.0 | 0.5 | ||
丙烯酸酯/丙烯酸C10-C30烷基酯交互聚合物 | 1.0 | 0.75 | 1.0 | |||
羟丙基纤维素 | 0.4 | 1.0 | 1.0 | |||
黄原胶 | 0.6 | 0.2 | 1.0 | 1.0 | ||
化合物I | 4.0 | 0.5 | 3.0 | 2.0 | 4.0 | 1.5 |
二辛基丁酰胺基三嗪酮 | 2.0 | 2.0 | 2.0 | 1.0 | ||
乙基己基三嗪酮 | 4.0 | 5.0 | 4.0 | |||
Anisotriazine | 1.0 | 1.0 | 2.5 | 1.0 | ||
双辛基三唑 | 4.0 | |||||
Drometrizole三硅氧烷 | 3.0 | |||||
苯基苯并咪唑磺酸 | 2.0 | 1.0 | ||||
Bisimidazylate | 1.5 | 3.5 | ||||
对苯二亚甲基二樟脑磺酸 | 0.2 | 1.0 | ||||
甲氧基肉桂酸乙基己基酯 | 10.0 | 5.0 | ||||
Octocrylene | 10.0 | 5.0 | ||||
二甲基聚硅氧烷亚苄基丙二酸二乙酯 | 4.0 | |||||
水杨酸乙基己基酯 | 5.0 | |||||
Homosalate | 5.0 | |||||
丁基甲氧基二苯甲酰基甲烷 | 1.0 | 1.0 | 4.0 | 0.5 | ||
二氧化钛 | 1.0 | 4.0 | 1.5 |
氧化锌 | 4.0 | |||||
辛酸/癸酸甘油三酯 | 2.0 | |||||
石蜡油 | 1.0 | |||||
苯甲酸C12-C15烷基酯 | 2.0 | 2.5 | 3.0 | |||
二辛基醚 | 4.0 | |||||
异十六碳烯 | 4.0 | 2.0 | 6.0 | |||
碳酸二辛基酯 | 2.0 | |||||
己二酸二丁酯 | 2.0 | 0.5 | 1.0 | |||
环甲基聚硅氧烷 | 3.0 | |||||
霍霍巴油 | 2.0 | |||||
PVP/十六碳烯共聚物 | 0.5 | 0.05 | 0.5 | 0.5 | ||
丁二醇 | 3.0 | 7.5 | 7.5 | 2.5 | 5.0 | |
抗坏血酰棕榈酸酯 | 0.5 | 0.75 | 0.2 | 0.3 | ||
辛氧基甘油 | 1.0 | 0.5 | 1.0 | |||
大豆甘氨酸(Glycinesoya) | 2.0 | 1.5 | ||||
EDTA三钠 | 1.0 | 0.5 | 0.5 | 1.5 | 0.5 | |
氢氧化钠溶液 | 1.0 | 0.2 | 0.25 | |||
丁基氨基甲酸碘丙基酯 | 0.6 | 0.2 | ||||
苯氧基乙醇 | 0.4 | 1.0 | ||||
乙醇 | 5.0 | 2.0 | 7.0 | |||
香料 | 0.2 | 0.2 | 0.2 | |||
水 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 |
Claims (6)
1.属于水包油型细分散体系的化妆品或皮肤用制剂,包含
a)油相,
b)水相,
c)一种或多种稳定剂,
d)至多2.00wt%的一种或多种乳化剂,
e)通式I的氨基取代的羟基二苯甲酮化合物
2.权利要求1的制剂,其中一种或多种乳化剂的含量在0.5wt%-1.5wt%之间,基于制剂的总重量。
3.根据权利要求1和2中任何一项的制剂,它是水分散体。
4.根据权利要求1-3中任何一项的制剂,其中稳定剂选自甲基纤维素,乙基纤维素,黄原胶,角叉菜,丙烯酸C10-C30-烷基酯和一种或多种丙烯酸单体的共聚物,聚氨酯类和层状硅酸盐。
5.根据权利要求4的制剂,其中乙基纤维素用作稳定剂。
6.权利要求1-5中任何一项的制剂,其中一种或多种稳定剂在制剂中的含量在0.1wt%-10wt%之间,基于制剂的总重量。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10143964.4 | 2001-09-07 | ||
DE10143964A DE10143964A1 (de) | 2001-09-07 | 2001-09-07 | Emulgatorarme oder emulgatorfreie Systeme vom Typ Öl-in-Wasser mit einem Gehalt an Stabilisatoren und einem aminosubstituierten Hydroxybenzophenon |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1406576A true CN1406576A (zh) | 2003-04-02 |
Family
ID=7698103
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN02141655.9A Pending CN1406576A (zh) | 2001-09-07 | 2002-09-09 | 含有稳定剂和氨基取代的羟基二苯甲酮的水包油型的低乳化剂或无乳化剂体系 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20030124158A1 (zh) |
EP (1) | EP1291007A1 (zh) |
JP (1) | JP2003146865A (zh) |
CN (1) | CN1406576A (zh) |
DE (1) | DE10143964A1 (zh) |
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-
2001
- 2001-09-07 DE DE10143964A patent/DE10143964A1/de not_active Withdrawn
-
2002
- 2002-08-27 EP EP02019206A patent/EP1291007A1/de not_active Withdrawn
- 2002-09-03 US US10/232,376 patent/US20030124158A1/en not_active Abandoned
- 2002-09-06 JP JP2002260758A patent/JP2003146865A/ja active Pending
- 2002-09-09 CN CN02141655.9A patent/CN1406576A/zh active Pending
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CN1650845B (zh) * | 2003-12-01 | 2010-09-29 | 约翰逊及约翰逊法国消费者有限公司 | 高脂质含量的可喷雾乳液 |
CN1968674B (zh) * | 2004-06-15 | 2010-05-26 | 巴斯福股份公司 | 化妆品和皮肤病制剂中着色剂的稳定 |
CN102387781A (zh) * | 2009-03-26 | 2012-03-21 | 株式会社资生堂 | 防晒化妆品 |
CN103284909A (zh) * | 2013-05-29 | 2013-09-11 | 薛羽佳 | 一种不含乳化剂的防护霜 |
CN113727692A (zh) * | 2019-05-30 | 2021-11-30 | 欧莱雅 | 不含乳化剂的羟基酸凝胶霜组合物 |
CN115025002A (zh) * | 2022-06-24 | 2022-09-09 | 广东博然堂生物科技有限公司 | 一种不含乳化剂的0/w型分散体系及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2003146865A (ja) | 2003-05-21 |
US20030124158A1 (en) | 2003-07-03 |
DE10143964A1 (de) | 2003-03-27 |
EP1291007A1 (de) | 2003-03-12 |
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