CN1204873C - 含有磺基琥珀酸单酯的稳定的高甘油液体 - Google Patents
含有磺基琥珀酸单酯的稳定的高甘油液体 Download PDFInfo
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Abstract
本发明公开了一种含有磺基琥珀酸单酯的高甘油含量(大于或者等于10重量%)的液体组合物,该组合物是稳定的。稳定性是由一种稳定体系提供,该体系含有极少量的一种所定义的盐和一种所定义的增稠剂。本发明还公开了一种增强高含量甘油组合物稳定性的方法。
Description
发明领域
本发明涉及含有一种或者多种所定义的磺基琥珀酸单酯的高甘油含量的液体组合物。更明确的说,尽管高甘油含量使得所述组合物不稳定,申请人发现结合极少量的脂肪酸盐(如碱金属盐或者链烷醇胺盐)及选自丙烯酸酯共聚物、羟烷基纤维素、阳离子型瓜尔胶(如JaguarC13S)的增稠剂能使该组合物稳定。本发明组合物可用于皮肤清洗、沐浴凝胶和毛发组合物。
含有磺基琥珀酸单酯的组合物在Miyamoto等的美国专利4,749,515中有公开。
然而,由于其增湿特性,非常有利的是向此种组合物中加入甘油以减轻皮肤干燥。然而,在上述组合物中,人们发现大量的甘油(如大约10重量%及以上)导致了不稳定及相分离。虽然不愿意被理论所束缚,人们认为该现象应归结为甘油的大比重。
出乎意料的是,现在申请人发现这种不稳定性可以通过利用一种稳定体系来克服,该体系包含:
(a)至少4重量%的C12-C24脂肪酸的碱金属皂和/或链烷醇胺皂;和
(b)0.01到5重量%的增稠共聚物,其选自丙烯酸酯共聚物、羟烷基纤维素(如羟乙基或者丙基纤维素)、阳离子型瓜尔胶和异硬脂酸。丙烯酸酯共聚物是特别优选的。
发明简述
本发明涉及稳定的高甘油液体洗涤剂组合物。更具体而言,该组合物含有:
(1)1-25%、优选5-20%的一种或者多种磺基琥珀酸单酯,其如分子式(I)、(II)、(III)或(IV)所示;
或
其中M1到M4的每一项都是H、NH4、碱金属或者羟烷基取代的铵。R1和R2各自为具有约8到20个碳原子的烷基或者羟烷基,R3是H或者CH3,AO是具有2个或者3个碳原子的氧化烯基团,n是0到20的整数。
(2)10%及以上、优选10到50重量%、优选15到40重量%的甘油;
(3)至少4重量%、优选至少5到15重量%的C12-C24脂肪酸的碱金属皂和/或链烷醇胺皂;
(4)0.01到5重量%、优选0.1到3重量%(含量可随着使用哪种增稠剂而改变)的增稠剂,其选自丙烯酸酯共聚物(如烷基丙烯酸酯共聚物)、羟烷基纤维素、阳离子型瓜尔胶和异硬脂酸;和
(5)平衡水。
在第二实施方案中,本发明涉及一种增加上述含所定义的磺基琥珀酸单酯的高甘油组合物稳定性的方法,这通过向其中加入含有组分(3)和组分(4)的稳定体系而实现。
组合物的pH大约为6到8.5,优选6.5到8.5,粘度大约为100到5000厘沲,优选100到200厘沲,使用Brookfield粘度计、2号或3号测杆(spindle)以12转/分的速度在25℃下旋转30秒进行粘度的测量。
将组合物在室温下放置4周后未有分离现象,以此定义组合物的稳定性。
发明详述
本发明涉及含有一种或者多种所定义的磺基琥珀酸单酯和相对较高量的甘油、而能保持稳定性的液体组合物。更具体而言,通过结合使用脂肪酸盐和特定的增稠剂(优选丙烯酸酯共聚物和异硬脂酸),据发现可以形成稳定的、高含量甘油(大于或者等于10%重量到大约50重量%的甘油)、磺基琥珀酸单酯的组合物。
本发明组合物将在下文中有详细的阐述。
本发明组合物包含1-25%、优选5-20重量%的一种或者多种如下式I、II、III或IV所示的磺基琥珀酸单酯及其混合物。
或
在上式中,M1到M4中每一项可以选自H、NH4、碱金属和羟烷基取代的铵基团。M1和M2以及M3和M4可以是相同的或者是不同的。碱金属可以包括锂、钠、钾等。羟烷基取代的铵类优选在羟烷基中具有1到3个碳原子,可包括单乙醇铵、二乙醇铵、三乙醇铵、甲基二乙醇铵等等。优选M1到M4是H、钠或者三乙醇铵。
R1和R2各自是具有约8到20个碳原子的直链或者支链烷基或者羟烷基,如己基、癸基、羟癸基、十二烷基、羟十四烷基、十四烷基、十九烷基等等。任何具有少于8个或者多于20个碳原子的烷基可任选地包含于所述分子中,条件是:本发明洗涤剂组合物中所含的磺基琥珀酸单酯中的碳原子总数在8到20之间。该数量的碳原子提供了良好的发泡特性,而当碳原子数少于8或者大于20的时候,观察到的泡沫要少一些。
在式(II)和(IV)中,R3是H或者CH3。
在上述各式中,AO表示含有2或者3个碳原子的氧化烯基团,即氧乙烯或氧丙烯。氧乙烯和氧丙烯基均可存在于所述分子中。
字母n代表了从0到20之间的整数,优选0到10。如果n超过了20,所得的液体洗涤剂组合物的发泡性质差。
由式(I)、(II)、(III)和(IV)所表示的化合物可以通过已知方法制备。
例如,通式(I)或者(II)所代表的磺基琥珀酸单酯可通过以下方法制备:高级脂肪酸的烯化氧加合物与马来酸酐反应,生成马来酸酐酯,进一步将该马来酸酣酯与一种亚硫酸盐反应。
或者,通式(II)或者(IV)表示的磺基琥珀酸单酯可通过以下方法制备:高级脂肪酸的低级醇酯和链烷醇胺反应,向反应产物中加入烯化氧,进一步将所得加成产物与马来酸酐反应,产生马来酸酐酯,然后使该马来酸酣酯与亚硫酸盐反应。
作为本发明所需的稳定体系的一部分,本发明组合物还需要至少4%、优选至少5%到大约15重量%的C12-C14脂肪酸碱金属皂和/或链烷醇胺盐。
适宜的脂肪酸皂包括但是不限于月桂酸或者肉豆蔻酸的钠盐或者钾盐。适宜的链烷醇胺盐包含但是不限于乙醇胺、三乙醇胺等。
该稳定体系中的第二组分是增稠剂。增稠剂选自丙烯酸酯共聚物、羟烷基纤维素、阳离子型瓜尔胶和异硬脂酸。
可使用的丙烯酸酯包括:烷基丙烯酸酯共聚物,如Leoarl MS200 exLion和Acuryn 33 ex Rohm and Haas;丙烯酸系共聚物,例如Auryn 22ex Rohm and Haas。羟烷基纤维素包括羟乙基、羟丙基或者羟甲基纤维素。阳离子型瓜尔胶包括美洲虎树胶(Jaquar gums)。
尽管增稠剂的量可随使用哪种增稠剂而变化,其用量可在0.01到5重量%之间。例如,丙烯酸酯共聚物可含所述组合物重量的0.1-3%,而异硬脂酸可含所述组合物重量的1-5%。
所述组合物的平衡物质(一般大约为20-70%,优选25-65重量%)是水。
任选组分
本发明组合物可含有0.1到10重量%的表面活性剂,其选自阴离子型、非离子型、两性和阳离子型的表面活性剂及其混合物。
适宜的阴离子型洗涤剂包括但不限于具有10到20个碳原子的烷基和亚烷基羧化物、烷基醚羧化物、脂肪醇硫酸盐、脂肪醇醚硫酸盐、烷基醇酰胺基硫酸盐和磺酸盐、脂肪酸烷基醇酰胺基-聚乙二醇醚硫酸盐、链烷磺酸盐和羟基链烷磺酸盐、烯属磺酸盐、羟乙基磺酸酰基酯、α-磺基脂肪酸酯、烷基苯磺酸盐、烷基酚二醇醚磺酸盐、磺基琥珀酸盐、磺基琥珀酸半酯和二酯、脂肪醇醚磷酸盐、蛋白质脂肪酸缩合产物、烷基单甘油酯硫酸盐和磺酸盐、烷基甘油酯醚磺酸盐、脂肪酸甲基氨基乙磺酸盐、脂肪酸肌氨酸盐、磺基蓖麻醇酸酯。这些化合物及其混合物以水溶性或水分散性的盐形式使用,如钠盐、钾盐、镁盐、铵盐、单、双及三乙醇铵盐和类似的烷基醇铵盐。
特别优选的阴离子型表面活性剂是聚氧化烯烷基醚硫酸盐,其用量可为例如0.01到0.5重量%。
适宜的非离子型表面活性剂包括例如脂肪醇乙氧基化物(烷基聚乙二醇)、烷基酚聚乙二醇、烷基化聚乙二醇、脂肪胺乙氧基化物(烷基氨基聚乙二醇)、脂肪酸乙氧基化物(酰基聚乙二醇)、聚丙二醇乙氧基化物(Pluronic(注册商标))、脂肪酸烷基酰胺(脂肪酸氨基聚乙二醇)、蔗糖酯、山梨醇酯和聚乙二醇醚。
适于加入洗发剂中的两性表面活性剂包括:N-烷基-β-氨基二丙酸盐,其具有12到18个烷基碳原子,如碱金属盐和单、二和三烷基醇铵盐;N-酰氨基-烷基-N,N-二甲基乙酰甜菜碱,优选具有8到18个酰基碳原子的N-酰基-酰氨基丙基-N,N-二甲基乙酰甜菜碱、具有12到18个烷基碳原子的烷基-二甲基磺丙基-甜菜碱;咪唑啉型两性表面活性剂(商标为:Miranol Steinapon),优选1-(β-羧基-甲基乙氧基)-1-(羧甲基)-2-月桂基-咪唑啉鎓钠盐;氧化胺,如具有12到18个烷基碳原子的烷基二甲胺氧化、脂肪酸酰氨烷基-二甲胺氧化物。
尤其优选的两性表面活性剂是椰油酰氨基(cocoamido)丙基甜菜碱。
所含适宜的阳离子型表面活性剂中,例如季铵盐,如二烷基-二甲基铵;在烷基部分中具有10到24个、优选12到18个碳原子的氯化物或者溴化物;具有10到24个烷基碳原子的烷基-二甲基-乙基氯化铵或溴化铵;具有10到24个烷基碳原子的烷基-三甲基-氯化铵或者溴化铵,优选鲸蜡基三甲基氯化铵或溴化铵;具有10到22个烷基碳原子的烷基-三甲基氯化铵或溴化铵;或者在烷基部分具有10到24、优选12到18个碳原子的烷基-二甲基-苄基氯化铵或者溴化铵。
其他任选的组分如下:
本发明的液体个人清洗组合物也可任选地包含水分散的凝胶状聚合物。此聚合物优选是阴离子型、非离子型、阳离子型或者疏水改性聚合物,选自1,000到3,000,000分子量的阳离子型瓜尔胶类的阳离子型多糖,从丙烯酸和/或甲基丙烯酸衍生的阴离子、阳离子和非离子型均聚物,阴离子、阳离子和非离子型纤维素树脂;二甲基二烷基氯化铵和丙烯酸的阳离子型共聚物;二甲基二烷基氯化铵的阳离子型均聚物;分子量10,000到4,000,000的阳离子型聚亚烷基和乙氧基聚亚烷基亚胺聚乙二醇;及它们的混合物。优选的聚合物选自聚丙烯酸钠、羟乙基纤维素、鲸蜡基羟乙基纤维素和聚季铵(Poly quarternium)10。
所述聚合物在本发明组合物中的优选含量为组合物的大约0.1份到大约1份,更优选为0.1份到0.5份。除了提供产品的稳定性,所述聚合物还改善皮肤上脂质的质感。改善的质感源于粘性和油腻性的减弱和柔滑性的提高。在特别优选的实施方案中,使用了聚合物的混合体,例如,那些优选用于产品稳定性的聚合物,和/或那些优选用于改善质感的聚合物。优选用于改善质感的聚合物选自聚乙二醇、羟丙基瓜尔胶、瓜尔胶羟丙基三铵氯化物(guar hydroxypropyl trimoniumchloride)、polyquaternary 3,5,6,7,10,11和24及它们的混合物。
各种附加成分可以并入本发明的组合物中。这些材料包括但是不限于液体表观助剂、盐类和它们的水合物及其他的如在Kacher等的美国专利5,340,492及Deckner等的美国专利4,919,934中列出的“填充剂材料”,两篇均在此引用作为参考。
这些附加成分的其他非限制性实例包括:维生素及其衍生物(如抗坏血酸、维生素E、乙酸生育酚酯等等);防晒剂;增稠剂(如多元醇烷氧基酯、以Crothix形式从Croda以最高含量为2%得到,和从黄原胶中以最高含量为2%得到);保持组合物抗微生物整体性的防腐剂;抗痤疮药剂(间苯二酚、水杨酸等等);抗氧化剂;皮肤缓解和康复剂,如库拉索芦荟提取物、尿囊素等等;螯合剂(如EDTA和羟基乙烷焦磷酸)和多价螯合剂;及适用于美观目的的试剂,如香味剂、香精油、皮肤感觉剂、色素、珠光剂(如云母和二氧化钛),赋予拖拽清洗感(draggyrinse feel)的添加剂(如煅制二氧化硅)、增强沉积的添加剂(如马来酸豆油,最高含量为3%)、色淀、着色剂等等(如丁香油、薄荷醇、樟脑、桉油和丁香酚)。
本发明组合物具有大约6到8.5的pH值,优选为6.5到8.5。
本发明的组合物具有的粘度为100-5000厘沲,该粘度在25℃下,通过使用Brookfield粘度计的2号和3号Spindle(测杆),以12转/分钟旋转30秒测得。
本发明组合物在室温下(如约25℃)储存四周后没有显示沉淀或相分离的迹象。
实施例
实施例1、2和3
下述各例制备如下:
实施例1 | 实施例2 | 实施例3 | |
月桂基醚磺基琥珀酸二钠(DSLES) | 4.25% | 5% | 7% |
月桂基磺基琥珀酸二钠(DSLS) | 4.25% | 5% | 7% |
月桂酸钾 | 3% | 3% | |
肉豆蔻酸钾 | 2% | 2% | |
月桂酸 | 4.25% | ||
异硬脂酸 | 4% | ||
氢氧化钾 | 0.6% | ||
柯卡酰氨基(cocamido)丙基甜菜碱(CAPB) | 2.6% | 3% | 0.6% |
月桂基醚硫酸钠(SLES) | 1.7% | 2% | 0.4% |
甘油 | 20% | 20% | 20% |
二丙二醇 | 3% | ||
两性聚合物 | 0.3% | 0.3% | |
阳离子型聚合物 | 0.6% | ||
烷基丙烯酸酯聚合物 | 0.5% | 0.5% | 0.5% |
乙二醇二硬脂酸酯(EGDS) | 2% | 2% | 2% |
二丁羟基甲苯(BHT) | 0.05% | 0.05% | 0.05% |
EDTA | 0.05% | 0.05% | 0.05% |
羟基乙烷焦磷酸 | 0.2% | 0.2% | |
防腐剂 | 0.3% | 0.3% | 0.3% |
香料 | 0.7% | 0.7% | 0.7% |
水 | 加至100% | 加至100% | 加至100% |
操作:实施例1
上述实施例1按如下方法操作:
1)将甘油、水、氢氧化钾和SLES的混合物加热至75-80℃,直至完全成为流体(混合物-1);
2)将月桂酸、防腐剂和BHT搅拌加入混合物-1中(混合物-2);
3)将DSLES、DSLS和CAPB搅拌加入混合物-2(混合物-3);
4)在75-80℃下混合EDTA和水的混合物(混合物-4);
5)将两性聚合物和水的混合物搅拌加入混合物-4中(混合物-5);
6)分别将EGDS和烷基丙烯酸酯聚合物搅拌加入到混合物-5中(混合物-6);
7)将混合物-6冷却至45℃;
8)将香料加入混合物-9中,冷却至35℃。
实施例5、6和比较实施例A
实施例5 | 比较例A | 实施例6 | 比较例A | |
月桂基醚磺基琥珀酸二钠(DSLES) | 7% | 7% | 4.25% | 4.25% |
月桂基磺基琥珀酸二钠(DSLS) | 7% | 7% | 4.25% | 4.25% |
月桂酸钾 | 3% | 3% | ||
肉豆蔻酸钾 | 2% | 2% | ||
月桂酸 | 4.25% | 4.25% | ||
异硬脂酸 | 4% | |||
氢氧化钾 | 0.6% | 0.6% | ||
柯卡酰氨基丙基甜菜碱(CAPB) | 0.6% | 0.6% | 2.6% | 2.6% |
月桂基醚硫酸钠(SLES) | 0.4% | 0.4% | 1.7% | 1.7% |
甘油 | 20% | 20% | 20% | 20% |
二丙二醇 | ||||
两性聚合物 | 0.3% | 0.3% | 0.3% | 0.3% |
阳离子型聚合物 | ||||
丙烯酸烷基酯聚合物 | 0.5% | 0.5% | 0.5% | |
乙二醇二硬脂酸酯(EGDS) | 2% | 2% | 2% | 2% |
二丁羟基甲苯(BHT) | 0.05% | 0.05% | 0.05% | 0.05% |
EDTA | 0.05% | 0.05% | 0.05% | 0.05% |
羟基乙烷焦磷酸 | 0.2% | 0.2% | ||
防腐剂 | 0.3% | 0.3% | 0.3% | 0.3% |
香料 | 0.7% | 0.7% | 0.7% | 0.7% |
水 | 加至100% | 加至100% | 加至100% | 加至100% |
室温稳定性:分离状况 | 良好 | 不好 | 良好 | 不好 |
从实施例5和比较例A中的数据中可以发现,4%的异硬脂酸可提供良好的稳定性(不产生相分离),而当缺乏异硬脂酸时(比较例A),将导致不稳定性。同样,使用烷基丙烯酸酯(实施例6)产生稳定性,而缺之(对比例B)则导致不稳定性。
Claims (5)
2.权利要求1的组合物,其中,该组合物还含有0.01-10%的表面活性剂,其选自阴离子型、非离子型及两性和阳离子型表面活性剂及其混合物。
3.权利要求2的组合物,其中的两性表面活性剂是甜菜碱。
4.权利要求1到3中任一项的组合物,其中,该组合物的pH值为大约6-8.5。
5.前述任一项权利要求的组合物,其中,该组合物粘度为100到5000厘沲。
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GBGB9928820.1A GB9928820D0 (en) | 1999-12-06 | 1999-12-06 | Stable high glycerol liquids comprising sulfosuccinic acid monoesters |
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FR2837697B1 (fr) * | 2002-03-28 | 2005-01-28 | Oreal | Composition cosmetique moussante ; utilisations pour le nettoyage ou le demaquillage |
US6812192B2 (en) | 2002-03-28 | 2004-11-02 | L'oreal S.A. | Foaming cosmetic compositions, uses for cleansing or make-up removal |
DE10252396A1 (de) * | 2002-11-12 | 2004-05-27 | Beiersdorf Ag | Temperaturstabile kosmetische Reinigungszubereitung mit Polyacrylaten |
DE10257984A1 (de) * | 2002-12-12 | 2004-06-24 | Beiersdorf Ag | Verwendung von Fettsäuresalzen zum Erzielen oder Erhöhen der Selektivität von Reinigungszubereitungen |
US20060217287A1 (en) * | 2005-03-22 | 2006-09-28 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Fabric softening composition |
US20070027050A1 (en) * | 2005-07-27 | 2007-02-01 | Conopco, Inc., D/B/A Unilever | Liquid cleansing composition |
DE102006054894A1 (de) * | 2006-11-20 | 2008-05-21 | Henkel Kgaa | Wasch- oder Reinigungsmittel mit stabiler Viskosität |
US7879780B2 (en) | 2008-09-23 | 2011-02-01 | Conopco, Inc. | Stable cleansing compositions containing fatty acyl isethionate surfactant products having more than 10 wt. % of fatty acid/fatty soap content using high level of polyol and methods thereof |
KR101969286B1 (ko) * | 2008-10-24 | 2019-04-16 | 코그니스 아이피 매니지먼트 게엠베하 | 알킬 술포숙시네이트 혼합물, 및 이의 용도 |
US8124574B2 (en) | 2009-10-12 | 2012-02-28 | Conopco, Inc. | Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content |
US8105994B2 (en) | 2010-03-31 | 2012-01-31 | Conopco, Inc. | Personal wash cleanser comprising defined alkanoyl compounds, defined fatty acyl isethionate surfactant product and skin or hair benefit agent delivered in flocs upon dilution |
US8268767B2 (en) | 2010-03-31 | 2012-09-18 | Conopco, Inc. | Personal wash cleanser comprising defined alkanoyl compounds, defined fatty acyl isethionate surfactant product and skin or hair benefit agent |
US8263538B2 (en) | 2010-03-31 | 2012-09-11 | Conopco, Inc. | Personal wash cleanser with mild surfactant systems comprising defined alkanoyl compounds and defined fatty acyl isethionate surfactant product |
CA2805704A1 (en) | 2010-08-18 | 2012-02-23 | Unilever Plc | Anti-dandruff shampoo |
CN103492542B (zh) * | 2011-04-13 | 2016-05-25 | Elc管理公司 | 适用于个人护理组合物的温和型阴离子表面活性剂 |
JP5875827B2 (ja) * | 2011-10-12 | 2016-03-02 | 花王株式会社 | 手洗い用食器洗浄剤組成物 |
WO2015038601A1 (en) * | 2013-09-11 | 2015-03-19 | Lubrizol Advanced Materials, Inc. | Soap compositions and treatment methods for the mitigation of winter season pruritus |
CN109789069A (zh) | 2016-09-22 | 2019-05-21 | 荷兰联合利华有限公司 | 包含特定表面活性剂和高含量甘油的组合物 |
BR112019014914B1 (pt) | 2017-02-08 | 2022-10-04 | Unilever Ip Holdings B.V. | Composição e processos para produzir uma composição |
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US4284534A (en) * | 1979-04-03 | 1981-08-18 | Jack S. Wachtel | Aqueous bubble blowing composition |
DE3902374A1 (de) * | 1989-01-27 | 1990-08-02 | Solvay Werke Gmbh | Wasch- reinigungs- und/oder koerperreinigungsmittel |
US5132037A (en) * | 1989-05-05 | 1992-07-21 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous based personal washing cleanser |
JPH06102684A (ja) * | 1992-09-24 | 1994-04-15 | Kao Corp | 電子写真感光体 |
GB9307449D0 (en) * | 1993-04-08 | 1993-06-02 | Unilever Plc | Surfactant composition |
JPH07291839A (ja) * | 1993-12-29 | 1995-11-07 | Sunstar Inc | 洗浄剤組成物 |
JP3207034B2 (ja) * | 1993-12-29 | 2001-09-10 | サンスター株式会社 | 洗浄剤組成物 |
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US20010001783A1 (en) * | 1998-10-13 | 2001-05-24 | Glenn Nystrand | Retinol stabilized cleansing compositions |
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