CN105308167B - 具有增强的抗菌活性的液体皂 - Google Patents
具有增强的抗菌活性的液体皂 Download PDFInfo
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- CN105308167B CN105308167B CN201480022099.3A CN201480022099A CN105308167B CN 105308167 B CN105308167 B CN 105308167B CN 201480022099 A CN201480022099 A CN 201480022099A CN 105308167 B CN105308167 B CN 105308167B
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Abstract
使用水性皂组合物清洁人体皮肤的方法，所述组合物包含脂肪酸皂、具有至少1×10‑4mol/L银离子溶解度(在水中，25℃)的至少一种银(I)化合物和水，所述组合物提供在相对短的接触时间内对抗革兰氏阳性细菌，特别是金黄色葡萄球菌的杀生物活性。
Description
发明领域
本发明涉及基于皂的液体清洁制剂，其具有增强的对抗革兰氏阳性和革兰氏阴性微生物的抗菌活性，以及涉及在具有相对短的接触时间的皮肤清洁应用中增强对抗革兰氏阳性和革兰氏阴性微生物的抗菌活性的方法。
发明背景
已知皂组合物，例如条和液体，具有与从皮肤通过此类产品的清洁/去污作用来除去生物体非常相关的抗菌益处。此外，这样的组合物通常具有对抗许多革兰氏阴性细菌的杀生物作用。皂组合物对抗革兰氏阳性细菌例如金黄色葡萄球菌的杀生物作用，然而，在对产品使用而言典型的接触时间(一般在1分钟内，以及更通常为约30秒或更短)内有相当多的限制。在高pH液体皂产品(即在25℃，具有8至11，更特别的9至11的pH的液体皂组合物)的情况下，实现对抗革兰氏阳性细菌的杀生物作用特别成问题。
已经提出各种改善皂组合物的杀生物活性的途径。例如，美国专利号6,794,344(Taylor等人)公开了皂条，其包含至少约50％的具有8-10个碳原子的烷基链长度的皂、约10％至约30％的含羟溶剂(hydric solvent)以及游离酸，优选游离脂肪酸，使得所述皂条的10％水溶液的pH不大于约9。皂条在其中的特征在于，显示出在其中所述的测试中，在40℃下在30秒的接触后，至少为3的对抗革兰氏阳性细菌的对数降低，如针对金黄色葡萄球菌测定的。在Taylor等人的表3中示出的信息，比较游离脂肪酸含量作为pH功能对对抗金黄色葡萄球菌的抗菌活性的影响。
实现在清洁组合物中抗微生物益处的路径也包括一种或多种具有杀生物效果的试剂的使用，所述清洁组合物包括基于皂的组合物，以及基于合成阴离子表面活性剂，即“合成去污剂(syndet)”的组合物。
美国专利申请公开号2012/003413(Levison等人)公开了其中据说能够在延长的时间提供抗微生物性的消毒制剂。其中公开的制剂包括螯合金属离子(包括螯合的银离子)以及具有将螯合金属离子结合至皮肤的能力的固定聚合物(fixative polymer)。在其表IV中，Levison等人提供了基于合成的阴离子表面活性剂的液体皂制剂。制剂包括，在其他成分中，月桂基聚醚硫酸钠、月桂基硫酸钠、丙二醇、椰油酰胺丙基甜菜碱、椰油酰胺DEA、乙二醇(ethyol alcohol)、澳洲坚果甘油酯(macadamia glycerides)、丙烯酸酯交联聚合物、柠檬酸二氢银和EDTA四钠。
WO01/1131422公开了其中特征在于具有抗微生物性的香皂，该皂包含其中称为“皂基”的物质、功能性添加剂以及插入Ag+和/或Cu2+离子的膨润土粉末。
美国专利申请公开号2010/0098776(Carnali等人)公开了其中据说具有增强的抗菌活性的基于皂的液体洗涤制剂，该组合物包含0.01至10重量％的抗微生物剂，例如银粒子、锌粒子、铜粒子或其混合物。所述基于皂的制剂据说包括10至50重量％，优选25至40重量％，更优选30至40重量％的C12-C18脂肪酸的脂肪酸混合物(脂肪酸混合物进一步的特征在于具有70％至90％的中和度)；10至40重量％的助溶剂，例如甘油、乙二醇、丙二醇、二甘醇、二丙二醇及其混合物，以及小于18％，优选小于16重量％的水，使得助溶剂与水的比在0.4-10，优选0.8至7，更优选1.0至5的范围中。
美国专利号3,050,467(Horowitz等人)公开了消毒清洁剂(例如皂和去污剂)，其包括约90至约99重量％的水溶性皂和约10％至约1重量％的部分解聚的藻酸的银盐的混合物。所列举的藻酸的量据说为该组合物提供0.01至1重量％的银含量。
美国专利申请公开号2006/0115440(Arata等人)公开了个人护理产品，其包含柠檬酸二氢银和生理学上可接受的介质。所述组合物据说包括浓度为50ppb至10,000ppm的银离子，这样的浓度为基于每单位体积的最终组合物(如果为液体)或每单位重量的最终组合物(如果为固体)的银离子总重量。
仍然需要对提供在对洗去型清洁应用而言典型的相对短的接触时间(即小于1分钟，更特别的是30秒或更短，甚至更特别是10秒或更短的接触时间)内改善的对抗革兰氏阳性细菌的杀生物活性的个人清洁方法，以及需要适用于此类方法的液体皂制剂，特别是高pH液体皂制剂。
发明概述
现已发现，能够通过在其中引入选定的银(I)化合物，更特别是具有选定的银离子溶解度值的银(I)化合物增强在与液体皂使用有关的短接触时间内的直接的杀生物作用，即液体皂对抗革兰氏阳性细菌(包括例如金黄色葡萄球菌)的细菌杀死，在下文进行更具体地描述。此外，已经发现，此类细菌杀死可通过以一定浓度使用银(I)化合物实现，在该浓度下，以可比较的pH(即8至11，更特别地9至11)在水中的化合物本身，在对液体皂应用而言典型的需要的短期接触时间(即小于1分钟，更特别地30秒或更短，甚至更特别的10秒或更短的接触时间)内不能提供有效的杀生物活性。
不希望被理论所束缚，本发明人已经发现，在使用基于皂的液体清洁制剂的情况下，如此低含量的银(I)化合物的作用在于改变微生物的环境，从而使皂分子能够充当杀生物剂。因此，本发明的部分目的是增加皂自身对抗革兰氏阳性和革兰氏阴性微生物的抗菌活性。
考虑到银的成本相对较高，相比于银化合物自身所需以具有在有益的接触时间内显著的杀生物效果的高含量，如此低含量的银化合物提供显著的成本效益。此外，低含量的银化合物从感官和加工优势上来说都是需要的。
在一个实施方案中，提供一种用于个人护理应用的液体清洁制剂(在本文中术语“液体清洁制剂”或者称为“个人清洁制剂”或“液体皂制剂”)，该制剂包含：
(a)基于制剂总重量的5至65重量％的脂肪酸皂，
(b)基于制剂总重量的0.1至100ppm按重量计，优选1至50ppm，更优选5至20ppm的至少一种银(I)化合物，其具有至少1×10-4mol/L的银离子溶解度(在水中，25℃)；和
(c)20至90重量％的水，
其中：在25℃，制剂具有8至11，更特别的9至11的pH。
在进一步的实施方案中，提供基于脂肪酸皂的高pH液体清洁制剂增强对抗革兰氏阳性细菌的抗菌有效性的方法，其包括在所述液体清洁制剂中引入0.1至100ppm按重量计，更特别的为1至50ppm，甚至更特别的为5-20ppm的至少一种银(I)化合物，其具有至少1×10-4mol/L的银离子溶解度(在水中，25℃)，其中，在下面描述的体外-时间-杀灭程序(InVitro Time-Kill Protocol)中，所得制剂优选提供在30秒的接触时间内至少2.5，优选至少3的对抗金黄色葡萄球菌ATCC6538的Log10降低，以及甚至更优选提供在10秒的接触时间内至少1.5，更优选至少2的对抗金黄色葡萄球菌ATCC 6538的Log10降低。
在另一个实施方案中，提供清洁人体皮肤的方法，更特别的，清洁人体皮肤以减少在其上的革兰氏阳性细菌的方法，其包括：
(i)使液体清洁制剂起泡或发泡(foaming)，所述液体清洁制剂包含：
(a)基于制剂总重量的5至65重量％的脂肪酸皂，
(b)基于制剂总重量的0.1至100ppm按重量计，更优选1至50ppm的至少一种银(I)化合物，其具有至少1×10-4mol/L的银离子溶解度(在水中，25℃)；和
(c)20至90重量％的水，
任选地，另外的水，
(ii)将经发泡的组合物施用于皮肤，接触时间小于1分钟，更特别的30秒或更短，甚至更特别的10秒或更短，和
(iii)冲洗皮肤上的经发泡的组合物。
在另一个实施方案中，提供降低在人体皮肤上的革兰氏阳性细菌的方法，其包括：
(I)向人体皮肤施用水性皂组合物，其包含：
(a)0.2至25重量％的脂肪酸皂，
(b)至少一种银(I)化合物，其具有至少1×10-4mol/L的银离子溶解度(在水中，25℃)，
按需要通过稀释液体清洁制剂至0.2至25重量％的所述脂肪酸含量制备所述水性皂组合物，所述液体清洁制剂包含：
(i)基于制剂总重量的5至65重量％的脂肪酸皂，
(ii)基于制剂总重量的0.1至100ppm按重量计，更优选1至50ppm的至少一种银(I)化合物，其具有至少1×10-4mol/L的银离子溶解度(在水中，25℃)；和
(iii)20至90重量％的水，
(II)使所述水性皂组合物保持在皮肤上持续小于1分钟，优选30秒或更短，更优选10秒或更短的接触时间，和
(III)冲洗皮肤上的水性皂组合物。
用于主题方法的液体清洁制剂通常具有8至11，更特别的为9至11的pH。在一个或多个实施方案中，用于主题方法的液体清洁制剂中的银含量为基于制剂的总重量的5-20ppm，更特别的5至15ppm。
在本发明的另一个实施方案中，已经发现，当如上所述包含脂肪酸皂、银化合物以及水的液体清洁制剂(优选所给的pH浓度)进一步与精油抗微生物活性物百里酚和萜品醇组合使用时，获得优异的抗菌效果。具体的，银盐与百里酚和萜品醇两者的组合具有对抗革兰氏阳性和革兰氏阴性细菌的总体抗菌效果。
百里酚和萜品醇的每一种的优选存在含量为总组合物的0.01至2重量％。
优选的，百里酚和萜品醇可被加入到本发明的含银组合物中，作为(a)包含0.01至2％的百里酚和萜品醇的精油活性混合物的抗微生物组合物和(b)助水溶物(优选选自由苯甲酸钠、甲苯磺酸钠、枯烯磺酸钠、二甲苯磺酸钠、水杨酸钠、乙酸钠及其混合物组成的组)。
优选的，含银组合物包含0.01至1％的总百里酚和萜品醇。可使用另外的精油活性物，例如丁子香酚、香叶醇或混合物。在含银组合物中用于增加抗菌效果的另一优选的油混合物为百里酚、萜品醇和丁子香酚。
发明详述
除了在操作和对比实施例中，或在另行明确说明的情况下，本说明书中表示数量、部分、百分比、比和材料的比率、材料的物理性质和反应条件的所有数字应理解为被词语“大约”修饰。除非另外说明，这一说明书中提到的所有的部分、百分比、比以及材料的比例均按重量计。
术语“包含”是指不被限制成任何随后所述的要素，而是包括具有主要或次要功能重要性的非特定要素。换句话说，所列出的步骤、要素或选择不必是穷举的。当无论何时使用词语“包括”或“具有”时，这些术语的意思等同于上面定义的“包含”。在本发明组合物或制剂被描述为“包括”或“包含”特定组分或材料的情况下，也可以考虑其中组合物或制剂可“基本上由所列举的成分或材料组成”或“由所列举的成分或材料组成”的更窄的实施方案。
还应当指出的是，在指定浓度或量的任意范围中，任何特定的上限浓度或量可与任意特定的下限浓度或量相关。
脂肪酸皂
在本文中以其普遍含义使用术语“脂肪酸皂”或更简单的，“皂”，即优选具有6至22个碳原子，以及优选具有8至18个碳原子的脂族烷烃或烯烃单羧基脂肪酸的盐。
脂肪酸皂应该包含5至65重量％，优选10至55重量％的主题液体清洁制剂。所涉及的脂肪酸含量为通常提供给消费者的形式的制剂，而不考虑使用中稀释。在使用中，以此范围内的较高含量包含脂肪酸皂的制剂通常用水稀释，从而施用于皮肤上的稀释的组合物通常包含25％或更少，更特别的为0.2至25％或更少的脂肪酸皂。
典型的皂盐为此类脂肪酸的碱金属或烷醇铵盐，尽管也可使用其的其他金属盐，例如镁盐。这样酸的钠、钾、镁、单-、二-和三乙醇铵盐包括在适宜在本文中使用的更普通皂中。在一个或多个中，通常，本发明制剂中使用钾皂，但最高至约25％的皂可以是钠或镁皂。
如上所述，衍生出皂盐的脂肪酸可含有不饱和度。不饱和度水平应该与商业上可接受的标准一致。通常避免过度的不饱和度以最小化颜色和气味问题。通常，不超过40重量％的形成皂盐的脂肪酸是不饱和的。在一个或多个实施方案中，10至40重量％，更特别的20至40重量％的形成皂盐的脂肪酸是不饱和的。
在一个或多个实施方案中，优选C12、C14、C16和C18脂肪酸的组合占形成皂盐的总脂肪酸的90至100重量％，更特别是95至100重量％，以及优选的，C16和C18脂肪酸的组合占形成皂盐的总脂肪酸的10至35重量％，更特别是12至30重量％，甚至更特别是14至28重量％。优选的，C8和C10脂肪酸的总量为形成皂盐的脂肪酸的小于5重量％，以及优选小于3重量％。
银化合物
作为主题制剂和组合物中使用的银化合物为一种或多种水溶性银(I)化合物，其具有至少为1×10-4mol/L的银离子溶解度(在水中，25℃)。本文中涉及的银离子溶解度为25℃来自水中溶度积(Ksp)的值，在许多来源均有报告的熟知参数。更特别的，可以使用下式计算银离子溶解度[Ag+]，以mol/L给出的值：
[Ag+]＝(Ksp·x)(1/(x+1))，
其中Ksp为25℃在水中的目标化合物的溶度积，以及x表示每摩尔化合物的银离子摩尔数。已经发现，本文中适宜使用具有至少1×10-4mol/L的银离子溶解度的银(I)化合物。在表1中给出多种银化合物的银离子溶解度值：
表1
银离子溶解度值
适宜本文中使用的银(I)化合物包括氧化银、硝酸银、醋酸银、硫酸银、苯甲酸银、水杨酸银、碳酸银、柠檬酸银和磷酸银，其中在一个或多个实施方案中，特别有益的是氧化银、硫酸银和柠檬酸银。在至少一个优选的实施方案中，银(I)化合物包含氧化银。
在至少一个实施方案中，银化合物不是柠檬酸二氢银。在另一个实施方案中，银化合物不是藻酸或基本上解聚的藻酸的盐。在一个优选的实施方案中，银化合物不是纳米颗粒形式、不附着在纳米颗粒上或不是插层硅酸盐，例如膨润土的一部分。
在一个或多个实施方案中，在用于主题方法的水性皂组合物中银化合物与皂盐的重量比为1∶500至1∶650,000，优选1∶1000至1∶250,000，更优选1∶1200至1∶200,000。
水
本发明的个人清洁制剂通常的含水量为基于制剂的总重量的20至90重量％，更特别的为50至85重量％。这样的水含量代表了制剂的相对宽的范围，包括浓缩和非浓缩产品，其中具有的水含量为20至小于50重量％的水的制剂通常为浓缩产品。
在使用中，制剂通常用水稀释。稀释程度取决于具体的产品形式。较不常用的，但也可考虑用于本文的是在不稀释下经发泡的制剂，通常通过使用其中产品经过泵中筛的泵分配器。
在优选的实施方案中，本发明的含银组合物与精油抗微生物活性物百里酚和萜品醇组合使用。优选的，每一种以组合物的0.01至2％的含量存在于总含银组合物中。
百里酚优选以组合物的0.02至0.5％，更优选至多0.3重量％，进一步更优选至多0.2重量％存在。百里酚可以纯的形式添加到抗微生物组合物中。或者，包含百里酚的百里香油或百里香提取物可添加到抗微生物组合物中，同时确保百里酚以所需浓度存在于本发明的组合物中。百里香油或百里香提取物获自百里香植物。百里香植物指的是属于百里香属的植物，以及包括但不限于下列物种：银斑百里香(Thymus vulgaris)、洋百里香(Thymuszygis)、龙脑百里香(Thymus satureoides)、乳香百里香(Thymus mastichina)、Thymusbroussonetti、Thymus maroccanus、Thymus pallidus、Thymus algeriensis、欧百里香(Thymus serpyllum)、宽叶百里香(Thymus pulegoide)和柠檬百里香(Thymuscitriodorus)。
百里酚及其异构体香芹酚的结构在下面给出：
香芹酚
百里酚
萜品醇优选以组合物重量的0.05至1％，更优选至多0.5重量％存在。萜品醇优选选自α-萜品醇、β-萜品醇、γ-萜品醇或其混合物。特别优选的是萜品醇为α-萜品醇。萜品醇可以纯的形式添加到抗微生物组合物中。或者，包含萜品醇的松油可添加到抗微生物组合物中。
萜品醇化合物的结构在下面给出：
任选成分
如果需要，除了脂肪酸皂之外，制剂可任选包括去污表面活性剂。这样的去污表面活性剂包括，例如阴离子、两性离子和/或非离子表面活性剂。
在本文中适用的阴离子表面活性剂的例子包括，但不限于，月桂基硫酸铵、月桂基聚醚硫酸铵、三乙胺月桂基硫酸盐、三乙胺月桂基聚醚硫酸盐、三乙醇胺月桂基硫酸盐、三乙醇胺月桂基聚醚硫酸盐、单乙醇胺月桂基硫酸盐、单乙醇胺月桂基聚醚硫酸盐、二乙醇胺月桂基硫酸盐、二乙醇胺月桂基聚醚硫酸盐、月桂酸单甘油酯硫酸钠、月桂基硫酸钠、月桂基聚醚硫酸钠、月桂基聚醚硫酸钾、月桂基肌氨酸钠、月桂酰肌氨酸钠、月桂基硫酸钾、十三烷基聚醚硫酸钠、甲基月桂酰牛磺酸钠、月桂酰羟乙基磺酸钠、月桂基聚醚磺基琥珀酸钠、月桂酰磺基琥珀酸钠、十三烷基苯磺酸钠、十二烷基苯磺酸钠、十二烷基两性乙酸钠及其混合物。
阴离子表面活性剂可以是，例如脂族磺酸盐，例如伯C8-C22烷烃磺酸盐、伯C8-C22烷烃二磺酸盐、C8-C22烯烃磺酸盐、C8-C22羟基烷烃磺酸盐或烷基甘油基醚磺酸盐。
在本文中适用的两性离子表面活性剂包括，但不限于，脂族季铵、鏻和锍化合物的衍生物，其中的脂族基团可以是直或支链，以及其中一个脂族取代基包含约8至约18个碳原子，一个取代基包含阴离子基团，例如羧基、磺酸根、硫酸根、磷酸根或膦酸根。示例性的两性离子表面活性剂为椰油二甲基羧甲基甜菜碱、椰油酰胺丙基甜菜碱、椰油甜菜碱、油基甜菜碱、鲸蜡基二甲基羧甲基甜菜碱、月桂基双-(2-羟乙基)羧甲基甜菜碱、硬脂基双-(2-羟丙基)羧甲基甜菜碱、油基二甲基γ-羧丙基甜菜碱、月桂基双-(2-羟丙基)α-羧乙基甜菜碱及其混合物。磺基甜菜碱可以包括硬脂基二甲基磺基丙基甜菜碱、月桂基二甲基磺基乙基甜菜碱、月桂基双-(2-羟乙基)磺基丙基甜菜碱及其混合物。
可使用的非离子表面活性剂包括具有疏水基团和反应性氢原子的化合物的反应产物。实例为与环氧烷，特别是单独或与环氧丙烷一起的环氧乙烷反应的醇、酸、酰胺或烷基酚。特定的非离子表面活性剂为C6-C22烷基酚-环氧乙烷缩合物、C8-C18脂族伯或仲直链或支链醇与环氧乙烷的缩合产物，以及通过环氧乙烷和环氧丙烷与乙二胺的反应产物的缩合制备的产品。其它非离子表面活性剂包括长链叔胺氧化物、长链叔膦氧化物和二烷基亚砜。也可使用烷基多糖。
当存在时，另外的去污表面活性剂的量部分取决于其选择以及脂肪酸皂的量。主题个人清洁制剂为皂基，即，在其中脂肪酸皂存在的总量超过不是脂肪酸皂的去污表面活性剂的总量。通常，脂肪酸皂包含存在于个人清洁制剂中的85至100重量％，更特别的90至100重量％的总去污表面活性剂。
制剂通常包括一种或多种皮肤有益试剂。术语“皮肤有益试剂”定义为通过增加其水含量、添加或替代脂质和其它皮肤营养剂，或两者，来软化或改善皮肤(角质层)的弹性、外观以及年轻度，以及通过延缓其水含量的降低来保持其柔软的物质。适宜的皮肤有益试剂包括润肤剂，包括，例如疏水润肤剂、亲水润肤剂或其混合物。
有用的皮肤有益试剂包括下面的：(a)硅酮油及其改性物，例如线型和环状聚二甲基硅氧烷；氨基、烷基、烷基芳基和芳基硅酮油；(b)脂肪和油，包括天然脂肪和油，例如霍霍巴油、大豆油、向日葵油、米糠油、鳄梨油、杏仁油、橄榄油、芝麻油、桃仁油、蓖麻油、椰子油和貂油；可可脂；牛油和猪油；通过氢化上述的油获得的硬化油；以及合成的单-、二-和三甘油酯，例如肉豆蔻酸甘油酯和2-乙基己酸甘油酯；(c)蜡，例如巴西棕榈蜡、鲸蜡、蜂蜡、羊毛脂及其衍生物；(d)疏水和亲水植物提取物；(e)烃，例如液体石蜡、凡士林、微晶蜡、纯地蜡、角鲨烯、姥鲛烷(pristan)和矿物油；(f)高级脂肪酸，例如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山萮酸、油酸、亚油酸、亚麻酸、羊毛脂、异硬脂酸、花生四烯酸和多不饱和脂肪酸(PUFA)；(g)高级醇，例如月桂醇、鲸蜡醇、硬脂醇、油醇、山萮醇、胆固醇和2-己基癸醇；(h)酯，例如辛酸鲸蜡酯、乳酸肉豆蔻酯、乳酸鲸蜡酯、肉豆蔻酸异丙酯、肉豆蔻酸肉豆蔻酯、棕榈酸异丙酯、己二酸异丙酯、硬脂酸丁酯、油酸癸酯、胆固醇异硬脂酸酯、甘油单硬脂酸酯、甘油单月桂酸酯、甘油二硬脂酸酯、甘油三硬脂酸酯、乳酸烷基酯、柠檬酸烷基酯和酒石酸烷基酯；(i)精油及其提取物，例如薄荷、茉莉、樟树、白雪松、苦橙皮、ryu、松节油、肉桂、佛手柑、蜜柑、菖蒲、松树、薰衣草、月桂、丁香、丝柏、桉树、柠檬、开星状花的植物(starflower)、百里香、薄荷(peppermint)、玫瑰、鼠尾草、芝麻、生姜、罗勒、杜松、柠檬草、迷迭香、花梨木、鳄梨、葡萄、葡萄籽、没药、黄瓜、豆瓣菜、金盏花、接骨木花、天竺葵、菩提花、苋菜、海藻、银杏、人参、胡萝卜、瓜拉拿(guarana)、茶树、霍霍巴油、紫草、燕麦、可可、橙花、香草、绿茶、Penny royal、芦荟、薄荷脑、桉树脑、丁香油酚、柠檬醛、香茅油、冰片、芳樟醇、香叶醇、月见草油、樟脑、百里酚、spirantol、penene、柠檬烯和萜类油；(j)多羟基醇，例如甘油、山梨糖醇、丙二醇等；以及多元醇，例如聚乙二醇类，其例子为：Polyox WSR-205PEG14M、Polyox WSR-N-60K PEG 45M或Polyox WSR-N-750和PEG 7M；(k)脂质，例如胆固醇、神经酰胺、蔗糖酯和欧洲专利说明书号556,957中描述的假神经酰胺；(1)维生素、矿物质和皮肤营养剂，例如牛奶、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、锌等其他金属成分；(m)防晒剂，例如辛基甲氧基肉桂酸酯(Parsol MCX)和丁基甲氧基苯甲酰甲烷(Parsol 1789)；(n)磷脂；和(o)抗衰老化合物，例如α-羟酸和β-羟酸。皮肤有益试剂通常占液体皂制剂的至多30重量％，其中0至25重量％，更特别的0至20重量％的含量为在很多主题制剂中使用通常称为“润肤剂”的那些皮肤有益试剂的典型含量。优选的皮肤有益试剂包括脂肪酸、烃、多羟基醇、多元醇及其混合物，其中包括至少一种C12至C18脂肪酸、凡士林、甘油、山梨糖醇和/或丙二醇的润肤剂在一个或多个实施方案中是特别有益的。
其它任选成分包括水溶性/可分散聚合物。这些聚合物可以是阳离子、阴离子、两性或非离子型，分子量超过100,000道尔顿。已知它们增加液体个人清洁制剂的粘度和稳定性，以提高在使用中和使用后的皮肤感觉特性，以及提高泡沫乳脂和泡沫稳定性。当存在时，这样的聚合物总量通常为个人清洁制剂的0.1至10重量％。
水溶性或可分散聚合物的例子包括糖胶，例如纤维素胶、微晶纤维素、纤维素凝胶、羟乙基纤维素、羟丙基纤维素、羧甲基纤维素钠、甲基纤维素、乙基纤维素、瓜尔胶、刺梧桐树胶、黄蓍树胶(gum tragacanth)、阿拉伯胶、金合欢树胶、琼脂胶、黄原胶及其混合物；改性和非改性淀粉颗粒以及预胶化冷水可溶性淀粉；乳液聚合物，例如28、22或Aqua SF1；阳离子聚合物，例如改性多糖，包括可以下面的商标名Jaguar C13S、Jaguar C14S、Jaguar C17或Jaguar C16购自Rhone Poulenc的阳离子瓜尔胶；阳离子改性纤维素，例如来自Amerchol的UCARE Polymer JR30或JR40；来自Hercules的3000、3196、GPX 215或GPX 196；合成阳离子聚合物，例如Nalco出售的100、280、281和550；阳离子淀粉，例如Staley Inc.销售的100、200、300和400；阳离子半乳甘露聚糖，例如Hankel，Inc.的800系列；LM-200和Polyquaternium-24。还适宜的为高分子量聚乙二醇，例如WSR-205(PEG 14M)、WSR-N-60K(PEG 45)和WSR-301(PEG90M)。
防腐剂/抗微生物剂可理想地结合到本发明的个人清洁制剂中以防止潜在的有害微生物的生长。适宜本发明制剂的传统防腐剂为对羟基苯甲酸的烷基酯。其它最近已经开始使用的防腐剂/抗微生物剂包括乙内酰脲衍生物、丙酸盐和各种季铵化合物。在防腐剂/抗微生物剂中，特别有益的是苯氧基乙醇、对羟基苯甲酸甲酯、对羟基苯甲酸丙酯、咪唑烷基脲、脱氢乙酸钠和苄醇。其它特别有益的防腐剂为例如二羟甲基二甲基乙内酰脲(dimethyloldimethylhydantoin)(Glydant XL 1000)、对羟基苯甲酸酯、山梨酸、百里酚和萜品醇(其中，例如，在引入本文中作为参考的美国专利申请公开号2011/0223114中描述的百里酚和萜品醇的组合，在一个或多个实施方案中是特别有益的)。
应该考虑制剂的应用以及防腐剂和其它成分之间的可能的不相容性来选择防腐剂/抗微生物剂。防腐剂的优选使用量为个人清洁制剂的0.01至2重量％。
可存在于主题个人清洁制剂中的另外的任选成分为，例如香料、螯合和络合剂(sequestering and chelating agent)，例如乙二胺四乙酸四钠(EDTA)、乙烷羟基二膦酸盐(HEDP)和依替膦酸(etidronic acid)，又名1-羟基乙叉基二膦酸(l-hydroxyethylidenediphosphonic acid)(HEDP)；着色剂、遮光剂和珠光剂，例如硬脂酸锌、硬脂酸镁、TiO2、乙二醇单硬脂酸酯(EGMS)、乙二醇二硬脂酸酯(EGDS)或Lytron 621(苯乙烯/丙烯酸酯共聚物)等；pH调节剂；抗氧化剂，例如丁基化羟基甲苯(BHT)等；稳定剂；增泡剂，例如椰油酰基单-或二乙醇酰胺；电离盐，例如氯化钠和硫酸钠，以及其它成分，例如通常用于液体皂制剂中的。此类另外的任选成分的总量基于个人清洁制剂的总重量，通常为0至10重量％，更特别是0.1至5重量％。
本发明的个人清洁制剂致力于对抗革兰氏阳性细菌(包括特别是金黄色葡萄球菌)的杀生物活性。皂制剂所对抗起作用的其它革兰氏阳性细菌为表皮葡萄球菌(S.epidermidis)和/或棒状杆菌(Corynebacteria)，特别是致使腋窝分泌物水解至恶臭化合物的杆菌(Corynebacteria)菌株。理想的是，制剂提供在30秒的接触时间内对抗金黄色葡萄球菌ATCC 6538的至少2.5，优选至少3的log10降低的杀生物活性，以及甚至更优选提供在10秒的接触时间内对抗金黄色葡萄球菌ATCC 6538的至少1.5，甚至更优选至少2的log10降低。
在使用中，按需要稀释个人清洁制剂以形成水性清洁组合物，其施用于皮肤，接触时间少于1分钟，更特别的为30秒或更短(其中对于持续中等至相对长的接触时间，有益的是10至30秒的接触时间，对于持续短至中等的接触时间，有益的是10秒或更短的接触时间)，以及随后通常通过用水冲洗从皮肤去除。个人清洁制剂可在置于皮肤上之前、之后或同时被稀释，其中稀释通常通过制剂在手上或施用器，例如面巾、海绵或蒲团(pouf)上处理成泡沫进行。
制造
本文中描述的个人清洁制剂可通过本领域常规的制备技术来产生。在一个非常常规的方法中，向加热的水相加入熔化的脂肪酸，随后加入苛性碱(caustic)(以中和脂肪酸以及形成皂)、合成去污剂和助溶剂；随着产品冷却至室温，视情况而定，添加剩余成分。
个人清洁制剂可以多种不同产品形式提供，包括例如，手、脸和身体洗液、沐浴凝胶等。制剂可以瓶、泵式分配器、管、小袋(sachet)或适宜产品形式的其它包装来提供。
实施例
提供下面的非限制性实施例进一步示例本发明；本发明不以任何方式被限制于此。使用下面的程序来评估杀生物活性。
体外时间-杀灭程序
皂溶液制备
溶液制备部分取决于液体皂制剂的特定形式。例如，在使用时不稀释的制剂，例如自发泡制剂原样使用。包含30重量％或更少的去污表面活性剂并且意欲其目的是在使用中稀释的制剂，与等重量水混合以形成包含50重量％的初始制剂的皂溶液。包含超过30重量％的去污表面活性剂并且意欲在使用中稀释的制剂与水混合以形成包含16重量％的初始制剂的皂溶液。
细菌
金黄色葡萄球菌ATCC 6538用于这一研究以代表革兰氏阳性细菌。细菌在-80℃保存。在每一次实验前，新鲜分离物在Tryptic Soy Agar平板上在37℃下培养两次达24小时。
体外时间-杀灭分析
时间-杀灭分析依照并入本文中作为参考的欧洲标准，EN1040：2005题目为“Chemical Disinfectants and Antiseptics-Quantitative Suspension Test for theEvaluation of Basic Bactericidal Activity of Chemical Disinfectants andAntiseptics-Test Method and Requirements(第一阶段)”来完成。在这个程序之后，在25℃下，用皂溶液(如上所述制备)处理每毫升1.5×108至5×108个菌落形成单元(cfu/ml)的生长阶段细菌培养物。在形成测试样品中，8重量份的如上所述的皂溶液与1重量份培养物和1重量份的水组合。在10、30以及60秒的暴露后，中和样品以抑制(arrest)皂溶液的抗菌活性。然后，将测试溶液连续稀释，铺板于固体介质上，孵育24小时以及计数存活细胞。抗菌活性被定义为相对于0秒时细菌浓度以cfu/ml计的log降低。未暴露于任何皂溶液的培养物作为未处理对照物。
使用下式来计算log10降低：
log10降低＝log10(对照物数)-log10(测试样品存活数)
实施例1至3
制备下表2所示的液体皂制剂。
表2
按照上述体外时间-杀灭程序来评估液体皂制剂的杀生物活性。杀生物活性结果报告在表3中。
表3
杀生物活性
对抗金黄色葡萄球菌ATCC 6538的Log10降低
如表3数据示范的，在指定的接触时间内，液体皂2和液体皂3比液体皂1(不含银成分)具有更好的对抗金黄色葡萄球菌ATCC 6538的抗菌效果。
Claims (6)
1.降低在人体皮肤上的革兰氏阳性细菌的方法，其包括：
(I)向人体皮肤施用水性皂组合物，其包含：
(a)0.2至25重量％的脂肪酸皂，
(b)至少一种银(I)化合物，其在25℃在水中具有至少1×10-4mol/L的银离子溶解度，
通过按需要稀释液体清洁制剂至0.2至25重量％的所述脂肪酸皂的含量制备所述水性皂组合物，所述液体清洁制剂包含：
(i)基于制剂总重量的5至65重量％的脂肪酸皂，
(ii)基于制剂总重量的0.1至100ppm按重量计的至少一种银(I)化合物，其在25℃在水中具有至少1×10-4mol/L的银离子溶解度；和
(iii)20至90重量％的水，
(II)使水性皂组合物保持在皮肤上持续小于1分钟的接触时间和
(Ⅲ )冲洗皮肤上的水性皂组合物，
其中组分(b)为一种或多种银化合物，其选自由氧化银、硝酸银、醋酸银、硫酸银、苯甲酸银、水杨酸银、碳酸银和柠檬酸银组成的组；以及
其中所述制剂在25℃具有8至11的pH。
2.如前述权利要求任一项所述的方法，其中银(I)化合物以基于制剂的总重量的1至50ppm的量存在于液体清洁制剂中。
3.如前述权利要求任一项所述的方法，其中所述银化合物包含氧化银。
4.用于个人护理应用的液体清洁制剂，该制剂包含：
(a)基于制剂总重量的5至65重量％的脂肪酸皂，
(b)基于制剂总重量的0.1至100ppm按重量计的至少一种银(I)化合物，其在25℃在水中具有至少1×10-4mol/L的银离子溶解度；和
(c)20至90重量％的水，
其中：在25℃，所述制剂具有8至11的pH，
其中所述至少一种银(I)化合物选自由氧化银、硝酸银、醋酸银、硫酸银、苯甲酸银、水杨酸银、碳酸银和柠檬酸银组成的组。
5.根据权利要求4的液体清洁制剂，其中所述银(I)化合物包含氧化银。
6.清洁人体皮肤的方法，其降低在人体皮肤上的革兰氏阳性细菌，该方法包括：
(I)使液体清洁制剂起泡或发泡，该液体清洁制剂包含：
(a)基于制剂总重量的5至65重量％的脂肪酸皂，
(b)基于制剂总重量的0.1至100ppm按重量计的至少一种银(I)化合物，其在25℃在水中具有至少1×10-4mol/L的银离子溶解度；和
(c)20至90重量％的水，
任选地，另外的水，
(II)将经发泡的组合物施用于皮肤持续小于1分钟的接触时间；和
(III)冲洗皮肤上的该经发泡的组合物，
其中所述至少一种银(I)化合物选自由氧化银、硝酸银、醋酸银、硫酸银、苯甲酸银、水杨酸银、碳酸银和柠檬酸银组成的组；以及
其中所述制剂在25℃具有8至11的pH。
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| DE202014010787U1 (de) | 2016-08-22 |
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