CN1341012A - 清洁组合物 - Google Patents
清洁组合物 Download PDFInfo
- Publication number
- CN1341012A CN1341012A CN00804246A CN00804246A CN1341012A CN 1341012 A CN1341012 A CN 1341012A CN 00804246 A CN00804246 A CN 00804246A CN 00804246 A CN00804246 A CN 00804246A CN 1341012 A CN1341012 A CN 1341012A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- water
- personal cleansing
- cleansing composition
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 156
- 238000004140 cleaning Methods 0.000 title description 27
- -1 antifungals Substances 0.000 claims abstract description 85
- 239000003921 oil Substances 0.000 claims abstract description 66
- 239000004094 surface-active agent Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229920013639 polyalphaolefin Polymers 0.000 claims abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 11
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- 229940088594 vitamin Drugs 0.000 claims abstract description 8
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- 239000004599 antimicrobial Substances 0.000 claims abstract description 6
- 229940121375 antifungal agent Drugs 0.000 claims abstract description 5
- 239000003205 fragrance Substances 0.000 claims abstract description 4
- 239000000077 insect repellent Substances 0.000 claims abstract 2
- 239000000194 fatty acid Substances 0.000 claims description 42
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 41
- 229930195729 fatty acid Natural products 0.000 claims description 41
- 150000004665 fatty acids Chemical class 0.000 claims description 28
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 18
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- 239000003795 chemical substances by application Substances 0.000 claims description 14
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- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 8
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 7
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- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
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- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
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- LVGSUQNJVOIUIW-UHFFFAOYSA-N 5-(dimethylamino)-2-methylpent-2-enamide Chemical compound CN(C)CCC=C(C)C(N)=O LVGSUQNJVOIUIW-UHFFFAOYSA-N 0.000 claims 1
- 229940009098 aspartate Drugs 0.000 claims 1
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- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 claims 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 claims 1
- 229940104261 taurate Drugs 0.000 claims 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 6
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- 230000000694 effects Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 14
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Abstract
一种可洗掉的液体个人清洁组合物,含有:(a)水;(b)约1%-约60%(重量)的水溶性表面活性剂;(c)水不溶性的油,选自式(A)的高度支化的聚α-烯烃,其中R1是H或C1-C20烷基,R4是C1-C20烷基,R2是H或C1-C20,R3是C3-C20,优选C5-C20,n是0-3的整数且m是1-1000的整数,具有约1000-25000的数均分子量;和(d)疏水性护肤活性成分,选自抗微生物剂、防晒剂、维生素、芳香油、驱虫剂、抗真菌剂和它们的混合物,其中疏水性护肤活性成分的ClogP值大于3。本发明的个人清洁组合物改善了疏水性护肤活性物质的沉积,具有良好的清洗感和皮肤温和性。
Description
技术领域
本发明涉及清洁组合物。本发明尤其涉及温和的个人清洁组合物,该组合物显示出护肤活性物质例如抗微生物剂、防晒剂和维生素的改善的沉积作用。此外,本发明的组合物还显示出改善的清洗感和良好的皮肤接触感以及发泡性,它们适于同时清洁和调理皮肤和/或毛发,例如可以泡沫洗浴制品、淋浴产品、皮肤清洁剂、手、面部和身体清洁剂、香波等形式使用。
发明背景
温和的化妆品组合物必须满足包括清洁力、发泡性和温和性/低刺激性/良好的皮肤、毛发和眼部粘膜感觉在内的多种标准。皮肤由覆盖和保护下层组织的数层细胞构成。角蛋白和胶原纤维蛋白形成其结构骨架。这些层的最外层被称为角质层。同样,毛发也具有围绕毛发纤维的保护性外衣,被称为护膜(角质层)。阴离子表面活性剂可以穿透角质层膜和护膜,并通过脱脂作用破坏膜的完整性,使其失去屏障作用和保水功能。
对于皮肤和毛发保护膜的这种干扰作用可导致粗糙的肤感和眼部刺激,最终促使表面活性剂引发免疫反应产生刺激作用。
理想的化妆品清洁剂应温和地清洁皮肤或毛发,而不应使毛发和皮肤脱脂和/或发干,同时不刺激眼部粘膜或者在日常使用后不会使皮肤紧绷。大多数发泡皂、淋浴及洗浴产品、香波和块状清洁产品不能满足这些要求。
已知某些合成表面活性剂是温和的。但在配制香波和个人清洁剂时,某些温和的合成表面活性剂体系的一个主要缺点是具有为某些顾客所不喜爱的可描述为“滑溜”或“无涩感”的清洗感。另一方面,某些表面活性剂例如月桂酸钾的使用可产生“涩感”的清洗感,但损害临床皮肤温和性。这两种情况说明在选择适当表面活性剂时必须在清洗感和温和性之间进行平衡。
因此,仍然需要具有“涩感”清洗感的个人清洁组合物,该组合物除具有良好的产品特性,例如发泡、清洁、稳定、增稠、流变性和皮肤使用感外,还具有良好的皮肤温和性。
也希望使护肤活性成分从个人清洁组合物提供给皮肤。这类护肤活性成分包括,例如防晒剂、抗微生物剂和维生素。过去曾尝试从个人清洁组合物提供护肤活性物质。然而,基于这些活性物质足量沉积在皮肤上才能产生作用的观点,这些尝试并不总是能获得成功。
WO 97/16168公开了一种个人清洁组合物,含有(a)表面活性剂,(b)疏水性活性成分,选自:皮肤调理剂、皮肤保护和抗菌剂,(c)含烃的成分和(d)阳离子聚合物,选择(c)和(d)的量以使组分(b)对皮肤的作用高于(c)和(d)单独的加合作用。
现在出人意料地发现,通过某些水不溶性油,例如某些聚α-烯烃油和某些疏水性护肤活性成分与温和的、水溶性表面活性剂体系结合,可提供在具有发涩清洗感和良好温和特性的同时还具有疏水性护肤活性物质的改善的沉积作用的个人清洁组合物。
发明概述
本发明提供一种可洗掉的液体个人清洁组合物,含有:(a)水;(b)约1%-约60%(重量)的水溶性表面活性剂;(c)水不溶性的油,选自下式的高度支化的聚α-烯烃其中R1是H或C1-C20烷基,R4是C1-C20烷基,R2是H或C1-C20,R3是C3-C20,优选C5-C20,n是0-3的整数且m是1-1000的整数,数均分子量约1000-约25000;和(d)疏水性护肤活性成分,选自抗微生物剂、防晒剂、维生素、芳香油、驱虫剂、抗真菌剂和它们的混合物,其中疏水性护肤活性成分的ClogP值大于3。
本发明的组合物在对皮肤异常温和的同时,改善了护肤活性成分的沉积作用,具有“发涩”的清洗感。
除非另有说明,本发明的所有浓度和比率均以清洁组合物的重量计。除非另有说明,表面活性剂的链长也基于重均链长。
发明详述
本文的液体清洁组合物含有水、表面活性剂、疏水性护肤活性成分和某些水不溶性油,下面将对它们进一步描述。
本文采用的术语“清洗感”是指用清洁组合物清洗后,从皮肤上洗去泡沫过程中皮肤的感觉。本发明的组合物产生的清洗感的类型可用下列术语进行描述:例如“涩感”清洗感、“皂样”清洗感和“不滑溜”或“不粘”(non-slimy)清洗感。这种“涩感”、“皂样”、“不滑溜”或“不粘”清洗感可通过清洗皮肤上的泡沫过程中手与皮肤之间的摩擦增加来察觉。
本文采用的术语“水不溶性”(油)是指室温下,在不加入例如本文所述的其它辅剂和/或成分的情况下,基本上不溶于蒸馏水的物质。
本文采用的术语“疏水性”(护肤活性成分)是指与其水溶性相比,更易脂溶的,即非水溶性的物质。优选在水中溶解度很低而且基本上是非离子性的(与离子性相对的)物质。水不溶性油
用于本发明的水不溶性油选自(a)下式的高度支化的聚α-烯烃其中R1是H或C1-C20烷基,R4是C1-C20烷基,R2是H或C1-C20,R3是C3-C20,优选C5-C20,n是0-3的整数且m是1-1000的整数,具有约1000-25000,优选约2500-6000,更优选约2500-4000的数均分子量。在40℃下,采用ASTM D-445粘度测定方法,用于本发明的聚α-烯烃(a)优选具有约300cst至约50,000cst,优选约1000cst至约12,000cst,更优选约1000cst至约4000cst的粘度。(a)类型的油也可以具有不饱和度,但优选是饱和的。
上述的适宜的聚α-烯烃(a)可由具有约4-20个碳原子,优选约6-12个碳原子,尤其是约8-12个碳原子的1-链烯单体得到。用于本发明的聚α-烯烃优选是氢化的聚α-烯烃聚合物。
用于制备本发明的聚α-烯烃聚合物的1-链烯单体的非限制性实例包括1-己烯,1-辛烯,1-癸烯,1-十二碳烯,1-十四碳烯,它们的支链异构体,例如4-甲基-1-戊烯,及其混合物。适于制备聚烯烃液体的还有1-己烯至1-十六碳烯及其混合物,更优选1-辛烯至1-十二碳烯或其混合物。
这类油的实例包括聚癸烯油,例如由Mobil Chemical Company(P.O.Box 3140,Edison,New Jersey 08818,USA)以Puresyn 40和Puresyn 100商品名市售的那些产品。
基于组合物的清洗感改善的观点,特别优选的是高度支化的(a)类型聚α-烯烃物质,其数均分子量为约2500-4000并且粘度为约100cst至约2000cst(ASTM D-445于45℃测定),例如由Mobil以商品名Puresyn 100市售的产品。
上述油的混合物也适用于本发明。
在优选实施方案中,用于本发明的水不溶性油的数均粒径在约1微米-500微米,优选约5-200微米,更优选约5-50微米,尤其优选约5-20微米。
本发明的组合物优选含有约0.1%-20%,更优选约0.5%-10%,尤其优选约1%-5%(重量)的水不溶性油。疏水性护肤活性成分
本发明的组合物含有占组合物重量优选约0.01%-10%,更优选约0.01%-5%,尤其优选约0.1%-3%的疏水性护肤活性成分。
适用于本发明的疏水性护肤活性物质包括抗微生物剂、防晒剂、维生素、芳香油、驱虫剂、抗真菌剂和它们的混合物。
根据其辛醇/水分配系数(P或Kow)可以选择适用于本发明的疏水性护肤活性物质。Kow提供了化学物质亲油性的估算值。Kow是在辛醇-水的平衡两相系统中,物质在正辛醇相中的浓度与其在水相中的浓度的比值。本发明的疏水性护肤活性物质的分配系数方便地以其对数底为10的对数,即logP形式给出。
“1ogP”可通过实验测定(MlogP)或者可计算得到(ClogP)。例如,ClogP值可采用Biobyte(Claremont,CA,USA)的“ClogP forWindows”软件或者采用Advanced Chemistry Development Inc.(Toronto,Ontario,加拿大)的ACD/LogP Calculator程序计算。Biobyte程序还包括某些可以得到的测定的logP值。本领域普通技术人员都清楚,对于某些化学物质难以获得计算的logP值,在这种情况下,可用测量logP值。相反,对于某些化学物质,难以获得测量logP值,在这种情况下,可用计算logP值。测量logP值与计算logP值通常认为具有可比性。
适用于本发明的疏水性护肤活性物质选自ClogP值大于3,优选大于5的疏水性护肤活性物质。疏水性护肤活性物质的ClogP值优选不大于20。
可用于本发明的适宜抗菌剂的实例包括但不限于二苯脲(dicarbanilide)(例如三氯二苯脲,也称为三氯碳酰替苯胺)、三氯森、六氯酚和3,4,5-三溴水杨酰苯胺。本发明优选的抗菌剂是三氯二苯脲。
用于本发明的适宜防晒剂的实例包括但不限于二甲基对氨基苯甲酸辛酯、3,3,5-三甲基环己基水杨酸酯(胡莫柳酯)、2-羟基-4-甲氧基-二苯酮(二苯酮-3)、丁基甲氧基二苯甲酰甲烷、甲氧基肉桂酸辛酯、4-甲氧基-2,2’-二羟基二苯酮(二羟苯酮)、二羟基二甲氧基二苯酮(二苯酮-6)、愈创兰油烃、2-氰基-3,3-二苯基丙烯酸酯-2-乙基己基酯(氰双苯丙烯酸辛酯)和它们的混合物。本发明优选的防晒剂是甲氧基肉桂酸辛酯。
用于本发明的适宜维生素的实例包括但不限于维生素A及其酯、维生素E及其酯、维生素D和维生素K以及它们的混合物。
适用于本发明的驱虫剂的实例包括但不限于邻苯二甲酸二丁酯。
用于本发明的适宜芳香油的实例包括但不限于黄葵内酯(购自International Flavors & Fragrances (IFF),Liebegerweg72-98,l221 JT Hilversum,The Netherlands),Ambrinol T(购自Takasago International Corp.(USA),11 Volvo Drive,Rockleigh,NJ 07647-0932,USA),水杨酸苄酯,香茅醇乙酸酯,大马烯酮(购自Firmenich SA,1,Route des Jeunes,CH-1211 Geneva 8,瑞士,Habanolide(Firmenich),紫罗兰酮γMethyle(购自Givaudan-Roure,19-23 voie des Bans,BP98,95101 Argenteuil Cedex France),紫罗兰酮β(购自Givaudan-Roure),Norlimbanol(Firmenich),Sanjinol(IFF),Undelactone gamma(购自Givaudan-Roure),乙酸岩兰草酯(购自 Bonpard,HGH Fragrance Resources,Borstelmannsweg 169,D-20537 Hamburg,德国),甲基柏木酮(IFF),和它们的混合物。
用于本发明的适宜抗真菌剂的实例包括但不限于尼泊金丁酯、六氯酚、氯氟苯脲、十一碳烯酸及其酯和它们的混合物。
用于本发明的特别优选的疏水性护肤活性物质是抗微生物剂、维生素及其衍生物和防晒剂,尤其是抗微生物剂,特别是三氯二苯脲。表面活性剂体系
作为另一个基本特征,本发明的组合物含有水溶性表面活性剂的表面活性剂体系。如本发明所定义,水溶性表面活性剂是指分子量小于约20,000的表面活性剂,其中在室内条件下所述表面活性剂以0.2%w/w浓度溶于水时能形成透明的各向同性溶液。适用于包含在本发明组合物中的表面活性剂通常具有链长为约6-22个碳原子的亲油性链,可以选自阴离子性、非离子性、两性离子性和两性表面活性剂以及它们的混合物。表面活性剂的总含量优选为约2%-40%,更优选约3%-25%(重量),尤其是约5%-20%(重量)。所述组合物优选含有阴离子表面活性剂与两性离子和/或两性表面活性剂的混合物。阴离子表面活性剂:两性离子和/或两性表面活性剂的重量比为约1∶10-10∶1,优选约1∶5-5∶1,更优选约1∶3-3∶1。本发明范围内的其它适合的组合物包括阴离子表面活性剂、两性离子和/或两性表面活性剂与一种或多种非离子表面活性剂的混合物。
本发明的组合物可含有约0.1%-25%,更优选约1%-20%,尤其是约5%-15%(重量)的水溶性阴离子表面活性剂。
适用于本发明组合物中的水溶性阴离子表面活性剂包括烷基硫酸盐,乙氧基化的烷基硫酸盐,烷基乙氧基羧酸盐,烷基甘油基醚磺酸盐,乙氧基醚磺酸盐,甲基酰基牛磺酸盐,脂肪酰基甘氨酸盐,N-酰基谷氨酸盐,酰基羟乙基磺酸盐,烷基磺基琥珀酸盐,烷基乙氧基磺基琥珀酸盐,α-磺化脂肪酸,它们的盐和/或它们的酯,烷基磷酸盐,乙氧基化的烷基磷酸盐,酰基肌氨酸盐和脂肪酸/蛋白质缩合物,皂类(例如月桂酸、肉豆蔻酸和棕榈酸的铵盐、镁盐、钾盐、三乙醇胺盐和钠盐),酰基天冬氨酸盐,烷氧基椰油酰胺羧酸盐,(乙氧基化的)链烷醇酰胺磺基琥珀酸盐,乙氧基化的烷基柠檬酸磺基琥珀酸盐,酰基乙二胺三乙酸盐,酰基羟乙基羟乙磺酸盐,酰胺烷氧基硫酸盐,直链烷基苯磺酸盐,石蜡烃磺酸盐,α-烯烃磺酸盐,烷基烷氧基硫酸盐和它们的混合物。这些表面活性剂的烷基和/或酰基链长是C6-C22,优选C12-C18,更优选C12-C14。
适用于本发明组合物的其它水溶性阴离子表面活性剂是1摩尔高级脂肪醇与约1-12摩尔的环氧乙烷的反应产物的硫酸酯的盐,优选的抗衡离子是钠、铵和镁。特别优选的是含约2-6,优选2-4摩尔的环氧乙烷的烷基乙氧基硫酸盐,例如月桂基醚-2硫酸钠,月桂基醚-3硫酸钠,月桂基醚-3硫酸铵和月桂基醚-3.6硫酸钠镁。在优选的实施方案中,阴离子表面活性剂含有至少约50%,尤其是至少约75%(重量)的乙氧基化的烷基硫酸盐。
除了通过常规钠催化的乙氧基化技术和随后的硫酸化工艺获得的宽范围的乙氧基化的烷基硫酸盐外,由窄范围的乙氧基化物(NRE)获得的乙氧基化的烷基硫酸盐也是适用于本发明组合物的水溶性阴离子表面活性剂。适用于本发明的窄范围的乙氧基化的烷基硫酸盐选自平均含约1-6,优选约2-4,尤其是3摩尔环氧乙烷的硫酸化烷基乙氧基化物,例如NRE月桂基醚-3硫酸钠。适用于本发明的NRE物质具有如下所期望的环氧乙烷(EOn)分布:15%-约30%(重量)的EOn,约10%-20%(重量)的EOn+1和约10%-20%(重量)的EOn-1。高度优选的NRE物质含有小于约9%(重量)的具有7摩尔或多于7摩尔的环氧乙烷的乙氧基化的烷基硫酸盐和小于约13%(重量)的非乙氧基化的烷基硫酸盐。适宜的月桂基醚3硫酸盐NRE物质可购自Hoechst,其商品名为GENAPOL ZRO Narrow Range和GENAPOL Narrow Range。
本发明的组合物可包含作为水溶性阴离子表面活性剂的烷基乙氧基羧酸盐表面活性剂,其含量为约0.5%-15%,优选约1%-10%,更优选约1%-6%,尤其是约1%-4%(重量)。在本发明的组合物中,烷基乙氧基羧酸盐表面活性剂对于提供良好的皮肤温和性以及良好的清洗性能和理想的发泡性非常重要。
适用于本发明的烷基乙氧基羧酸盐具有通式(I)的结构:
R3O(CH2CH2O)kCH2COO-M+其中R3是C10-C16烷基或链烯基,优选C11-C15,更优选C12-C14烷基或C12-C13烷基,k是2-约7,优选约3-6,更优选约3.5-5.5,尤其是约4-5,最优选约4-4.5的乙氧基化平均值,并且M是水溶性阳离子,优选碱金属、碱土金属、铵、低级链烷醇铵以及一、二和三乙醇铵,更优选钠、钾和铵,最优选钠、铵及其与镁和钙离子的混合物。
适用于本发明的特别优选的水溶性阴离子表面活性剂是具有所选择的烷基链长和/或乙氧基化物分布的烷基乙氧基羧酸盐表面活性剂。因此,适用于本发明组合物的烷基乙氧基羧酸盐表面活性剂可具有R3和/或k的平均值不同的分布。
当平均R3是C11,C12,C13或C14时,k的平均值一般为约3-6。适用于本发明的优选的水溶性阴离子烷基乙氧基羧酸盐表面活性剂是C12-C14(平均EO 3-6)乙氧基羧酸盐和C12-C13(平均EO 3-6)乙氧基羧酸盐。适宜的物质包括可购自Shell Inc.(Houston,Texas,USA)的NEODOX 23-4(RTM)的盐和EMPICOL(RTM)CBCS(Albright &Wilson)。用于本发明的高度优选的烷基乙氧基羧酸盐表面活性剂中,当R3是C12-C14或C12-C13烷基时,k的平均值是约3-6,更优选约3.5-5.5,尤其是约4-5,最优选约4-4.5。
在优选的实施方案中,所述组合物基本上不含皂类,即它们含有小于约5%,优选小于约1%,优选0%(重量)的皂类。
本发明的组合物还可含有约0.1%-20%,更优选0.1%-10%,尤其是约1%-8%(重量)的水溶性非离子表面活性剂。这类表面活性剂包括蔗糖多酯表面活性剂、C10-C18烷基多糖苷和通式(III)的多羟基脂肪酰胺表面活性剂。
优选的式(III)的N-烷基、N-烷氧基或N-芳氧基多羟基脂肪酰胺表面活性剂中,R8是C5-C31烷基,优选C6-C19烷基,包括直链和支链烷基和链烯基或者它们的混合物;R9通常是氢、C1-C8烷基或羟烷基,优选甲基,或者R9是式-R1-O-R2的基团,其中R1是C2-C8烃基,包括直链和支链的以及环状的(包括芳基)烃基,并且优选是C2-C4亚烷基;R2是C1-C8直链和支链的以及环状的烃基,包括芳基和羟烃基(oxyhydrocarbyl),并且优选是C1-C4烷基,尤其是甲基或苯基。Z2是具有线性烃基链的多羟基烃基部分(或其烷氧基化的(优选乙氧基化的或丙氧基化的)衍生物),带有直接与链相连的至少2个(在甘油醛的情况下)或至少3个羟基(在其它还原糖的情况下)。Z2优选来自于还原胺化反应中的还原糖,Z2最优选是缩水甘油基(glycityl)部分。适宜的还原糖包括葡萄糖,果糖,麦芽糖,乳糖,半乳糖,甘露糖和木糖,以及甘油醛。可用作原料的有高葡萄糖的玉米糖浆,高果糖的玉米糖浆和高麦芽糖的玉米糖浆以及上面列出的各种糖。这些玉米糖浆可以得到Z2的糖成分的混合物。应该清楚,在此没有排除其它适合原料之意。Z2优选选自CH2(CHOH)n-CH2OH,CH(CH2OH)-(CHOH)n-1-CH2OH,CH2(CHOH)2(CHOR’)CHOH)CH2OH,其中n是1-5(包括1和5)的整数,并且R’是H或环状的单糖或多糖及其烷氧基化衍生物。如上所述,最优选的缩水甘油基中,n是4,尤其是CH2-(CHOH)4-CH2OH。
最优选的多羟基脂肪酰胺具有式R8(CO)N(CH3)CH2(CHOH)4CH2OH的结构,其中R8是C6-C19的直链烷基或链烯基。在上式化合物中,R8-CO-N<可以是,例如椰油酰胺、硬脂酰胺、油酰胺、月桂酰胺、肉豆蔻酰胺、癸酰胺、辛酰胺、棕榈酰胺、牛油酰胺等。
适用于本发明组合物的示例性非离子表面活性剂包括伯胺,例如椰油胺(以Adagen 160D(TM)商品名购自Witco)和链烷醇酰胺,例如椰油酰胺MEA(以Empilan CME (TM)商品名购自Albright & Wilson),PEG-3椰油酰胺,椰油酰胺DEA (以Empilan CDE(TM)购自Albright &Wilson),月桂酰胺MIPA,月桂酰胺 MEA (以Empilan LME(TM)购自Albright & Wilson),月桂酰胺DEA和它们的混合物。
适用于本发明的两性表面活性剂包括(a)式[V]的铵衍生物:其中R1是C5-C22烷基或链烯基,R2是CH2CH2OH或CH2CO2M,M是H、碱金属、碱土金属、铵或链烷醇铵,并且R3是CH2CH2OH或H;(b)式[VI]的氨基链烷酸盐
R1NH(CH2)nCO2M
式[VII]的亚氨基二链烷酸盐
R1N[(CH2)mCO2M]2
其中n,m,p和q是1-4的数,并且R1和M独立地选自上面定义的基团;和
(c)它们的混合物。
(a)类的适宜两性表面活性剂包括式(V)的化合物,其中R1是C8H17(尤其是异辛基)、C9H19和C11H23烷基。(a)类的适宜两性表面活性剂有市售,商品名为Miranol和Empigen。
在CTFA命名中,适用于本发明的物质包括椰油两性羧基丙酸盐,椰油两性羧基丙酸,椰油两性乙酸盐,椰油两性二乙酸盐(或者称为椰油两性羧基甘氨酸盐),月桂基两性(lauroampho)乙酸钠(或者称为月桂基两性羧基甘氨酸钠)。具体的商品包括商品名为Ampholak 7TX的产品(羧甲基牛油多丙胺钠),Empigen CDL60和CDR 60(Albright& Wilson),Miranol H2M Conc.Miranol C2M Conc.N.P.,MiranolC2M Conc.O.P.,Miranol C2M SF,Miranol CM Special,MiranolUltra L32和C32(Rhone-Poulenc);Alkateric 2CIB(AlkarilChemicals);Amphoterge W-2(Lonza,Inc.);Monateric CDX-38,Monateric CSH-32(Mona Industries);Rewoteric AM-2C(RewoChemical Group);和Schercotic MS-2(Scher Chemicals)。
应该清楚有多种市售的该类两性表面活性剂都是以与例如氢氧化物抗衡离子或与阴离子硫酸盐或磺酸盐表面活性剂,尤其是硫酸化C8-C18醇、C8-C18乙氧基化的醇或C8-C18酰基甘油酯类的电中性络合物形式制备和销售的。基于温和性和产品稳定性的观点,优选基本上不含(非乙氧基化的)硫酸化醇表面活性剂的组合物。还需注意两性表面活性剂的浓度和重量比是基于表面活性剂的未络合形式,任何阴离子表面活性剂抗衡离子应认为是整个阴离子表面活性剂成分的一部分。
(b)类的适宜的两性表面活性剂的实例包括N-烷基聚亚丙基聚-,羧甲基胺(其商品名为Ampholak X07和Ampholak 7CX,由Berol Nobel销售)及其盐,尤其是三乙醇胺盐及N-月桂基-β-氨基丙酸和N-月桂基-亚氨基-二丙酸的盐。这类原料的商品名为Henkel销售的Deriphat和由Rhone-Poulenc销售的Mirataine。
本发明的组合物还可含有约0.1%-20%,更优选约0.1%-10%,尤其是约1%-8%(重量)的两性离子表面活性剂。
适用于本发明组合物中的水溶性甜菜碱表面活性剂包括式R5R6R7N+(CH2)nCO2M的烷基甜菜碱和式(IX)的酰胺基甜菜碱:其中R5是C5-C22烷基或链烯基,R6和R7独立地是C1-C3烷基,M是H、碱金属、碱土金属、铵或链烷醇铵,并且n、m各自是1-4的数。优选的甜菜碱包括椰油酰胺基丙基二甲基羧甲基甜菜碱(由THGoldschmidt以Tego甜菜碱商品名销售)和月桂酰胺基丙基二甲基羧甲基甜菜碱(由Albright and Wilson以Empigen BR商品名销售,由TH Goldschmidt以Tegobetaine L10S商品名销售)。
适用于本发明组合物的水溶性磺基甜菜碱表面活性剂包括下式的烷基酰胺基磺基甜菜碱;其中R1是C7-C22烷基或链烯基,R2和R3独立地是C1-C3烷基,M是H、碱金属、碱土金属、铵或链烷醇铵,并且m和n是1-4的数。适用于本发明的是椰油酰胺基丙基羟基磺基甜菜碱,其由Rhone-Poulenc以Mirataine CBS商品名销售。
适用于本发明组合物的水溶性氧化胺表面活性剂包括烷基氧化胺R5R6R7NO和下式的酰胺基氧化胺其中R5是C11-C22烷基或链烯基,R6和R7独立地是C1-C3烷基,M是H、碱金属、碱土金属、铵或链烷醇铵,并且m是1-4的数。优选的氧化胺包括椰油酰胺基丙胺氧化物、月桂基二甲胺氧化物和肉豆蔻基二甲胺氧化物。悬浮剂
本发明组合物优选还包含一种或多种悬浮剂。用于本发明的适宜的悬浮剂包括若干长链的酰基衍生物或这类物质的混合物。包括约16-22个碳原子的脂肪酸的乙二醇酯。优选乙二醇硬脂酸酯,包括一硬脂酸酯和二硬脂酸酯,但尤其优选含小于约7%一硬脂酸酯的二硬脂酸酯。可使用的其它悬浮剂是具有约16-22个碳原子,优选约16-18个碳原子的脂肪酸的链烷醇酰胺。优选的链烷醇酰胺是硬脂酸单乙醇酰胺、硬脂酸二乙醇酰胺、硬脂酸一异丙醇酰胺和硬脂酸单乙醇酰胺硬脂酸酯。
其它适宜的悬浮剂是烷基(C16-C22)二甲基氧化胺,例如硬脂基二甲基氧化胺和三羟基硬脂精,后者由Rheox以Thixcin(RTM)商品名销售。用于本发明的优选悬浮剂是Rheox的Thixcin(RTM)。
悬浮剂的含量优选为约0.1%-5%,更优选约0.1%-3%。悬浮剂用以有助于水不溶性油的悬浮,可使产品具有珍珠般的光泽。本发明的组合物中也可使用悬浮剂的混合物。任选成分聚合阳离子调理剂
本发明的组合物可任选地含有聚合阳离子调理剂。在本发明的组合物中,聚合阳离子调理剂非常重要,它用以提供理想的皮肤感觉。此外,聚合阳离子调理剂与水不溶性油结合,有可能促进疏水性护肤活性物质的沉积。如果存在的话,聚合的皮肤调理剂的含量优选为约0.01%-5%,更优选为0.01%-3%,尤其是约0.01%-2%(重量)。
适宜的聚合物是高分子量物质(例如通过光散射法测定的重均分子量通常为约2,000-5,000,000,优选约5,000-3,000,000,更优选约100,000-1,000,000)。
聚合物的代表性类型包括阳离子瓜耳胶,阳离子多糖,由丙烯酸和/或甲基丙烯酸衍生的阳离子均聚物和共聚物,阳离子纤维素树脂,季铵化的羟乙基纤维素醚,二甲基二烯丙基氯化铵和丙烯酰胺和/或丙烯酸的阳离子共聚物,二甲基二烯丙基氯化铵的阳离子均聚物,二甲基氨乙基甲基丙烯酸酯和丙烯酰胺的共聚物,丙烯酸/二甲基二烯丙基氯化铵/丙烯酰胺的共聚物,氨基醇的季铵化乙烯基吡咯烷酮丙烯酸酯或甲基丙烯酸酯共聚物,乙烯基吡咯烷酮和二甲基氨基乙基甲基丙烯酰胺的季铵化共聚物,乙烯基吡咯烷酮/乙烯基咪唑鎓甲氯化物共聚物及聚亚烷基和乙氧基聚亚烷基亚胺;季铵化硅酮,丙烯酸、甲基丙烯酰胺基丙基三甲基氯化铵和丙烯酸甲酯的三元共聚物;以及它们的混合物。
例如,适用于本发明的阳离子聚合物包括阳离子瓜耳胶,如羟丙基三甲基铵瓜耳胶(取代度(d.s.)为0.11-0.22)(商品名为JaguarC-14-S(RTM)、Jaguar C-17(RTM)和Jaguar C-16(RTM)),它除含有上述指出的阳离子基团外,还含有羟丙基取代基(取代度为0.8-1.1);和季铵化的羟乙基纤维素醚(商品名为Ucare PolymerJR-30M,JR-400,LR400,Catanal(RTM)和Celquat)。其它适宜的阳离子聚合物是二甲基二烯丙基氯化铵的均聚物(商品名Merquat 100),二甲基氨基乙基甲基丙烯酸酯和丙烯酰胺的共聚物,二甲基二烯丙基氯化铵与丙烯酰胺的共聚物(商品名Merquat 550和Merquat S),丙烯酸/二甲基二烯丙基氯化铵/丙烯酰胺共聚物(商品名Merquat 3330),丙烯酸、甲基丙烯酰胺基丙基三甲基氯化铵和丙烯酸甲酯的三元共聚物(商品名Merquat 2001),氨基醇的季铵化乙烯基吡咯烷酮丙烯酸酯或甲基丙烯酸酯共聚物(商品名Gafquat),例如聚季铵盐11,23和28(乙烯基吡咯烷酮和二甲氨基乙基甲基丙烯酸酯的季铵化共聚物-Gafquat 755N及乙烯基吡咯烷酮和二甲基氨基乙基甲基丙烯酰胺的季铵化共聚物-HS-100),乙烯基吡咯烷酮/乙烯基咪唑鎓甲氯化物共聚物(商品名Luviquat FC370)聚季铵盐2及聚亚烷基亚胺,例如聚亚乙基亚胺和乙氧基化的聚亚乙基亚胺。适用于本发明的其它聚合物是以Aqualon N-Hance商品名市售的阳离子聚合物。
本发明的组合物还可含有约0.1%-20%,优选约1%-15%,更优选约2%-10%(重量)的油衍生的非离子表面活性剂或者油衍生的非离子表面活性剂的混合物。在本发明的组合物中,油衍生的非离子表面活性剂对于使用时和使用后的皮肤感觉有益效果起着重要作用。用于本发明的适宜的油衍生的非离子表面活性剂包括水溶性、由动植物得到的润肤剂,例如有聚乙二醇链插入的甘油三酯;乙氧基化的甘油单酯和二酯,多乙氧基化羊毛脂和乙氧基化的奶油衍生物。用于本发明的一类优选的油衍生的非离子表面活性剂具有通式(XII)的结构:其中n是约5-200,优选约20-100,更优选约30-85,并且其中R包含平均约5-20个碳原子,优选约7-18个碳原子的脂族基团。
这类适宜的乙氧基化的油脂包括椰油酸甘油酯、己酸甘油酯、辛酸甘油酯、牛油酸甘油酯、棕榈酸甘油酯、硬脂酸甘油酯、月桂酸甘油酯、油酸甘油酯、蓖麻油酸甘油酯,以及由甘油三酯衍生的脂肪酸甘油酯,例如棕榈油、杏仁油和玉米油,优选牛油酸甘油酯和椰油酸甘油酯的聚乙二醇衍生物。
该类适宜的油衍生的非离子表面活性剂是可购自Croda Inc.(美国,纽约)的Crovol系列的商品,例如Crovol EP40(PEG 20月见草甘油酯),Crovol EP 70(PEG 60月见草甘油酯),Crovol A-40(PEG20杏仁甘油酯),Crovol A-70(PEG 60杏仁甘油酯),Crovol M-40(PEG 20玉米甘油酯),Crovol M-70(PEG 60玉米甘油酯),CrovolPK-40(PEG 12棕榈仁甘油酯)和Crovol PK-70(PEG 45棕榈仁甘油酯)以及可购自Westbrook Lanolin的Solan系列产品,例如Solan E,E50和X多乙氧基化的羊毛脂及Aqualose L-20(PEG 24羊毛脂醇)和Aqualose W15(PEG 15羊毛脂醇)。该类的其它适宜的表面活性剂是可购自Sherex Chemical Co.(Dublin,Ohio,USA)的Varonic LI系列表面活性剂和可购自Rewo的Rewoderm系列表面活性剂。这些包括,例如,Varonic LI 48(聚乙二醇(n=80)牛油酸甘油酯,或者称为PEG 80牛油酸甘油酯),Varonic LI 2(PEG 28牛油酸甘油酯),Varonic LI 420(PEG 200牛油酸甘油酯),和Varonic Ll63和67(PEG30和PEG 80椰油酸甘油酯),Rewoderm LI5-20(PEG-200棕榈酸酯),Rewoderm LIS-80(PEG-200棕榈酸酯与PEG-7椰油酸甘油酯)和Rewoderm LIS-75(PEG-200棕榈酸酯与PEG-7椰油酸甘油酯)及它们的混合物。适用的其它油衍生的润肤剂是玉米油、鳄梨油和巴巴苏油的PEG衍生物,以及Softigen 767(PEG(6)辛酸/癸酸甘油酯)。
适用于本发明的还有由从Shea Tree(Butyrospermum KarkiiKotschy)中提取的混合植物脂肪衍生的非离子表面活性剂及其衍生物。这些已知称为Shea Butter的植物脂肪在中非被广泛用于各种领域,例如制皂和作为遮挡霜,其由Sederma(78610 Le Perray EnYvelines,法国)销售。特别适合的是Shea Butter的乙氧基化衍生物,它是可购自Karlshamn Chemical Co.(Columbos,Ohio,USA)的Lipex系列化学产品,例如Lipex 102 E-75和Lipex 102 E-3(Sheabutter的乙氧基化的一和二甘油酯)和可购自Croda Inc.(美国,纽约)的Crovol系列化学产品,例如Crovol SB-70(Shea butter的乙氧基化的一、二甘油酯)。同样,芒果、可可和东印度山榄科植物脂的乙氧基化衍生物也可用于本发明的组合物中。虽然将这些归为乙氧基化非离子表面活性剂,但应该清楚也可存在一定比例的非乙氧基化的植物油或脂肪。
其它适宜的油衍生的非离子表面活性剂包括下列油的乙氧基化衍生物:杏仁油、花生油、米糠油、小麦胚芽油、亚麻籽油、西蒙得木油、杏核油、胡桃油、棕榈坚果油、乳香黄连木油、芝麻油、油菜籽油、杜松油、玉米油、桃核油、罂粟籽油、松油、蓖麻油、大豆油、鳄梨油、红花油、椰子油、榛子油、橄榄油、葡萄籽油和向日葵籽油。
基于最佳温和性和皮肤感觉性,高度优选的油衍生的非离子表面活性剂是Lipex 102-3(RTM)(Shea Butter的PEG-3乙氧基化衍生物)和Softigen 767(RTM)(PEG-6辛酸/癸酸甘油酯)。
本发明的组合物还可含有作为另外的护肤活性物质的亲油性乳化剂。适宜的亲油性护肤活性物质包括食用级的阴离子乳化剂,所述乳化剂包含与单甘油酯例如琥珀酰化单甘油酯、柠檬酸一硬脂酸酯、二乙酰基酒石酸一硬脂酸甘油酯及其混合物混合的二酸。
除了上述的水不溶性聚α-烯烃油外,其它水不溶性油也可用于本发明的组合物中。用于本发明的个人清洁组合物的其它水不溶性油是下式的支链烷基或链烯基物质的(b)类油:其中R1是H或C1-C4烷基,R4是C1-C4烷基,R2是H或C1-C4烷基或者C2-C4链烯基,并且R3是H或C1-C4烷基或者C2-C4链烯基,n是0-3的整数,m是1-1000的整数,具有约600-1000,优选约750-1000,尤其是约800-1000的数均分子量。在40℃下,采用ASTM D-445粘度测定方法,支链烷基或链烯基类油优选具有约500cst至约50,000cst,优选约1000cst至约10,000 cst的粘度。
用于本发明的(b)类的适宜的烷基或链烯基物质是丁烯、异戊二烯、萜烯、苯乙烯或异丁烯的聚合物,优选丁烯或异丁烯的聚合物。
(b)类烷基或链烯基油的实例包括聚丁烯油,例如可购自Amoco的商品名为Indopol 40和Indopol 100的产品;聚异丁烯油,例如可购自Presperse Inc.的商品名为Permethyl 104A的产品和购自ExxonChemicals Co.的Parapol 950。
用于本发明的其它适宜物质有下式的疏水性改性硅酮:其中R是C1-C4烷基或者苯基,R’是C1-C20烷基或者苯基,z是5-21,并且x是平均值约为20-400的数,y是平均值约为0-10的数并且x+y在30-400范围内。优选的物质的x值为40-200,优选60-100,y值为0-5,优选0并且x和y值之和为60-100。亚烷基链z可以是直链或支链的。另外,硅酮骨架可具有低程度的分支化结构以形成树脂(如,MDQ或MDT树脂)。
这类油的实例包括可购自GE Silicones的商品名为SF1632(C16-C18烷基甲基硅酮)的疏水性改性硅酮,以及辛基和癸基甲基硅酮。
在优选的实施方案中,其它水不溶性油的数均颗粒直径为约1微米-500微米,优选约5-200微米,更优选约5-50微米,尤其是约5-20微米。
另一种适用于本发明发泡组合物的水不溶性皮肤/毛发护理成分是液体的多元醇羧酸酯。
优选用于本发明的多元醇酯是非堵塞性的液体的或可液化的多元醇羧酸酯。这些多元醇酯由多羟基基团或部分和一种或多种羧酸基或部分衍生。换句话说,这些酯包含由多元醇衍生的部分和一个或多个由羧酸衍生的部分。这些羧酸酯还可由羧酸衍生。这些羧酸酯还可以描述为液体多元醇脂肪酸酯,因为在本领域中术语羧酸和脂肪酸常互换使用。
用于本发明的优选的液体多元醇多酯包含用至少四个脂肪酸基酯化的某些多元醇,尤其是糖或糖醇。因此,多元醇原料必须具有至少四个可酯化的羟基。优选的多元醇的实例是糖,包括单糖和二糖以及糖醇。含四个羟基的单糖的实例是木糖和阿拉伯糖,以及由木糖衍生的糖醇即木糖醇(带有五个羟基)。单糖赤藓糖不适用于本发明,因为它仅含有三个羟基,但由赤藓糖衍生的糖醇,即赤藓糖醇含有四个羟基,因而可以使用。适宜的含五个羟基的单糖是半乳糖、果糖和山梨糖。由蔗糖的水解产物以及葡萄糖和山梨糖衍生的含六个羟基的糖醇,如山梨糖醇也是适宜的。可使用的二糖多元醇的实例包括麦芽糖、乳糖和蔗糖,它们都带有8个羟基。
用于制备本发明使用的多酯的优选多元醇选自赤藓糖醇、木糖醇、山梨糖醇、葡萄糖和蔗糖。尤其优选蔗糖。
具有至少四个羟基的多元醇原料的至少四个羟基被含约8-22碳原子的脂肪酸酯化。这类脂肪酸的实例包括辛酸、癸酸、月桂酸、肉豆蔻酸、肉豆蔻脑酸、棕榈酸、棕榈油酸、硬脂酸、油酸、蓖麻油酸、亚油酸、亚麻酸、桐酸、花生酸、花生四烯酸、山萮酸、芥酸。脂肪酸可以得自天然的或合成的脂肪酸;它们可以是饱和的或不饱和的,包括位置和几何异构体。然而,为提供优选用于本发明的液体多酯,进入多酯分子中的至少约50%重量的脂肪酸应是不饱和的。特别优选的是油酸和亚油酸及它们的混合物。
用于本发明的多元醇脂肪酸多酯应包含至少四个脂肪酸酯基。多元醇的所有羟基不必都被脂肪酸酯化,但多酯优选含有至多两个未酯化的羟基。最优选多元醇的基本上所有的羟基都被脂肪酸酯化,即多元醇部分基本上是完全酯化的。酯化到多元醇分子中的脂肪酸可以相同或是混合物形式,但如上所述,必须存在相当数量的不饱和酸酯基以提供流动性。
为了阐述上述观点,蔗糖三脂肪酸酯不适用于本发明,因为它不含有所需的四个脂肪酸酯基。蔗糖四脂肪酸酯是适宜的,但不是优选的,因为它具有多于两个未酯化的羟基。蔗糖六脂肪酸酯是优选的,因为它具有不超过两个的未酯化的羟基。高度优选的是其中所有羟基都被脂肪酸酯化的化合物,包括液体的蔗糖八取代的脂肪酸酯。
下列是适用于本发明的含有至少四个脂肪酸酯基的具体多元醇脂肪酸多酯的非限制性实例:葡萄糖四油酸酯、葡萄糖四大豆油脂肪酸(不饱和的)酯、甘露糖四混合大豆油脂肪酸酯、半乳糖四油酸酯、阿拉伯糖四亚油酸酯、木糖四亚油酸酯、半乳糖五油酸酯、山梨醇四油酸酯、山梨醇六不饱和大豆油脂肪酸酯、木糖醇五油酸酯、蔗糖四油酸酯、蔗糖五油酸酯、蔗糖六油酸酯、蔗糖七油酸酯、蔗糖八油酸酯和它们的混合物。
如上所示,高度优选的多元醇脂肪酸酯是其中脂肪酸含约14-18个碳原子的那些。
用于本发明的优选的液体多元醇多酯的完全熔点低于约30℃,优选低于约27.5℃,更优选低于约25℃。本文的完全熔点是通过示差扫描量热法(DSC)测定的。
适用于本发明的多元醇脂肪酸多酯可通过本领域普通技术人员已知的各种方法制备。这些方法包括:采用各种催化剂,用脂肪酸甲酯、乙酯或甘油酯的多元醇酯交换法;用脂肪酰氯酰化多元醇的方法;用脂肪酸酐酰化多元醇的方法;和用脂肪酸酰化多元醇的方法等。参见美国专利2,831,854;Jandacek的美国专利4,005,196(1977年1月25日授权)。
本发明组合物还可以包括辅助的非离子或阴离子性聚合增稠组分,尤其是分子量大于约20,000的水溶性聚合物。“水溶性聚合物”是指在25℃下,在水中1%浓度时能形成基本上透明溶液的物质并且该物质能增高水的粘度。用作本发明组合物的附加增稠组分的理想的水溶性聚合物的实例是羟乙基纤维素、羟丙基纤维素、羟丙甲基纤维素、聚乙二醇、聚丙烯酰胺、聚丙烯酸、聚乙烯醇(实例包括日本KuraryChemical Co.的PVA 217)、聚乙烯吡咯烷酮K-120、葡聚糖(例如可购自D&O Chemiicals的Dextran纯品2P)、羧甲基纤维素、植物渗出物(如阿拉伯胶、茄替胶和黄蓍胶)、海草提取物(如藻酸钠、丙二醇藻酸酯和角叉菜胶钠)。作为本发明附加增稠剂的优选物质是天然多糖。这类物质的实例是瓜耳胶、刺槐豆胶和黄原胶。适用于本发明的其它优选物质是分子量为约700,000的羟乙基纤维素。水溶助长剂
本发明的组合物的一个选择性的特征是可以含有水溶助长剂。适用于本发明的水溶助长剂是本领域熟知的,包括二甲苯磺酸钠、二甲苯磺酸铵、异丙基苯磺酸钠、短链烷基硫酸盐及其混合物。本发明组合物中水溶助长剂的含量可以为约0.01%-5%,优选约0.1%-4%,更优选约0.5%-3%(重量)。本文定义的水溶助长剂是指当加到未稀释的、水溶性表面活性剂体系中时,可调节体系粘度和流变性的物质。
除上述的水不溶性油外,本发明的组合物还可包括至多约10%,优选至多约3%(重量)的不溶性香料或者润肤油(cosmetic oil)或蜡或者它们的混合物,其中在25℃下所述油或蜡在产品基质中是不溶性的。
用于本发明的适宜的不溶性润肤油和蜡可选自水不溶性硅酮,包括不挥发的聚烷基和聚芳基硅氧烷胶以及流体、挥发性环状聚二甲基硅氧烷、多烷氧基化的硅酮、氨基和季铵改性的硅酮、刚性交联的和增强硅酮及它们的混合物、C8-C30脂肪酸的C1-C24酯(如肉豆蔻酸异丙酯、肉豆蔻酸肉豆蔻醇酯和蓖麻油酸鲸蜡酯),苯甲酸的C8-C30酯、蜂蜡、饱和的和不饱和的脂肪醇(如二十二醇)、烃(如矿物油、凡士林、角鲨烷和角鲨烯)、脂肪酸的脱水山梨醇酯(参见Seiden的US-A-3988255,1976年10月26日颁发)、羊毛脂和类油羊毛脂衍生物、动物和植物的三甘油酯(例如杏仁油、花生油、小麦胚芽油、米糠油、亚麻籽油、西蒙得木油、杏核油、胡桃油、棕榈仁油、乳香黄连木油、芝麻油、油菜籽油、杜松油、玉米油、桃核油、罂粟籽油、松油、蓖麻油、大豆油、鳄梨油、红花油、椰子油、榛子油、橄榄油、葡萄籽油和向日葵籽油)以及二聚和三聚酸的C1-C24酯,例如二聚酸二异丙酯、二异硬脂基苹果酸酯、二聚酸二异硬脂基酯和三聚酸三异硬脂酯。
最终组合物的粘度(Brookfield DV II,用Cone CP41或CP52,25℃,纯的)优选为至少约500 cps,更优选约1,000-50,000 cps,尤其是约1,000-30,000 cps,更优选约1,000-15,000 cps。
本发明的清洁组合物可任选地包括溶于清洁组合物基质中的其它毛发或皮肤保湿剂。这类保湿剂的优选含量为约0.5%-20%(重量)。在优选的实施方案中,保湿剂选自天然存在于皮肤角质层中的基本氨基酸化合物和水溶性非闭塞性多元醇(nonpolyol nonocclusive)以及它们的混合物。
优选的非闭塞性保湿剂的一些实例是角鲨烷,吡咯烷酮羧酸钠,D-泛醇,乳酸,L-脯氨酸,胍,吡咯烷酮,水解蛋白质和其它胶原衍生的蛋白质,库拉索芦荟胶,乙酰胺MEA和乳酰胺MEA以及它们的混合物。
本发明的组合物还可包括遮光剂或珠光剂。这类物质的含量可以为约0.01%-5%,优选约0.1%-1.3%(重量)。
适用于本发明组合物的遮光剂/珠光剂包括:二氧化钛,TiO2;EUPERLAN 810(RTM);TEGO-PEARL(RTM);长链(C16-C22)酰基衍生物,例如具有约16-22个碳原子的脂肪酸的二醇或聚乙二醇酯,它具有至多7个亚乙氧基单元;具有约16-22个碳原子,优选约16-18个碳原子的脂肪酸的链烷醇酰胺,例如硬脂酸单乙醇酰胺、硬脂酸二乙醇酰胺、硬脂酸一异丙醇酰胺和硬脂酸单乙醇酰胺以及烷基(C16-C22)二甲胺氧化物例如硬脂基二甲胺氧化物。
在优选的组合物中,遮光剂/珠光剂以晶体形式存在。在高度优选的组合物中,遮光剂/珠光剂是粒径约为0.05微米-0.45微米,优选约0.17微米-0.3微米的颗粒状聚苯乙烯分散体,从提供最佳流变学和剪切稀化性能考虑,这类分散体是优选的。高度优选的是苯乙烯丙烯酸酯共聚物和由Morton International销售的OPACFIER 680(RTM)。
各种其它的任选物质可各自以约0.1%-2%(重量)含量加到清洁组合物中。这类物质包括蛋白质和多肽及它们的衍生物;水溶性或水增溶性防腐剂,例如DMDM乙内酰脲,Germall 115,羟基苯甲酸的甲酯、乙酯、丙酯和丁酯,EDTA,Euxyl(RTM)K400,天然防腐剂例如苄醇、山梨酸钾和没药醇;苯甲酸钠和2-苯氧基乙醇;其它增湿剂,例如透明质酸、壳多糖和淀粉接枝的聚丙烯酸钠,如可购自CelaneseSuperabsorbent Materials(Portsmith,VA,USA)和记载于US-A-4,076,663中的Sanwet(RTM)IM-1000、IM-1500和IM-2500;溶剂;低温相改性剂例如铵离子源(如NH4Cl);粘度控制剂如硫酸镁和其它电解质;着色剂;TiO2和TiO2-涂覆的云母;香料和香料增溶剂;及沸石如Valfour BV400及其衍生物和Ca2+/Mg2+螯合剂如多元羧酸酯(或盐),氨基多元羧酸酯(或盐),多膦酸酯(或盐),氨基多膦酸酯(或盐),EDTA等,水软化剂如柠檬酸钠和不溶性颗粒例如硬脂酸锌和热解法二氧化硅。水的含量优选占本发明组合物重量的约20%-99.89%,优选约40%-90%,更优选至少约75%。
组合物的pH优选为约3-10,更优选约5-9,尤其是约5-8,最优选约5-7。
本发明的组合物可用于各种皮肤和毛发护理应用中,例如沐浴凝胶、浴液、洗发香波等。
本发明的组合物可用手施用或者优选用个人清洁用具例如泡沫体(puff)施用。用于本发明组合物的适宜个人清洁用具包括下列专利文献中公开的那些,这些文献在本文引作参考:Campagnoli的US-A-5,144,744(1992年9月8日授权),Barnhouse的US-A-3,343,196,宝洁公司的WO95/26671,宝洁公司的WO95/00116和宝洁公司的WO95/26670。
本发明的组合物通过下列非限制性实施例加以说明。
实施例I-III是浴液组合物。实施例IV和V是香波组合物。
实施例VI是浴液。
I/% | II/% | III/% | IV/% | V/% | |
月桂基醚-3硫酸铵(EmpicolEAC/TP)1 | 8.4 | 8.4 | 10.5 | 15 | 15 |
月桂基硫酸铵(Empicol AL30)1 | - | - | - | 5 | 5 |
月桂基两性乙酸钠(Empigen CDL60P)1 | 3.6 | 3.6 | 4.5 | - | 2 |
月桂酰肌氨酸钠(Hamposyl L30)2 | 0.5 | 0.5 | 3 | - | - |
椰油酰胺基MEA(Empilan CME)1 | - | - | 1.0 | 1.0 | |
鲸蜡醇 | - | - | - | 0.4 | 0.4 |
硬脂醇 | - | - | - | 0.2 | 0.2 |
乙二醇二硬脂酸酯 | - | - | - | 2.0 | 2.0 |
Thixcin R3 | 1.5 | 1.5 | 0.3 | - | - |
聚α-烯烃(Puresyn 100)4 | 6.0 | 0 | 3.0 | 4.0 | 0 |
聚α-烯烃(Puresyn 40)4 | 0 | 5 | 0 | 0 | 2 |
香料 | 0.5 | 0.5 | 1.0 | 1.0 | 1.0 |
EDTA | 0.11 | 0.11 | 0.11 | 0.11 | 0.11 |
苯甲酸钠 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
DMDM乙内酰脲 | 0.138 | 0.138 | 0.138 | 0.138 | 0.138 |
NaCl | 0.5 | 0.5 | 1.3 | 0.5 | 0.5 |
三氯二苯脲 | 0.15 | 0.0 | 0.0 | 0.15 | 0.15 |
甲氧基肉桂酸辛酯 | 0.0 | 2.1 | 0.0 | 0.0 | 0.0 |
维生素E乙酸酯 | 0.0 | 0.0 | 0.2 | 0.0 | 0.0 |
柠檬酸 | 0.9 | 0.9 | 0.9 | 0.4 | 0.4 |
水 | 加至100 |
VI(%) | |
月桂基醚-3硫酸铵(Empicol EAC/TP)1 | 9 |
二甲苯磺酸铵(AXS)1 | 0-1.66 |
烷基硫酸铵 | 5 |
硬脂酸锌 | 1.0 |
磷酸二氢钠 | 0-0.6 |
磷酸氢二钠 | 0-0.6 |
鲸蜡醇 | 0.4 |
硬脂醇 | 0.2 |
聚乙二醇600 | 1.4 |
聚丁烯 | 0.1-1.2 |
香料 | 0.6 |
EDTA二钠 | 0.1 |
椰油单乙醇酰胺(CMEA)1 | 1.0 |
乙二醇二硬脂酸酯(EGDS) | 2.0 |
NaCl | 0-2 |
Kathon CG | 0.02 |
三氯二苯脲 | 0.15 |
三氯森 | 0.25 |
水 | 加至100 |
1.供应商:Albright & Wilson UK Limited,P.O.Box 15,Whitehaven,Cumbria,CA28 9QQ
2.供应商:Hampshire Chemicals,Corp.,55 Hayden Ave.,Lexington,MA 02173,USA
3.供应商:Rheox,Inc.,Wyckoffs Mill Road,P.O.Box 700,Hightstown,NJ 08520,USA
4.供应商:Mobil Chemical Company,P.O.Box 3140,Edison,New Jersey,08818-3140,USA制造方法
组合物可通过首先制备部分表面活性剂、悬浮剂和增稠剂的预混物来制备。该预混物含占组合物总重50-70%的表面活性剂和所有月桂基两性乙酸盐。通过在温和搅拌下,将表面活性剂(除肌氨酸盐外)、部分水、粉末防腐剂和pH调节剂混合制备预混物。然后将该混合物加热到约90℃,在此期间搅拌下加入悬浮剂。
使该混合物在高温保持数分钟后,使用热交换器控制其冷却速率,从而使悬浮剂结晶出来。
往该预混物中加入剩余的水,然后加入剩余的表面活性剂、防腐剂、香料、氯化钠和疏水性护肤活性组分。对于某些疏水性护肤活性组分,需要高剪切混合。最后,加入水不溶性油。这部分工艺在室温下采用温和的搅拌进行,以得到平均粒径为5-20微米的优选液滴。
该产品在贮存、分配和使用过程中具有良好的流变学特性,提供了护肤活性成分的良好的沉积作用,并且具有良好的清洗感觉和温和性以及良好的功效,包括皮肤调理、皮肤保湿、良好的稳定性、清洁和发泡性。
Claims (17)
1.一种可洗掉的液体个人清洁组合物,含有:(a)水;(b)约1重量%-约60重量%的水溶性表面活性剂;(c)水不溶性的油,选自通式如下的高度支化的聚α-烯烃,
其中R1是H或C1-C20烷基,R4是C1-C20烷基,R2是H或C1-C20,R3是C3-C20,优选C5-C20,n是0-3的整数且m是1-1000的整数,具有约1000-约25000的数均分子量;和
(d)疏水性护肤活性成分,选自抗微生物剂、防晒剂、维生素、芳香油、驱虫剂、抗真菌剂和它们的混合物,其中疏水性护肤活性成分的ClogP值大于3。
2.权利要求1的个人清洁组合物,其中疏水性护肤活性成分的ClogP值大于5。
3.权利要求1或2的个人清洁组合物,其中疏水性护肤活性成分是抗微生物剂。
4.权利要求3的个人清洁组合物,其中抗微生物剂选自二苯脲例如三氯二苯脲、六氯酚、3,4,5-三溴水杨酰苯胺和它们的混合物。
5.权利要求1-4任一项的个人清洁组合物,其中抗微生物剂是三氯二苯脲。
6.权利要求1-5任一项的个人清洁组合物,含有约0.1%-5%重量的疏水性护肤活性成分。
7.权利要求1-6任一项的个人清洁组合物,其中水不溶性油的数均分子量为约2500-约6000,优选约2500-约4000。
8.权利要求1-7任一项的个人清洁组合物,其中在40℃下,用ASTM D-445方法测定粘度时,水不溶性油的粘度为约300cst-约50,000cst,优选约1000cst-约12,000cst,更优选约1000cst-约4000cst。
9.权利要求1-8任一项的个人清洁组合物,含有约0.1%-约10%、优选约2%-约7%重量的水不溶性油。
10.权利要求1-9任一项的个人清洁组合物,其中水溶性表面活性剂选自阴离子表面活性剂、非离子、两性离子和两性表面活性剂以及它们的混合物。
11.权利要求10的个人清洁组合物,其中水溶性阴离子表面活性剂选自烷基硫酸盐、乙氧基化的烷基硫酸盐、烷基甘油醚磺酸盐、烷基乙氧基甘油醚磺酸盐、酰基甲基牛磺酸盐、脂肪酰基甘氨酸盐、烷基乙氧基羧酸盐、N-酰基谷氨酸盐、酰基羟乙磺酸盐、烷基磺基琥珀酸盐、烷基乙氧基磺基琥珀酸盐、α-磺化脂肪酸、其盐和/或其酯、烷基磷酸盐、乙氧基化的烷基磷酸盐、酰基肌氨酸盐和脂肪酸/蛋白质缩合物、酰基天冬氨酸盐、烷氧基酰胺基羧酸盐、(乙氧基化的)链烷醇酰胺磺基琥珀酸盐、乙氧基化的烷基柠檬酸磺基琥珀酸盐、酰基乙二胺三乙酸盐、酰基羟乙基羟乙磺酸盐、酰胺基烷氧基硫酸盐、直链烷基苯磺酸盐、石蜡烃磺酸盐、烷基烷氧基硫酸盐和它们的混合物。
12.权利要求10或11的个人清洁组合物,其中水溶性阴离子表面活性剂是乙氧基化的烷基硫酸盐。
13.权利要求1-12任一项的个人清洁组合物,其中所述组合物基本上不含皂类。
14.权利要求11的个人清洁组合物,其中水溶性两性表面活性剂选自式[V]的铵衍生物:
其中R1是C5-C22烷基或链烯基,R2是CH2CH2OH或CH2CO2M,M是H、碱金属、碱土金属、铵或链烷醇铵,并且R3是CH2CH2OH或H。
15.权利要求11的个人清洁组合物,其中两性离子表面活性剂选自式R5R6R7N+(CH2)nCO2M的烷基甜菜碱和式(IX)的酰胺基甜菜碱:
其中R5是C5-C22烷基或链烯基,R6和R7独立地是C1-C3烷基,M是H、碱金属、碱土金属、铵或链烷醇铵,并且n、m各自是1-4的数。
16.权利要求1-15任一项的组合物,还含有约0.01%-5%重量的阳离子聚合皮肤调理剂,它们选自阳离子瓜耳胶,阳离子多糖,由丙烯酸和/或甲基丙烯酸衍生的阳离子均聚物和共聚物,阳离子纤维素树脂,季铵化的羟乙基纤维素醚,二甲基二烯丙基氯化铵和丙烯酰胺和/或丙烯酸的阳离子共聚物,二甲基二烯丙基氯化铵的阳离子均聚物,二甲基氨乙基甲基丙烯酸酯和丙烯酰胺的共聚物,丙烯酸/二甲基二烯丙基氯化铵/丙烯酰胺的共聚物,氨基醇的季铵化乙烯基吡咯烷酮丙烯酸酯或甲基丙烯酸酯共聚物,乙烯基吡咯烷酮和二甲基氨基乙基甲基丙烯酰胺的季铵化共聚物,乙烯基吡咯烷酮/乙烯基咪唑鎓甲氯化物共聚物及聚亚烷基和乙氧基聚亚烷基亚胺,季铵化硅酮,丙烯酸、甲基丙烯酰胺基丙基三甲基氯化铵和丙烯酸甲酯的三元共聚物,以及它们的混合物。
17.权利要求1-16任一项的个人清洁组合物,其中水不溶性油的数均粒径为约1微米-约500微米,优选约5微米-约200微米,尤其是约5-约50微米。
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AU2469099A (en) | 2000-08-07 |
WO2000042984A1 (en) | 2000-07-27 |
EP1156779A1 (en) | 2001-11-28 |
JP2003521466A (ja) | 2003-07-15 |
KR100501784B1 (ko) | 2005-07-18 |
WO2000042985A1 (en) | 2000-07-27 |
CA2359481A1 (en) | 2000-07-27 |
AU771123B2 (en) | 2004-03-11 |
AU2853900A (en) | 2000-08-07 |
KR20010102994A (ko) | 2001-11-17 |
CN1203840C (zh) | 2005-06-01 |
CZ20012650A3 (cs) | 2002-01-16 |
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