CN102186449A - 液体个人清洗组合物 - Google Patents
液体个人清洗组合物 Download PDFInfo
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- CN102186449A CN102186449A CN2009801397415A CN200980139741A CN102186449A CN 102186449 A CN102186449 A CN 102186449A CN 2009801397415 A CN2009801397415 A CN 2009801397415A CN 200980139741 A CN200980139741 A CN 200980139741A CN 102186449 A CN102186449 A CN 102186449A
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- Prior art keywords
- vaseline
- blend
- acid
- premix
- compositions
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Abstract
描述了稳定、多相液体各向同性的清洗组合物,其包含高水平的矿脂并且和含其它油的各向同性的清洗组合物与具有类似水平的油的液晶组合物相比,显示出反射率的显著降低。本发明组合物具有总共小于2wt%的其它油如甘油酯,矿物油和硅油,或其共混物。
Description
技术领域
本发明涉及液体清洗组合物,其适用于局部施用以便清洗人体如皮肤和毛发。特别地,其涉及具有低反射率的稳定、多相各向同性或凝胶类型(在下文中“各向同性”)个人清洗组合物,其包含作为主要疏水润肤剂的具有特定的熔点范围的矿脂。
背景技术
市售可得的液体个人清洗组合物,即沐浴露(shower gels)、洁面乳/霜和洗手液(facial and hand
cleansers),其富集疏水润肤油(emollient oils),通常被施用以便同时清洗和增湿皮肤。液晶清洗组合物可以使相当大量的油结构化,但外观上是乳白色的,一些使用者发现其是无吸引力的。各向同性的清洗组合物常常是透明的或者在其他方面是低反射率的,这给许多使用者带来有吸引力的外观,但不利地不能使相当水平的疏水润肤剂结构化以便得到稳定产品用于有效的皮肤润湿。稳定产品在本文中定义为在如下所述的稳定性测试条件下没有显著的相分离。令人惊讶地,发现稳定、多相各向同性结构化的清洗组合物兼备有吸引力的较低的反射率,还可以使相当水平的矿脂结构化,其中矿脂具有在35和80C之间的熔点和在32C下10Kps的最小粘度(在下文中“矿脂”)以便有效的润湿并且其中组合物必须没有高于特定水平的其它疏水润肤剂以便实现它的有吸引力的外观和独特的矿脂粒度分布。
各向同性的液体清洗剂已知具有疏水的润肤油。1999年12月14日授权于Villa等人的美国专利6,001,344公开了一种各向同性的清洗组合物,其具有平均直径为1至500微米的大油滴。
分别于1998年12月29日和2000年5月23日授权给Glenn Jr.的美国专利5,854,293和6,066,608公开了增湿液体个人清洗乳液,其中其亲油皮肤增湿剂液滴的至少10%具有大于200微米的直径。Glenn Jr.进一步公开了使用稳定剂,其选自结晶、含羟基的稳定剂,聚合增稠剂,C10-C18二酯,无定形二氧化硅或蒙脱石粘土。
1999年10月12日授权给Puvvada的美国专利5,965,500公开了稳定的各向同性液体清洗组合物,其包含等于或超过表面活性剂水平的高水平的润肤剂。在优选实施方案中,该组合物进一步包含C2-C24脂肪酸和/或阳离子聚合物。
1997年8月26日授权给Grieveson等人的美国专利5,661,189公开了各向同性的水性液体清洗和增湿组合物,其具有加权平均粒度为50至500微米的增稠有益试剂和选自粘土,脂肪酸和其衍生物,交联的聚丙烯酸酯,聚乙烯吡咯烷酮,天然的树胶,多糖衍生物,多元醇,多元醇酯和无机盐的任选的结构化剂。
2006年8月29日授权给Ganopolsky等人的美国专利7,098,180公开了各向同性的清洗组合物,其包含阴离子和两性表面活性剂,和疏水改性交联的阴离子丙烯酸系共聚物。
2004年6月24日出版的Harmalker的美国专利公开号2004/0121925公开了一种稳定的各向同性的清洗组合物,其包含阴离子和两性表面活性剂,黄原胶(xanthan)和瓜尔胶增稠剂,和直径范围为200-2500微米的调节剂的分散相悬浮颗粒,并且在颗粒不存在的情况下,连续相的透明度(clarity)小于或等于20NTU。颗粒由树胶、明胶等组成并且在颗粒内可以包含(一种或多种)油。
2006年8月1日授权给Martin等人的美国专利7,084,104公开了各向同性的清洗组合物,其包含阴离子和两性表面活性剂,疏水改性交联的阴离子丙烯酸系共聚物增稠剂,挥发性硅氧烷调节剂和湿润剂。
发明内容
本发明的一个方面是稳定、多相各向同性的清洗组合物,包括但不限于:
a. 约99-84wt%的水,基于整个组合物;
b. 约1-16wt%的矿脂,基于整个组合物,其中矿脂的熔点在35和80C间和在32C下最小粘度为10Kps;
c. 其中水相包括约1-25wt%的非皂阴离子表面活性剂,基于整个组合物和约1-20wt%的两性表面活性剂,基于整个组合物;
d. 其中水相包含约0.5-10wt%的总聚合分散稳定剂(一种或多种),基于整个组合物;
e. 小于约2wt%的总疏水甘油酯(一种或多种),除矿脂的烃(一种或多种),或硅油或其共混物和衍生物,基于整个组合物;和
f. 小于约1.5wt%的总液晶结构化剂(一种或多种),结晶含羟基的稳定剂(一种或多种),C10-C22脂肪酸乙二醇酯(一种或多种),二氧化硅(一种或多种),粘土(一种或多种)或其共混物,基于整个组合物。
本发明的另一个方面是一种制备稳定、多相各向同性的清洗组合物的方法,其包括但不限于如下的步骤,没有特定的顺序:
a. 共混水、表面活性剂(一种或多种)、和聚合分散稳定剂(一种或多种)直到均匀来制备无油的、透明的各向同性的水性预混合物;
b. 将水性预混合物进料到共混管中,水性预混合物以约22.7-113.7千克(50-250磅)/分钟的速率通过共混管;和
c. 通过多口注射器(被定义为具有2个或更多个管道出口)以足以形成重量百分数比值范围为约1%矿脂:99%水性预混合物至约16%矿脂:84%水性预混合物的共混物的速率将熔点在35和80C间和在32C下最小粘度为10Kps的矿脂进料到共混管中。
附图说明
图1是本发明方法的优选的实施方案的示意性工艺流程图。
图2是图1中举例说明的多口阀100的优选的实施方案的细部、分解、透视图。
图3是实施例3中所述的对照样品M,本发明样品B和对比样品L中的颗粒的粒度分布的图解表示。
图4是实施例4中所述的本发明实施例B4至B7中的矿脂液滴的粒度分布的图解表示。
图5是实施例4中所述的本发明实施例B8和B9中的矿脂液滴的粒度分布的图解表示。
具体实施方式
本发明的一个方面是稳定、多相各向同性的清洗组合物,包括但不限于:
a. 约99-84wt%的水,基于整个组合物;
b. 约1-16wt%的矿脂,基于整个组合物,其中矿脂的熔点在35和80C间和在32C下最小粘度为10Kps;
c. 其中水相包括约1-25wt%的非皂阴离子表面活性剂,基于整个组合物(优选地,最小浓度为约4、8或12wt%和最高浓度为约16、20或25wt%)和约1-20wt%的两性表面活性剂,基于整个组合物(优选地,最小浓度为约2、4或6wt%和最高浓度为约12、16或20wt%);
d. 其中水相包含约0.5至10wt%的总聚合分散稳定剂(一种或多种),基于整个组合物(优选地,最小浓度为约1.0、1.5或2wt%和最高浓度为约8或9wt%);
e. 小于约2wt%(优选地小于约1.5. 1或0.5wt%)的总疏水甘油酯(一种或多种),除矿脂的烃(一种或多种),或硅油或其共混物和衍生物,基于整个组合物;和
f. 小于约1.5wt%(优选地小于约1.0或0.5wt%)的总液晶结构化剂(一种或多种),结晶含羟基的稳定剂(一种或多种),C10-C22脂肪酸乙二醇酯(一种或多种),二氧化硅(一种或多种),粘土(一种或多种),任选地不溶性着色剂,或其共混物,基于整个组合物。
稳定的组合物在本文中定义为这样的产品,其中在45C,37C,25C,或4C的储存温度3个月后,或在50C存储2周后,没有观察到相分离。优选地,矿脂以最小浓度约2.5,3,3.5或4wt%和最高浓度约4,6,8或12wt%存在。更优选地,矿脂在32C下具有约20Kps,35Kps或50Kps的最大粘度。
在优选实施方案中,本发明的清洗组合物仅仅包含水和油相。优选地,清洗组合物具有80%的最大反射率,如通过如下所述的标准反射率方法测量的。更优选地,最大反射率是70,60或50%。
有利地,清洗组合物具有大于50体积%的直径大于50,100,150或200微米的矿脂相颗粒,如通过标准粒度方法测量的。优选地,大于90体积%的矿脂相颗粒具有大于10,20,30或40微米的直径。
本发明的另一个方面是一种制备稳定、多相各向同性的清洗组合物的方法,其包括但不限于如下的步骤,没有特定的顺序:
a. 共混水、表面活性剂(一种或多种)、和聚合分散稳定剂(一种或多种)直到均匀来制备无油的、透明的各向同性的水性预混合物;
b. 将水性预混合物进料到共混管中,水性预混合物以约22.7-113.7千克(50-250磅)/分钟的速率通过共混管;和
c. 通过多口注射器以足以形成重量百分数比值范围为约1%矿脂:99%水性预混合物至约16%矿脂:84%水性预混合物的共混物的速率将熔点在35和80C间和在32C下最小粘度为10Kps的矿脂进料到共混管中。在将矿脂进料到水性预混合物中以前,矿脂可以任选地共混以其它组分而形成矿脂预混合物。
优选地,水性预混合物的温度被调节到约40C或更小(优选地低于35C和最优选地约32C)并且矿脂的温度被调节到50-70C,然后共混在一起。更优选地,矿脂被调节高于50C或55C并且最优选地约60C。最优选地,在共混后最终产物的温度不超过37C。
有利地,多口注射器具有最少3,4,5,6,7,或8个管道口。在优选实施方案中,多口注射器的口以对称图案排列。优选地,在3点或更多点星状物的端点处,与水性预混合物的流动正交取向并且沿混合管道的外围设置。更优选地,所述口的直径为约2-20mm,其中最小直径为约4,6或8mm并且最大直径为约18,16,14或12mm。最优选地,直径为约9mm。
方法描述:
在优选实施方案中通过下述方式制备本发明组合物:使用如下所述的和图1的工艺流程图中描述的方法,将矿脂或任选的其非水性预混合物注射到各向同性的水性预混合物中。矿脂预混合物由以下组成:矿脂和任选地活性剂(如下定义)或其它任选的成分,其可能包括颗粒如聚乙烯或microthene或其它颗粒或者其共混物,其可以稳定地溶解或悬浮在矿脂基质中并且其没有被特别地排斥在本发明外,也没有提高产品反射率超过50、60、70或80%。矿脂或矿脂预混合物,当在规定的流量和温度条件下通过注射加入水性预混合物时,产生矿脂粒度分布和产品皮肤沉积性能,其通过分批加工不能容易地或可复制地得到。在优选实施方案中多口注射用于注射矿脂预混合物并且合适的八口星形的注射器100的实例在图2中举例说明。在其中矿脂被注射到水相的点处,口的其它多口的星或非星形的对称或非对称构型可以有利地用于将矿脂或矿脂预混合物分为多个物流。
在本发明的另一实施方案中,可以使用改进的分批法来制备各向同性的水相,随后在批料罐中在受控混合的情况下注射矿脂或矿脂预混合物。过度混合导致不透明的产品外观即乳化(非常小)的油滴,其平均直径低于50,30,10或1微米并且典型地在亚微米范围内。这样的过度混合的产品不会具有本发明组合物的有益的粒度分布,反射率水平或产品性能品质。
相比于分批加工,借助于多口注射的在线注射实施方案被发现获得了更一致的产品品质。用图1中举例说明的在线注射方法观察到的另一令人期望的特征是在恒压下在混合前后水性和矿脂预混合物物流中的每一个的恒定流速。恒定流速被发现使得产品粒度分布和反射率变化最小化。
在优选实施方案中,矿脂预混合物罐20具有热水夹套以便控制温度并且搅拌器24由偏置混合器和刮壁混合器组成。
多口注射器28的作用是将矿脂预混合物流动细分并且在特定的温度和流量条件下将油物流破碎成液滴。通过注射器的液体的流量取决于系统压力,通常注射器的上游压力和排出压力(通常大气压)的差。对于在线注射来说,流量可以如下计算:
GPM=K(Psig(上游)-Psig(注射器出口))
K=所用的特定的注射器的常数。
液体物流的粘度将影响注射器性能,因为通常粘度大于100cps(在体系温度)的流体难以雾化,除用空气外。空气不用于雾化是本发明的方法或本发明产品(Air is not used for
atomization is the inventive process or with the inventive product)。优选地,本文中所用的粘度范围为约100至20,000cps,在所用的工艺温度(例如用Brookfield锭子5在20rpm下测量的)在优选实施方案中,观察到在图2中所描述的八(8)口星形的注射器允许在100-1000微米的范围内显著的矿脂预混合物液滴形成。这种注射器的其它特征包括在管道130的出口端上被注射口110围绕的中心孔120。法兰140设置在管道130的相对端并且包含适应于容纳密封垫160的同心凹槽(未示)。管道170具有延伸管道164和在第一端连接的法兰172和在第二端连接的法兰180。法兰172包含适应于容纳密封垫160的同心凹槽174。延伸管道164的尺寸是这样的,容纳球150并且被容纳在管道130中。在正流动操作中,液体流过管道170,然后通过管道164和130,借此球150移动来密封孔120的中心部,同时仍然允许液体流过口110。
对于系统压力的适度变化(在Δ40PSIG的量级)来说,单流体喷嘴(非空气系统)的液滴尺寸形成可以通过以下公式来确定。
已知液体比重影响通过注射器喷嘴的液体流量。在具有不同的比重(SG)的流体之间存在以下关系,其中Q是以体积/时间的单位给出的。
在注射时粘度的特定的增加对于在本发明方法中液滴形成来说是关键的。水性预混合物流量(近似地95%的总配方)提供了为冷却矿脂预混合物所必需的热容量,这导致粘度的增加并且有利于矿脂液滴形成和较大的粒度。
在图1的方法的优选实施方案中,使用静态混合器56而无论流速、粘度或密度分布,得到产品一致性即液滴尺寸分布。静态混合器56包含这样的元件,其有效地混合,其中层流条件典型地存在在例如最终产品输送管路62中。尽管不希望受以下理论解释的束缚,据信层流条件将形成在常规开放管道的中心处具有最大速度的速度梯度。在水介质中致密性(dense)较低的矿脂液滴将倾向于迁移到最大速度区域。位于静态混合器56中心的混合元件将破坏这种速度梯度并且由此提供更完全的最终产品均一性。
对于静态混合器如KMR-SAN6(Chemineer Corp.,
Andover, MA),(M)与元件的#(N)成正比,按照下式:
例如,具有6个元件/混合器的两个(2)静态混合器提供了足够的混合从而获得本发明产品一致性。
矿脂预混合物处理步骤(200kg批料)
1.) 现在参考图1,将矿脂预混合物罐20热水加热器(未示)设置到60C.
2.) 添加108.8kg的矿脂到罐20.
3.) 设置罐搅拌器24至以下:涡轮-40Htz 刮擦-0Htz
4.) 继续加热矿脂预混合物至60C。当温度到达57-60C,可任选地添加聚乙烯珠。慢慢地添加38kg的珠-添加时间大约2分钟。随着珠添加,在没有油相飞溅的情况下,提高涡轮速度至最大值.
5.) 在完成任选的珠添加后,设置搅拌如下:涡轮-40Htz 刮擦-最大值。在这些速度下混合2.0分钟.
6.) 在完成2.0分钟混合后,改变搅拌器24至以下:涡轮-40Htz 刮擦-80Htz.
7.) 继续混合并且加热这种预混合物至60C。
水性基础材料处理过程(4000kg批料).
1.) 将1600kg的去离子水添加到基础材料制备罐30并且加热到55C.
2.) 在搅拌下,将240kg的Carbopol Aqua SF-1聚合物溶解在水中.
3.) 在使用搅拌器32的搅拌下,700kg的SLES和CMEA的共混物(51.4wt% SLES,6.67wt% CMEA),并且在55C共混20分钟.
4.) 在搅拌下依次添加240.4kg的椰油酰胺丙基甜菜碱(cocamidopropyl betaine),2kg的EDTA四钠,39%;89kg的去离子水,6kg的氢氧化钠,50wt%;和925.66kg的去离子水直到溶解并且然后将共混物冷却至35至40C.
5.) 然后,顺序地添加7.2kg的DMDM乙内酰脲,55%;0.72kg的颜料黄(Colorant Yellow),40kg的香料和20kg的Captivates HC® 1576 (蓝)黄色珠[(Blue) Yellow beads]并且共混直到均匀。
矿脂预混合物注射到基础材料水相
1.) 打开矿脂预混合物罐循环管路27.
2.) 在罐顶部口25处切断矿脂预混合物循环管路并且置于废物容器中.
3.) 打开侧面安装的矿脂预混合物罐阀29.
4.) 设置矿脂预混合物泵22至2.47磅/分钟.
5.) 开启矿脂预混合物泵22以便吹扫管路的任何水或矿物油,并且然后关掉泵.
6.) 直接将循环管路27连接到矿脂预混合物罐20的顶部并且开启矿脂预混合物泵22。检查确定矿脂预混合物再循环回到罐20的顶部中。水和油相现已备用于共混.
7.) 将基础材料泵42设置在期望的输送速率(对于50磅/分钟的总速率来说,将基础材料泵42设置到47.53磅/分钟。检查计量器处的矿脂预混合物泵以便确保它正以2.47磅/分钟循环.
8.) 填料输送管路62应当被吹扫3.0分钟.
9.) 基础材料泵42和矿脂预混合物泵22的流速必须被分别控制到47.53磅/分钟的+/-3%和2.47磅/分钟的+/-3%.
10.) 矿脂预混合物的温度必须被控制到60C的设置点的+/-2℃,水性基础材料必须是35C或更低.
11.) 共混压力(如在静态混合器元件56后直接用压力计测量的)必须被保持到32psi+/-3psi.
12.) 在贮存罐泵42的出口处记录的泵压力必须是80psi或更低。
表面活性剂:
表面活性剂是本发明的清洗组合物的必需组分。它们是具有疏水和亲水部分的化合物,其作用是降低水溶液(它们被溶解在该水溶液中)的表面张力。有用的表面活性剂可以包括阴离子、非离子、两性和阳离子表面活性剂,和其共混物。
阴离子表面活性剂:
本发明的清洗组合物包含一种或多种非皂阴离子洗涤剂。非皂阴离子表面活性剂优选地以低到1或4、8或12wt%的水平和以高达16、20或25wt%的水平使用。皂的含量小于0.1wt%并且优选地本发明的清洗组合物不含皂,这由于要求组合物是中性至微酸性的,即,最大pH为约7.0,优选地约6.8或更优选地约6.5。最小pH优选地是约3.5,更优选地约4.5和最优选地约5.5。
在本发明中可用的阴离子洗涤剂活性物可以是脂族磺酸盐/酯,如伯烷烃(例如C8-C22)磺酸盐/酯,伯烷烃(例如C8-C22)二磺酸盐/酯,C8-C22烯烃磺酸盐/酯,C8-C22羟基烷烃磺酸盐/酯或烷基甘油基醚磺酸盐/酯(AGS);或芳族磺酸盐/酯如烷基苯磺酸盐/酯。阴离子也可是烷基硫酸盐/酯(例如C12-C18烷基硫酸盐/酯)或烷基醚硫酸盐/酯(包括烷基甘油基醚硫酸盐/酯)。在烷基醚硫酸盐/酯中是具有下式的那些:
其中R是具有8至18个碳,优选地12至18个碳的烷基或烯基,n具有大于1.0,优选地大于3的平均值;和M是溶解性阳离子如钠,钾,铵或被取代的铵。月桂基醚硫酸铵和钠是优选的。
阴离子也可是烷基磺基琥珀酸盐/酯(包括单和二烷基,例如,C6-C22磺基琥珀酸盐/酯);烷基和酰基牛磺酸盐/酯(taurates),烷基和酰基肌氨酸盐/酯(sarcosinate),磺基乙酸盐/酯,C8-C22烷基磷酸盐/酯和磷酸盐/酯,烷基磷酸(盐)酯和烷氧基烷基磷酸(盐)酯,酰基乳酸盐/酯,C8-C22单烷基琥珀酸盐/酯和马来酸盐/酯,磺基乙酸盐/酯,烷基糖苷和酰基羟乙基磺酸盐/酯(acyl isethionates)等。
磺基琥珀酸盐/酯可以是具有下式的单烷基磺基琥珀酸盐/酯:
下式的酰胺-MEA磺基琥珀酸盐/酯;
其中R4为C8-C22烷基和M是溶解性阳离子。
肌氨酸盐通常由下式表示:
其中R1为C8-C20烷基和M是溶解性阳离子。
牛磺酸盐(taurates)通常由下式表示:
其中R2为C8-C20烷基,R3为C1-C4烷基和M是溶解性阳离子。
本发明的清洗组合物可以包含C8-C18酰基羟乙基磺酸盐/酯。这些酯是通过碱金属羟乙基磺酸盐/酯与具有6-18个碳原子并且碘值小于20的混合脂族脂肪酸之间的反应制备的。至少75%的混合脂肪酸具有12至18个碳原子和至多25%具有6至10个碳原子。
酰基羟乙基磺酸盐/酯可以是烷氧基化的羟乙基磺酸盐/酯,如Ilardi等的题目为"Fatty Acid Esters of
Polyalkoxylated isethonic acid"的美国专利5,393,466(1995年2月28日出版)中所述的,其引入本文作为参考。该化合物具有以下通式:
其中R是具有8至18个碳的烷基,m是1至4的整数,X和Y是氢或具有1至4个碳的烷基和M+是一价阳离子,例如钠,钾或铵。
两性表面活性剂
一种或多种两性表面活性剂用于本发明。两性表面活性剂优选地以低到2、4或6wt%的水平和以高达12、16或20wt%的水平使用。这样的表面活性剂包括至少一个酸根。这可以是羧酸或磺酸基团。它们包括季氮并且因此是季酰胺酸。它们将通常包括7-18个碳原子的烷基或烯基基团。它们将通常符合以下的总结构式:
其中R1是7-18个碳原子的烷基或烯基;
R2和R3各自独立地是1-3个碳原子的烷基、羟烷基或羧烷基;
n是2至4;
m是0-1;
X是1-3个碳原子的亚烷基,其任选被羟基取代,和
Y是-CO2-或-SO3-
在上述通式中合适的两性表面活性剂包括下式的简单甜菜碱:
和下式的酰胺基甜菜碱:
其中n是2或3。
在两式中,R1、R2和R3是如前所定义的。R1可以特别地是衍生自椰油的C12和C14烷基的混合物以便至少一半,优选地至少四分之三的基团R1具有10至14个碳原子。R2和R3优选地是甲基。
进一步的可能性是两性洗涤剂是下式的磺基甜菜碱:
或
其中m是2或3,或这些的变体,其中-(CH2)3SO3 -被以下替代:
在这些式中,R1、R2和R3是如上所述的。
两性乙酸盐(amphoacetate)和双两性乙酸盐(diamphoacetate)也意图被包括在可被使用的可能的两性离子和/或两性化合物中,例如,月桂酰两性基乙酸钠,椰油酰两性基乙酸钠,和其共混物等。
总非皂阴离子、非离子、两性表面活性剂和聚合分散稳定剂(一种或多种)(如下所讨论的)的组合将优选地为组合物的约5至30wt%。
非离子型表面活性剂
一种或多种非离子型表面活性剂可以用于本发明的清洗组合物中。非离子型表面活性剂优选地以低到0.5、1、1.5或2wt%的水平和以高达6、8、10或12wt%的水平使用。可以使用的非离子特别地包括具有疏水基团和活泼氢原子的化合物,例如脂族醇、酸、酰胺或烷基酚与烯化氧,特别地氧化乙烯,单独地或与氧化丙烯一起的反应产物。特定的非离子型洗涤剂化合物是烷基(C6-C22)酚氧化乙烯缩合物,脂族(C8-C18)伯或仲直链或支链醇与氧化乙烯的缩合产物,通过氧化乙烯与氧化丙烯和乙二胺的反应产物的缩合制备的产物。其他所谓的非离子型洗涤剂化合物包括长链叔胺氧化物,长链叔膦氧化物和二烷基亚砜等。
优选的非离子型表面活性剂包括具有以下结构的脂肪酸/醇乙氧基化物
其中m,n独立地是<18;和x,y独立地是>1。优选地m,n独立地是6至18;x,y独立地是1至30;
其中i,k独立地是5至15;和z独立地是5至50。优选地i,k独立地是6至12;和z独立地是15至35。
非离子也可包括糖酰胺,如多糖酰胺。特别地,该表面活性剂可以是描述于Au等人的题目为"Compositions
Comprising Nonionic Glycolipid Surfactants"的1995年2月14日出版的美国专利5,389,279(其引入本文作为参考)中的乳糖酰胺(lactobionamides)之一或者其可以是描述于Kelkenberg的题目为"Use of N-Poly
Hydroxyalkyl Fatty Acid Amides as Thickening Agents for Liquid Aqueous
Surfactant Systems"的1991年4月23日出版的专利5,009,814(其引入本主题申请作为参考)中的糖酰胺之一。
阳离子皮肤调节剂
在根据本发明的组合物中的有用组分是阳离子肤感剂或聚合物,例如阳离子纤维素。阳离子聚合物优选地以低到约0.1至2%的水平直至高达特定的聚合物的溶解度极限的水平,或优选地高达约4至5wt%的水平使用,条件是没有超过特定的阳离子聚合物或其共混物的溶解度极限。
阳离子纤维素可得自Amerchol Corp.(Edison, NJ,
USA),以其Polymer JR(商标)和LR(商标)系列的聚合物,以与三甲基铵取代的环氧化物反应的羟乙基纤维素的盐的形式,这在业(CTFA)内称为Polyquaternium 10。另一种类型的阳离子纤维素包括与月桂基二甲基铵-取代的环氧化物反应的羟乙基纤维素的聚合季铵盐,这在业(CTFA)内称为Polyquaternium 24。这些材料可在商品名Polymer LM-200下获自Amerchol Corp.(Edison, NJ,
USA)。
可以使用的特别合适类型的阳离子多糖聚合物是阳离子瓜尔胶衍生物,如瓜尔胶羟丙基三甲基氯化铵(市售可得自Rhone-Poulenc,在其JAGUAR商标系列中)。实例是JAGUAR C13S,其具有阳离子基团低取代度和高粘度,JAGUAR C15,具有适度的取代度和低粘度,JAGUAR C17(高取代度,高粘度),JAGUAR C16,其是包含低水平的取代基团以及阳离子季铵基团的羟丙基化阳离子型瓜尔胶衍生物,和JAGUAR 162,其是具有低取代度的高透明度,中粘度瓜尔胶。
特别优选的阳离子聚合物是JAGUAR C13S,JAGUAR C15,JAGUAR C17和JAGUAR C16和JAGUAR C162,特别地JAGUAR C13S,和JAGUAR C-14/BFG。JAGUAR C14/BFG材料是与JAGUAR C13相同的分子,区别在于乙二醛交联剂已经替代了硼。可以使用本领域已知的其它阳离子肤感剂,条件是它们与本发明制剂相容。
可用的上述表面活性剂的其他合适的实例描述于以下文献中:"Surface Active
Agents and Detergents"(Vol. I & II),Schwartz, Perry & Berch,其全盘引入本主题申请作为参考。
另外,本发明的清洗组合物可以包括0-15wt%任选的成分如下:香料;螯合剂,如乙二胺四乙酸四钠(EDTA),EHDP或混合物,其数量为:0.01至1%,优选地0.01至0.05%;和可溶性着色剂等;全部这些可用于提高产品的外观或化妆用性能。
组合物可以进一步包括抗微生物剂如2-羟基-4,2',4'三氯二苯醚(DP300);防腐剂如二羟甲基二甲基乙内酰脲(Glydant XL1000),对羟基苯甲酸酯(parabens),山梨酸等。
组合物也可包括椰油酰基单或二乙醇酰胺作为增泡剂,并且也可有利地使用强电离盐如氯化钠和硫酸钠。优选地强电离盐,或者称为电解质,的含量将小于3、2、1wt%。
抗氧化剂,例如,丁羟甲苯(BHT)等,可以有利地使用,其数量为约0.01%或更高,如果合适的话。
润肤剂
术语"润肤剂"被定义为这样的物质,其通过或者提高它的水含量,添加,或代替脂质及其他皮肤营养物;或两者,软化或者改善皮肤(角质层)的弹性、外观和年轻性,并且通过延迟它的水含量的降低来保持它柔软。
保湿剂,其也是湿润剂,如多羟基醇,例如甘油和丙二醇等;和多元醇如聚乙二醇等,可以用作亲水润肤剂。湿润剂优选地以低到1、3或5wt%的水平和以高达6、8或10wt%的水平使用。
矿脂用于本发明,优选地以低到1、3或4wt%的水平并且以高达5、6、8、12或16wt%的水平。矿脂被定义为衍生自石油的熔点为35至80C(如根据ASTM D127-08, "Standard
Test Method for Drop Melting Point of Petroleum Wax, including
Petrolatum", ASTM International, West Conshohocken, PA测定的)和在32C下最小粘度为10Kps的液烃的混合物。优选地,在32C下,它的粘度范围为10至35Kps。更优选地,在32C,粘度的上限是25或50Kps。
其它非矿脂疏水润肤剂优选地以小于约1.5、1.0或0.5wt%的总水平存在于本发明组合物中,更优选地不存在于组合物中。这些疏水润肤剂包括但不限于以下:
(a) 硅油和其改性物如线性和环状聚二甲硅氧烷;氨基、烷基、烷基芳基和芳基硅油;
(b) 脂肪和油,包括天然的脂肪和油如希蒙德木、大豆、向日葵、米糠、鳄梨、杏仁、橄榄、芝麻、桃仁、蓖麻、椰子、貂油;可可脂;牛脂、猪油;通过氢化上述的油获得的硬化油;和合成甘油单、二和三酯如肉豆蔻酸甘油酯和2-乙基己酸甘油酯;
(c) 蜡如巴西棕榈蜡、鲸蜡、蜂蜡、羊毛脂和其衍生物;
(d) 疏水和亲水植物提取物;
(e) 非矿脂烃如聚丁烯、液状石蜡、微晶蜡、地蜡、角鲨烯、姥鲛烷(pristan)和矿物油;
(f) 高级脂肪酸如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山萮酸、油酸、亚油酸、亚麻酸、羊毛酸(lanolic)、异硬脂酸、花生四烯酸和多不饱和脂肪酸(PUFA);
(g) 高级醇如月桂醇、鲸蜡醇、硬脂醇、油醇、山萮醇、胆固醇和2-十六烷醇(hexydecanol);
(h) 酯如辛酸十六烷基酯、乳酸十四烷基酯、乳酸十六烷基酯、肉豆蔻酸异丙酯、肉豆蔻酸十四烷基酯、棕榈酸异丙酯、己二酸异丙基酯、硬脂酸丁酯、油酸癸基酯、异硬脂酸胆固醇酯、单硬脂酸甘油酯、二硬脂酸甘油酯、三硬酯酸甘油酯、乳酸烷基酯、柠檬酸烷基酯和酒石酸烷基酯;
(i) 香精油和其萃取物如薄荷、茉莉、樟脑、白杉、苦橙皮、ryu、松节油、肉桂、香柠檬、温州蜜柑、菖蒲、松木、熏衣草、月桂、丁香、hiba、桉树、柠檬、七瓣莲、百里香、胡椒薄荷、玫瑰、鼠尾草、芝麻、姜、罗勒、桧柏、柠檬草、迷迭香、蔷薇木、鳄梨、葡萄、葡萄籽、没药、黄瓜、豆瓣菜、金盏花、接骨木花(elder flower)、天竺葵、菩提树花、苋菜、海藻、银杏(ginko)、人参、胡萝卜、巴西可可、茶树、希蒙德木、紫草、燕麦、可可、橙花油、香草、绿茶、薄荷(penny royal)、库拉索芦荟、薄荷脑、桉油精、丁香酚、柠檬醛、香茅(citronelle)、龙脑、里哪醇、香叶醇、月见草、樟脑、麝香草酚、spirantol、penene、苧烯和类萜油;
(j) 任何上述组分的混合物等。
各向同性的胶束相组合物:
本发明的清洗组合物具有各向同性的胶束相显微结构。全部表面活性剂溶液,包括液体清洗溶液,的流变特性强烈地取决于胶束或其它自组装结构在溶液中的显微结构,即,形状和浓度。
当存在足够的表面活性剂以形成胶束(高于临界胶束浓度或CMC的浓度)时,例如,球状的,柱状的(棒状的或盘状的),球柱状的,或椭圆状的胶束可以形成。随着表面活性剂浓度增加,排序的液晶相如片状相,六角相,立方相或L3海绵相可以形成。非各向同性的六角相,由在六方点阵中排列的长柱状胶束构成。一般说来,大多数个人护理产品的显微结构由以下构成:各向同性的分散体,包括球状胶束;和棒胶束;或排序液晶相如片状分散体。
如上所述,胶束可以是球状的或棒状的。具有球状胶束的制剂往往具有低粘度并且显示出牛顿剪切行为(即,作为剪切速率的函数,粘度保持恒定;因此,如果期望容易倾倒产品的话,溶液是较小粘滞的。在这些体系中,随着表面活性剂浓度粘度线性地增加。
棒胶束溶液是更加粘滞的,因为限制了较长的胶束的运动。在临界剪切速率,胶束排列并且溶液变为剪切稀释。添加盐增加了其棒胶束的尺寸,这提高了零剪切粘度(即,当位于瓶中时的粘度),这有助于悬浮颗粒而且增加临界剪切速率(产品变为剪切稀释时的点;更高的临界剪切速率意味着产品更难以倾倒)。
片状及其他液晶分散体不是本发明的一部分。这样的分散体不同于球状和棒状胶束,因为它们可以具有高零剪切粘度(因为组成片状液滴的密集排列),然而这些溶液是非常剪切稀释的(当倾倒时容易分配)。也就是说,在适度的剪切速率下,相比于棒胶束溶液,该溶液可以变为更稀释。
表征各向同性的胶束分散体(在下文中"各向同性的组合物")的一种方法包括如下所述的锥体和板粘度测量。本发明的各向同性的组合物的粘度,在1/秒剪切速率下在25C,如通过如下所述的锥体和板技术测量的,为约500至约300,000cps。优选地,在25C,粘度为约1,000至20,000cps。
聚合分散稳定剂(一种或多种):
水溶性或可分散的聚合分散剂被包括在本发明组合物中。合适的试剂包括糖胶(carbohydrate gums)如纤维素胶,微晶纤维素,纤维素胶(cellulose gel),羟乙基纤维素,羟基丙基纤维素,羧甲基纤维素钠,羟甲基羧甲基纤维素,角叉菜胶,羟甲基羧丙基纤维素,甲基纤维素,乙基纤维素,瓜尔胶,刺梧桐树胶,黄蓍树胶,阿拉伯树胶,金合欢胶,琼脂胶,黄原胶和其混合物。
优选的糖胶(carbohydrate gums)是羟丙基甲基纤维素(Hydroxypropyl
Methocellulose)如Methocel ®40-100和Methocel 40-202(Dow Chemicals, Midland, Michigan),羟丙基淀粉磷酸钠如Pure-Gel B990(Grain
Processing Corp., Muscatine, Iowa),和黄原胶如Keltrol CG(CPKelco,, Atlanta,
Georgia)。
合适的聚合分散剂还包括含丙烯酸酯的均和共聚物如在CARBOPOL商品名下可得的交联的聚丙烯酸酯,在AQUA商品名和PEMULEN商品名下可得的疏水改性交联的聚丙烯酸酯(全部由Lubrizol Company,
Wickliffe, Ohio出售)和在ARYSOL或ACULYN商品名下由Rohm and
Haas(Philadelphia, PA)出售的碱性可膨胀的丙烯酸胶乳聚合物。优选的丙烯酸酯是Aqua SF-1®和Carbopol Ultrez 21 ®聚合物。
液晶、粘土和二氧化硅结构化剂:
参与形成液晶网络结构如片状组织(如上所述)的结构化剂(一种或多种)和在表面活性剂溶液中形成或参与形成胶体或其它网络的不溶性试剂如粘土和二氧化硅,以小于1.5、1或0.5wt%总浓度存在并且优选地不存在于本发明组合物中。被排除的液晶结构化剂包括但不限于饱和C14至C30脂肪醇、饱和C16至C30脂肪醇(包含约1至约5摩尔的氧化乙烯)、饱和C16至C30二醇、饱和C16至C30单甘油醚、饱和C16至C30羟脂肪酸、C14至C30羟基化的和非羟基化的饱和脂肪酸、C14至C30饱和乙氧基化脂肪酸、胺和醇(包含约1至约5摩尔的氧化乙烯二醇)、C14至C30饱和甘油基单酯(甘油单酯含量为至少40%)、C14至C30饱和聚甘油酯(具有约1至约3个烷基和约2至约3个饱和甘油单元)、C14至C30甘油基单醚、C14至C30脱水山梨糖醇单/二酯、C14至C30饱和乙氧基化脱水山梨糖醇单/二酯(具有约1至约5摩尔的氧化乙烯)、C14至C30饱和甲基糖苷酯、C14至C30饱和蔗糖单/二酯、C14至C30饱和乙氧基化甲基糖苷酯(具有约1至约5摩尔的氧化乙烯)、C14至C30饱和多聚葡糖苷(具有平均1至2个葡萄糖单元)和其混合物。上述结构化剂(一种或多种)包括HLB为约1至约8和熔点为至少约45℃的那些。
对比的液晶结构化剂的附加实例包括但不限于硬脂酸、棕榈酸、硬脂醇、鲸蜡醇、山萮醇、硬脂酸、棕榈酸、具有平均约1至约5个氧化乙烯单元的硬脂醇的聚乙二醇醚、具有平均约1至约5个氧化乙烯单元的鲸蜡醇的聚乙二醇醚和其混合物。还包括硬脂醇、鲸蜡醇、山萮醇、具有平均约2个氧化乙烯单元的硬脂醇的聚乙二醇醚(steareth-2)、具有平均约2个氧化乙烯单元的鲸蜡醇的聚乙二醇醚和其混合物。
其他的对比的液晶结构化剂包括但不限于结晶、含羟基的稳定剂如含羟基的脂肪酸、脂肪酸酯或脂肪皂水不溶性的蜡状物质等。
例如,结晶、含羟基的稳定剂可以选自:
其它对比的含羟基的稳定剂包括但不限于12-羟基硬脂酸、9,10-二羟硬脂酸、三-9,10-二羟基硬脂精(stearin)和三-12-羟基硬脂精(stearin)(氢化蓖麻油大部分是三-12-羟基硬脂精(stearin))。
在这种类型的对比的结构化剂中还包括C10-C22脂肪酸乙二醇酯。
如上所述的,粘土、二氧化硅及其他颗粒基的对比的结构化剂(一种或多种)以小于1.5、1或0.5wt%存在并且优选地不存在于本发明组合物中。这些试剂包括但不限于分散无定形二氧化硅,其选自火成二氧化硅和沉淀二氧化硅和其混合物。如本文中使用的,术语“分散无定形二氧化硅”是指小的、细碎的非结晶的二氧化硅,其具有小于约100微米的平均聚集粒度。
对比的结构化剂的其它实例包括但不限于分散蒙脱石粘土,其包括膨润土和锂蒙脱石和其混合物。膨润土是胶体铝粘土硫酸盐。锂蒙脱石是包含钠、镁、锂、硅、氧、氢和氟的粘土。
任选的活性剂
有利地,除以上定义的调节剂如润肤剂或保湿剂以外的活性剂可以在配制期间以安全和有效量添加到清洗组合物以便在使用产品期间处理皮肤,条件是它们不超过溶解度极限,其中在清洗组合物中反射率增加超过80%。合适的活性成分包括可溶于水相、矿脂相或两相中的那些。合适的活性剂可以有利地选自抗微生物和抗真菌活性物,维生素,抗粉刺活性物;抗皱纹、抗皮肤萎缩和皮肤修补活性物;皮肤屏障修补活性物;非类固醇化妆用抚慰活性物;人造变棕剂和促进剂;亮肤活性物;遮光活性物;皮脂(sebum)激活剂;皮脂抑制剂;抗氧化剂;蛋白酶抑制剂;皮肤紧绷剂;抗痒成分;毛发生长抑制剂;5-α还原酶抑制剂;剥落酶增强剂;抗糖化(anti-glycation)剂;局部麻醉剂,或其混合物;和类似物。
这些活性剂可以选自水溶性活性剂,油溶性活性剂,药用可接受的盐和其混合物。有利地,所述试剂在清洗组合物中将是可溶的或可分散的。如本文中使用的术语“活性剂”,是指这样的个人护理活性物,其可用于将益处提供给皮肤和/或毛发并且通常不用来给予调节益处,后者是通过本文中前面描述的湿润剂和润肤剂给予的。如本文中使用的术语“安全和有效量”是指高到足以改变待处理的状况或者提供期望的皮肤护理益处、但低到足以避免严重的副作用的活性剂的数量。如本文中使用的术语“益处”是指与用本文中所述的一种或多种活性剂处理特定的状况有关的治疗、预防和/或长期益处。何谓安全和有效量的活性剂成分将随着特定的活性剂、活性物穿透皮肤的能力、年龄、健康状况和使用者的皮肤状况和其他类似的因素而变化。优选地,本发明的组合物包括约0.01%至约50%、更优选地约0.05%至约25%、更优选地0.1%至约10%和最优选地0.1%%至约5%,按重量计,的活性剂组分。
抗粉刺活性物可能在治疗寻常痤疮(毛皮脂腺囊的长期病症)中是有效的。有用的抗粉刺活性物的非限制性实例包括角质层分离剂如水杨酸(o-羟基苯甲酸),水杨酸的衍生物如5-辛酰基水杨酸和4甲氧基水杨酸、和间苯二酚;类维生素A如视黄酸和它的衍生物(例如顺式和反式);含硫的D和L氨基酸和它们的衍生物和盐,特别地它们的N-乙酰衍生物,其混合物等。
抗微生物和抗真菌活性物可以有效地预防细菌和真菌的增殖和生长。抗微生物和抗真菌活性物的非限制性实例包括b-内酰胺(lactam)药物,喹诺酮(quinolone)药物,环丙沙星(ciprofloxacin),诺氟沙星(norfloxacin),四环素(tetracycline),红霉素(erythromycin),阿米卡星(amikacin),2,4,4'-三氯-2'-羟基二苯醚,3,4,4'-trichlorobanilide,苯氧乙醇,三氯生(triclosan);三氯卡班(triclocarban);和其混合物等。
抗皱纹、抗皮肤萎缩和皮肤修补活性物可能在补充或复原表皮层中是有效的。通过促进或保持剥落的自然过程,这些活性物通常提供了这些令人期望的皮肤护理益处。抗皱和抗皮肤萎缩活性物的非限制性实例包括维生素,矿物质,和皮肤营养物如乳,维生素A,E,和K;维生素烷基酯,包括维生素C烷基酯;镁,钙,铜,锌及其他金属组分;视黄酸和它的衍生物(例如顺式和反式);视黄醛;视黄醇;视黄酯如乙酸视黄酯,棕榈酸视黄酯,和丙酸视黄酯;维生素B3化合物(如烟酰胺和烟酸),α羟基酸,β羟基酸,例如水杨酸和其衍生物(如5-辛酰基水杨酸,庚氧基4水杨酸,和4-甲氧基水杨酸);其混合物等。
皮肤屏障修补活性物是那些皮肤护理活性物,其可能有助于修补和补充表皮的天然水分屏障功能。皮肤屏障修补活性物的非限制性实例包括脂质如胆固醇,神经酰胺,蔗糖酯和拟神经酰胺(如欧洲专利说明书No.556,957所述);抗坏血酸;生物素;生物素酯;磷脂,其混合物等。
非类固醇化妆用抚慰活性物可能在预防或治疗皮肤的炎症中是有效的。抚慰活性物提高了本发明的皮肤外观益处,例如,这样的试剂有助于更加均匀和可接受的皮肤色调或颜色。化妆用抚慰试剂的非限制性实例包括以下种类:丙酸衍生物;乙酸衍生物;灭酸衍生物;其混合物等。这些化妆用抚慰活性物中的许多描述于1991年1月15日出版的Sunshine等的美国专利4,985,459中,其全盘引入本文作为参考。
人造变棕活性物可能有助于通过提高皮肤中的黑色素或者通过在皮肤中产生提高的黑色素的外观模拟天然晒黑。人造变棕剂和促进剂的非限制性实例包括二羟基丙酮(dihydroxyacetaone);酪氨酸;酪氨酸酯如酪氨酸乙酯和酪氨酸葡萄糖;其混合物等。
亮肤活性物可能实际上降低皮肤中的黑色素的量或者通过其它机理提供这样的效果。在本文中有用的亮肤活性物的非限制性实例包括芦荟提取物,α-甘油基-L-抗坏血酸,氨基酪氨酸(aminotyroxine),乳酸铵,羟基乙酸,氢醌,4羟基苯甲醚,其混合物等。
还在本文中有用的是遮光活性物。多种遮光剂描述于以下文献中:Haffey等1992年2月11日出版的美国专利5,087,445;Turner等1991年12月17日出版的美国专利5,073,372;Turner等1991年12月17日出版的美国专利5,073,371;和Segarin等的Cosmetics Science and
Technology的第VIII章的第189页及以下,其全部以其全部内容引入本文作为参考。可用于本发明的组合物的遮光剂的非限制性实例是选自以下的那些:肉桂酸辛基甲氧酯(Parsol MCX)和丁基甲氧基苯甲酰甲烷(Parsol 1789),对甲氧基肉桂酸2-乙基己酯,N,N-二甲基-p-氨基苯甲酸2-乙基己酯,对氨基苯甲酸,2-苯基苯并咪唑-5-磺酸,羟甲氧苯酮,其混合物等。
皮脂激活剂可能通过皮脂腺提高皮脂的产生。皮脂刺激活性物的非限制性实例包括泻根酸(bryonolic acid),脱氢表雄酮(dehydroetiandrosterone)(DHEA),阿魏酸脂(orizanol),其混合物等。
皮脂抑制剂可能降低通过皮脂腺产生皮脂。有用的皮脂抑制活性物的非限制性实例包括羟基氯化铝,皮质类固醇,脱氢乙酸和它的盐,二氯苯基咪唑二氧戊环(dichlorophenyl
imidazoldioxolan)(可获自Elubiol),其混合物等。
在本发明中还可用作活性物的是蛋白酶抑制剂。蛋白酶抑制剂可被分为两大类:蛋白酶和肽酶。蛋白酶作用于蛋白质的特定的内部肽键,肽酶作用于邻近于蛋白质末端上的游离氨基或羧基的肽键并且因此从外部断开蛋白质。适用于本发明的蛋白酶抑制剂包括但不局限于蛋白酶如丝氨酸蛋白酶,金属蛋白酶,半胱氨酸蛋白酶,和天冬氨酰蛋白酶,和肽酶,如羧基肽酶(pepidases),二肽酶和氨基肽酶(pepidases),其混合物等。
在本发明中其它可用作活性成分的是皮肤紧绷剂。可用于本发明的组合物的皮肤紧绷剂的非限制性实例包括可结合聚合物至皮肤的单体如以下的三聚物:乙烯基吡咯烷酮,(甲基)丙烯酸和疏水性单体,包括长链(甲基)丙烯酸烷基酯在内,其混合物等。
在本发明中的活性成分也可包括抗痒成分。可用于本发明的组合物的抗痒成分的合适的实例包括氢化可的松,methdilizine和trimeprazineare,其混合物等。
可用于本发明的组合物的毛发生长抑制剂的非限制性实例包括17β雌二醇,抗血管形成甾体,姜黄提取物,环氧化酶抑制剂,月见草油,亚油酸等。合适的5-α还原酶抑制剂如乙炔基雌二醇(ethynylestradiol)和,genistine其混合物等。
可用于本发明的组合物的剥落酶增强剂的非限制性实例包括丙氨酸,天门冬氨酸,N甲基丝氨酸,丝氨酸,三甲基甘氨酸,其混合物等。
可用于本发明的组合物的抗糖化剂的非限制性实例将是Amadorine(可获自Barnet Products
Distributor)等。
现将通过以下非限制性的实施例更详细地描述本发明。实施例仅仅是说明性目的,而非意图以任何方式限制本发明。物理测试方法描述如下:
除在工作和对比实施例中,或者在另外明确指明的情况下,本说明书中表示材料或状况或反应的量或比例,材料和/或用途的物理性能的全部数字应被理解为被单词“约”修饰。
在说明书中使用的情况下,术语“包括”意图包括存在所述的特征、整数、步骤、组分,然而并非排除一种或多种特征、整数、步骤、组分或其子组的存在或添加。
说明书和实施例中的全部百分比意图是按重量计的,除非另有说明。
实施例1:
对分别具有2、4、6和8wt%的矿脂(本发明样品A-D)的组合物,研究混合强度和水性基础材料温度对反射率和粒度的效果。根据下列工序制备样品。表1A和2A列出了用低强度混合制备的样品的反射率。同样,表1B和2B列出了用高强度混合(200rpm)制备的样品的粒度。样品A-D的组成示于表3中。发现组合物A-D,相比于在以下实施例2中显示的(一个或多个)对比例,通常提供了低反射率和较大的平均粒度。
表1A:反射率(%)
基础材料温度 | A | B | C | D |
43.3C | 45.57 | 54.77 | 57.49 | 61.87 |
37.8C | 45.12 | 50.54 | 53.77 | 50.17 |
32.2C | 45.02 | 43.66 | 44.03 | 45.08 |
表1B:粒度(微米)
样品 | A | A | A | B | B | B |
基础材料温度 | d(0.1) | d(0.5) | d(0.9) | d(0.1) | d(0.5) | d(0.9) |
43.3C | 13.08 | 53.93 | 113.68 | 15.7 | 47.95 | 316.74 |
37.8C | 6.58 | 105.34 | 665.2 | 16.86 | 65.93 | 532.11 |
32.2C | 2.79 | 94.3 | 861.9 | 2.85 | 74.85 | 639.97 |
样品 | C | C | C | D | D | D |
基础材料温度 | d(0.1) | d(0.5) | d(0.9) | d(0.1) | d(0.5) | d(0.9) |
43.3C | 17.31 | 56.86 | 224.72 | 22.53 | 55.18 | 149.26 |
37.8C | 12.78 | 53.07 | 411.61 | 33.18 | 204.6 | 1031.88 |
32.2C | 3.18 | 102.89 | 692.34 | 45.35 | 308.9 | 1011.31 |
注:
d(0.1)是指10体积%的颗粒是较小的和90体积%的颗粒是较大的;
d(0.5)是指50体积%的颗粒是较小的和50体积%的颗粒是较大的;
d(0.9)是指90体积%的颗粒是较小的和10体积%的颗粒是较大的。
表2A:反射率(%)
基础材料温度 | A | B | C | D |
43.3C | 46.85 | 58.07 | 66.46 | 68.13 |
37.8C | 50.29 | 53.48 | 51.56 | 58.53 |
32.2C | 44.63 | 43.52 | 46.26 | 50.88 |
表2B:粒度(微米)
A | A | A | B | B | B | |
基础材料温度 | d(0.1) | d(0.5) | d(0.9) | d(0.1) | d(0.5) | d(0.9) |
43.3C | 16.16 | 71.6 | 481.62 | 16.35 | 57.41 | 233.34 |
37.8C | 17.12 | 55.61 | 254.54 | 19.06 | 74.97 | 693.42 |
32.2C | 6.15 | 102.68 | 973.39 | 52.13 | 414.43 | 1026.47 |
C | C | C | D | D | D | |
基础材料温度 | d(0.1) | d(0.5) | d(0.9) | d(0.1) | d(0.5) | d(0.9) |
43.3C | 13.01 | 38.6 | 93.22 | 17.48 | 48.91 | 110.64 |
37.8C | 22.82 | 122.13 | 609.97 | 19.17 | 67.8 | 406.55 |
32.2C | 80.66 | 387.82 | 989.47 | 46.76 | 284.73 | 862.28 |
表3:浓度(wt%)
组分 | A | B | C | D |
SLES (1) | 9.00 | 9.00 | 9.00 | 9.00 |
CMEA (2) | 1.15 | 1.15 | 1.15 | 1.15 |
椰油酰胺丙基甜菜碱 | 1.70 | 1.70 | 1.70 | 1.70 |
丙烯酸酯共聚物(3) | 1.8 | 1.8 | 1.8 | 1.8 |
氢氧化钠 | 0.1 | 0.1 | 0.1 | 0.1 |
矿脂(4) | 2 | 4 | 6 | 8 |
香料 | 1 | 1 | 1 | 1 |
防腐剂,其它(5) | 2 | 2 | 2 | 2 |
水 | q.s.至100 | q.s.至100 | q.s.至100 | q.s.至100 |
注:
(1) 月桂醇聚醚硫酸酯钠(Sodium Laureth
Sulfate)(Steol CS170, Stepan, Northfield, Illinois)
(2) 椰油酰胺(Cocamide) MEA(Mackamide
MEA, McIntyre Group, University Park, Illinois)
(3) Aqua
SF-1, Lubrizol, Wickliffe, Ohio
(4) 雪白矿脂, Penreco (Woodlands,
Texas) ,熔点51.67至57.22℃(125/135°F),粘度28.8Kps,Brookfield,锭子5,20rpm@ 32C.
(5) 包括颜料,活性剂,珠粒等。
实施例2
使用下列的工序,根据表4,配制对比清洗组合物E-K,测量它们的反射率并且与本发明样品B1相比。样品B1在组成上与实施例1中所示的样品B相同并且以相同方式制备,区别在于当水性基础材料被添加到油相中时,使用32.2C的水性基础材料温度。对比配方包括C12和C18脂肪酸(即E和F),和非矿脂油,其在矿脂的定义之外(即G至K)。相比于B1,全部对比例显示出明显更大的反射率。
表4:
浓度(wt%)
组分 | B1 | E | F | G | H | I | J | K |
SLES (1) | 9.00 | 9.00 | 9.00 | 9.00 | 9.00 | 9.00 | 9.00 | 9.00 |
CMEA (2) | 1.15 | 1.15 | 1.15 | 1.15 | 1.15 | 1.15 | 1.15 | 1.15 |
椰油酰胺丙基甜菜碱 | 1.70 | 1.70 | 1.70 | 1.70 | 1.70 | 1.70 | 1.70 | 1.70 |
丙烯酸酯共聚物(3) | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 |
氢氧化钠 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
月桂酸 | 0 | 4 | 0 | 0 | 0 | 0 | 0 | 0 |
硬脂酸 | 0 | 0 | 4 | 0 | 0 | 0 | 0 | 0 |
矿物油 | 0 | 0 | 0 | 4 | 0 | 0 | 0 | 0 |
大豆油 | 0 | 0 | 0 | 0 | 4 | 0 | 0 | 0 |
巴西棕榈蜡(4) | 0 | 0 | 0 | 0 | 0 | 4 | 0 | 0 |
Versagel M 500 (5) | 0 | 0 | 0 | 0 | 0 | 0 | 4 | 0 |
矿脂(6) | 4 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
白色矿脂胶状物(7) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 4 |
香料 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
防腐剂,其它(8) | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
水 | q.s.至100 | q.s.至100 | q.s.至100 | q.s.至100 | q.s.至100 | q.s.至100 | q.s.至100 | q.s.至100 |
反射率(%) | 44.03 | 64.96 | 60.01 | 71.65 | 75.65 | 63.56 | 56.47 | 73.87 |
注:
(1) 月桂醇聚醚硫酸酯钠(Sodium Laureth Sulfate)(Steol
CS170, Stepan, Northfield, Illinois)
(2)
Mackamide MEA (McIntyre, University Park, Illinois)
(3) Aqua
SF-1, Lubrizol (Wickliffe, Ohio)
(4) 巴西棕榈蜡 (Rita Corporation,
Crystal Lake, Illinois)
(5) 用乙烯/丙烯/苯乙烯共聚物&丁烯/乙烯/苯乙烯共聚物增稠的矿物油 (Penreco, Woodlands,
Texas)
(6) 雪白矿脂 USP (Penreco)
(7) Protopet液体矿脂(Sonneborn, Mahwah, NJ),熔点46.67C(116F)和粘度为740cps,在32C(Brookfield,锭子5,20rpm @ 32C).
(8) 包括颜料,活性剂,珠粒等。
实施例3:
根据以下表5配制对比例L和对照物M并且相比于本发明组合物B,测量它们的反射率和粒度分布,在图3中举例说明。通过图1中所示的在线注射方法,进行实施例B。通过如下所述的常规分批方法进行实施例L并且包含大豆油和液晶结构化剂月桂酸。相比于本发明实施例B,实施例L显示出明显转变为较小的粒度和更高的反射率,这被认为部分由于尺寸低于10微米的较小的矿脂颗粒,这有害地影响产品外观。
对于没有矿脂预混合物的对照实施例M所用的水性基础材料配方显示出粒度范围为1至100微米。这些颗粒据信由以下构成:单个或聚集的聚合物和表面活性剂(例如SLES/共聚物)颗粒,其没有完全分散和/或溶解。通过注射方法添加矿脂预混合物(实施例B)清楚地显示出100至1000微米的较大的粒度分布,这代表所添加的矿脂颗粒的特征。
表5:
Wt.%
组分 | L | M |
SLES (1) | 10.00 | 9.00 |
CMEA (2) | 1.15 | 1.15 |
椰油酰胺丙基甜菜碱 | 4.00 | 1.70 |
丙烯酸酯共聚物(3) | 0 | 1.8 |
氢氧化钠 | 0 | 0.1 |
月桂酸 | 3.1 | 0 |
大豆油 | 3 | 0 |
矿脂(6) | 3 | 0 |
甘油 | 1 | 0 |
瓜尔胶羟丙基三甲基氯化铵 | 0.7 | 0 |
香料 | 1 | 1 |
防腐剂,其它 | 2 | 2 |
水 | q.s.至100 | q.s.至100 |
反射率(%) | 80.94 | 44.03 |
进行实施例L的方法:
1. 向主混合罐中添加1383份的去离子水并且加热至65C
2. 在混合下添加150份白矿脂,165份月桂酸,15份PEG8硬脂酸酯,100份椰油酰胺(Cocamide)MEA
3. 加热至80C.
4. 在以3:1的比例的再循环回路中,在>65C注射100份椰油酰胺(cocamido)丙基甜菜碱,714份SLES 1 EO 70%,并且混合10分钟.
5. 开始冷却至35C.
6. 注射614份椰油酰胺(cocamido)丙基甜菜碱和1328份去离子水,混合10分钟.
7. 添加50份甘油
8. 在单独的罐A中添加100份去离子水,5份无水柠檬酸和2份二氧化钛并且混合直到均匀.
9. 在单独的罐B中添加150份大豆油和35份瓜尔胶羟丙基三甲基铵
10. 在再循环的情况下,将罐A和B的内容物添加到主混合罐.
11. 冷却至<44C
12. 添加9份DMDM乙内酰脲,6份EDTA四钠,39%0.5份异硬脂酸,和5份的颜料溶液.
13. 添加65份的香料.
14. 继续再循环20分钟。
实施例4
研究1)共混前的水和油相温度和2)油相流速(正比于注射压力)对本发明实施例B的粒度分布的影响(参见图4和5)。发现粒度分布在所研究的注射温度和流速(压力)的窄定义限度内变化。
更具体地说,图4比较在32和42psig的结果,其中平均粒度呈现与压力反比。图5显示在降低的水性基础材料温度下矿脂粒度的总增加,即在60C较大的矿脂颗粒对在65.5C较小的矿脂颗粒。
B4:油相温度60C,注射点的压力32psig.
B5:油相温度65.5C,注射点的压力42psig.
B6:油相温度60C,注射点的压力42psig.
B7:油相温度65.5C,注射点的压力32psig.
B8:水性基础材料温度35C,注射点的压力42psig.
B9:水性基础材料温度31C,注射点的压力42psig.
样品B4至B7;水性基础材料温度是32C
样品B8和B9;油相温度是60C。
样品制备方法:
实施例A-K是如下制备的:
1. 将水加入混合容器并且开始加热至57.2C.
2. 将Aqua SF-1添加到主容器中.
3. 将月桂醇聚醚硫酸酯钠(Sodium Laureth Sulfate)和椰油酰胺(Cocamide)MEA添加到容器中并且继续加热至76.7C.
4. 将EDTA四钠添加到主烧杯中.
5. 将椰油酰胺(cocamido)丙基甜菜碱添加到主容器中并且继续混合.
6. 添加氢氧化钠并且中和至pH=6.1-6.5.
7. 添加聚丙二醇稀释剂以降低粘度.
8. 添加防腐剂和香料.
9. 在35C,检查产品粘度,外观,稠度(consistency)并且根据需要添加稀释剂以便获得期望的粘度.
10. 将矿脂(或其它疏水油或脂肪酸)添加到主烧杯中,同时用IKA® RW20混合器(IKA Works, Inc., 德国)保持低混合速度(<100rpm);利用Lightnin® A320混合器桨叶,直到矿脂(或其它疏水油或脂肪酸)被均匀分散。
方法:
A) 反射率方法
使用Hunterlab Labscan XE分光光度计(Hunter Associates
Laboratory, Inc., Reston, VA)确定产品反射率,如下:
1. 使用2"口,用标准黑白瓦片使设备标准化.
2. 使用大约50g的产品,填充持样器至恒定的高度,对于所有样品.
3. 进行测量.
4. 用多个样品重复并且平均读数。
B) 粒度方法:
标准粒度(液滴尺寸)测量规程:
在主体洗涤原型(body wash prototype)中润肤油的粒度分布特征为在环境条件下使用Malvern Mastersizer®
2000(Malvern Instruments, Malvern, UK)的光衍射测量。通过Mastersizer 2000软件进行原始数据分析。
样品制备是光散射测量的关健。样品用去离子水以1:1的比例预稀释来估算实际的淋浴状况。稀释的样品被平缓地共混并且输入到分散室中,借此测量含典型的矿脂及其他颗粒的良好分散的样品。
实验程序:
1. 依次接通Malvern样品分散辅助设备,光学装置和Mastersizer 2000软件.
2. 使系统自动地净化样品分散辅助设备,校准光学系统,测量光学背景,计算粒度分布并且保存记录.
3. 对于每次实验,进行10次实验循环,其中每次循环之间有5秒延迟。报道平均结果
4. 确定标准灵敏度和不规则颗粒形状来计算液滴粒度分布。矿脂的折射率是1.4847和水是1.3300.
5. 添加去离子水来净化样品辅助设备直到激光信号强度达到80%或更高.
6. 将样品添加到辅助设备直到模糊棒(obscuration bar)达到绿色区域中的中值。如果样品是非常粘的,在添加到辅助设备前,可能需要预分散.
7. 进行测量。
C) 粘度测量
这种方法包括本文中所讨论的粘度测量。它还用于测量产品的结构化度。
装置:
Brookfield
RVT粘度计;
用于RV连接的卡盘、砝码和闭合器组件;
RV-锭子 5;
塑料杯直径大于2.5英寸
工序:
1. 通过参考仪器背面的气泡水准仪来检验粘度计是水平的.
2. 将卡盘/闭合器/砝码组件连接到粘度计
3. 用去离子水净化锭子5并且用Kimwipe®薄片扑干。在闭合器中滑动锭子并且上紧.
4. 设置转速为20RPM。在数字粘度计(DV)的情况下,选择%模式和压力自动调零,马达接通.
5. 将产品置于内径大于2.5英寸的塑料杯。杯中产品的高度应该至少3英寸。产品的温度应该是250C,除非文中另有说明.
6. 将锭子降到产品中.
7. 启动粘度计.
8. 运行粘度计1分钟.
9. 将仪表读数乘以2,000并且以cps报告粘度读数。
虽然本发明已经参考其特定的实施方案进行描述,显然本发明的许多其它形式和变体将对本领域技术人员来说是显见的。所附权利要求和本发明通常将应被解释为覆盖所有这些显见的形式和变体,这些在本发明的真实精神和范围之内。
Claims (8)
1. 稳定、多相各向同性的清洗组合物,其包括:
a.
99-84wt%的水,基于整个组合物;
b.
1-16wt%的矿脂,其熔点在35和80C之间并且最小粘度在32C下为10Kps,其中浓度基于整个组合物;
c.
其中水相包括1-25wt%的非皂阴离子表面活性剂和1-20wt%的两性表面活性剂,基于整个组合物;
d.
其中水相包含0.5-10wt%的总聚合分散稳定剂(一种或多种),基于整个组合物;
e. 小于2wt%的总疏水甘油酯(一种或多种),除矿脂外的烃(一种或多种),或硅油或其共混物和衍生物,基于整个组合物;和
f. 小于1.5wt%的总液晶结构化剂(一种或多种),结晶含羟基的稳定剂(一种或多种),C10-C22脂肪酸乙二醇酯(一种或多种),二氧化硅(一种或多种),粘土(一种或多种)或其共混物,基于整个组合物。
2. 权利要求1的清洗组合物,其中组合物仅仅包含水和油相。
3. 权利要求1的清洗组合物,其具有80%的最大反射率,如通过标准反射率方法测量的。
4. 权利要求1的清洗组合物,其中大于50体积%的矿脂相颗粒具有大于50微米的直径,如通过标准粒度方法测量的。
5. 一种制备稳定、多相各向同性的清洗组合物的方法,其包括如下的步骤,没有特定的顺序:
a. 共混水、表面活性剂(一种或多种)、和聚合分散稳定剂(一种或多种)直到均匀来制备无油的、透明的各向同性的水性预混合物;
b.
将水性预混合物进料到共混管中,水性预混合物以22.7-113.7千克(50-250磅)/分钟的速率通过共混管;和
c. 通过多口注射器以足以形成重量百分数比值范围为1%矿脂:99%水性预混合物至16%矿脂:84%水性预混合物的共混物的速率将熔点在35和80C间和在32C下最小粘度为10Kps的矿脂进料到共混管中。
6. 权利要求5的方法,其中水性预混合物的温度被调节到40C或更小和矿脂的温度被调节到50-70C,然后共混。
7. 权利要求5的方法,其中多口注射器具有最少3个管道口。
8. 权利要求7的方法,其中多口注射器的口以对称图案排列。
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