CN113490736A - 包含c10皂并最小化不饱和c18皂与葵酸盐的比率的皂条组合物 - Google Patents
包含c10皂并最小化不饱和c18皂与葵酸盐的比率的皂条组合物 Download PDFInfo
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- CN113490736A CN113490736A CN202080016972.3A CN202080016972A CN113490736A CN 113490736 A CN113490736 A CN 113490736A CN 202080016972 A CN202080016972 A CN 202080016972A CN 113490736 A CN113490736 A CN 113490736A
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Classifications
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/007—Soaps or soap mixtures with well defined chain length
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/02—Compositions of detergents based essentially on soap on alkali or ammonium soaps
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
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Abstract
本发明涉及包含最低底层水平的C10皂同时使不饱和C18皂与癸酸盐的比率最小化的皂条组合物。这种皂条提供了增强的快速抗菌活性。公开了一种皂条组合物，其包含：a)25‑85％，优选地35‑75％重量的C8至C24脂肪酸皂，其包含：(i)总皂条组合物重量的8％或15％或更高，更优选地16至32％的C10皂；和(ii)不饱和C18皂，其中所述不饱和C18皂与C10(癸酸盐)皂的重量比为1.2至0.1；b)组合物重量的1％至45％的有机和无机辅助材料；和c)组合物重量的5至30％，优选地13至28％的水，其中C10皂相对于不饱和C18皂的过量为至少6％。
Description
技术领域
本发明涉及基于脂肪酸的皂条，其通常通过甘油三酯油的皂化(例如，中和)制备，所述甘油三酯油包含不同链长的脂肪酸酯(与甘油三酯油的甘油基连接)。它还涉及使用最小量的特定链长(例如，C10)的形成皂的酯的新组合，同时使其他的最小化(包括最小化某些脂肪酸酯的链长的量和/或饱和或不饱和的水平)以增强抗菌活性。
背景技术
商购的皂条通常包含一种或多种“皂”，为了描述本发明皂条的这一组分的目的，所述皂具有本领域通常理解的含义：单羧脂肪酸的单价盐。如所述的，它们通常通过甘油三酯油的皂化形成。该盐的反离子(counterion)一般包括钠、钾、铵和链烷醇铵离子，但可以包括本领域已知的其他合适的离子。最终的皂条还可以包括任选的辅助成分，如保湿剂(moisturizers)、润湿剂(humectants)、水、填充剂、聚合物、染料、香料等，以对使用者的皮肤进行清洁和/或调理。
通常，常规皂条中的皂组分包含长链脂肪酸的盐，其烷基链长度为约8个碳原子至24个碳原子，优选地长度为12个碳原子至约18个碳原子。选择皂的特定烷基链长度是出于各种原因，包括清洁能力、起泡能力、成本等。已知与较长链长的皂相比，较短链长的皂的水溶性更高(即疏水性较低)并产生更多泡沫。出于成本原因和为皂条提供结构，通常选择较长链长的皂。
为了向这种常规皂条提供抗菌性能，一般需要向皂条中添加杀菌剂或抗菌剂。因此，例如，含有抗微生物剂如三氯生(即，2,4,4'-三氯-2'-羟基-二苯醚)和三氯卡班(triclocarbanilide)的皂条是已知的。然而，由于抗菌剂本身的成本和皂条生产中增加的成本，将抗菌剂添加到皂条中以实现抗菌效果会增加皂条的成本。
增强抗微生物活性的另一种方法是通过使用低总脂肪物质的皂条(例如，其中脂肪酸皂被高含量的有机溶剂和/或电解质代替)。
联合利华(Unilever)的WO2017/016803和WO2017/016807公开了一种清洁皂条，其包含10-30％的皂、20-45％的水溶性有机溶剂、20-40％的水和3-20％的电解质，从而形成低总脂肪物质(“TFM”)的皂条。同样属于联合利华的WO2017/016802显示了这种皂条的抗微生物益处是因为较低的可溶性表面活性剂水平。
许多其他参考文献公开了皂条，其含有广泛公开的量的癸酸皂(C10皂)和/或不饱和酸皂如油酸(例如，具有一个顺式构型不饱和基团的C18)。
然而，没有任何地方认识到在保持C10皂的特定底层水平与同时最小化(任何链长的)总不饱和皂的水平和最小化C18不饱和皂和C10皂的特定比例之间的关系。
发明内容
出乎意料的是，申请人现在发现，在通常包含25％至85％，优选地30％至75％的脂肪酸皂的脂肪酸皂条中，其中癸酸盐(C10皂)的量为总皂条组合物重量的7％至32％或8％至32％或9％或10％至32％或11％或12％或13％或14％或15％至32％或16％至32％。上限可能是31％或30％或29％或28％或25％。上面提到的上限和下限可以互换使用。优选的范围是组合物重量的8至24％；并且进一步其中同时地，不饱和C18脂肪酸皂，尤其是油酸(但可以包括具有一个或多个不饱和基团的C18)的水平受到限制，使得不饱和C18与C10(癸酸盐)脂肪酸皂的比率保持在优选地1.2及以下(低至0.2或0.1或0％)，更优选地1.1或以下或者1.05及以下或者1.0及以下或者0.80及以下，更优选地0.55及以下，甚至更优选地0.30及以下(例如，油酸皂与癸酸皂的比率为0至0.30)；则该皂条组合物的抗菌活性相对于例如该比率较高(例如1.35)的皂条显著增强。
值得注意的是，当更多的皂存在时，在相同比率下杀菌更有效。因此，例如，具有60重量％的皂和1:1比率的皂条比具有40重量％的皂和相同不饱和C18与癸酸盐比率的皂条更有效。
优选的皂条具有组合物重量的8％至28％或8％至24％的癸酸盐和1.1至0或1.05至0或1.0至0的不饱和C18脂肪酸皂与癸酸盐的比率。优选地癸酸盐相对于C18不饱和脂肪酸皂是过量的。在本发明的皂条中，癸酸盐相对于不饱和C18的过量为至少6％或有时为10％或更多或者14％或更多。
皂反离子可以是碱金属如钠或钾，或者可以是例如链烷醇胺(如三乙醇胺)。
我们所指的不饱和C18脂肪酸皂可以具有一个、两个或三个不饱和基团及其混合物。它们还包括不饱和C18皂的羟基衍生物，例如羟基油酸盐和蓖麻油酸的皂。通常，C18油酸皂(一个不饱和基团)是最主要的C18皂，但C18皂也可能包括反油酸皂(这种构型的带有一个不饱和的C18皂)，或基于具有一个以上不饱和键的脂肪酸(例如，亚油酸、α亚油酸)的C18皂。优选地，具有三个不饱和基团的C18脂肪酸的含量小于0.2％，更优选地小于0.1％。
具体实施方式
本发明涉及脂肪酸皂条(例如，包含25％至85％重量的脂肪酸皂的皂条)，其中C10皂如上所述的占皂条的8％至32％并且也如上所述，C18不饱和皂与C10皂的比率为1.2至0.1，或1.1至0.1，优选地1.05至0.1。
更具体地，本发明涉及一种皂条组合物，其包含：
a)25-85％，优选地35-75％重量的C8-C24脂肪酸皂，其包含：
(i)总皂条组合物重量的8％或15％或更高，更优选地16至32％的C10皂；和
(ii)不饱和C18皂，其中所述不饱和C18皂与C10(癸酸盐)皂的比率为1.2至0.1，
b)组合物重量的1％至45％的有机和无机辅助材料；和
c)组合物重量的5至30％，优选地13至28％的水。
此外具体地说，本发明涉及一种皂条组合物，其包含：
a)25-85％，优选地28-76％重量的C8-C24脂肪酸皂，其中：
(i)C10皂占总皂条组合物重量的8％或9％或10％或15％或更多，更优选地16至32％；和
(ii)不饱和C18皂(优选地具有1、2或3个不饱和基团，包括具有羟基的C18不饱和分子或其他衍生物(例如羟基油酸)及其混合物)的含量使得不饱和C18皂与C10(癸酸盐)皂的比率为1.2或1.1或1.05或0.80或0.55或0.30；
b)1至45％重量，优选2至45％重量的有机和无机辅助材料；和
c)5至30％，优选地13至28％重量的水。
应注意保持高C10脂肪酸皂水平(例如，以保持不饱和C18与C10脂肪酸皂的低比率)并不是本领域技术人员有理由去做的事情，所以没有如此富集的量的供应。富集量的C10脂肪酸皂也不容易自然发生。例如，在坚果油中，C10皂的最大存在量为6至7重量％。
更具体地，本发明的皂条包含25至85％重量的C8至C24脂肪酸皂的基质。脂肪酸皂和可能另外存在的任何其他表面活性剂应适合与人类皮肤日常接触。
术语“皂”在本文中以其通俗意义使用，即脂肪族的、烷烃的或烯烃的单羧酸的碱金属盐或烷醇铵盐。钠、钾、镁、单乙醇铵、二乙醇铵和三乙醇铵阳离子或其组合最适合于本发明的目的。一般而言，在本发明的组合物中使用钠皂，但高达约15％的皂可以是钾、镁或三乙醇胺皂。可用于本文的皂是公知的具有约8至约24个碳原子的天然或合成脂肪族酸(链烷酸或链烯酸)的碱金属盐。它们可被描述为具有约8至约24个碳原子的饱和或不饱和烃的碱金属羧酸盐。
脂肪酸皂由脂肪酸(其可以是不同的脂肪酸)制成，通常包含链长为C8至C24的脂肪酸部分的脂肪酸。符合具有至少一定量的C10、保持油酸盐与C10的确定比例、使油酸盐以外的不饱和C18最小化以及保持C10皂与不饱和脂肪酸皂的确定摩尔比的规定要求，脂肪酸共混物可以含有相对纯的量的一种或多种脂肪酸。合适的脂肪酸包括但不限于丁酸、己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、反式-9-十四碳烯酸(myristelaidic acid)、十五碳烷酸、棕榈酸、棕榈油酸、十七碳烷酸、十七烯酸、硬脂酸、油酸、亚油酸、亚麻酸、花生酸、鳕油酸、山嵛酸和木蜡酸及其异构体。在一些优选形式中，脂肪酸共混物具有低含量的饱和脂肪酸部分链长为14个碳原子的脂肪酸(肉豆蔻酸)。
通常，脂肪酸皂的链长度根据起始脂肪或油原料而变化(出于本说明书的目的，“油”和“脂肪”可互换使用，除非上下文另有要求)。较长链的脂肪酸皂(例如，C16棕榈酸或C18硬脂酸)通常从牛脂和棕榈油中获得，而较短链的皂(例如，C12月桂酸)通常可以从例如椰子油或棕榈仁油中获得。所产生的脂肪酸皂也可以是饱和的或不饱和的(例如油酸)，只要符合如所述的本发明的要求。
通常，较大分子量的脂肪酸皂(例如，C14至C22皂)，尤其是较长的饱和皂是不溶性的，并且不产生良好的泡沫量，尽管它们可以帮助使得由其他可溶性皂产生的泡沫更加柔滑和更加稳定。相反，较小分子量的皂(例如C8至C12)和不饱和皂(例如来自油酸的)会迅速起泡。然而，较长链的皂(通常是饱和的，尽管它们也可能含有一定的不饱和水平，如油酸)是希望的，因为它们保持结构并且不会轻易溶解。不饱和皂(例如油酸)可溶解并像短链皂一样迅速起泡，但像较长链皂一样形成更密集、更柔滑的泡沫。
皂原液通常不具有7％或更高，尤其是8％或更高的C10脂肪酸材料的水平(例如，棕榈仁油(PKO)、椰子油)。低于7％重量的这些C10皂含量低于本发明的皂条的优选含量。具有例如76％总脂肪物质含量的皂条最高也只有4％的C10脂肪酸皂。在PKO/椰子油的70/30混合物的常见商购皂条中，这个水平可能是1.7％。此外，C18皂的含量通常为约30％，远高于C10皂的含量。如果不了解高C10、低C18皂(例如，不饱和C18与C10的低比率)的优势，则没有理由制造这类皂条。这样做的优点是在室温条件下实现快速起效的抗菌效果，并且就申请人所知，该优点在本领域中未被认识到。因此，没有理由选择或设计此类商品。
应该注意的是，通常，较大分子量的饱和脂肪酸皂(例如，C14至C22皂)是不溶性的，并且不会产生良好的泡沫体积，尽管它们可以帮助使得由其他可溶性皂产生的泡沫更加柔滑和更加稳定。
有机和无机辅助材料
用于皂条组合物的辅助材料的总水平应不高于皂条组合物重量的50％，优选地为1至50％，更优选地1至45％，进一步优选地3至45％。
可以使用的合适的淀粉质材料包括天然淀粉(来自玉米、小麦、大米、马铃薯、木薯等)、预胶化淀粉、各种物理和化学改性淀粉及其混合物。术语天然淀粉是指未经化学或物理改性的淀粉-也称为生淀粉或原淀粉(native starch)。
优选的淀粉是来自玉蜀黍(maize)(玉米(corn))、木薯、小麦、马铃薯、大米和它的其他天然淀粉来源的天然或原淀粉。具有不同直链淀粉和支链淀粉比率的生淀粉：例如玉米(25％直链淀粉)；糯玉米(0％)；高直链淀粉玉米(70％)；马铃薯(23％)；大米(16％)；西米(27％)；木薯(18％)；小麦(30％)和其他。生淀粉可直接使用或在制备皂条组合物的过程中进行改性以使得淀粉变得胶化，部分或完全胶化。
另一种合适的淀粉是预胶化的，它是在作为本发明皂条组合物中的成分加入之前已经胶化的淀粉。有多种形式是可用的，其在不同温度下胶凝，例如可冷水分散的淀粉。一种合适的商业预胶化淀粉由National Starch Co.(巴西)以商品名
CS 3400提供，但具有类似特性的其他市售材料也是合适的。
多元醇
另一种有机辅助剂可以是多元醇或多元醇的混合物。多元醇是本文中用于表示具有多个羟基(至少两个，优选地至少三个)的化合物的术语，其是高度水溶性的，优选地易溶于水。
有多种类型的多元醇可用，包括：相对低分子量的短链多羟基化合物，如甘油和丙二醇；糖类，如山梨糖醇、甘露糖醇、蔗糖和葡萄糖；改性碳水化合物，如水解淀粉、糊精和麦芽糊精，以及聚合的合成多元醇，如聚亚烷基二醇(例如聚乙二醇(PEG)和聚丙二醇(PPG))。
尤其优选的多元醇是甘油、山梨糖醇和它们的混合物。
多元醇的含量对于形成热塑性物料可能是重要的，该热塑性物料的材料特性适合高速制造(300-400条/分钟)，也适合用作个人洗涤皂条。例如，当多元醇含量太低时，在挤出温度(例如40℃至45℃)下，该物料可能没有足够的塑性，并且皂条往往表现出较高的软糊性和磨损率。相反，当多元醇含量太高时，物料可能变得太软而无法在正常工艺温度下才高速形成皂条。
在优选的实施方案中，本发明的皂条包含0至35％，优选0.5至15％重量的多元醇。如所述的，优选的多元醇包括甘油、山梨糖醇及其混合物。
辅助剂系统可任选地包括包含一种材料或材料组合的不溶性颗粒。不溶性颗粒是指以固体颗粒形式存在并适用于个人洗涤的材料。优选地，存在矿物(例如，无机的)或有机颗粒。
不溶性颗粒不应被感觉为是粗糙的或颗粒状的，因此粒径应小于300微米，更优选地小于100微米，最优选地小于50微米。
优选的无机颗粒材料包括滑石和碳酸钙。滑石是一种硅酸镁矿物材料，具有片状硅酸盐结构和Mg3Si4(OH)22的组成，并且可以水合形式获得。它具有板状形态，基本上是亲油/疏水性的，即它被油而不是水润湿。
碳酸钙或白垩以三种晶体形式存在：方解石、文石和球霰石。方解石的天然形态为菱面体或立方体形，文石为针状或树枝状，球霰石为球状。
商业上，碳酸钙或被称为沉淀碳酸钙的白垩是通过碳酸化方法生产的，其中二氧化碳气体鼓泡通过氢氧化钙的水性悬浮液。在这个过程中，碳酸钙的晶体类型是方解石或方解石和文石的混合物。
其他任选的不溶性无机颗粒材料的例子包括铝硅酸盐、铝酸盐、硅酸盐、磷酸盐、不溶性硫酸盐、硼酸盐和粘土(例如高岭土、瓷土)及它们的组合。
有机颗粒材料包括不溶性多糖，如高度交联或不溶解的淀粉(例如，通过与疏水物如琥珀酸辛酯反应)和纤维素；合成聚合物，如各种聚合物胶乳(polymer lattice)和悬浮聚合物；不溶性皂及其混合物
皂条组合物优选地包含皂条组合物的0.1至25％重量的，优选5至15％重量的这些矿物或有机颗粒。
水
本发明的皂条包含5至30％重量，优选13至28％重量的水。
任选成分
合成表面活性剂：皂条组合物可以任选地包括非皂合成型表面活性剂(洗涤剂)—所谓的合成洗涤剂(syndet)。合成洗涤剂可包括阴离子表面活性剂、非离子表面活性剂、两性或两性离子表面活性剂和阳离子表面活性剂。
皂条中存在的合成表面活性剂的含量基于皂条组合物的总重量一般小于25％，优选地小于15％，优选地最多10％，最优选地0至7％。
阴离子表面活性剂可以是，例如脂肪族磺酸盐，如伯烷烃(例如，C8-C22)磺酸盐、伯烷烃(例如，C8-C22)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醚磺酸盐(AGS)；或芳族磺酸盐，如烷基苯磺酸盐。α-烯烃磺酸盐是另一种合适的阴离子表面活性剂。
阴离子也可以是烷基硫酸盐(例如，C12-C18烷基硫酸盐)，尤其是伯醇硫酸盐或烷基醚硫酸盐(包括烷基甘油醚硫酸盐)。阴离子表面活性剂也可以是磺化脂肪酸(如α磺化牛脂脂肪酸)、磺化脂肪酸酯(如α磺化甲基牛脂酸)或其混合物。
阴离子表面活性剂也可以是烷基磺基琥珀酸盐(包括单烷基和二烷基，例如，C6-C22磺基琥珀酸盐)；烷基和酰基牛磺酸盐、烷基和酰基肌氨酸盐、磺基乙酸盐、C8-C22烷基磷酸盐和磷酸盐、烷基磷酸酯和烷氧基烷基磷酸酯、酰基乳酸盐或乳酸盐、C8-C22单烷基琥珀酸盐和马来酸盐、磺基乙酸盐和酰基羟乙磺酸盐。
另一类阴离子表面活性剂(anionics)是C8至C20烷基乙氧基(1-20EO)羧酸盐。
另一种合适的阴离子表面活性剂是C8-C18酰基羟乙磺酸盐。这些酯是通过碱金属羟乙基磺酸盐与具有6至18个碳原子且碘值小于20的混合脂肪族脂肪酸的反应制备的。至少75％的混合脂肪酸具有12至18个碳原子，且最多25％具有6至10个碳原子。酰基羟乙磺酸盐也可以是烷氧基化羟乙磺酸盐。
酰基羟乙磺酸盐，当存在时，通常占总组合物重量的约0.5％至约25％。
一般而言，阴离子组分将构成皂条组合物中使用的大部分合成表面活性剂。
可用于本发明的两性洗涤剂包括至少一个酸基团。这可以是羧酸或磺酸基团。它们包括季氮，且因此是季酰胺酸。它们通常应包括7至18个碳原子的烷基或烯基。合适的两性表面活性剂包括两性乙酸盐、烷基和烷基酰胺基甜菜碱以及烷基和烷基酰胺基磺基甜菜碱。
两性乙酸盐和二两性乙酸盐也意图包括在可以使用的可能的两性离子和/或两性化合物中。
合适的非离子表面活性剂包括具有疏水基团和活性氢原子的化合物(例如脂族醇或脂肪酸)与环氧烷(尤其是环氧乙烷，单独或与环氧丙烷一起)的反应产物。例子包括脂肪族(C8-C18)伯或仲直链或支链醇与环氧乙烷的缩合产物，以及由环氧乙烷与环氧丙烷和乙二胺的反应产物缩合而成的产物。其他所谓的非离子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。
非离子表面活性剂还可以是糖酰胺，如烷基多糖和烷基多糖酰胺。
阳离子洗涤剂的例子是季铵化合物，如烷基二甲基卤化铵。
可以使用的其他表面活性剂在Parran Jr.的第3,723,325号美国专利和Schwartz,Perry&Berch”的"Surface Active Agents and Detergents"(Vol.I&II)中有所描述，两者也通过引用并入本申请。
精修辅助材料
这些成分直接(香料)或间接(防腐剂)改善皂条的美学品质，尤其是视觉、触觉和嗅觉特性。在本发明的皂条组合物中可以加入广泛多样的任选成分。辅剂的例子包括但不限于：香料；乳浊剂，如脂肪醇、乙氧基化脂肪酸、固体酯和TiO2；染料和颜料；珠光剂如TiO2涂覆的云母和其他干涉颜料；板状镜面颗粒，如有机闪光剂；感觉剂，如薄荷醇和生姜；防腐剂，如二羟甲基二甲基乙内酰脲(Glydant XL1000)、对羟基苯甲酸酯、山梨酸等；抗氧化剂，如，例如丁基化羟基甲苯(BHT)；螯合剂，如乙二胺四乙酸(EDTA)的盐和依曲膦酸三钠(trisodium etridronate)；乳化稳定剂；辅助增稠剂；缓冲剂；及其混合物。
基于皂条组合物的总重量，珠光剂的含量应在约0.1％至约3％之间，优选地在0.1％至0.5％之间，最优选地在约0.2至约0.4％之间。
皮肤有益剂
这里强调的一个特定类别的任选成分是皮肤有益剂，其用于促进皮肤和头发的健康和状况。潜在的有益剂包括但不限于：脂质，如胆固醇、神经酰胺和假神经酰胺；抗微生物剂，如三氯生；防晒剂，如肉桂酸盐；其他类型的去角质颗粒，如聚乙烯珠、核桃壳、杏仁、花瓣和种子，及无机物，如二氧化硅和浮石；额外的润肤剂(皮肤软化剂)，如长链醇和蜡如羊毛脂；额外的保湿剂；肤色调节剂；皮肤营养物质，如维生素C、D和E等的维生素以及如佛手柑、柑橘、菖蒲等的精油；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、胡萝卜的水溶性或不溶性提取物；凤仙花、卡姆木、高山草(alpina)叶和其他植物提取物如金缕梅，及其混合物。
该组合物还可以包括提供额外皮肤(包括头皮)益处的多种其他活性成分。例子包括祛痘剂，如水杨酸和间苯二酚；含硫的D和L氨基酸及其衍生物和盐，特别是它们的N-乙酰基衍生物；抗皱、抗皮肤萎缩和皮肤修复活性物质，如维生素(例如，A、E和K)、维生素烷基酯、矿物质、镁、钙、铜、锌和其他金属成分；视黄酸及酯和衍生物，如视黄醛和视黄醇、维生素B3化合物、α-羟基酸、β-羟基酸，例如水杨酸及其衍生物；皮肤舒缓剂，如芦荟、荷荷巴油、丙酸和乙酸衍生物、芬那酸衍生物；人造晒黑剂，如二羟基丙酮；酪氨酸；酪氨酸酯，如酪氨酸乙酯、酪氨酸葡萄糖；亮肤剂，如芦荟提取物和烟酰胺、α-甘油基-L-抗坏血酸、aminotyroxine、乳酸铵、乙醇酸、氢醌、4-羟基茴香醚，皮脂刺激剂，如泻根醇酸、脱氢表雄酮(DHEA)和orizano；皮脂抑制剂，如羟基氯化铝、皮质类固醇、脱氢乙酸及其盐、二氯苯基咪唑二氧戊环(可从Elubiol获得)；抗氧化作用，蛋白酶抑制；紧肤剂，如乙烯基吡咯烷酮、(甲基)丙烯酸和由长链(甲基)丙烯酸烷基酯组成的疏水单体的三元共聚物；止痒剂，如氢化可的松、甲地利嗪和曲美拉嗪；毛发生长抑制；5-α还原酶抑制剂；促进脱屑的药剂；抗糖化剂；抗头皮屑剂，如吡啶硫酮锌；毛发生长促进剂，如非那雄胺、米诺地尔、维生素D类似物和视黄酸及其混合物。
电解质
皂条包括0.5重量％至5重量％的电解质。优选的电解质包括碱金属或碱土金属的氯化物、硫酸盐和磷酸盐。不希望受理论束缚，据信电解质有助于构造固化的皂团块并且还通过同离子效应增加熔融团块的粘度。发现不含任何电解质的对比皂条更软。氯化钠和硫酸钠是最优选的电解质，更优选地为0.6至3.6重量％，最优选地为1.0至3.6重量％。
聚合物
皂条可包括0.1至5重量％的选自丙烯酸酯或纤维素醚的聚合物。优选的丙烯酸酯包括交联的丙烯酸酯、聚丙烯酸或聚丙烯酸钠。优选的纤维素醚包括羧甲基纤维素或羟烷基纤维素。也可以使用这些聚合物的组合，只要聚合物的总量不超过5重量％。
丙烯酸酯
优选的皂条包括0.1至5％的丙烯酸酯。更优选的皂条包括0.15至3％的丙烯酸酯。丙烯酸酯聚合物的例子包括丙烯酸与聚烯丙基蔗糖交联的聚合物和共聚物，如美国专利2,798,053中所述，该专利通过引用并入本文。其他例子包括聚丙烯酸酯、丙烯酸酯共聚物或碱溶胀乳液丙烯酸酯共聚物(例如，
33，来自Rohm and Haas；
Aqua SF-1，来自Lubrizol Inc.)、疏水改性碱溶胀共聚物(例如，
22,
28和
38，来自Rohm and Haas)。市售的丙烯酸交联均聚物包括可从Lubrizol Inc获得的
934,940,941,956,980以及996。其他市售的交联丙烯酸共聚物包括可从Lubrizol Inc.获得的
Ultrez等级系列(
10,20和21)和ETD系列(ETD 2020和2050)。
纤维素醚
优选的皂条包括0.1至5％的纤维素醚。更优选的皂条包括0.1至3％的纤维素醚。优选的纤维素醚选自烷基纤维素、羟烷基纤维素和羧烷基纤维素。更优选的皂条包括羟烷基纤维素或羧烷基纤维素并且特别优选的皂条包括羧烷基纤维素。
优选的羟烷基纤维素包括羟甲基纤维素、羟乙基纤维素、羟丙基纤维素和乙基羟乙基纤维素。
优选的羧烷基纤维素包括羧甲基纤维素。特别优选的羧甲基纤维素为羧甲基纤维素钠盐的形式。
蜡和聚亚烷基二醇
优选的蜡包括石蜡和微晶蜡。当使用聚亚烷基二醇时，优选的皂条可包括0.01至5重量％、更优选地0.03至3重量％且最优选地0.5至1重量％的聚亚烷基二醇。合适的例子包括聚乙二醇和聚丙二醇。优选的商业产品是陶氏化学公司出售的
本发明的优选组合物包含(按重量计)：
1)25-85％的皂，优选地是钠皂；
2)0-35％的多元醇，优选地甘油、山梨糖醇或混合物；
3)0至25％的颗粒；和
4)10％到30％的水。
方案
体外抗微生物方案
皂浆制备
被评估的固体皂条通过细奶酪磨碎器磨碎成小片。皂条碎片以10重量％与水混合，并在磁力搅拌板上在25℃下搅拌过夜。选择搅拌棒的尺寸以在整个混合过程中保持涡旋是很重要的。均匀的凝胶样皂浆被制备并新鲜地用于体外时间-杀伤(in-vitro time-kill)试验。
细菌
大肠杆菌ATCC 10536作为冻干培养物从美国典型培养物保藏中心获得。每次实验前，新鲜的测试培养物在胰蛋白酶大豆琼脂(TSA)条带平板上于37.0℃下生长两次，每次24小时。然后在功效测试之前用胰蛋白胨氯化钠(Tryptone Sodium Chloride)制备大肠杆菌的悬浮液。
体外时间杀伤试验
根据题为“Chemical Disinfectants and Antiseptics–QuantitativeSuspension Test for the Evaluation of Basic Bactericidal Activity of ChemicalDisinfectants and Antiseptics–Test Method and Requirements(Phase 1)”的欧洲标准EN 1040:2005在25℃下进行了时间杀伤试验，其以引用方式并入本文。按照这一程序，在25℃下用皂溶液(如上所述制备)处理1.5x108至5x108菌落形成单位/毫升(cfu/ml)的生长期细菌培养物。在形成测试样品时，将如上所述制备的8重量份皂溶液与1重量份培养物和1重量份水混合。暴露10、20和30秒后，样品被中和以抑制皂溶液的抗菌活性。然后将测试溶液系列稀释，接种在固体培养基上，孵育24小时并计数存活的细胞。杀菌活性定义为相对于0秒时细菌浓度的cfu/ml对数降低。未暴露于任何皂溶液的培养物用作无处理对照。
使用以下公式计算log10降低：
Log10降低＝log10(对照数量)–log10(测试样本存活数)
基质洗涤测定
为了确定皂条制剂从基质去除细菌的功效，在人造皮肤样品(VITRO-SKINTM,IMSCorp.，一种设计为模拟人类皮肤表面化学的合成基质)上进行了体外性能测试。为了制备基质，将VITRO-SKIN片在具有85％水和15％甘油的储液器的水合室中水合过夜。大约24小时后，将VITRO-SKIN片从腔室中取出并在环境温度和湿度下静置大约1小时，然后将直径5厘米的圆形片段安装在XRF杯的相对部件之间。通过使用从上述过夜生长中获得的100μl培养物，为每个使用的VITRO-SKIN均匀接种1.5x108–5x108CFU的大肠杆菌。让细菌在VITRO-SKIN上干燥30分钟。
为了模拟清洗皮肤，将条皂组合物切成直径为1厘米的圆柱体，并将条在去离子水中润湿。在用0.7ml水润湿VITRO-SKIN后，将条皂组合物在XRF杯内整个VITRO-SKIN表面轻轻地摩擦15秒。然后，通过用聚四氟乙烯棒连续摩擦VITRO-SKIN 45秒(例如，没有皂条组合物的情况下)产生泡沫。除去洗涤液，通过向XRF杯中加入10ml去离子水并用干净的聚四氟乙烯棒摩擦基质30秒来清洗VITRO-SKIN。清洗步骤再重复一次。
除去清洗液后，立即将10ml冰冷的D/E肉汤加入每个XRF杯中。杯子用聚四氟乙烯紧紧覆盖并剧烈摇晃1分钟以驱散细菌。制备液体的系列稀释液并在37℃下接种在胰蛋白酶大豆琼脂上24小时用于菌落计数。然后，计数并计算CFU/ml，结果报告为log10 CFU。较小的log10(CFU/ml)值对应于皂条从基质去除细菌的更好效率。
实施例
以下实施例进一步描述和阐明了本发明范围内的实施方案。给出的实施例仅用于说明的目的并且不应被解释为限制，因为在不脱离本发明的精神和范围的情况下，其许多变化是可能的。
表1
随不饱和C18皂(例如油酸)/癸酸钠比率变化的时间杀伤功效。
在混合物中，癸酸钠保持在固定水平，以模拟含有16重量％癸酸钠的皂条，以及C18钠皂在0至22重量％范围内变化。
表1
如表1数据所证明的，当不饱和C18皂与癸酸盐的比率低于1.2时，不饱和C18脂肪酸的钠皂开始抑制癸酸钠的杀生物功效(我们定义为对大肠杆菌ATCC 10536的log10降低至少1.0，优选地至少1.2，更优选地至少1.4)。当不饱和C18钠皂/癸酸钠比率增加到1.3以上时，癸酸钠几乎完全失去了其杀生物功效。测试溶液包含固定浓度1.64重量％的癸酸钠，模拟16.4重量％的皂条含量，以及浓度范围0至2.15重量％的不饱和C18钠皂，模拟0和17.2重量％范围的皂条含量。如所述的，C10皂的重量可低至7％。只要C18不饱和与C10的比率为1.2及以下。
表2
比较C10至C14之间的短链皂对抗微生物功效的影响(同时保持长的饱和皂和不饱和皂不变)
表3
随C10和C14之间短链皂变化的时间杀伤功效。
正如表2和表3中的数据所证明的那样，在富含不同短链皂的皂条中，含有癸酸钠的皂条具有最佳的抗微生物时间杀伤功效。换句话说，使用最低水平的C10皂具有出人意料的活性。25.64的C10含量(其中特定不饱和C18与C10的比率为1.20)提供了杀伤。C8、C12和C14提供的活性要小得多。
表4
具有增加的癸酸钠的皂条制剂。
表5
随皂条中癸酸钠含量变化的抗微生物功效
正如表4和5中的数据所证明的，抗微生物时间杀伤效力随着皂条制剂中癸酸钠的含量而增加。实施例显示低至8％的C10水平是有效的。关键是将油酸保持在相对于C10较低的水平。
表6
用0.4重量％碳酸盐缓冲的具有15.2重量％癸酸钠的模型皂条的时间杀伤功效，包括不同水平的油酸钠。
表6模拟了具有15.2％和不同量油酸盐的组合物。当不存在不饱和C18(例如油酸盐)时(C10活性不受阻碍)，实施例10显示出良好的抗微生物活性(log10降低3.7)。只要C10与油酸盐的比率低，活性在6.1％的油酸盐存在时仍然良好(实施例11)。当比率太高时(对比例G)，效果非常低。
表7
油酸钠/癸酸钠重量比介于1和3之间的配方皂条的组成。
| 对比例H | 对比例I | 对比例J | |
| 癸酸钠 | 8.0 | 12.00 | 16.00 |
| 月桂酸钠 | 0.00 | 0.00 | 0.00 |
| 肉豆蔻酸钠 | 0.00 | 0.00 | 0.00 |
| 棕榈酸钠 | 35.22 | 35.22 | 35.22 |
| 硬脂酸钠 | 2.76 | 2.76 | 2.76 |
| 油酸钠 | 24.29 | 24.29 | 24.29 |
| 亚油酸钠 | 5.79 | 5.79 | 5.79 |
| 亚麻酸钠 | 0.00 | 0.00 | 0.00 |
| 蓖麻油酸钠 | 0.00 | 0.00 | 0.00 |
| 甘油 | 4.00 | 4.00 | 4.00 |
| 二水柠檬酸三钠 | 2.00 | 2.00 | 2.00 |
| 滑石 | 6.00 | 6.00 | 6.00 |
| 氯化钠 | 0.70 | 0.70 | 0.70 |
| 依替膦酸四钠 | 0.04 | 0.04 | 0.04 |
| Na4EDTA | 0.17 | 0.17 | 0.17 |
| 香料 | 1.185 | 1.185 | 1.185 |
| CI 11980 | 0.06 | 0.06 | 0.06 |
| CI 12490 | 0.06 | 0.06 | 0.06 |
| 水 | 17.31 | 17.31 | 17.31 |
表8
油酸钠/癸酸钠重量比在1.5和3之间的配方皂条的时间杀伤功效。
如表7和8所示，1.5至3的油酸钠/癸酸钠的比率完全抑制了抗微生物活性。
表9
数据显示组合物在约8％癸酸钠水平下在30秒时表现出2.2log杀伤。油酸盐与癸酸盐的比率为0.76。该配方在本发明之外。
表10
数据显示组合物在约7％癸酸钠水平下在30秒时表现出3.5log杀伤。油酸盐与癸酸盐的比率为0.26。
Claims (5)
1.一种皂条组合物，其包含：
a)25-85％，优选地35-75％重量的C8至C24脂肪酸皂，其包含：
(i)总皂条组合物重量的8％或15％或更高，更优选地16至32％的C10皂；和
(ii)不饱和C18皂，其中所述不饱和C18皂与C10(癸酸盐)皂的重量比为1.2至0.1，
b)所述组合物重量的1％至45％的有机和无机辅助材料；和
c)所述组合物重量的5至30％，优选地13至28％的水，其中C10皂相对于不饱和C18皂的过量为至少6％。
2.根据权利要求1的组合物，其中不饱和C18脂肪酸皂是具有1、2或3个不饱和基团的不饱和C18脂肪酸皂；或其混合物。
3.根据权利要求1或2的组合物，其在30秒的接触时间提供1.2或更大的大肠杆菌ATCE10536的log10减少。
4.根据前述权利要求1至3中任一项的组合物，其中所述有机和无机辅助材料选自填充剂、多元醇、盐及其混合物。
5.如前述权利要求中任一项所述的组合物用于增强抗菌活性的用途，其中所述活性根据说明书中的体外抗微生物方案确定。
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| PCT/EP2020/053435 WO2020177988A1 (en) | 2019-03-01 | 2020-02-11 | Bar compositions comprising c10 soap while minimizing ratio of unsaturated c18 soap to caprate |
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| CN1172499A (zh) * | 1995-01-31 | 1998-02-04 | 普罗克特和甘保尔公司 | 含特制脂肪酸皂的改进的清洁皂条 |
| CN1230214A (zh) * | 1996-07-11 | 1999-09-29 | 尤尼利弗公司 | 基于最低含量脂肪酸皂和最低饱和皂对不饱和皂比率的增进了加工性的含两性表面活性剂的合成条块组合物 |
| WO2004046294A1 (en) * | 2002-11-20 | 2004-06-03 | The Dial Corporation | Soap bars exhibiting antibacterial effectiveness and method of producing same |
| GB0922649D0 (en) * | 2009-12-29 | 2010-02-10 | Unilever Plc | Low TMF extruded soap bars having reduced cracking |
| WO2013076047A1 (en) * | 2011-11-23 | 2013-05-30 | Unilever Plc | Toilet soap with improved lather |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2020177988A1 (en) | 2020-09-10 |
| JP2022522759A (ja) | 2022-04-20 |
| EP3931294A1 (en) | 2022-01-05 |
| CA3131455A1 (en) | 2020-09-10 |
| US12006494B2 (en) | 2024-06-11 |
| MX2021010271A (es) | 2021-09-23 |
| EP3931294B1 (en) | 2024-08-21 |
| ZA202105108B (en) | 2023-01-25 |
| JP7439118B2 (ja) | 2024-02-27 |
| US20220135910A1 (en) | 2022-05-05 |
| BR112021014250A2 (pt) | 2021-09-28 |
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