CN1140257C - 润肤剂含量高的稳定液体组合物 - Google Patents

润肤剂含量高的稳定液体组合物 Download PDF

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CN1140257C
CN1140257C CNB988093499A CN98809349A CN1140257C CN 1140257 C CN1140257 C CN 1140257C CN B988093499 A CNB988093499 A CN B988093499A CN 98809349 A CN98809349 A CN 98809349A CN 1140257 C CN1140257 C CN 1140257C
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S·普瓦达
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Abstract

本发明提供油/润肤剂含量等于或大于表面活性剂含量的高发泡含水液体组合物。意想不到的是如此高含量润肤剂条件下仍可保持适量泡沫。除了表面活性剂和润肤剂外，组合物还优选含有C12～C24脂肪酸和/或阳离子聚合物。

Description

润肤剂含量高的稳定液体组合物
本发明是关于一般用于皮肤清洗剂或淋浴胶凝剂中的液体清洁组合物。具体地说，本发明是关于润肤剂含量高，具体是润肤剂含量等于或大于总表面活性剂含量的液体组合物。
液体清洁剂和淋浴凝胶在本技术领域是众所周知的。含有润湿剂的所述含水液体清洁剂的使用也是已知的(例如，参见Dias等的美国专利5,308,526号或Greene等的美国专利5,234,619号)。
在Greene等的美国专利5,234,619中说明可以含有高达约20％的润湿剂，介绍的润湿剂包括凡士林、矿物油、聚硅氧烷、和各种动物或植物油(参见权利要求3，第8-28行)。
但是，在这些参考文献中，油/润肤剂的用量总是低于表面活性剂用量。
JP 07/025726涉及含15-30％重量阴离子表面活性剂和两性表面活性剂及30-60％重量油和水的皮肤清洁剂。
WO 93/19149涉及含5-约50％重量混合表面活性剂体系，和3-40％重量不溶性非离子油或蜡的含水产生泡沫的清洁产品，其中表面活性剂总重与非离子油或蜡之比为约10∶1至1∶3。该组合物是水包油乳液型，其粘度为10,000-40,000cps。
EP 0,111,895涉及用于湿性皮肤的含水皮肤护理乳液，其中含液态油成分、碱性皂类、烷基硫酸盐和/或其量占乳液重量0.5-1.5％的烷基聚乙二醇醚硫酸盐。
申请人意想不到的发现，油/润肤剂含量等于或大于表面活性剂量的组合物能提供温和的清洁剂，且有适当的泡沫和消费者需要的其他优点。
具体地说，本发明是关于含水的液体组合物，含有：
(1)3-30％，优选10-25％(重量)表面活性剂，特别是含有阴离子和两性或两性离子表面活性剂混合物的表面活性剂体系；和
(2)10-35％，优选10-30％油或润肤剂，其中油/润肤剂含量等于或大于表面活性剂总含量。所述组合物优选粘度50,000-300,000cps，该粘度用带有helipath附件和T-形锭子A的Brookfield粘度计在0.5 RPM室温下测定的。
在优选实施方案中，所述组合物还含有0-10％，优选0.1-8％，更优选0.1-4％(重量)C12-C24脂肪酸和/或0.01-5％，优选0.01-3％阳离子聚合物调理剂。
本发明是关于含有表面活性剂体系和油/润肤剂的含水清洁剂或淋浴凝胶组合物，其中油/润肤剂含量等于或大于表面活性剂含量。用本发明的组合物可以得到高泡沫超温和的浴液，该液稳定性好，不会分离成富含油的相和富含表面活性剂的相。即使油含量高的情况下也产生大量泡沫，而同时油能防止对皮肤刺激性和皮肤干燥。下面更详细地说明该组合物。
本发明的表面活性剂体系含有3％-30％，优选约10-25％表面活性剂，而至少一种表面活性剂是阴离子表面活性剂。
所述阴离子表面活性剂可以是，例如，脂族磺酸盐，例如伯烷基(例如C8-C22)磺酸盐、伯烷基(例如C8-C22)二磺酸盐、C8-C22烯基磺酸盐、C8-C22羟基烷基磺酸盐或烷基甘油醚磺酸盐(AGS)；或芳族磺酸盐，例如烷基苯磺酸盐。
所述阴离子表面活性剂也可以是烷基硫酸盐(例如C12-C18烷基硫酸盐)或烷基醚硫酸盐(包括烷基甘油醚硫酸盐)。在烷基醚硫酸盐中有下式的烷基醚硫酸盐：
                 RO(CH2CH2O)nSO3M式中R是含有8-18个碳原子，优选12-18个碳原子的烷基或烯基，n为大于1.0，优选2-3的平均值；M是增溶阳离子，例如钠、钾、铵或取代铵。优选月桂基醚硫酸铵和月桂基醚硫酸钠。
所述阴离子表面活性剂也可以是烷基磺基琥珀酸盐(包括一烷基和二烷基，例如C6-C22烷基磺基琥珀酸盐)；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、C8-C22单烷基琥珀酸盐和马来酸盐、磺基乙酸盐，和酰基羟乙基磺酸盐。
磺基琥珀酸盐可以是或包括：
—下式的一烷基磺基琥珀酸盐：
               R4O2CCH2CH(SO3M)CO2M；
—下式的酰氨基-MEA磺基琥珀酸盐：
            R4CONHCH2CH2O2CCH2CH(SO3M)CO2M式中R4是C8-C22烷基，M是增溶阳离子；和
—下式的酰氨基-MIPA磺基琥珀酸盐
           RCONH(CH2)CH(CH3)(SO3M)CO2M式中M如同上述定义。
合适的磺基琥珀酸盐还包括烷氧基化柠檬酸磺基琥珀酸盐和烷氧基化磺化琥珀盐，例如下式的化合物：
Figure C9880934900061
式中n＝1-20；而M如同上述定义。
肌氨酸盐一般由式RCON(CH3)CH2CO2M表示，式中R是C8-C20烷基和M是增溶阳离子。
牛磺酸盐一般由下式表示：
                 R2CONR3CH2CH2SO3M式中R2是C8-C20烷基，R3是C1-C4烷基，和M是增溶阳离子。
另一种合适的阴离子表面活性剂是如下所示的羧酸盐：
                 R-(CH2CH2O)nCO2M式中R是C8-C20烷基；n是0-20；和M如同上述定义。
可以使用的另一种羧酸盐是酰氨基烷基多肽羧酸盐，例如由Seppic生产的Monteine  LCQ(R)。
可以使用的另一种表面活性剂是C8-C18酰基羟乙基磺酸酯盐。这些酯盐由羟乙基磺酸碱金属盐与含有6-18个碳原子和碘值小于20的混合脂肪酸之间反应制备的。至少75％混合脂肪酸含有12-18个碳原子和最多25％混合脂肪酸含有6-10个碳原子。
在使用时，酰基羟乙基磺酸盐可以是烷氧基化的羟乙基磺酸盐，例如Ilardi等的美国专利5,393,466号描述的烷氧基化的羟乙基磺酸盐。该化合物具有下面通式：式中R是含有8-18个碳原子的烷基，m是1-4的整数，X和Y是氢或含有1-4个碳原子的烷基，和M+是一价阳离子，例如钠、钾或铵。
一般，阴离子组分占所述组合物的约1-20％(重量)，优选2-15％(重量)，最优选5-12％(重量)。
本发明的优选方案中，有至少一种阴离子表面活性剂与两性离子或两性表面活性剂共同使用。
两性离子表面活性剂从广义上说来为脂族季铵、磷鎓和硫鎓化合物的衍生物，其中脂族基可以是直链或支链的，一个脂族取代基含有约8-约18个碳原子，且一个含有阴离子基，例如羧基、磺酸根、硫酸根、磷酸根，或膦酸根。这些化合物的通式是：
Figure C9880934900072
式中R2是含有0-约10个亚乙基氧部分和0-约1个甘油部分的约8-约18个碳原子的烷基、烯基或羟烷基；Y选自氮、磷或硫原子；R3是含有约1-约3个碳原子的烷基或一羟基烷基；X和Y是硫原子时是1，而Y是氮或磷原子时是2；R4是约1-约4个碳原子的亚烷基或羟亚烷基，和Z是选自羧酸根、羧酸根、硫酸根、膦酸根或磷酸根的基团。
上述合适的表面活性剂的例子包括：
4-〔N，N-二(2-羟乙基)-N-十八烷基铵基〕-丁烷-1-羧酸盐；
5-〔S-3-羟丙基-S-十六烷基硫鎓基〕-3-羟基戊烷-1-硫酸盐；
3-〔P，P-二乙基-P-3，6，9-三氧杂十四烷氧基磷鎓基〕-2-羟基丙烷-1-磷酸盐；
3-〔N，N-二丙基-N-3-十二烷氧基-2-羟丙基铵基〕-丙烷-1-膦酸盐；
3-(N，N-二甲基-N-十六烷基铵基)丙烷-1-磺酸盐；
3-(N，N-二甲基-N-十六烷基铵基)-2-羟基丙烷-1-磺酸盐；
4-〔N，N-二(2-羟乙基)-N-〔2-羟十二烷基)铵基〕-丁烷-1-羧酸盐；
3-〔S-乙基-S-(3-十二烷氧基-2-羟丙基)硫鎓基〕-丙烷-1-磷酸盐；
3-〔P，P′-二甲基-P-十二烷基磷鎓基〕-丙烷-1-膦酸盐；和
5-〔N，N-二(3-羟丙基)-N-十六烷基铵基〕-2-羟基戊烷-1-硫酸盐。
在本发明中可以使用的两性洗涤剂包括至少一个酸基。该酸基可以是羧酸基或磺酸基。两性洗涤剂包含季铵氮，因此是季铵酰氨基酸。季铵酰氨基酸一般包括7-18个碳原子的烷基或烯基。季酰氨基酸一般具有下列一般结构式：式中R1是7-18个碳原子的烷基或烯基；
R2和R3分别各自是1-3个碳原子的烷基、羟烷基或羧烷基；
n是2-4；
m是0-1；
X是任选被羟基取代的1-3个碳原子的亚烷基；和
Y是-CO2-或-SO3-。
上面通式中合适的两性洗涤剂包括下式的简单甜菜碱：和下式的酰氨基甜菜碱
Figure C9880934900092
式中m是2或3。
在上面两个结构式中R1、R2和R3同上述定义。R1具体可以是由椰子产生的混合的C12和C14烷基，以便至少一半，优选四分之三R1含有10-14个碳原子。R2和R3优选甲基。
其他两性洗涤剂可以是下式的磺基甜菜碱或式中m是2或3。或这些甜菜碱的衍生物，其中(CH2)3SO- 3被下式代替在这些式中R1、R2和R3同上述定义。
两性乙酸盐类(Amphoacetates)和双两性乙酸盐类(diamphoacetates)也包括在可以使用的两性离子和/或两性化合物中。
两性表面活性剂一般占所述组合物约0.1-20％，优选5-15％。
如上所述，表面活性剂总量不应超过组合物的约30％。
特别优选的体系含有约5-15％阴离子表面活性剂，特别是5-15％碱金属C8-C16醚硫酸盐(例如月桂基醚硫酸钠)，和约5-15％两性表面活性剂，其选自两性乙酸盐类(例如月桂基两性乙酸钠)或酰氨基烷基甜菜碱(例如椰子酰氨基丙基甜菜碱)，或其混合物。
所述表面活性剂体系也可以任选含有非离子表面活性剂。
可以使用的非离子表面活性剂，具体包括含有疏水基团和活泼氢原子的化合物，例如脂族醇、酸、酰胺或烷基酚的化合物，与氧化烯特别是环氧乙烷(单独的或与环氧丙烷一起)的反应产物。具体的非离子洗涤剂化合物是烷基(C6-C22)酚-环氧乙烷缩合物、脂族(C8-C18)伯或仲直链或支链醇与环氧乙烷的缩合产物，和环氧乙烷与环氧丙烷和乙二胺的反应产物缩合制备的产物。其他所谓非离子洗涤剂化合物包括长链氧化叔胺，长链氧化叔膦和二烷基亚砜。
非离子表面活性剂也可以是糖的酰胺，例如多糖酰胺。具体地说，所述表面活性剂可以是Au等的美国专利5,389,279中描述的一种乳糖酰胺，或可以是Kelkenberg的美国专利5,009,814中描述的一种糖酰胺。
可以使用的其他表面活性剂在Parran Jr的美国专利3,723,325中描述过，而Llenado等的美国专利4,565,647中公开过烷基多糖非离子表面活性剂。
优选的烷基多糖是下式的烷基多糖：
              R2O(CnH2nO)t(糖基)x式中R2选自烷基、烷基苯基、羟烷基、羟烷基苯基，或其混合基，其中烷基含有约10-约18个碳原子，优选约12-约14个碳原子；n是0-3，优选2；t是0-约10，优选0；x是1.3-约10，优选1.3-约2.7。糖基优选从葡萄糖衍生。为了制备这些化合物，首先制备醇或烷基聚乙氧基醇，然后与葡萄糖或葡萄糖源反应，生成葡糖苷(在1-位上连接)。其他糖基单元可以在其1-位和上述糖基单元的2-，3-，4-和/或6-位，优选主要2-位之间连接。
非离子表面活性剂一般可占所述组合物的0-10％(重量)。
本发明还包括要求等于或大于总表面活性剂量的油/润肤剂。所述油/润肤剂选自植物油、酯类、动物脂、矿物油、凡士林、硅油和其混合物，具体为：
植物油：花生油、蓖麻油、可可脂、椰子油、玉米油、棉子油、橄榄油、棕榈仁油、菜子油、红花子油、芝麻油、大豆油，和向日葵油。
酯：肉豆蔻酸丁基、棕榈酸鲸蜡基酯、油酸癸酯、月桂酸甘油酯、蓖麻油酸甘油酯、硬脂酸甘油酯、异硬脂酸甘油酯、月桂酸己酯、棕榈酸异丁酯、硬脂酸异鲸蜡基酯、异硬脂酸异丙酯、月桂酸异丙酯、亚油酸异丙酯、肉豆蔻酸异丙酯、棕榈酸异丙酯、硬脂酸异丙酯、丙二醇单月桂酸酯、丙二醇蓖麻油酸酯、丙二醇硬脂酸酯、和丙二醇异硬脂酸酯。
动物脂：羊毛脂醇、酰化的羊毛脂醇、羊毛脂、猪脂、貂油和牛脂。
脂肪酸和醇：山萮酸、棕榈酸、硬脂酸、山萮醇、鲸蜡醇、二十醇和异鲸蜡醇。
油/润肤剂的其他例子包括矿物油、凡士林、硅油，例如二甲基聚硅氧烷、乳酸月桂基酯和乳酸肉豆蔻基酯。
特别优选的润肤剂包括植物油，特别是向日葵子油。在本发明的优选实施方案中，向日葵子油至少占所述组合物的约20％(重量)。
润肤剂一般占组合物的10％-35％，优选10％-30％。
在本发明的优选实施方案中，所述组合物含有促进形成层状相的脂肪酸“结构剂”(层状相组合物特别优选)。所述结构剂能促进润肤剂悬浮，同时保持良好的剪切稀化性质。
所述脂肪酸一般是C12-C24脂肪酸。特别优选的脂肪酸是月桂酸。其他优选的脂肪酸包括(但是不限于)棕榈仁酸、棕榈脂肪酸和异硬脂酸。所述酸一般占所述组合物的0％-10％，优选0.1％-8％，更优选0.1％-4％。
在另一个优选实施方案中，所述组合物含有阳离子调理剂。所述聚合物的例子包括由Calgon得到的Quatrisoft LM-200、Polyquaternium-24，Polyquaternium 39，和由Rhone Poulenc得到的Jaguar(R)型阳离子聚合物。一般，阳离子调理剂占所述组合物0.01％-3％。
最后，水为组合物的平衡量。水一般占所述组合物约30％以上，优选约40％以上(重量)。
此外，本发明的组合物可以含有如下任选组分：
有机溶剂，例如乙醇；增稠助剂，例如羧甲基纤维素、硅酸铝镁、羟乙基纤维素、甲基纤维素、聚羧乙烯、葡糖酰胺，或由Rhone Poulenc得到的Antil(R)；香料；含量占0.01-1％，优选0.01-0.05％的螯合剂，例如乙二胺四乙酸四钠(EPTA)、EHDP或混合物；以及着色剂，遮光剂和珠光剂，例如硬脂酸锌，硬脂酸镁、TiO2、EGMS(乙二醇一硬脂酸酯)或Lytron 621(苯乙烯/丙烯酸酯共聚物)。所有上述任选组分用于提高产品的外观或美容性质。
所述组合物还可以含有抗微生物剂，例如2-羟基-4，2′，4′-三氯二苯醚(DP 300)；防腐剂，例如二羟甲基二甲基乙内酰脲(GlydantXL 1000)、对羟基苯甲酸酯类、山梨酸等等。
所述组合物也可以含有增泡剂椰子酰基一乙醇酰胺或椰子酰基二乙醇酰胺，也可以使用强离子化盐，例如氯化钠和硫酸钠。
在合适情况下使用抗氧化剂也很有益，例如丁基化的羟基甲苯(BHT)，其含量约0.01％或更高。
可以使用的增稠剂包括Amerchol Polymer HM 1500(Nonoxynyl羟乙基纤维素)；Glucam DOE 120(PEG 120甲基葡萄糖二油酸酯)；从Rewo化学公司得到的Rewoderm(R)(PEG改性的甘油椰子酸酯、棕榈酸酯或牛油酸酯)；Antil(R)141(从Goldschmidt得到的)。
可以使用的另一个任选组分是抗絮凝聚合物，例如Montague的美国专利5,147,576号中介绍的。
可以包含的另一个组分是表皮脱落剂，例如聚氧乙烯珠粒、核桃片和杏仁。
一般，本发明的组合物的粘度约50,000-300,000厘泊(cps)，用带有helipath附件和T-形锭子A的Brookfield粘度计在0.5 RPM室温下测定。
除非另有说明，本说明书和实施例中的所有百分数均以重量表示。
                    实施例
本发明组合物的下列实施例成分列于下表中。
组分     I     II     III     IV     V
表面活性剂     15     17.5     17.5     17.5     17.5
椰子酰氨基丙基甜菜碱     0     10.5     10.5     0     0
月桂基两性乙酸钠     10     0     0     10.5     8.75
月桂基硫酸钠     5     7     7     7     8.75
润肤剂     15     35     35     25     26
二甲基硅油     0     0     0     0     2
向日葵子油     15     30     30     20     21
甘油     0     5     5     5     3
凡士林     0     0     0     0     0
羊毛脂醇     0     0     0     0     0
脂肪酸
月桂酸     2.5     0     0     2.6     2.6
异硬脂酸     0     5     5     0     0
其它组分
柠檬酸     0.8     0     0     1     1
硫酸镁     1.5     0     0     1     0.4
瓜尔胶羟丙基氯化三铵     0     0.5     1.5     1     0.5
季化羟乙基纤维素37/丙二醇二辛酸二癸酸酯/Tridecth 6     0     0.1     0.2     0     0
PEG 20山梨醇一月桂酸酯     0     0     2     0     0
PEG 80山梨醇一月桂酯酯     0     0     0     4     0
香料     1.0     1.0     1     1     1
杂物     0-1     0-1.0     0-1   0-1.0     0-1.0
水     to100.0     to100.0     to100.0     to100.0     to100.0
组合物I-V按下述方法制备。在65.6-82.2℃(150-180°F)下将表面活性剂与去离子水混合，接着加入柠檬酸和/或硫酸镁、润肤剂油、脂肪酸、防腐剂和抗氧化剂。在实施例I，IV-V中，将脂肪酸溶于向日葵子油中然后加入所述油预混合物。当该批物料被冷却后，在约37.8-48.8℃(100-120°F)下加入香料。
正如各个实施例中可看到的，所述油或润肤剂等于或大于表面活性剂含量。

Claims (8)

1.含水液体组合物，含有：
(a)3-30重量％的表面活性剂体系，其中含有选自阴离子、两性、阳离子和非离子表面活性剂和其混合物的表面活性剂，其中必须有至少一种阴离子表面活性剂存在；和
(b)10-35重量％的油/润肤剂，所述油/润肤剂选自植物油、酯类、动物脂、矿物油、凡士林、硅油和其混合物，其中油/润肤剂含量等于或大于表面活性剂含量；
(c)0.1-8重量％的C12-C24脂肪酸；
(d)0.01-3重量％的阳离子聚合物；和
(e)超过30重量％的水；其中所述组合物处于层状相，且所述组合物室温下粘度为50,000-300,000cps。
2.根据权利要求1的组合物，其中表面活性剂体系含有阴离子和两性表面活性剂的混合物。
3.根据权利要求1或2的组合物，其中阴离子表面活性剂是碱金属C8-C16醚硫酸盐。
4.根据上述权利要求任一项的组合物，其中两性表面活性剂选自两性乙酸盐类和酰氨基烷基甜菜碱。
5.根据上述权利要求任一项的组合物，其中阴离子表面活性剂是碱金属C8-C16醚硫酸盐，而两性表面活性剂选自两性乙酸盐类和酰氨基烷基甜菜碱。
6.根据上述权利要求任一项的组合物，其中植物油是向日葵子油。
7.根据上述权利要求任一项的组合物，其中脂肪酸是月桂酸、棕榈仁酸、棕榈脂肪酸或异硬脂酸。
8.根据上述权利要求任一项的组合物，含有10-25％表面活性剂。
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CN1271269A (zh) 2000-10-25
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BR9810801A (pt) 2000-09-12
CA2297921C (en) 2008-05-20
CZ290163B6 (cs) 2002-06-12
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WO1999004751A3 (en) 1999-04-08
HUP0003344A3 (en) 2003-02-28
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US5965500A (en) 1999-10-12
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