CN109843258A - 表示毛发调理有益效果的浓缩型洗发剂泡沫剂型 - Google Patents
表示毛发调理有益效果的浓缩型洗发剂泡沫剂型 Download PDFInfo
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- CN109843258A CN109843258A CN201780064638.3A CN201780064638A CN109843258A CN 109843258 A CN109843258 A CN 109843258A CN 201780064638 A CN201780064638 A CN 201780064638A CN 109843258 A CN109843258 A CN 109843258A
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- Prior art keywords
- foam
- cationic
- acid
- group
- alkyl
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- 239000004094 surface-active agent Substances 0.000 claims abstract description 41
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- 238000009826 distribution Methods 0.000 claims abstract description 21
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical class CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims description 83
- 229920000642 polymer Polymers 0.000 claims description 71
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 238000005259 measurement Methods 0.000 claims description 20
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- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims description 7
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- 239000000178 monomer Substances 0.000 description 53
- 125000000217 alkyl group Chemical group 0.000 description 32
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- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 26
- 239000003638 chemical reducing agent Substances 0.000 description 26
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- 239000004215 Carbon black (E152) Substances 0.000 description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 23
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- 150000001721 carbon Chemical group 0.000 description 14
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 14
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- 150000002500 ions Chemical class 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 13
- 229920003118 cationic copolymer Polymers 0.000 description 13
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 11
- 239000006210 lotion Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000002888 zwitterionic surfactant Substances 0.000 description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 10
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- 125000000129 anionic group Chemical group 0.000 description 10
- 239000002736 nonionic surfactant Substances 0.000 description 10
- 125000002811 oleoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- YBBJKCMMCRQZMA-UHFFFAOYSA-N pyrithione Chemical compound ON1C=CC=CC1=S YBBJKCMMCRQZMA-UHFFFAOYSA-N 0.000 description 10
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- 235000017858 Laurus nobilis Nutrition 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 244000125380 Terminalia tomentosa Species 0.000 description 9
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- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 8
- 229920013822 aminosilicone Polymers 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 8
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
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- 239000003513 alkali Substances 0.000 description 7
- 239000002280 amphoteric surfactant Substances 0.000 description 7
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
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- JZIARAQCPRDGAC-UHFFFAOYSA-N Linalyl isobutyrate Chemical compound CC(C)C(=O)OC(C)(C=C)CCC=C(C)C JZIARAQCPRDGAC-UHFFFAOYSA-N 0.000 description 6
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- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 4
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/046—Aerosols; Foams
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
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Abstract
本文描述的是包含约5cm3至约70cm3的泡沫的泡沫剂型。该泡沫包含约0.5g至约4g的去污表面活性剂;约0.001g至约4g的推进剂,约0.05g/cm3至约0.35g/cm3的泡沫密度;包含约5μm至约100μm的R32的气泡尺寸分布;以及约4GU至约40GU的光泽度单位测量值。推进剂选自1,3,3,3‑四氟丙‑1‑烯、1,1二氟乙烷、以及它们的混合物。
Description
技术领域
本文描述的是一种表示毛发调理有益效果的浓缩型洗发剂泡沫剂型。
背景技术
用于毛发护理的泡沫对消费者来说是一种有吸引力的形式。通过泡沫递送的洗发剂产品易于扩散在毛发上并能够使毛发清洁而不会在毛发上留下明显的残留物。泡沫的低密度需要高表面活性剂组合物,以使消费者在一个剂量的实际产品体积中接受适当水平的清洁。通过泡沫递送洗发剂和调理产品在今天并不常见。因此,递送形式的外观必须令消费者满意并影响所需产品有益效果的感知。基于前述内容,需要浓缩型洗发剂产品,其以消费者优选的视觉外观性质作为泡沫递送。
本文描述的是具有光泽度单位测量值的泡沫剂型,其基于对泡沫剂型的目视检查,在毛发调理有益效果方面提供高消费者接受度。
发明内容
本文描述的是一种泡沫剂型,其包含约5cm3至约70cm3的泡沫,其中泡沫包含:(a)按泡沫的重量计约0.5g至约4g的去污表面活性剂;(b)按泡沫的重量计约0.001g至约4g的推进剂,其中推进剂选自氢氟烃(HFC)、氢氟烯烃(HFO)、以及它们的混合物;(c)约0.05g/cm3至约0.35g/cm3的泡沫密度;(d)包含约5μm至约100μm的R32的气泡尺寸分布;以及(e)约4GU至约40GU的光泽度单位测量值。
本文还描述的是一种泡沫剂型,其包含约5cm3至约70cm3的泡沫,其中泡沫包含:(a)按泡沫的重量计约0.5g至约4g的去污表面活性剂;(b)按泡沫的重量计约0.001g至约4g的推进剂,其中推进剂选自氢氟烃(HFC)、氢氟烯烃(HFO)、以及它们的混合物;(c)约0.05g/cm3至约0.35g/cm3的泡沫密度;(d)按泡沫的重量计约0.00005g至约0.25g阳离子沉积聚合物;(e)包含约5μm至约100μm的R32的气泡尺寸分布;以及(f)约4GU至约40GU的光泽度单位测量值。
具体实施方式
虽然本说明书以特别指出并清楚地要求保护本发明的权利要求书作为结尾,但据信通过下列说明可更好地理解本发明。
如本文所用,术语“流体”包括液体和凝胶。
如本文所用,当用于权利要求中时,包括“一个”和“一种”的冠词应被理解为是指一种或多种受权利要求书保护或所描述的物质。
如本文所用,“包括/包含”是指可加入不影响最终结果的其它步骤和其它成分。该术语涵盖术语“由……组成”和“基本上由……组成”。
如本文所用,“混合物”旨在包括物质的简单组合以及由它们的组合所可能产生的任何化合物。
如本文所用,除非另外指明,“分子量”是指重均分子量。聚合物的分子量可使用工业标准方法、凝胶渗透色谱法(“GPC”)测量。
如本文所用,术语“包括”、“包含”和“含有”旨在是非限制性的,并且理解为分别是指“具有”、“具备”和“涵盖”。
如本文所用,术语“粘度降低剂”可指分子量为约100道尔顿至约300道尔顿,或者约125道尔顿至约300道尔顿的有机化合物。另外地,粘度降低剂可在23与25摄氏度之间具有约900至50,000mg/L的水中溶解度。
除非另外说明,否则所有百分比、份数和比率均基于本发明组合物的总重量。所有涉及所列成分的这些重量均基于活性物质的含量,因此不包括可能被包含在可商购获得的物质中的载体或副产物。
除非另外指明,否则所有组分或组合物水平均是就该组分或组合物的活性部分而言,且不包括可能存在于此类组分或组合物的可商购获得的来源中的杂质,例如残余溶剂或副产物。
应当理解,贯穿本说明书给出的每一最大数值限度包括每一较低数值限度,如同该较低数值限度在本文中明确写出。贯穿本说明书给出的每一最小数值限度将包括每一较高数值限度,如同该较高数值限度在本文中明确写出。贯穿本说明书给出的每一数值范围将包括落在该较大数值范围内的每一更窄的数值范围,如同该更窄的数值范围全部在本文中明确写出。
泡沫剂型
泡沫剂型可具有如下范围的体积:约5cm3至约70cm3,或者约10cm3至约70cm3,或者约15cm3至约70cm3,或者约20cm3至约70cm3,或者来自约30cm3至约70cm3,或者约5cm3至约40cm3,或者约7.5cm3至约30cm3,或者约10cm3至约90cm3,或者约5cm3至约150cm3,或者约5cm3至约30cm3,或者约2.5cm3至约40cm3,或者约10cm3至约50cm3,或者约2.5cm3至约40cm3,或者约15cm3至约90cm3,或者约15cm3至约150cm3,或者约15cm3至约30cm3,或者约15cm3至约40cm3,或者约15cm3至约50cm3,或者约20cm3至约60cm3,或者约20cm3至约50cm3,或者约15cm3至约40cm3。
泡沫剂型可包含按泡沫的重量计约0.5g至约12g,或者约0.5g至约8g,或者约0.5g至约4g,或者约0.5g至约3g,或者约0.5g至约1.75g,或者约1g至约1.25g,或者约1g至约8g,或者约1.25g至约4g,或者约1.5g至约3g,或者约1.25g至约2.0g,或者约1g至约1.75g,或者约1g至约1.25g的去污表面活性剂。
泡沫剂型还可包含按泡沫的重量计约0.0001g至约5g,或者约0.001g至约5g,或者约0.001g至约4g,或者约0.01g至约4g,或者约0.05g至约3g,或者约0.1g至约2g,或者约0.075g至约2g的推进剂,或者约0.05g至约1g,或者约0.05g至约0.5g。
泡沫剂型也可具有约0.05g/cm3至约0.35g/cm3,或者约0.08g/cm3至约0.25g/cm3,或者约0.08g/cm3至约0.2g/cm3,或者约0.08g/cm3至约0.18g/cm3,或者约0.08g/cm3至约0.15g/cm3,或者约0.08g/cm3至约0.12g/cm3;或者约0.1g/cm3至约0.12g/cm3;或者约0.12g/cm3至约0.2g/cm3;或者约0.15g/cm3至约0.2g/cm3的泡沫密度。
泡沫剂型还可具有气泡尺寸分布,其包含约5μm至约100μm,或者约10μm至约60μm,或者约20μm至约50μm的R32;或者约25μm至约40μm的R32。
泡沫剂型可具有约5Pa至约100Pa,或者约15Pa至约100Pa,或者约20Pa至约100Pa,或者约25Pa至约100Pa,或者约38Pa至约100Pa,或者约4Pa至约39Pa,或者约5Pa至约20Pa,或者约6Pa至约19Pa的屈服点。
泡沫剂型可具有按泡沫的重量计约0.00005g至约0.25g的阳离子沉积聚合物。
泡沫剂型可具有约4GU至约150GU,或者约4GU至约100GU,或者约4GU至约75GU,或者约4GU至约40GU,或者约5GU至约30GU,或者约5GU至约20GU,或者约5GU至约15GU,或者约20GU至约100GU,或者约40GU至约75GU,或者约40GU至约75GU,或者约30GU至约40GU,或者约10GU至约30GU,或者约5GU至约10GU,或者约40GU至约150GU的光泽度单位测量值。
毛发护理组合物
本文还描述的是毛发护理组合物,其可在经由气溶胶分配器致动时递送本文所述的泡沫剂型。
去污表面活性剂
本文所述的毛发护理组合物可包含大于约20重量%的表面活性剂体系,其为组合物提供清洁性能。表面活性剂体系包含阴离子表面活性剂和/或阴离子表面活性剂与选自两性、两性离子、非离子以及它们的混合物的辅助表面活性剂的组合。去污表面活性剂的各种示例和描述示于美国专利8,440,605、美国专利申请公布2009/155383、和美国专利申请公布2009/0221463中,这些文献全文以引用方式并入本文。
毛发护理组合物可包含按重量计约10%至约40%,约15%至约36%,约18%至约32%,约20%至约30%,和/或约22%至约28%的一种或多种阴离子表面活性剂。
适用于本文的阴离子表面活性剂包括具有式ROSO3M和RO(C2H4O)xSO3M的烷基硫酸盐和烷基醚硫酸盐,其中R为具有约8至约18个碳原子的烷基或烯基,x为1至10,并且M为水溶性阳离子如铵、钠、钾和三乙醇胺阳离子,或具有两个阴离子表面活性剂阴离子的二价镁离子的盐。烷基醚硫酸盐可作为环氧乙烷和具有约8至约24个碳原子的一元醇的缩合产物制备。醇可衍生自脂肪,诸如椰子油、棕榈油、棕榈仁油或牛脂,或可为合成的。
本发明的组合物还可包含选自以下的阴离子表面活性剂:
a)R1O(CH2CHR3O)ySO3M;
b)CH3(CH2)zCHR2CH2O(CH2CHR3O)ySO3M;以及
c)它们的混合物,
其中R1表示CH3(CH2)10,R2表示H或包含1至4个碳原子的烃基,使得z和R2中的碳原子之和为8,R3为H或CH3,y为0至7,当y不为零(0)时,y的平均值为约1,并且M是一价或二价带正电荷的阳离子。
适用于组合物中的阴离子表面活性剂为烷基硫酸盐和烷基醚硫酸盐。其它适宜的阴离子表面活性剂为有机硫酸反应产物的水溶性盐。其它合适的阴离子表面活性剂为用羟乙磺酸酯化并且用氢氧化钠中和的脂肪酸的反应产物。其它类似的阴离子表面活性剂描述于美国专利2,486,921;2,486,922;和2,396,278中,这些文献全文以引用方式并入本文。
适用于本文的附加阴离子表面活性剂的示例包括但不限于月桂基硫酸铵、月桂基聚氧乙烯醚硫酸铵、月桂基硫酸三乙基胺、月桂基聚氧乙烯醚硫酸三乙基胺、月桂基硫酸三乙醇胺、月桂基聚氧乙烯醚硫酸三乙醇胺、月桂基硫酸单乙醇胺、月桂基聚氧乙烯醚硫酸单乙醇胺、月桂基硫酸二乙醇胺、月桂基聚氧乙烯醚硫酸二乙醇胺、月桂酸甘油单酯硫酸钠、月桂基硫酸钠、月桂基聚氧乙烯醚硫酸钠、月桂基聚氧乙烯醚硫酸钾、月桂基肌氨酸钠、月桂酰肌氨酸钠、月桂基肌氨酸、椰油基肌氨酸、椰油基硫酸铵、月桂酰基硫酸铵、椰油基硫酸钠、月桂酰硫酸钠、椰油基硫酸钾、月桂基硫酸钾、椰油酰硫酸单乙醇胺、十三烷基聚氧乙烯醚-1硫酸钠,硫酸盐、十三烷基聚氧乙烯醚-2硫酸钠,硫酸盐、十三烷基聚氧乙烯醚-3硫酸钠、十三烷基硫酸钠、甲基月桂酰牛磺酸钠、十一烷基硫酸钠、癸基硫酸钠、甲基椰油基牛磺酸钠、月桂酰羟乙基磺酸钠、椰油基羟乙基磺酸钠、月桂基聚氧乙烯醚磺基琥珀酸钠、月桂基磺基琥珀酸钠、十三烷基苯磺酸钠、十二烷基苯磺酸钠、以及它们的混合物。
阴离子表面活性剂的一些非限制性示例是:
烷基硫酸盐:
其中R为C8-C24烷基(直链或支链的,饱和或不饱和的)或它们的混合物,并且M+是一价阳离子。示例包括月桂基硫酸钠(其中R是C12烷基,并且M+是Na+)、月桂基硫酸铵(其中R是C12烷基,并且M+是NH3 +)、以及椰油硫酸钠(其中R是椰油烷基,并且M+是Na+);
烷基醚硫酸盐:
其中R为C8-C24烷基(直链或支链,饱和或不饱和的)或它们的混合物,n=1-12,并且M+是一价阳离子。示例包括月桂基聚氧乙烯醚硫酸钠(其中R为C12烷基且M+为Na+,n=1-3)、月桂基聚氧乙烯醚硫酸铵(其中R为C12烷基,M+为NH3 +,n=1-3)、以及十三烷基聚氧乙烯醚硫酸钠(其中R是C13烷基,M+为Na+,并且n=1-4)。
烷基甘油醚磺酸盐:
其中R=C8-C24烷基(直链或支链,饱和或不饱和的)或它们的混合物,并且M+=一价阳离子,诸如椰油甘油醚磺酸钠(R=椰油烷基,M+=Na+);
通过磺化长链α-烯烃制备的α-烯烃磺酸盐。由烯烃磺酸盐的混合物组成的α-烯烃磺酸盐:
其中R=C8-C18烷基或它们的混合物,并且M+=一价阳离子。
羟烷基磺酸盐:
其中R=C4-C18烷基或它们的混合物,并且M+=一价阳离子。示例包括C12-14烯烃磺酸钠(R=C8-C10烷基,M+=Na+)和C14-16烯烃磺酸钠(R=C10-C12烷基,M+=Na+)。
组合物还可包含阴离子烷基硫酸盐和烷基醚硫酸盐表面活性剂,其具有可选自以下的由C8至C18支链醇合成的支链烷基链:格尔伯特醇、羟醛缩合物衍生的醇、羰基合成醇、以及它们的混合物。2-烷基支链醇的非限制性示例包括:羰基合成醇,诸如2-甲基-1-十一烷醇,2-乙基-1-癸醇,2-丙基-1-壬醇,2-丁基-1-辛醇,2-甲基-1-十二烷醇,2-乙基-1-十一烷醇,2-丙基-1-癸醇,2-丁基-1-壬醇,2-戊基-1-辛醇,2-戊基-1-庚醇,以及以下列商品名出售的那些:(Sasol)、(Sasol)、和(Shell);以及Guerbet和羟醛缩合衍生的醇,诸如2-乙基-1-己醇,2-丙基-1-丁醇,2-丁基-1-辛醇,2-丁基-1-癸醇,2-戊基-1-壬醇,2-己基-1-辛醇,2-己基-1-癸醇和以商品名称(Sasol)出售的那些或作为醇乙氧基化物和烷氧基化物以商品名LUTENSOL(BASF)和LUTENSOL(BASF)出售的那些。
阴离子烷基硫酸盐和烷基醚硫酸盐还可包括由衍生自丁烯或丙烯的C8至C18支链醇合成的那些,其以商品名EXXALTM(Exxon)和(Sasol)出售。这包括十三烷基聚氧乙烯醚-n硫酸钠(STnS)的亚型的阴离子表面活性剂,其中n为约0.5和约3.5之间。该亚型的示例性表面活性剂是十三烷基聚氧乙烯醚-2硫酸钠和十三烷基聚氧乙烯醚-3硫酸钠。本发明的组合物还可包括十三烷基硫酸钠。
毛发护理组合物可包含辅助表面活性剂。辅助表面活性剂可选自两性表面活性剂、两性离子表面活性剂、非离子表面活性剂、以及它们的混合物。辅助表面活性剂可包括但不限于月桂酰胺基丙基甜菜碱、椰油酰胺基丙基甜菜碱、月桂基羟基磺基甜菜碱、月桂酰两性基乙酸钠、椰油单乙醇酰胺、以及它们的混合物。
毛发护理组合物包含按重量计约1%至约15%,约2%至约12%,约3%至约10%、约4%至约8%选自两性表面活性剂、两性离子表面活性剂、非离子表面活性剂以及它们的混合物的一种或多种辅助表面活性剂。
适用于本文毛发护理组合物中的两性表面活性剂或两性离子表面活性剂包括已知用于洗发剂或其它毛发护理清洁的那些。适宜两性离子表面活性剂或两性表面活性剂的非限制性示例描述于美国专利5,104,646和5,106,609中,将所述文献全文以引用方式并入本文。
适用于组合物中的两性辅助表面活性剂包括被描述为脂族仲胺和叔胺的衍生物的那些表面活性剂,其中脂族基团可为直链或支链的,并且其中脂族取代基之一包含约8至约18个碳原子,并且一个包含阴离子基团诸如羧基、磺酸根、硫酸根、磷酸根、或膦酸根。合适的两性表面活性剂包括但不限于选自以下的那些:椰油基氨基丙酸钠、椰油基氨基二丙酸钠、椰油酰两性基乙酸钠、椰油酰两性基羟丙基磺酸钠、椰油酰两性基丙酸钠、玉米油酰两性基丙酸钠、月桂氨基丙酸钠、月桂酰两性基乙酸钠、月桂酰两性基羟丙基磺酸钠、月桂酰两性基丙酸钠、玉米油酰两性基丙酸钠、月桂亚氨基二丙酸钠、椰油基氨基丙酸铵、椰油基氨基二丙酸铵、椰油酰两性基乙酸铵、椰油酰两性基羟丙基磺酸铵、椰油酰两性基丙酸铵、玉米油酰两性基丙酸铵、月桂氨基丙酸铵、月桂酰两性基乙酸铵、月桂酰两性基羟丙基磺酸铵、月桂酰两性基丙酸铵、玉米油酰两性基丙酸铵、月桂亚氨基二丙酸铵、椰油基氨基丙酸三乙醇胺、椰油基氨基二丙酸三乙醇胺、椰油酰两性基乙酸三乙醇胺、椰油酰两性基羟丙基磺酸三乙醇胺、椰油酰两性基丙酸三乙醇胺、玉米油酰两性基丙酸三乙醇胺、月桂氨基丙酸三乙醇胺、月桂酰两性基乙酸三乙醇胺、月桂酰两性基羟丙基磺酸三乙醇胺、月桂酰两性基丙酸三乙醇胺、玉米油酰两性基丙酸三乙醇胺、月桂亚氨基二丙酸三乙醇胺、椰油酰两性基二丙酸、癸酰两性基二乙酸二钠、癸酰两性基二丙酸二钠、辛酰两性基二乙酸二钠、辛酰两性基二丙酸二钠、椰油酰两性基羧乙基羟丙基磺酸二钠、椰油酰两性基二乙酸二钠、椰油酰两性基二丙酸二钠、二羧乙基椰油基丙二胺二钠、月桂基聚氧乙烯醚-5羧基两性基二乙酸二钠、月桂亚氨基二丙酸二钠、月桂酰两性基二乙酸二钠、月桂酰两性基二丙酸二钠、油基两性基二丙酸二钠、PPG-2-异癸醇聚醚-7羧基两性基二乙酸二钠、月桂基氨基丙酸、月桂酰两性基二丙酸、月桂基氨丙基甘氨酸、月桂基二亚乙基二氨基甘氨酸,以及它们的混合物。
两性辅助表面活性剂可为符合以下结构的表面活性剂:
其中R12为C-连接的一价取代基,其选自:包含9至15个碳原子的取代的烷基体系、包含9至15个碳原子的未取代的烷基体系、包含9至15个碳原子的直链烷基体系、包含9至15个碳原子的支链烷基体系、和包含9至15个碳原子的不饱和烷基体系;并且其中R13、R14和R15各自独立地选自:包含1至3个碳原子的C-连接的二价直链烷基体系和包含1至3个碳原子的C-连接的二价支链烷基体系;并且M+为一价抗衡离子,其选自钠、铵和质子化三乙醇胺。在一个实施例中,所述两性表面活性剂选自椰油酰两性基乙酸钠、椰油酰两性基二乙酸钠、月桂酰两性基乙酸钠、月桂酰两性基二乙酸钠、月桂酰两性基乙酸铵、椰油酰两性基乙酸铵、月桂酰两性基乙酸三乙醇胺、椰油酰两性基乙酸三乙醇胺、以及它们的混合物。
组合物可包含两性离子辅助表面活性剂,其中两性离子表面活性剂为脂族季铵、鏻和锍化合物的衍生物,其中脂族基团可为直链或支链,并且其中一个脂族取代基包含约8至约18个碳原子,并且一个脂族取代基包含阴离子基团,如羧基、磺酸根、硫酸根、磷酸根或膦酸根。两性离子表面活性剂可选自:椰油酰胺基乙基甜菜碱、椰油酰胺基丙基氧化胺、椰油酰胺基丙基甜菜碱、椰油酰胺基丙基二甲基氨基羟丙基水解胶原、椰油酰胺基丙基二甲基铵羟丙基水解胶原、椰油酰胺基丙基羟基磺基甜菜碱、椰油甜菜碱酰胺基两性基丙酸盐、椰油基甜菜碱、椰油基羟基磺基甜菜碱、椰油基/油基酰胺基丙基甜菜碱、椰油基磺基甜菜碱、月桂酰胺基丙基甜菜碱、月桂基甜菜碱、月桂基羟基磺基甜菜碱、月桂基磺基甜菜碱,以及它们的混合物。合适的两性离子表面活性剂为月桂基羟基磺基甜菜碱。两性离子表面活性剂可选自:月桂基羟基磺基甜菜碱、椰油酰胺基丙基羟基磺基甜菜碱、椰油基甜菜碱、椰油基羟基磺基甜菜碱、椰油基磺基甜菜碱、月桂基甜菜碱、月桂基磺基甜菜碱、以及它们的混合物。
辅助表面活性剂可为两性离子表面活性剂,其中两性离子表面活性剂选自:月桂基羟基磺基甜菜碱、椰油酰胺基丙基羟基磺基甜菜碱、椰油基甜菜碱、椰油基羟基磺基甜菜碱、椰油基磺基甜菜碱、月桂基甜菜碱、月桂基磺基甜菜碱、以及它们的混合物。
辅助表面活性剂可为非离子表面活性剂,所述非离子表面活性剂选自:椰油酰胺、椰油酰胺甲基MEA、椰油酰胺DEA、椰油酰胺MEA、椰油酰胺MIPA、月桂酰胺DEA、月桂酰胺MEA、月桂酰胺MIPA、十四酰胺DEA、十四酰胺MEA、PEG-20椰油酰胺MEA、PEG-2椰油酰胺、PEG-3椰油酰胺、PEG-4椰油酰胺、PEG-5椰油酰胺、PEG-6椰油酰胺、PEG-7椰油酰胺、PEG-3月桂酰胺、PEG-5月桂酰胺、PEG-3油酰胺、PPG-2椰油酰胺、PPG-2羟乙基椰油酰胺、以及它们的混合物。
适用的非离子表面活性剂包括McCutcheion的“Detergents and Emulsifiers”北美版(1986年,Allured Publishing Corp.)和McCutcheion的“Functional Materials”北美版(1992)中描述的那些。适用于毛发护理组合物中的非离子表面活性剂包括但不限于聚氧乙烯烷基酚、聚氧乙烯醇、聚氧乙烯聚丙二醇、链烷酸甘油酯、链烷酸聚甘油酯、链烷酸丙二醇酯、链烷酸山梨醇酯、链烷酸聚氧乙烯山梨醇酯、链烷酸聚氧乙二醇酯、聚氧乙烯链烷酸、链烷醇酰胺、N-烷基吡咯烷酮、烷基糖苷、烷基多葡糖苷、烷基胺氧化物、和聚氧乙烯化硅氧烷。
代表性的聚氧乙烯化醇包括烷基链在C9-C16范围内,并且具有约1至约110个烷氧基的那些,包括但不限于月桂基聚氧乙烯醚-3、月桂基聚氧乙烯醚-23、十六烷基聚氧乙烯醚-10、硬脂基聚氧乙烯醚-10、硬脂基聚氧乙烯醚-100、山嵛醇聚醚-10、和可以商品名91、23、25、45、135、67、PC 100、PC 200、PC 600从Shell Chemicals(Houston,Texas)商购获得的那些、以及它们的混合物。
还可商购获得的是可以商品名从Uniqema(Wilmington,Delaware)商购获得的聚氧乙烯脂肪酯,包括但不限于,30、35、52、56、58、72、76、78、93、97、98、721、以及它们的混合物。
适宜的烷基糖苷和烷基多葡糖苷可由式(S)n-O-R表示,其中S为糖部分如葡萄糖、果糖、甘露糖、半乳糖等;n为约1至约1000的整数,并且R为C8-C30烷基。烷基可得自其的长链醇示例包括癸醇、月桂醇、十四烷醇、鲸蜡醇、硬脂醇、油醇等等。这些表面活性剂的示例包括烷基多葡糖苷,其中S为葡萄糖部分,R为C8-20烷基,并且n为约1至约9的整数。这些表面活性剂的可商购获得的示例包括以商品名325 CS、600 CS和625CS购自Cognis(Ambler,Pa)的癸基多葡糖苷和月桂基多葡糖苷。还可用于本文的是蔗糖酯表面活性剂如蔗糖椰油酸酯和蔗糖月桂酸酯,和可以商品名TritonTMBG-10和TritonTMCG-110得自The Dow Chemical Company(Houston,Tx)的烷基多葡糖苷。
适用的其他非离子表面活性剂为甘油酯和聚甘油酯,包括但不限于,甘油基单酯,C12-22饱和、不饱和和支链脂肪酸的甘油基单酯如油酸甘油酯、一硬脂酸甘油酯、一棕榈酸甘油酯、一山嵛酸甘油酯、以及它们的混合物,和C12-22饱和、不饱和和支链脂肪酸的聚甘油酯如聚甘油基-4异硬脂酸酯、聚甘油基-3油酸酯、聚甘油基-2-倍半油酸酯、二异硬脂酸三甘油酯、一油酸二甘油酯、一油酸四甘油酯、以及它们的混合物。
还可用作非离子表面活性剂的是脱水山梨糖醇酯。C12-22饱和、不饱和和支链脂肪酸的脱水山梨糖醇酯可用于本文中。这些脱水山梨糖醇酯通常包含一酯、二酯、三酯等的混合物。合适的脱水山梨糖醇酯的代表性示例包括一月桂酸脱水山梨糖醇酯(20)、一棕榈酸脱水山梨糖醇酯(40)、一硬脂酸脱水山梨醇酯(60)、三硬脂酸脱水山梨醇酯(65)、一油酸脱水山梨糖醇酯(80)、三油酸脱水山梨糖醇酯(85)、和异硬脂酸脱水山梨糖醇酯。
还适用于本文的是脱水山梨糖醇酯的烷氧基化衍生物,包括但不限于,均得自Uniqema的聚氧乙烯(20)脱水山梨糖醇一月桂酸酯(20)、聚氧乙烯(20)脱水山梨糖醇一棕榈酸酯(40)、聚氧乙烯(20)脱水山梨醇一硬脂酸酯(60)、聚氧乙烯(20)脱水山梨糖醇一油酸酯(80)、聚氧乙烯(4)脱水山梨糖醇一月桂酸酯(21)、聚氧乙烯(4)脱水山梨醇一硬脂酸酯(61)、聚氧乙烯(5)脱水山梨糖醇一油酸酯(81)、以及它们的混合物。
还适用于本文的是烷基酚乙氧基化物,包括但不限于壬基酚乙氧基化物(购自TheDow Chemical Company(Houston,Tx.)的TergitolTMNP-4、NP-6、NP-7、NP-8、NP-9、NP-10、NP-11、NP-12、NP-13、NP-15、NP-30、NP-40、NP-50、NP-55、NP-70)和辛基酚乙氧基化物(购自The Dow Chemical Company(Houston,Tx.)的TritonTMX-15、X-35、X-45、X-114、X-100、X-102、X-165、X-305、X-405、X-705)。
还适用于本文中的是链烷醇酰胺(包括椰油酰胺单乙醇胺(CMEA))和叔烷基胺氧化物(包括月桂基氧化胺和椰油基氧化胺)。
可用于本文的非离子表面活性剂具有至少8,在一个实施方案中大于10,以及在另一个实施方案中大于12的HLB(亲水亲油平衡)。HLB表示表面活性剂分子中亲水性部分与亲脂性部分间的平衡,并且通常用作分类方法。常用表面活性剂的HLB值易于在文献(例如McCutcheon的“Emulsifiers and Detergents”(MC Publishing Co.,2004)中的HLB索引)中获得。
其他适用于毛发护理组合物中的阴离子表面活性剂、两性离子表面活性剂、两性表面活性剂和非离子附加表面活性剂的非限制性示例描述于McCutcheon的《Emulsifiersand Detergents》(1989年鉴,由M.C.Publishing Co.出版和美国专利3,929,678、2,658,072;2,438,091;2,528,378中,这些文献全文以引用方式并入本文。
洗发剂组合物可包含20wt%至45wt%的去污表面活性剂,其中0wt%至10wt%是两性表面活性剂,2wt%至25wt%是具有含C12至C16碳原子的支链烷基碳链的硫酸盐,5wt%至30wt%是具有含C12至C16碳原子的直链烷基碳链的硫酸盐,约2wt%至约8wt%的水混溶性溶剂,和约40wt%至约80wt%的水载体,其中直链阴离子表面活性剂:支链阴离子表面活性剂的比例为约0.4至约5。
洗发剂组合物可包含20wt%至45wt%的去污表面活性剂,其中0wt%至10wt%是两性表面活性剂,6wt%至30wt%是具有含C12至C16碳原子的支链烷基碳链的硫酸盐,0wt%至20wt%是具有含C12至C16碳原子的直链烷基碳链的硫酸盐,约2wt%至约10wt%的水混溶性溶剂,和约40wt%至约80wt%的水载体,其中(直链阴离子表面活性剂/支链阴离子表面活性剂)/可混溶溶剂的重量比高于约0.2,并且其中支链阴离子表面活性剂/可混溶溶剂的重量比高于5。
该洗发剂组合物可包含5wt%至45wt%的去污表面活性剂,其中5wt%至35wt%为阴离子去污表面活性剂,水可混溶溶剂为约1wt%至约20wt%,氢氟烯烃发泡剂为约3wt%或更高,以及水载体为约20wt%至约90wt%,其中发泡剂与水混溶性溶剂的重量比低于约3。
该洗发剂组合物可包含20wt%至45wt%的去污表面活性剂,其中10wt%至40wt%是阴离子去污表面活性剂,1wt%至15wt%的一种或多种助表面活性剂选自两性表面活性剂、两性离子表面活性剂、非离子表面活性剂、以及它们的混合物;其中约1%或更多为两性离子表面活性剂,其在其分子结构中具有羟基,约0.1重量%至约35重量%的一种或多种粘度降低剂,约0.05重量%至约1重量%的一种或多种阳离子聚合物,其重均分子量小于约1,000,000g/mol。
该洗发剂组合物可包含20wt%至45wt%的去污表面活性剂,其中10wt%至40wt%是阴离子去污表面活性剂,1wt%至15wt%的一种或多种助表面活性剂选自月桂基羟基磺基甜菜碱、椰油羟基磺基甜菜碱、月桂酰两性基乙酸钠、椰油两性基乙酸钠、月桂酰基丙酸钠、椰油基丙酸钠、以及它们的混合物,约0.1重量%至约35重量%的一种或多种粘度降低剂,约0.05重量%至约1重量%的一种或多种阳离子聚合物,其重均分子量小于约1,000,000g/mol。
粘度降低剂
本文所述的毛发护理组合物可包含按毛发护理组合物的重量计约0.5%至约15%,或者约0.75%至约10.0%,或者约1%至约7.5%,或者约1.25%至约5.0%,或者约1.5%至约3.5%的粘度降低剂。合适的粘度降低剂的非限制性示例包括水混溶性溶剂、水溶助长剂、A类材料、B类材料、硅氧烷聚醚、以及它们的混合物。
本文所述的毛发护理组合物可具有约8厘泊至约15,000厘泊,或者约9厘泊至约12,000厘泊,或者约10厘泊至约11,000厘泊,或者约11厘泊至约5,000厘泊,或者约12厘泊至2,500厘泊,或者约13厘泊至约1,500厘泊,或者约14厘泊至约1,000厘泊的液相粘度。毛发组合物粘度值可使用附接有同心圆筒的TA仪器AR-G2流变仪在25℃下以100s-1的剪切速率测量。
1.与水混溶的溶剂
组合物可包含与水混溶的二醇和其它二醇。非限制性示例包括双丙二醇、三丙二醇、二甘醇、乙二醇、丙二醇、甘油、1,3-丙二醇、2,2-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、2-甲基-2,4-戊二醇以及它们的混合物。毛发护理组合物可包含两种或更多种与水混溶的溶剂,其中该溶剂中的至少一种是双丙二醇。
2.水溶助长剂
该组合物可包括水溶助长剂。非限制性示例包括低级脂族醇、低级烷基苯磺酸盐(二甲苯和甲苯的衍生物)、以及它们的组合。优选的是醇、脲、二甲苯磺酸钠、二甲苯磺酸铵和二甲苯磺酸钾。
3.A类材料
A类粘度降低剂可具有约-5至约-0.7,或者约-4.6至约-0.85,或者约-4.5至约-0.9,或者约-3.1至约-0.7,或者约-3至约-0.85的分配分散系数。A类粘度降低剂可具有约-4.6至约-1.9,或者约-4.5至约-2的分配分散系数,其中一种或多种粘度降低剂具有至少2个极性基团,或具有1个极性基团和在连续基团中彼此连接的少于5个非循环sp3杂化碳原子。A类粘度降低剂可具有约-4.6至约-1.9,或者约-4.5至约-2的分配分散系数,其中一种或多种粘度降低剂具有2至4个极性基团,或具有1个极性基团和在连续基团中彼此连接的1至3个非循环sp3杂化碳原子。A类粘度降低剂可具有约-4.6至约-1.9,或者约-4.5至约-2的分配分散系数,其中一种或多种粘度降低剂具有2至4个极性基团,或具有1个极性基团和在连续基团中彼此连接的2个非循环sp3杂化碳原子。当用于本文所述的毛发护理组合物中时,A类粘度降低剂可提供意想不到的粘度降低。
分配分散系数(PDC)由以下公式定义:
PDC=logP-0.3001*(δD)2+10.362*δD-93.251
其中logP是由Consensus算法计算的辛醇水分配系数,该算法是在AdvancedChemistry Development,Inc.(ACD/Labs,Toronto,Canada)公司的14.02版本的ACD/Percepta中实施的,并且其中D是使用Steven Abbott和Hiroshi Yamamoto的“HSPIP–Hansen Solubility Parameters in Practice”程序,第4版,4.1.07版本计算的在(MPa)1/2中的Hansen溶解度分散参数。
粘度降低剂可以是包含1个极性基团,或者至少1个极性基团,或者2至4个极性基团,以及另外的或者至少2个极性基团的有机化合物。极性基团可选自醇、醛、酯、内酯、香豆素、醚、酮、苯酚、苯基、氧化物、烯基、炔基以及它们的组合。粘度降低剂可具有介于100道尔顿与300道尔顿之间,或者约125道尔顿至约300道尔顿的分子量。另外地,粘度降低剂可在23与25摄氏度之间具有约900至50,000mg/L的水中溶解度。
A类粘度降低剂可选自覆盆子酮、柠檬酸三乙酯、5-甲基-3-庚酮肟、羟基香茅醛、樟脑胶、2-异丙基-5-甲基-2-己烯醛、桉树脑、1,1-二甲氧基辛烷、异丁基己酸酯、二氢异茉莉酮酸酯以及它们的组合。另选地,A类粘度降低剂可选自覆盆子酮、柠檬酸三乙酯、羟基香茅醛、乙醇、双丙二醇、以及它们的组合。
4.B类材料
B类粘度降低剂可具有约0.05至约5.1,或者约0.08至约4.5,或者约0.09至约4.4,或者约0.05至约2.0,或约0.08至约1.8,或者约0.09至约1.7,或者约0.095至约1.68的分配分散系数。当用于本文所述的毛发护理组合物中时,B类粘度降低剂可提供意想不到的粘度降低。
分配分散系数(PDC)由以下公式定义:
PDC=logP-0.3001*(δD)2+10.362*δD-93.251
其中logP是由Consensus算法计算的辛醇水分配系数,该算法是在AdvancedChemistry Development,Inc.(ACD/Labs,Toronto,Canada)公司的14.02版本的ACD/Percepta中实施的,其中δD是使用Steven Abbott和Hiroshi Yamamoto的“HSPIP–HansenSolubility Parameters in Practice”程序,第4版,4.1.07版本计算的在(MPa)1/2中的Hansen溶解度分散参数。
粘度降低剂可以是包含1个极性基团,或者至少1个极性基团,或者2至4个极性基团,以及另外的或者至少2个极性基团的有机化合物。极性基团可选自醇、醛、酯、内酯、香豆素、醚、酮、苯酚、苯基、氧化物、烯基、炔基以及它们的组合。粘度降低剂可具有介于100道尔顿与300道尔顿之间,或者约125道尔顿至约300道尔顿的分子量。另外地,粘度降低剂可在23℃与25℃之间具有约10mg/L至900mg/L的水中溶解度。
B类粘度降低剂可选自维隆松、水杨酸异戊酯、γ-萜品烯、里哪基异丁酸酯、α-萜品烯、柠檬烯、二戊烯、苯乙酸香叶酯、肉豆蔻酸异丙酯、十六烷以及它们的组合。另选地,B类粘度降低剂可选自维隆松、γ-萜品烯、里哪基异丁酸酯、α-萜品烯、柠檬烯、二戊烯、苯乙酸香叶酯、肉豆蔻酸异丙酯、十六烷以及它们的组合。另选地,B类粘度降低剂可选自维隆松、水杨酸异戊酯、γ-萜品烯、里哪基异丁酸酯、α-萜品烯、柠檬烯、二戊烯、苯乙酸香叶酯以及它们的组合。
5.硅氧烷聚醚
在本发明的另一实施方案中,个人护理组合物可包含硅氧烷聚醚。非限制性示例包括分子量在500g/mol至3500g/mol之间的PEG-8聚二甲基硅氧烷,包括SilsurfA208(MW为约855g/mol)和SilsurfD208(MW为约2706g/mol)。
C.水载体
毛发护理组合物可包含按毛发护理组合物的重量计约45%至约78%,或者约50%至约75%,或者约55%至约70%,或者约60%至约68%的水。
D.阳离子聚合物
毛发护理组合物还可包含阳离子聚合物。这些阳离子聚合物可包括以下中的至少一种:(a)阳离子瓜尔胶聚合物,(b)阳离子非瓜尔型半乳甘露聚糖聚合物,(c)阳离子木薯聚合物,(d)丙烯酰胺单体和阳离子单体的阳离子共聚物,和/或(e)合成的非交联阳离子聚合物,其在与去污表面活性剂混合后可形成或可不形成溶致液晶,(f)阳离子纤维素聚合物。另外地,阳离子聚合物可为阳离子聚合物的混合物。
毛发护理组合物可包含阳离子瓜尔胶聚合物,其为阳离子取代的半乳甘露聚糖(瓜尔)树胶衍生物。用于制备这些瓜尔胶衍生物的瓜尔胶通常以天然存在的得自瓜尔胶植物种子的材料形式获得。瓜尔胶分子自身为直链甘露聚糖,其在规则间隔处支化,在交替的甘露糖单元上具有单节半乳糖单元。甘露糖单元经由β(1-4)糖苷键连接基彼此连接。半乳糖分支通过α(1-6)连接产生。通过聚半乳甘露聚糖的羟基与反应性季铵化合物之间的反应,来获得瓜尔胶的阳离子衍生物。阳离子基团到瓜尔胶结构上的取代度应足以提供上文所述的所需阳离子电荷密度。
根据一个实施方案,阳离子聚合物,包括但不限于阳离子瓜尔胶聚合物,具有小于1,000,000g/mol、或约10,000至约1,000,000g/mol、或约25,000至约1,000,000g/mol、或约50,000至约1,000,000g/mol、或约100,000至约1,000,000g/mol的分子量。在一个实施方案中,阳离子瓜尔胶聚合物具有约0.2meq/g至约2.2meq/g、或约0.3meq/g至约2.0meq/g、或约0.4meq/g至约1.8meq/g;或约0.5meq/g至约1.7meq/g的电荷密度。
根据一个实施方案,阳离子瓜尔胶聚合物具有小于约1,000,000g/mol的重均分子量,并且具有约0.1meq/g至约2.5meq/g的电荷密度。在一个实施方案中,阳离子瓜尔胶聚合物具有小于950,000g/mol,或约10,000至约900,000g/mol,或约25,000至约900,000g/mol,或约50,000至约900,000g/mol,或约100,000至约900,000g/mol,约150,000至约800,000g/mol的重均分子量。在一个实施方案中,阳离子瓜尔胶聚合物具有约0.2meq/g至约2.2meq/g、或约0.3meq/g至约2.0meq/g、或约0.4meq/g至约1.8meq/g;或约0.5meq/g至约1.5meq/g的电荷密度。
毛发护理组合物可包含按毛发护理组合物的总重量计约0.01%至约1%,或者约0.05%至约1%,或者约0.05%至约0.9%,或者约0.1%至约0.8%,或者约0.2%至约0.7%阳离子聚合物(a)。
阳离子瓜尔胶聚合物可由季铵化合物形成。在一个实施方案中,用于形成阳离子瓜尔胶聚合物的季铵化合物符合通式1:
其中R3、R4和R5为甲基或乙基基团;R6为具有通式2的环氧烷基基团:
或R6为具有通式3的卤代醇基团:
其中R7为C1至C3亚烷基;X为氯或溴,并且Z为阴离子,如Cl-、Br-、I-或HSO4-。
在一个实施方案中,阳离子瓜尔胶聚合物符合通式4:
其中R8为瓜尔胶;并且其中R4、R5、R6和R7如上述定义;并且其中Z为卤素。在一个实施方案中,阳离子瓜尔胶聚合物符合式5:
合适的阳离子瓜尔胶聚合物包括阳离子瓜尔胶衍生物,诸如瓜尔羟丙基三甲基氯化铵。在一个实施方案中,阳离子瓜尔胶聚合物为瓜尔羟丙基三甲基氯化铵。瓜尔羟丙基三甲基氯化铵的具体示例包括可从Rhone-Poulenc Incorporated商购获得的系列,例如可从Rhodia商购获得的C-500。C-500具有0.8meq/g的电荷密度和500,000g/mol的分子量。其它合适的瓜尔羟丙基三甲基氯化铵为:具有约1.1meq/g的电荷密度和约500,000g/mol的分子量并且得自ASI的瓜尔羟丙基三甲基氯化铵,具有约1.5meq/g的电荷密度和约500,000g/mol的分子量并且得自ASI的瓜尔羟丙基三甲基氯化铵。其他合适的瓜尔胶羟丙基三甲基氯化铵是:Hi-Care 1000,其电荷密度为约0.7meq/g,并且分子量为约600,000g/mol,可从Rhodia获得;N-Hance 3269和N-Hance 3270,其电荷密度为约0.7meq/g,并且分子量为约425,000g/mol,可从ASIAquaCat CG518获得,其电荷密度为约0.9meq/g和分子量重量约为50,000g/mol,可从ASI获得。BF-13,其为具有约1.1meq/g的电荷密度和约800,000的分子量的无硼酸盐(硼)的瓜尔胶,以及BF-17,其为具有约1.7meq/g的电荷密度和约800,000的M.W.t的无硼酸盐(硼)的瓜尔胶,二者均得自ASI。
毛发护理组合物可包含半乳甘露聚糖聚合物衍生物,以单体对单体计,半乳甘露聚糖聚合物衍生物具有的甘露糖与半乳糖的比率大于2:1,半乳甘露聚糖聚合物衍生物选自:阳离子半乳甘露聚糖聚合物衍生物和具有净正电荷的两性半乳甘露聚糖聚合物衍生物。如本文所用,术语“阳离子半乳甘露聚糖”是指向其中添加阳离子基团的半乳甘露聚糖聚合物。术语“两性半乳甘露聚糖”是指向其中添加阳离子基团和阴离子基团以使得聚合物具有净正电荷的半乳甘露聚糖聚合物。
半乳甘露聚糖聚合物存在于豆科种子胚乳中。半乳甘露聚糖聚合物由甘露糖单体和半乳糖单体的组合构成。半乳甘露聚糖分子为按规则的间隔在特定甘露糖单元上以单节半乳糖单元支化的直链甘露聚糖。甘露糖单元经由β(1-4)糖苷键彼此连接。经由α(1-6)键产生半乳糖支化。甘露糖单体与半乳糖单体的比率根据植物的品种而改变,并且还受气候的影响。以单体对单体计,适用的非瓜尔胶半乳甘露聚糖聚合物衍生物可具有大于2:1的甘露糖与半乳糖的比率。合适的甘露糖与半乳糖的比率可大于约3:1,并且甘露糖与半乳糖的比率可大于约4:1。甘露糖与半乳糖比率的分析是本领域熟知的,并且通常基于半乳糖含量的测量。
用于制备非瓜尔胶半乳甘露聚糖聚合物衍生物的树胶通常以天然存在的材料形式获得,诸如来自植物的种子或豆形果实。多种非瓜尔胶半乳甘露聚糖聚合物的示例包括但不限于刺云豆胶(3份甘露糖/1份半乳糖)、长角豆胶或角豆胶(4份甘露糖/1份半乳糖)和肉桂胶(5份甘露糖/1份半乳糖)。
在本发明的一个实施方案中,非瓜耳胶半乳甘露聚糖聚合物衍生物具有约1,000至约1,000,000,和/或约5,000至约900,000的M.Wt.。
毛发护理组合物还可包含具有约0.5meq/g至约7meq/g的阳离子电荷密度的半乳甘露聚糖聚合物衍生物。半乳甘露聚糖聚合物衍生物可具有约1meq/g至约5meq/g的阳离子电荷密度。半乳甘露聚糖结构上的阳离子基团的取代度应足以提供所需的阳离子电荷密度。
半乳甘露聚糖聚合物衍生物可为非瓜尔胶半乳甘露聚糖聚合物的阳离子衍生物,该衍生物由聚半乳甘聚糖聚合物的羟基基团与反应性季铵化合物之间的反应获得。适用于形成阳离子半乳甘露聚糖聚合物衍生物的季铵化合物包括符合如上定义的通式1-5的那些。
由上述试剂形成的阳离子非瓜尔胶半乳甘露聚糖聚合物衍生物由通式6表示:
其中R为树胶。阳离子半乳甘露聚糖衍生物可为树胶羟丙基三甲基氯化铵,其可更具体地由通式7表示:
另选地,半乳甘露聚糖聚合物衍生物可为具有净正电荷的两性半乳甘露聚糖聚合物衍生物,当阳离子半乳甘露聚糖聚合物衍生物还包含阴离子基团时,获得两性半乳甘露聚糖聚合物衍生物。
阳离子非瓜尔胶半乳甘露聚糖可具有大于约4:1的甘露糖与半乳糖的比率,约50,000g/mol至约1,000,000g/mol、和/或约100,000g/mol至约900,000g/mol的分子量,以及约1meq/g至约5meq/g、和/或2meq/g至约4meq/g的阳离子电荷密度,并且还可来源于肉桂植物。
毛发护理组合物可包含按组合物的重量计至少约0.05%的半乳甘露聚糖聚合物衍生物,或者按组合物的重量计约0.05%至约2%的半乳甘露聚糖聚合物衍生物。
毛发护理组合物可包含水溶性阳离子改性淀粉聚合物。如本文所用,术语“阳离子改性淀粉”是指在使淀粉降解至具有较小分子量之前向其中添加阳离子基团的淀粉,或在使淀粉改性以获得期望的分子量之后向其中添加阳离子基团的淀粉。术语“阳离子改性淀粉”的定义还包括两性改性淀粉。术语“两性改性淀粉”是指向其中添加阳离子基团和阴离子基团的淀粉水解产物。
毛发护理组合物可包含按组合物的重量计约0.01%至约10%,和/或约0.05%至约5%范围内的阳离子改性淀粉聚合物。
本文公开的阳离子改性淀粉聚合物具有约0.5%至约4%的结合氮百分比。
用于毛发护理组合物中的阳离子改性淀粉聚合物可具有约50,000g/mol至约1,000,000g/mol、和/或约100,000g/mol至约1,000,000g/mol的分子量。
毛发护理组合物可包含阳离子改性淀粉聚合物,其具有约0.2meq/g至约5meq/g、和/或约0.2meq/g至约2meq/g的电荷密度。获得此类电荷密度的化学改性包括但不限于向淀粉分子中加入氨基和/或铵基团。这些铵基团的非限制性示例可包括取代基,诸如羟丙基三甲基氯化铵、三甲基羟丙基氯化铵、二甲基硬脂基羟丙基氯化铵和二甲基十二烷基羟丙基氯化铵。参见Solarek,D.B.,Cationic Starches in Modified Starches:Propertiesand Uses(Wurzburg,O.B.编辑,CRC Press,Inc.,Boca Raton,Fla.1986,第113-125页)。可将阳离子基团在淀粉降解至具有较小分子量之前添加到淀粉中,或可将阳离子基团在此类改性之后添加到其中。
阳离子改性淀粉聚合物通常具有约0.2至约2.5的阳离子基团取代度。如本文所用,阳离子改性淀粉聚合物的“取代度”是每个由取代基衍生的葡糖酐单元上羟基数的平均量度。由于每个葡糖酐单元具有三个可被取代的羟基,所以最大可能的取代度为3。以摩尔平均计,取代度表示为每摩尔葡糖酐单元具有的取代基摩尔数。取代度可使用本领域熟知的质子核磁共振光谱(“.sup.1H NMR”)方法来测定。合适的sup.1H NMR技术包括描述于“Observation on NMR Spectra of Starches in Dimethyl Sulfoxide,Iodine-Complexing,and Solvating in Water-Dimethyl Sulfoxide”(Qin-Ji Peng和ArthurS.Perlin,Carbohydrate Research,160(1987),57-72;和“An Approach to theStructural Analysis of Oligosaccharides by NMR Spectroscopy”,J.HowardBradbury and J.Grant Collins,Carbohydrate Research,71,(1979),15-25中。
在化学改性之前的淀粉来源可选自多种来源,例如块茎、豆类、谷类和粮食。这种来源的淀粉的非限制性示例可包括玉米淀粉、小麦淀粉、稻米淀粉、蜡质玉米淀粉、燕麦淀粉、木薯淀粉(cassaya starch)、蜡质大麦淀粉、蜡质稻米淀粉、麸质稻米淀粉、糯米淀粉、支链淀粉、马铃薯淀粉、木薯淀粉(tapioca starch)、燕麦淀粉、西米淀粉、甜稻米淀粉、或它们的混合物。
阳离子改性淀粉聚合物可选自降解的阳离子玉米淀粉、阳离子木薯、阳离子马铃薯淀粉以及它们的混合物。另选地,阳离子改性淀粉聚合物为阳离子玉米淀粉和阳离子木薯。
在降解至具有较小分子量之前或在改性至具有较小分子量之后,淀粉可包含一种或多种附加的改性。例如,这些改性可包括交联、稳定化反应、磷酸化和水解。稳定性反应可包括烷基化和酯化。
阳离子改性淀粉聚合物可以水解淀粉(例如酸、酶或碱降解)、氧化淀粉(例如过氧化物、过酸、次氯酸盐、碱或任何其它氧化剂)、物理/机械降解淀粉(例如经由处理设备的热机械能输入)或它们组合的形式掺入所述组合物中。
淀粉的最佳形式是一种易于溶解于水中并且在水中形成基本上澄清(600nm下的透射%.gtoreq.80)溶液的形式。组合物的透明度通过紫外/可见(UV/VIS)分光光度测定法来测定,其使用Gretag Macbeth Colorimeter Color i5根据相关指导说明,测定样品对UV/VIS射线的吸收或透过。已示出,600nm的光波长足以表征化妆品组合物的透明度。
适用于毛发护理组合物中的阳离子改性淀粉可购自已知的淀粉供应商。还适用于毛发护理组合物中的是非离子改性淀粉,如本领域所已知的,非离子改性淀粉可被进一步衍生为阳离子改性淀粉。如本领域已知的是,其它合适的改性淀粉原料可被季铵化以产生适用于毛发护理组合物中的阳离子改性淀粉聚合物。
淀粉降解过程:通过在水中混合颗粒状淀粉,可制得淀粉浆液。将温度升至约35℃。然后加入按淀粉计约50ppm浓度的高锰酸钾水溶液。用氢氧化钠将pH升至约11.5,并且将浆液充分搅拌,以防止淀粉沉降。然后加入在水中稀释的约30%的过氧化氢溶液,使过氧化物的含量基于淀粉计为约1%。然后通过加入附加的氢氧化钠,将pH恢复至约11.5。将反应在约1至约20小时的时段内完成。然后将该混合物用稀盐酸中和。降解淀粉通过过滤接着洗涤并干燥来重新获得。
毛发护理组合物可包含丙烯酰胺单体和阳离子单体的阳离子共聚物,其中共聚物具有约1.0meq/g至约3.0meq/g的电荷密度。阳离子共聚物可为丙烯酰胺单体和阳离子单体的合成阳离子共聚物。
阳离子共聚物可包含:
(i)具有下式AM的丙烯酰胺单体:
其中R9为H或C1-4烷基;并且R10和R11独立地选自H、C1-4烷基、CH2OCH3、CH2OCH2CH(CH3)2和苯基,或合在一起为C3-6环烷基;以及
(ii)符合式CM的阳离子单体:
其中k=1,v、v'和v”中的每一个独立地为1至6的整数,w为零或1至10的整数,并且X-为阴离子。
阳离子单体可符合式CM,并且其中k=1,v=3并且w=0,z=1,并且X-为Cl-,以形成以下结构:
上述结构可被称为二季铵盐。另选地,阳离子单体可符合式CM,并且其中v和v”各自为3,v'=1,w=1,y=1,并且X-为Cl-,如:
上述结构可被称为三季铵盐。
合适的丙烯酰胺单体包括但不限于丙烯酰胺或甲基丙烯酰胺。
在另选的实施方案中,阳离子共聚物是丙烯酰胺单体和阳离子单体,其中阳离子单体选自:(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸二甲基氨基丙酯、(甲基)丙烯酸二叔丁基氨基乙酯、二甲基氨甲基(甲基)丙烯酰胺、二甲基氨丙基(甲基)丙烯酰胺;乙烯亚胺、乙烯胺、2-乙烯基吡啶、4-乙烯基吡啶;三甲基(甲基)丙烯酰氧乙基氯化铵、三甲基(甲基)丙烯酰氧乙基甲酯硫酸铵、二甲基铵(甲基)丙烯酰氧乙基苄基氯化铵、4-苯甲酰基苄基二甲基丙烯酰氧乙基氯化铵、三甲基(甲基)丙烯酰胺基乙基氯化铵、三甲基(甲基)丙烯酰胺基丙基氯化铵、乙烯基苄基三甲基氯化铵、二烯丙基二甲基氯化铵、以及它们的混合物。
阳离子共聚物可包含阳离子单体,阳离子单体选自:阳离子单体包括三甲基(甲基)丙烯酰氧乙基氯化铵、三甲基(甲基)丙烯酰氧乙基甲酯硫酸铵、二甲基(甲基)丙烯酰氧乙基苄基氯化铵、4-苯甲酰基苄基二甲基丙烯酰氧乙基氯化铵、三甲基(甲基)丙烯酰胺基乙基氯化铵、三甲基(甲基)丙烯酰胺基丙基氯化铵、乙烯基苄基三甲基氯化铵、以及它们的混合物。
阳离子共聚物可为水溶性的。阳离子共聚物由以下形成:(1)(甲基)丙烯酰胺和基于(甲基)丙烯酰胺的阳离子单体和/或水解稳定的阳离子单体的共聚物,(2)(甲基)丙烯酰胺、基于阳离子(甲基)丙烯酸酯的单体、和基于(甲基)丙烯酰胺的单体、和/或水解稳定的阳离子单体的三聚物。基于阳离子(甲基)丙烯酸酯的单体可为包含季铵化N原子的(甲基)丙烯酸的阳离子化酯。在一个实施方案中,包含季铵化N原子的(甲基)丙烯酸的阳离子化酯为烷基和亚烷基基团中具有C1-C3的季铵化(甲基)丙烯酸二烷基氨基烷基酯。合适的包含季铵化N原子的(甲基)丙烯酸的阳离子化酯可选自:用氯甲烷季铵化的(甲基)丙烯酸二甲基氨基甲酯的铵盐、(甲基)丙烯酸二甲基氨基乙酯的铵盐、(甲基)丙烯酸二甲基氨基丙酯的铵盐、(甲基)丙烯酸二乙基氨基甲酯的铵盐、(甲基)丙烯酸二乙基氨基乙酯的铵盐;以及(甲基)丙烯酸二乙基氨基丙酯的铵盐。在一个实施方案中,包含季铵化的N原子的(甲基)丙烯酸的阳离子化酯是用卤代烷、或用氯甲烷、或苄基氯、或硫酸二甲酯季铵化的丙烯酸二甲基氨基乙酯(ADAME-Quat)。当基于(甲基)丙烯酰胺时,阳离子单体可以是在烷基和亚烷基中具有C1至C3的季铵化二烷基氨基烷基(甲基)丙烯酰胺,或者用卤代烷、或氯甲烷、或苄基氯、或硫酸二甲酯季铵化的二甲基氨基丙基丙烯酰胺。
合适的基于(甲基)丙烯酰胺的阳离子单体包括在烷基和亚烷基基团中具有C1-C3的季铵化二烷基氨基烷基(甲基)丙烯酰胺。基于(甲基)丙烯酰胺的阳离子单体可为二甲基氨基丙基丙烯酰胺,其用卤代烷(尤其是氯甲烷)或苄基氯或硫酸二甲酯季铵化。
阳离子单体可为水解稳定的阳离子单体。除了二烷基氨基烷基(甲基)丙烯酰胺以外,水解稳定的阳离子单体还可为OECD水解测试可以认为稳定的所有单体。阳离子单体可为水解稳定的,并且水解稳定的阳离子单体可选自:二烯丙基二甲基氯化铵和水溶性阳离子苯乙烯衍生物。
阳离子共聚物可为丙烯酰胺、用氯甲烷季铵化的(甲基)丙烯酸2-二甲基铵乙酯(ADAME-Q)、和用氯甲烷季铵化的3-二甲基铵丙基(甲基)丙烯酰胺(DIMAPA-Q)的三元共聚物。阳离子共聚物可由丙烯酰胺和丙烯酰胺基丙基三甲基氯化铵形成,其中丙烯酰胺基丙基三甲基氯化铵具有约1.0meq/g至约3.0meq/g的电荷密度。
阳离子共聚物可具有约1.1meq/g至约2.5meq/g、或约1.1meq/g至约2.3meq/g、或约1.2meq/g至约2.2meq/g、或约1.2meq/g至约2.1meq/g、或约1.3meq/g至约2.0meq/g、或约1.3meq/g至约1.9meq/g的电荷密度。
阳离子共聚物可具有约10,000g/mol至约1,000,000g/mol、或约25,000g/mol至约1,000,000g/mol、或约50,000g/mol至约1,000,000g/mol、或约100,000g/mol至约1,000,000g/mol、或约150,000g/mol至约1,000,000g/mol的分子量。
(a)阳离子合成聚合物
毛发护理组合物可包含可由以下形成的阳离子合成聚合物
i)一种或多种阳离子单体单元,和任选的
ii)一种或多种带有负电荷的单体单元,和/或
iii)非离子单体,
其中共聚物的随后电荷是正的。三种类型的单体的比率以“m”、“p”和“q”给出,其中“m”为阳离子单体的数目,“p”为带有负电荷的单体的数目,并且“q”为非离子单体的数目。
阳离子聚合物可为具有以下结构的水溶性或水可分散的非交联并且合成的阳离子聚合物:
其中A可为以下阳离子部分中的一种或多种:
其中@=酰胺基、烷基酰胺基、酯、醚、烷基、或烷基芳基;
其中Y=C1-C22烷基、烷氧基、烷叉基、烷基或芳氧基;
其中ψ=C1-C22烷基、烷氧基、烷基芳基、或烷基芳氧基;。
其中Z=C1-C22烷基、烷氧基、芳基、或芳氧基;
其中R1=H、C1-C4直链或支链烷基;
其中s=0或1,n=0或≥1;
其中T和R7=C1-C22烷基;并且
其中X-=卤素、氢氧根、链烷醇根、硫酸根或烷基硫酸根。
其中带有负电荷的单体由以下定义:R2'=H、C1-C4直链或支链烷基,并且R3为:
其中D=O、N、或S;
其中Q=NH2或O;
其中u=1-6;
其中t=0-1;并且
其中J=包含以下元素P、S、C的氧化官能团。
其中非离子单体由以下定义:R2”=H、C1-C4直链或支链烷基,R6=直链或支链烷基、烷基芳基、芳氧基、烷氧基、烷基芳氧基,并且β定义为
并且
其中G‘和G”彼此独立地为O、S或N-H,并且L=0或1。
阳离子单体的示例包括(甲基)丙烯酸氨基烷基酯、(甲基)氨基烷基(甲基)丙烯酰胺;包含至少一个仲、叔或季铵官能团,或包含氮原子的杂环基团、乙烯胺或乙烯亚胺的单体;二烯丙基二烷基铵盐;它们的混合物、它们的盐以及从它们衍生出的大分子单体。
阳离子单体的另外示例包括(甲基)丙烯酸二甲氨基乙酯、(甲基)丙烯酸二甲氨基丙酯、(甲基)丙烯酸二叔丁基氨乙酯、二甲氨基甲基(甲基)丙烯酰胺、二甲氨基丙基(甲基)丙烯酰胺、乙烯亚胺、乙烯胺、2-乙烯基吡啶、4-乙烯基吡啶、(甲基)丙烯酸三甲基氯化铵乙酯、(甲基)丙烯酸三甲基甲基硫酸铵乙酯、(甲基)丙烯酸二甲基苄基氯化铵乙酯、丙烯酸-4-苯甲酰基苄基二甲基氯化铵乙酯、三甲基氯化铵乙基(甲基)丙烯酰胺、三甲基氯化铵丙基(甲基)丙烯酰胺、乙烯基苄基三甲基氯化铵、二烯丙基二甲基氯化铵。
合适的阳离子单体包括包含式-NR3 +的季铵基团的那些,其中R相同或不同,代表氢原子、包含1至10个碳原子的烷基,或苄基,任选带有羟基,并且包含阴离子(抗衡离子)。阴离子的示例为卤离子(如氯离子、溴离子)、硫酸根、硫酸氢根、烷基硫酸根(例如,包含1至6个碳原子)、磷酸根、柠檬酸根、甲酸根和乙酸根。
合适的阳离子单体包括(甲基)丙烯酰氧乙基三甲基氯化铵、(甲基)丙烯酰氧乙基三甲基甲酯硫酸铵、(甲基)丙烯酰氧乙基苄基二甲基氯化铵、丙烯酰氧乙基4-苯甲酰基苄基二甲基氯化铵、(甲基)丙烯酰胺基乙基三甲基氯化铵、(甲基)丙烯酰胺基丙基三甲基氯化铵、乙烯基苄基三甲基氯化铵。
其它合适的阳离子单体包括(甲基)丙烯酰胺基丙基三甲基氯化铵。
带有负电荷的单体的示例包括包含磷酸根或膦酸根基团的α-烯键式不饱和单体、α-烯键式不饱和一元羧酸、α-烯键式不饱和二元羧酸的单烷基酯、α-烯键式不饱和二元羧酸的单烷基酰胺、包含磺酸基团的α-烯键式不饱和化合物、以及包含磺酸基团的α-烯键式不饱和化合物的盐。
具有负电荷的合适单体包括丙烯酸、甲基丙烯酸、乙烯基磺酸、乙烯基磺酸的盐、乙烯基苯磺酸、乙烯基苯磺酸的盐、α-丙烯酰胺基甲基丙磺酸、α-丙烯酰胺基甲基丙磺酸的盐、甲基丙烯酸2-磺基乙酯、甲基丙烯酸2-磺基乙酯的盐、丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酰胺基-2-甲基丙磺酸的盐、以及苯乙烯磺酸盐(SS)。
非离子单体的示例包括乙酸乙烯酯、α-烯键式不饱和羧酸的酰胺、具有氢化或氟化醇的α-烯键式不饱和一元羧酸的酯、聚环氧乙烷(甲基)丙烯酸酯(即,聚乙氧基化的(甲基)丙烯酸)、α-烯键式不饱和二元羧酸的单烷基酯、α-烯键式不饱和二元羧酸的单烷基酰胺、乙烯基腈、乙烯胺酰胺、乙烯醇、乙烯基吡咯烷酮和乙烯基芳族化合物。
合适的非离子单体包括苯乙烯、丙烯酰胺、甲基丙烯酰胺、丙烯腈、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸2-羟乙酯、以及甲基丙烯酸2-羟乙酯。
与合成阳离子聚合物缔合的阴离子抗衡离子(X-)可为任何已知的抗衡离子,只要聚合物在水中、在毛发护理组合物中、或在毛发护理组合物中的凝聚层相中保持可溶解或可分散,并且只要抗衡离子与毛发护理组合物的基本组分在物理上和化学上是相容的,或不会另外不当地破坏产品的性能、稳定性或美观性。此类抗衡离子的非限制性示例包括卤离子(例如,氯、氟、溴、碘)、硫酸根和甲硫酸根。
阳离子聚合物的浓度按毛发护理组合物的重量计在约0.025%至约5%、约0.1%至约3%、和/或约0.2%至约1%的范围内。
适宜的阳离子纤维素聚合物为与三甲基铵取代的环氧化物反应的羟乙基纤维素的盐,工业上(CTFA)称作聚季铵盐10,并且可以它们的Polymer LR、JR和KG聚合物系列购自Dow/Amerchol Corp.(Edison,N.J.,USA)。阳离子纤维素的其他合适类型包括羟乙基纤维素与月桂基二甲基铵取代的环氧化物反应而生成的聚合物季铵盐,其在工业上(CTFA)内被命名为聚季铵盐24。这些材料可以商品名Polymer LM-200购自Dow/Amerchol Corp.。其它合适类型的阳离子纤维素包括羟乙基纤维素与月桂基二甲基铵取代的环氧化物以及三甲基铵取代的环氧化物反应所得的聚合季铵盐,其在工业领域(CTFA)内被称为聚季铵盐67。这些材料以商品名SoftCAT Polymer SL-5、SoftCAT Polymer SL-30、Polymer SL-60、Polymer SL-100、Polymer SK-L、Polymer SK-M、Polymer SK-MH、和Polymer SK-H购自Dow/Amerchol Corp.。
E.调理剂
毛发护理组合物可以包含一种或多种调理剂。调理剂包括用于向毛发和/或皮肤提供特定调理有益效果的物质。可用于本发明的毛发护理组合物中的调理剂通常包括水不溶性、水可分散性、非挥发性、可形成乳化的液体颗粒的液体。用于毛发护理组合物中的合适的调理剂是通常特征为有机硅(例如硅油、阳离子有机硅、硅橡胶纯胶料、高折射有机硅和有机硅树脂)、有机调理油(例如烃油、聚烯烃和脂肪酸酯)或它们的组合的那些调理剂,或在含水表面活性剂基质中以其它方式形成液体分散颗粒的那些调理剂。
1.硅氧烷调理剂
毛发护理组合物可包含约0质量%至约20重量%,或者约6质量%至约18重量%;或者,约8质量%至约16重量%的一种或多种硅氧烷,其粒度小于约300nm,或者小于约200nm,或者小于约100nm。硅氧烷可以是纳米乳剂的形式。
可由动态光散射(DLS)来测量一种或多种硅氧烷的粒度。使用He-Ne激光器633nm的Malvern Zetasizer Nano ZEN3600系统(www.malvern.com)可用于在25℃下的测量。
可使用由Malvern Instruments提供的Zetasizer软件来分析自相关函数,其使用Stokes-Einstein公式确定有效的流体动力学半径:
其中kB为Boltzmann常数,T为绝对温度,η为介质的粘度,D为散射物质的平均扩散系数,并且R为颗粒的流体动力学半径。
粒度(即流体动力学半径)可通过将由于布朗运动引起的观察到的散斑图案与解出Stokes-Einstein方程相关联来获得,所述方程将粒度与测量的扩散常数相关联,如本领域中已知的。
对于每个样品,可进行3次测量,并且Z平均值可报告为粒度。
在一个实施方案中,所述一种或多种硅氧烷可以呈纳米乳液的形式。纳米乳液可包含适用于施用到皮肤或毛发上的任何硅氧烷。
在一个实施方案中,一种或多种硅氧烷可在其分子结构中包含极性官能团诸如Si-OH(以聚二甲基硅氧烷醇形式存在)、伯胺、仲胺、叔胺和季铵盐。所述一种或多种硅氧烷可选自氨基硅氧烷、侧链季铵硅氧烷、末端季铵硅氧烷、氨基聚环氧烷硅氧烷、季铵聚环氧烷硅氧烷、和氨基吗啉硅氧烷。
所述一个或多种硅氧烷可包含:
(a)至少一种对应于式(V)的氨基硅氧烷:
R′aG3-a—Si(OSiG2)n—(OSiGbR′2-b)m—O—SiG3-a—R′a (I)
其中:
G选自氢原子、苯基基团、OH基团和C1-C8烷基基团,例如甲基,
a为0至3范围内的整数,并且在一个实施方案中a为0,
b选自0和1,并且在一个实施方案中b为1,
m和n为使得总和(n+m)可在例如1至2 000的范围内的数,诸如例如50至150,其中n可例如选自在0至1999范围内的数,诸如例如49至149,并且其中m可选自例如在1至2000范围内的数,诸如例如1至10;
R'是式—CqH2qL的一价基团,其中q为2至8的数,并且L为选自以下基团的任选的季铵化胺基团:
—NR″—CH2—CH2—N′(R1)2,
—N(R″)2,
—N+(R″)3A-,
—N+H(R″)2A-,
—N+H2(R″)A-,和
—N(R″)—CH2—CH2—N+R″H2A-,
其中R″可选自氢原子、苯基基团、苄基基团和基于饱和一价烃的基团,诸如例如包含1至20个碳原子的烷基基团,并且A-选自卤离子,诸如例如氟离子、氯离子、溴离子和碘离子。
在一个实施方案中,一种或多种硅氧烷可包括对应于式(1)的那些,其中a=0,G=甲基,m和n为使得总和(n+m)可在例如1至2000的范围内的数,诸如例如50至150,其中n可例如选自在0至1999范围内的数,诸如例如49至149,并且其中m可选自在例如1至2000范围内的数,诸如例如1至10;并且L为–N(CH3)2或–NH2,或者–NH2。
另外所述至少一种本发明的氨基硅氧烷包括:
(b)具有式(VII)的侧链季铵硅氧烷:
其中:
R5选自包含1至18个碳原子的基于一价烃的基团,诸如C1-C18烷基基团和C2-C18烯基基团,例如甲基;
R6选自基于二价烃的基团,诸如二价C1-C18亚烷基基团和二价C1-C18亚烷氧基基团,例如C1-C8亚烷氧基基团,其中所述R6通过SiC键键合到Si;
Q-为阴离子,其可例如选自卤离子,诸如氯离子和有机酸盐(诸如乙酸盐);
r为在2至20范围内的统计平均值,诸如2至8;
s为在20至200范围内的统计平均值,诸如20至50。
此类氨基硅氧烷更具体地描述于美国专利4,185,087中,其公开内容以引用方式并入本文。
属于此类的硅氧烷是由公司Union Carbide以名称“Ucar Silicone ALE56”销售的硅氧烷。
所述至少一种氨基硅氧烷的另外的示例包括:
c)具有式(VIIb)的季铵硅氧烷:
其中:
基团R7可以相同或不同,其各自选自包含1至18个碳原子的基于一价烃的基团,诸如C1-C18烷基基团,例如甲基、C2-C18烯基基团,和包含5或6个碳原子的环;
R6选自基于二价烃的基团,诸如二价C1-C18亚烷基基团和二价C1-C18亚烷氧基基团,例如通过SiC键连接到Si的C1-C8基团;
R8可以相同或不同,其表示氢原子、包含1至18个碳原子的基于一价烃的基团,并且具体地讲C1-C18烷基基团、C2-C18烯基基团或基团—R6—NHCOR7;
X-为阴离子诸如卤离子,具体地讲氯离子,或有机酸盐(乙酸盐等);
r表示2至200的统计平均值,并且具体地讲5至100。
此类硅氧烷描述于例如专利申请EP-A-0 530 974中,其公开内容以引用方式并入本文。
属于此类的硅氧烷是由公司Eovnik以商品名Abil Quat 3270、Abil Quat 3272、Abil Quat 3474和Abil ME 45出售的硅氧烷。
所述至少一种氨基硅氧烷的另外的示例包括:
d)季铵和聚环氧烷硅氧烷
其中所述季氮基团位于聚硅氧烷主链中、末端处或上述两者。
此类硅氧烷描述于PCT专利公布WO 2002/010257中,其公开内容以引用方式并入本文中。
属于此类的硅氧烷是由公司Momentive以名称即Silsoft Q出售的硅氧烷。
(e)氨基官能化硅氧烷,其具有式(V)的吗啉代基团:
其中
A表示经由—O—键合的结构单元(I)、(II)或(III)
或低聚或聚合物残基,其经由—O—键合,包含式(I)、(II)或(III)的结构单元,或对结构单元(III)的连接氧原子的一半,或表示—OH,
*表示对结构单元(I)、(II)或(III)中的一个的键,或表示末端基团B(Si-键合的)或D(O-键合的)
B表示—OH、—O—Si(CH3)3、—O—Si(CH3)2OH、—O—Si(CH3)2OCH3基团,
D表示—H、—Si(CH3)3、—Si(CH3)2OH、—Si(CH3)2OCH3基团,
a、b和c表示0至1000的整数,前提条件是a+b+c>0,
m、n和o表示1至1000的整数。
这类氨基官能化硅氧烷具有INCI名称:氨基封端的聚二甲基硅氧烷/吗啉代甲基倍半硅氧烷共聚物。特别合适的氨基封端的聚二甲基硅氧烷是具有商品名WackerADM 8301E的产品。
此类硅氧烷的示例购自以下供应商:
由道康宁公司提供的:流体:2-8566、AP 6087、AP 6088、DC 8040流体、流体8822ADC、DC 8803和8813聚合物、7-6030、AP-8104、AP8201;乳液:CE-8170 AF微乳液、2-8177、2-8194微乳液、9224乳液、939、949、959、DC5-7113 Quat微乳液、DC5-7070乳液、DC CE-8810、CE 8401乳液、CE 1619、Dow Corning Toray SS-3551、Dow Corning Toray SS-3552;
由Wacker公司提供的:Wacker Belsil ADM 652、ADM 656、1100、1600、1650(流体)ADM 6060(直链氨基封端的聚二甲基硅氧烷)乳液;ADM 6057 E(支链氨基封端的聚二甲基硅氧烷)乳液;ADM 8020 VP(微乳液);SLM 28040(微乳液);
由Momentive公司提供的:Silsoft 331、SF1708、SME 253和254(乳液)、SM2125(乳液)、SM 2658(乳液)、Silsoft Q(乳液)
由Shin-Etsu公司提供:KF-889、KF-867S、KF-8004、X-52-2265(乳液);
由Siltech Silicones公司提供:Siltech E-2145、E-Siltech 2145-35;
由Evonik Industries公司提供:Abil T Quat60th
一些氨基硅氧烷的非限制性示例包括具有以下INCI名称的化合物:聚硅氧烷季铵盐-1、聚硅氧烷季铵盐-2、聚硅氧烷季铵盐-3、聚硅氧烷季铵盐-4、聚硅氧烷季铵盐-5、聚硅氧烷季铵盐-6、聚硅氧烷季铵盐-7、聚硅氧烷季铵盐-8、聚硅氧烷季铵盐-9、聚硅氧烷季铵盐-10、聚硅氧烷季铵盐-11、聚硅氧烷季铵盐-12、聚硅氧烷季铵盐-15、聚硅氧烷季铵盐-16、聚硅氧烷季铵盐-17、聚硅氧烷季铵盐-18、聚硅氧烷季铵盐-20、聚硅氧烷季铵盐-21、聚硅氧烷季铵盐-22、聚硅氧烷季铵盐-80、以及聚硅氧烷季铵盐-2泛醇琥珀酸酯和聚硅氧烷季铵盐-16/缩水甘油基聚二甲基硅氧烷交联聚合物。
氨基硅氧烷可以纳米乳液的形式提供,并且包括MEM 9049、MEM 8177、MEM 0959、MEM 8194、SME 253和Silsoft Q。
一种或多种硅氧烷可包括聚二甲基硅氧烷和/或聚二甲基硅氧烷醇。聚二甲基硅氧烷醇是由以下化学通式表示的羟基封端的聚二甲基硅氧烷
以及
其中R是烷基(优选R是甲基或乙基,更优选甲基),并且x是至多约500的整数,选择它们以获得所需的分子量。商业聚二甲基硅氧烷醇典型作为与聚二甲基硅氧烷或环状聚甲基硅氧烷的混合物出售(例如,Dow1401、1402和1403流体)。
2.非硅氧烷调理剂
本文所述的毛发护理组合物中的调理剂还可包含至少一种有机调理剂,其单独使用或与其他调理剂如上述硅氧烷组合使用。有机调理剂的非限制性示例描述如下。
a.烃油
用作毛发护理组合物中的调理剂的合适的有机调理剂包括但不限于具有至少约10个碳原子的烃油,诸如环烃、直链脂族烃(饱和或不饱和的)、和支链脂族烃(饱和或不饱和的),包括聚合物以及它们的混合物。直链烃油可为约C12至约C19。支链烃油(包括烃聚合物)典型地将包含多于19个碳原子。
b.聚烯烃
用于本文所述的毛发护理组合物中的有机调理剂还可包括液体聚烯烃,其包括液体聚-α-烯烃和/或氢化的液体聚-α-烯烃。用于本文的聚烯烃通过C4至约C14,并且在一个实施方案中约C6至约C12烯烃单体的聚合反应来制备。
c.脂肪酸酯
适用作本文所述的毛发护理组合物中调理剂的其他有机调理剂包括具有至少10个碳原子的脂肪酸酯。这些脂肪酸酯包括具有烃基链的酯,该烃基链衍生自脂肪酸或醇。脂肪酸酯的烃基基团可包括或具有与其共价键合的其它相容官能团,诸如酰胺和烷氧基部分(例如乙氧基或醚键等)。由不饱和甘油酯制备的其他低聚或聚合酯也可用作调理材料。
d.氟化调理化合物
适用于向毛发递送调理效果的用作有机调理剂的氟化化合物包括全氟聚醚、全氟化烯烃、可为与前述有机硅流体类似的流体或弹性体形式的基于氟的特定聚合物、和全氟化聚二甲基硅氧烷。
e.脂肪醇
适用于本文所述的毛发护理组合物中的其他有机调理油包括但不限于具有至少约10个碳原子,约10至约22个碳原子,以及在一个实施方案中约12至约16个碳原子的脂肪醇。
f.烷基葡糖苷和烷基葡糖苷衍生物
适用于本文所述的毛发护理组合物中的有机调理油包括但不限于烷基葡糖苷和烷基葡糖苷衍生物。合适的烷基葡糖苷和烷基葡糖苷衍生物的具体非限制性示例包括可从Amerchol商购获得的Glucam E-10、Glucam E-20、Glucam P-10和Glucquat 125。
g.聚乙二醇
可用于本文作为调理剂的附加化合物包括具有至多约2,000,000的分子量的聚乙二醇和聚丙二醇,诸如CTFA命名为PEG-200、PEG-400、PEG-600、PEG-1000、PEG-2M、PEG-7M、PEG-14M、PEG-45M的那些、以及它们的混合物。
F.发泡剂
本文所述的毛发护理组合物可包含发泡剂。本文所述的毛发护理组合物可包含按毛发护理组合物的重量计约1%至约10%的发泡剂,或者约2%至约9%的发泡剂,或者约3%至约8%的发泡剂。发泡剂可以是推进剂。本文所述的毛发护理组合物可包含按毛发护理组合物的重量计约1%至约10%的推进剂,或者约2%至约9%的推进剂,或者约3%至约8%的推进剂。
可用于本文所述的毛发护理组合物中的发泡剂/推进剂可选自氯氟烃(CFC),如二氯二氟甲烷、1,1-二氯-1,1,2,2-四氟乙烷、1-氯-1,1-二氟-2,2-三氟乙烷、1-氯-1,1-二氟乙烯、一氯二氟甲烷、以及它们的混合物;氢氟烃(HFC)如1,1-二氟乙烷、1,3,3,3-四氟丙烯、2,3,3,3-四氟丙烯、以及它们的混合物;氢氟烯烃(HFO),如2,3,3,3-四氟丙烯(HFO-1234yf)、1,3,3,3-四氟丙烯(HFO-1234ze)、以及它们的混合物;此外,发泡剂/推进剂预先可与一种或多种烃、氯氟烃、氢氟烃、氢氟烯烃、烷基醚和压缩气体混合。
可用于本文所述的毛发护理组合物中的发泡剂/推进剂可选自氢氟烃(HFC),如1,1-二氟乙烷、1,3,3,3-四氟丙烯、2,3,3,3-四氟丙烯、以及它们的混合物;氢氟烯烃(HFO),如2,3,3,3-四氟丙烯(HFO-1234yf)、1,3,3,3-四氟丙烯(HFO-1234ze)、以及它们的混合物;此外,列出的发泡剂/推进剂可与一种或多种烃、氯氟烃、氢氟烃、氢氟烯烃、烷基醚和压缩气体混合。
可用于本文所述的毛发护理组合物中的发泡剂/推进剂可选自1,3,3,3-四氟丙-1-烯、1,1-二氟乙烷、以及它们的混合物。此外,列出的发泡剂/推进剂可与一种或多种烃、氯氟烃、氢氟烃、氢氟烯烃、烷基醚和压缩气体混合。
G.粘度
毛发护理组合物可具有如本文所定义在26.5℃下测量的约1厘泊(cP)至约40,000cP,或者约1,000cP至约30,000cP,或者约3,000cP至约25,000cP,或者约5,000cP至约20,000cP,或者约7,000cP至约15,000cP,或者约9,000cP至约12,000cP,或者约1cP厘泊至约3000cP,或者约10cP厘泊至约3000cP,或者约20cP至约2000cP,或者约500cP至约2000cP,或者约750cP至约1250cP,或者约1000cP至约3000cP的液相粘度。粘度通过BrookfieldEngineering Laboratories,Stoughton,MA的锥和板控制应力布鲁克菲尔德流变仪R/SPlus测量。使用的锥体(主轴C-75-1)具有75mm的直径和1°的角度。粘度使用稳态流动实验在2s-1的恒定剪切速率和26.5℃的温度下测定。样品尺寸为2.5ml,并且总测量读数时间为3分钟。
H.香料
毛发护理组合物可包含按毛发护理组合物的重量计约0.5%至约7%,或者约1%至约6%,或者约2%至约5%的香料。
毛发护理组合物可具有约95:5至约50:50,或者约90:10至约60:40,或者约85:15至约70:30的硅氧烷与香料的比。
适宜香料的示例可在CTFA(化妆品、盥洗品和芳香剂协会)1992年国际买家指南中提供,其由CFTA出版物和OPD 1993年化学品买家名录第80期年鉴公布,由Schnell出版公司出版。多种香料组分可存在于毛发护理组合物中。
I.任选成分
本文所述的毛发调理组合物可任选包含一种或多种已知用于护发或个人护理产品的附加组分,前提条件是该附加组分与本文所述基本组分物理和化学地相容,或不会不适当地损害产品的稳定性、美观性或性能。上述任选成分最典型地为那些被认可用于化妆品中并描述于参考书诸如“CTFA Cosmetic Ingredient Handbook”第二版(The Cosmetic,Toiletries,and Fragrance Association,Inc.1988,1992)中的材料。此类附加组分的各个浓度按调理组合物的重量计可在约0.001重量%至约10重量%的范围内。
适于作为本文任选成分的乳化剂包括甘油一酯和甘油二酯、脂肪醇、聚甘油酯、丙二醇酯、脱水山梨糖醇酯、以及已知的或常用于稳定空气界面的其他乳化剂,例如在充气食品如糕饼和其他烤焙物以及蜜饯产品制备期间或在稳定化妆品如毛发摩丝期间使用的那些。
此类任选成分的其它非限制性示例包括防腐剂、香料或芳香剂、阳离子聚合物、粘度调节剂、着色剂或染料、调理剂、毛发漂白剂、增稠剂、保湿剂、发泡剂、附加的表面活性剂或非离子辅助表面活性剂、润肤剂、药物活性物质、维生素或营养物质、防晒剂、除臭剂、感觉剂、植物提取物、营养物质、收敛剂、化妆品颗粒、吸收剂颗粒、粘合剂颗粒、固发剂、纤维、反应剂、亮肤剂、皮肤美黑剂、去头皮屑剂、香料、剥脱剂、酸、碱、保湿剂、酶、悬浮剂、pH调节剂、毛发着色剂、烫发剂、颜料颗粒、抗痤疮剂、抗微生物剂、防晒剂、美黑剂、剥脱颗粒、毛发生长剂或恢复剂、驱虫剂、剃须洗剂、非挥发性溶剂或稀释剂(水溶性和水不溶性)、共溶剂或其它附加溶剂、以及类似的其它材料。
去头皮屑活性物质
本文所述的毛发护理组合物还可含有去头皮屑剂。去头皮屑颗粒的适宜的非限制性示例包括:吡啶硫酮盐、硫化硒、粒状硫、以及它们的混合物。此类去头皮屑颗粒应在物理和化学上与组合物的基本组分相容,并且不应以其它方式不当地损害产品的稳定性、美观性或性能。
1.吡啶硫酮盐
吡啶硫酮去头皮屑颗粒,尤其是1-羟基-2-吡啶硫酮盐,是用于本发明组合物中的颗粒去头皮屑剂的一个实施方案。吡啶硫酮去头皮屑颗粒浓度按组合物的重量计通常在约0.1%至约10%范围内。在一个实施方案中,吡啶硫酮去头皮屑颗粒的浓度在约0.1%至约8%范围内,并且在另一个实施方案中在约0.3%至约5%范围内。在本发明的一个实施方案中,吡啶硫酮盐包括由重金属如锌、铜、锡、镉、镁、铝和锆形成的那些。在本发明的一个实施方案中,为由重金属锌形成的吡啶硫酮盐,并且在另一个实施方案中为1-羟基-2-吡啶硫酮的锌盐(称为“吡啶硫酮锌”或“ZPT”),并且在另一个实施方案中为板粒形式的1-羟基-2-吡啶硫酮盐,其中颗粒具有至多约20μ的平均尺寸。在本发明的一个实施方案中,颗粒具有至多约5μ,并且在另一个实施方案中至多约2.5μ的平均尺寸。由其它阳离子诸如钠形成的盐也可为合适的。吡啶硫酮去头皮屑剂描述于例如美国专利2,809,971;美国专利3,236,733;美国专利3,753,196、美国专利3,761,418、美国专利4,345,080、美国专利4,323,683、美国专利4,379,753、和美国专利4,470,982中。可以设想,当将ZPT用作本文组合物中的去头皮屑颗粒时可刺激或调节或同时刺激和调节毛发的生长或再生,或者可降低或抑制毛发损失,或者毛发可将显得更浓密或更丰盈。
2.其它抗微生物活性物质
除了选自吡啶硫酮的多价金属盐的去头皮屑活性物质外,本发明还可包含除金属吡啶硫酮锌盐活性物质之外的一种或多种杀真菌或抗微生物活性物质。适宜的抗微生物活性物质包括煤焦油、硫、怀特菲耳德氏软膏、castellani的颜料、氯化铝、龙胆紫、羟甲辛吡酮(羟甲辛吡酮乙醇胺)、环已吡酮羟乙胺酮、十一碳烯酸及其金属盐,高锰酸钾、硫化硒、硫代硫酸钠、丙二醇、苦橙油、尿素制剂、灰黄霉素、8-羟基喹啉氯碘羟喹、硫代地巴唑、硫代氨基甲酸盐、卤普罗近、聚烯、羟基吡啶酮、吗啉、苄胺、烯丙胺(如特比萘芬)、茶树油、丁香叶油、胡荽、玫瑰草、小檗碱、百里香红、桂皮油、肉桂醛、香茅酸、日柏酚、鱼石脂白、SensivaSC-50、Elestab HP-100、壬二酸、溶酶、碘代丙炔基丁基氨基甲酸盐(IPBC),异噻唑啉酮如辛基异噻唑啉酮和唑类、以及它们的组合。在本发明的一个实施方案中,抗微生物剂包括伊曲康唑、酮康唑、硫化硒和煤焦油。
a.唑类
唑抗微生物剂包括咪唑类如苯并咪唑、苯并噻唑、联苯苄唑、丁康唑硝酸盐、甘宝素、克霉唑、克鲁康唑、依柏康唑、益康唑、elubiol、芬替康唑、氟康唑、氟三唑、异康唑、酮康唑、兰诺康唑、甲硝唑、咪康唑、奈康唑、奥莫康唑、奥昔康唑硝酸盐、舍他康唑、硝酸硫康唑、噻康唑、噻唑和三唑如特康唑和伊曲康唑、以及它们的组合。当存在于所述组合物中时,唑抗微生物活性物质的量为约0.01%至约5%。在本发明的一个实施方案中,唑抗微生物活性物质的量按所述组合物的重量计为约0.1%至约3%,并且在另一个实施方案中为约0.3%至约2%。在本发明的一个实施方案中,唑抗微生物剂为酮康唑。
b.硫化硒
硫化硒是适用于本发明抗微生物组合物中的颗粒去头皮屑剂,其有效浓度按所述组合物的重量计在约0.1%至约4%范围内,并且在本发明的一个实施方案中在约0.3%至约2.5%范围内,并且在另一个实施方案中在约0.5%至约1.5%范围内。硫化硒通常被认为是具有一摩尔硒和两摩尔硫的化合物,尽管它也可以为符合通式SexSy的环状结构,其中x+y=8。通过前向激光散射装置(例如Malvern 3600仪器)测量的硫化硒的平均粒径通常小于15μm,并且在本发明的一个实施方案中,小于10μm。硫化硒化合物描述于,例如,美国专利2,694,668;美国专利3,152,046;美国专利4,089,945、和美国专利4,885,107中。
c.硫
硫也可用作本发明的抗微生物组合物中的粒状抗微生物/去头皮屑剂。颗粒硫的有效浓度按所述组合物的重量计通常为约1%至约4%,并且在本发明的一个实施方案中为约2%至约4%。
d.角质层分离剂
本发明还可包含一种或多种角质层分离剂,如水杨酸。
e.附加抗微生物活性物质
本发明另外的抗微生物活性物质可包括白千层属灌木(茶树)和木炭的提取物。本发明还可包含抗微生物活性物质的组合。此类组合可包括羟甲辛吡酮和吡啶硫酮锌的组合、松树焦油和硫的组合、水杨酸和吡啶硫酮锌的组合、羟甲辛吡酮和氯咪巴唑的组合、和水杨酸和羟甲辛吡酮的组合、吡啶硫酮锌和氯咪巴唑的组合、以及它们的混合物。当用于本文时,这些活性物质的用量为约1%至约4%,并且在本发明的一个实施方案中为约2%至约4%。
在一个实施方案中,组合物包含有效量的含锌层状物质。在一个实施例中,所述组合物包含按所述组合物的总重量计约0.001%至约10%,或约0.01%至约7%,或约0.1%至约5%的含锌层状物质。
含锌层状物质可为主要在二维平面上具有晶体生长的那些。常规上将层状结构描述为不仅其中所有原子均掺入良好限定的层中的那些,而且其中在层之间存在称为隧道离子(A.F.Wells,“Structural Inorganic Chemistry”Clarendon Press,1975)的离子或分子的那些。含锌层状物质(ZLM)可具有掺入层中的锌和/或可作为隧道离子的组分。以下类别的ZLM代表了总类别中相对常见的示例,并且不旨在对范围更广的符合此定义的材料作出限制。
许多ZLM在自然界以矿物的形式出现。在一个实施方案中,ZLM选自:水锌矿(碳酸锌氢氧化物)、碱式碳酸锌、绿铜锌矿(碳酸锌铜氢氧化物)、斜方绿铜锌矿(碳酸铜锌氢氧化物)、以及它们的混合物。相关的含锌矿物质也可包含于组合物中。天然ZLM也可存在,其中阴离子层物质诸如粘土型矿物质(例如页硅酸盐)包含离子交换的锌隧道离子。所有这些天然物质也可通过合成获得,或在组合物中或在生产过程期间原位形成。
另一种通常但不总是合成获得的常见类别ZLM为层状二元氢氧化物。在一个实施方案中,ZLM为符合式[M2+ 1-xM3+ x(OH)2]x+Am- x/m·nH2O的层状二元氢氧化物,其中一些或所有的二价离子(M2+)为锌离子(Crepaldi,EL,Pava,PC,Tronto,J,Valim,JB J.ColloidInterfac.Sci.2002,248,429-42)。
可制备另一类别的ZLM,称为羟基复盐(Morioka,H.,Tagaya,H.,Karasu,M,Kadokawa,J,Chiba,K Inorg.Chem.1999,38,4211-6)。在一个实施方案中,ZLM为符合式[M2 + 1-xM2+ 1+x(OH)3(1-y)]+An- (1=3y)/n·nH2O的羟基复盐,其中两个金属离子(M2+)可以相同或不同。如果它们相同并且由锌表示,则该式简化为[Zn1+x(OH)2]2x+2x A-·nH2O。后一式代表了(其中x=0.4)材料诸如羟基氯化锌和碱式硝酸锌。在一个实施方案中,ZLM为羟基氯化锌和/或碱式硝酸锌。这些也涉及水锌矿,其中二价阴离子替换一价阴离子。这些材料还可在组合物中或在生产过程中或生产过程期间原位形成。
在一个实施方案中,组合物包含碱式碳酸锌。碱式碳酸锌的可商购获得的来源包括碱式碳酸锌(Cater Chemicals:Bensenville,IL,USA)、碳酸锌(Shepherd Chemicals:Norwood,OH,USA)、碳酸锌(CPS Union Corp.:New York,NY,USA)、碳酸锌(ElementisPigments:Durham,UK)和碳酸锌AC(Bruggemann Chemical:Newtown Square,PA,USA)。碱式碳酸锌,商业上还可以称作“碳酸锌”或“碳酸锌碱性物”或“羟基碳酸锌”,为合成型式,由与天然存在的水锌矿类似的材料组成。理想的化学计量表示为Zn5(OH)6(CO3)2,但实际化学计量比可稍有不同,并且晶格中可掺有其它杂质。
在具有含锌层状物质和吡啶硫酮或吡啶硫酮的多价金属盐的实施方案中,含锌层状物质与吡啶硫酮或吡啶硫酮的多价金属盐的比率为约5:100至约10:1、或约2:10至约5:1、或约1:2至约3:1。
处理毛发的方法
本文所述的处理毛发的方法可包括(1)提供如本文所述的毛发护理组合物,(2)使用气溶胶泡沫分配器将毛发护理组合物分配为液体形式或泡沫形式;(3)将该组合物施用在毛发上;以及(4)从毛发上冲洗组合物。毛发护理组合物可形成稳定的泡沫剂型。当从分配到施用在毛发上时,泡沫剂型基本上保持其体积,因此泡沫剂型是稳定的。
可使用本领域已知的标准方法用毛发护理组合物填充容器。在分配之前,可摇动容器以使组合物均匀化。例如,容器可在分配之前或在分配之前最多24小时之间摇动1至10次。
气溶胶泡沫分配器
本文所述的毛发护理组合物可通过气溶胶泡沫分配器分配。气溶胶泡沫分配器可包括用于容纳浓缩型毛发处理组合物的贮存器。贮存器可由任何合适的材料制得,所述材料选自塑料、金属、合金、层合体以及它们的组合。在一个实施方案中,贮存器可用于一次使用。在一个实施方案中,贮存器可从气溶胶泡沫分配器中取出。另选地,贮存器可与气溶胶泡沫分配器成一体。在一个实施方案中,可能存在两个或更多个贮存器。
贮存器可由选自刚性材料、柔性材料以及它们的组合的材料组成。当对贮存器施加内部部分真空时,如果其在外部大气压下不塌缩,则贮存器可由刚性材料组成。
气溶胶泡沫分配器可包括浸料管以实现直立分配。
气溶胶泡沫分配器可为阀上袋型,其中容器包括内袋和包封所述内袋的外部容器,同时内袋具有可在打开位置和闭合位置之间的移动的附接的阀机构。外容器可由金属或塑料等形成,并且本文所述的任何发泡剂可填充在外容器与内袋之间的空间中(在这种情况下,发泡剂将被本领域技术人员称为推进剂)。内袋可以为柔性的,并且可由单一材料或由包括塑料的复合材料制成,所述复合材料可包括至少聚合物层和例如由金属诸如铝制成的用作气体屏障的层。袋的内部材料可对组合物的内容物是惰性的,并且内部材料也可能不可被袋中组合物的内容物渗透。内袋可包括对袋内部的推进剂基本上不可渗透的材料层。内袋可包括对袋外部的推进剂基本上不可渗透的材料层,所述推进剂通常不旨在在储存期间与内袋中的组合物混合。
当从气溶胶泡沫分配器分配时,泡沫可具有约1g至约5g的剂型重量。当从气溶胶泡沫分配器分配时,泡沫还可具有约1g至约7g的剂型重量,或者约2g至约6g,或者约2.5g至约5g,或者约3g至约4.5g。剂型可经由气溶胶泡沫分配器的单次挤压或致动获得,但可经由气溶胶泡沫分配器的两次或更多次挤压或致动来实现。
本文举例说明的毛发护理组合物可使用以下气溶胶包装作为泡沫递送:铝罐,高度190mm,并且直径53mm,溢流容量330mL,由装配有以下的CCL容器提供:(a)Cozy-泡沫一体式致动器,由Lindal提供;致动器可设计成适合公杆并且可包括喷嘴通道,其中喷嘴通道终止于内径为0.80mm的区段,其具有相对于容器的长轴125°的方向,导致喷嘴直径为5.8mm;(b)阀门,其具有0.080英寸的阀门外壳孔口和2×0.040英寸阀杆孔口,由Aptar提供;以及(c)汲取管,其内径为0.025英寸,并且长度为190mm。
实施例和数据
以下实施例和数据说明了本文所述泡沫的配方和剂型。示例性的组合物可通过常规制剂和混合技术来制备。应当理解,在不脱离本文所述的制剂和泡沫剂型的精神和范围的情况下,洗发剂制剂领域的技术人员可进行本文所述的制剂和泡沫剂型的其他修改。除非另外指明,否则本文中所有份数、百分比和比率均按重量计。一些组分可作为稀释溶液来自供应商。除非另外指明,否则所示量反映了活性材料的重量百分比。
数据
消费者测试方法
建立了一个问卷,其标度为0-10(0表示不提供感知属性(调理),10表示提供感知属性(调理)。20名专门小组成员独立评估每个泡沫产品。泡沫在小型称重皿中以5g给药。如上所述,小组成员将泡沫评定为0-10。对消费者数据进行平均并在90%置信区间进行评估。数据确定在下表1中。
表1-测试结果
***表示从泡沫剂型的更多感知调理的90%置信度的显着差异
表2-测试组合物
1.月桂基聚氧乙烯醚-1硫酸钠,得自Stepan Company
2.十一烷基硫酸钠(C11,Isachem 123S)70%活性物质,供应商:P&G
3.LAPB(Mackam DAB),35%活性物质含量,供应商:Rhodia
4.双丙二醇,得自陶氏化学公司
5.Amphosol HCA,得自Stepan Company
6.乙二醇二硬脂酸酯,得自Golschmidt化学公司
7.羟甲辛吡酮,得自Clariant
8.U2 ZPT,得自Lonza
9.碳酸锌,得自Bruggeman Group
10.芳香剂,得自P&G
11.Jaguar C500,得自Solvay,具有500,000g/mol的M.Wt和0.8meq/g的电荷密度12.聚二甲基硅氧烷DM5500,Wacker Silicone
13.盐酸,得自Mallinckrodt Baker Inc.
14.防腐剂Kathon CG,得自Akzo Nobel
15.二甲苯磺酸钠,得自Stepan Company
16.氯化钠USP(食品级),供应商为Morton
17.柠檬酸,得自Cargill Inc.
18.苯甲酸钠,得自Kalama Chemical
19.水,得自Misty Mountain Spring Water
20.发泡剂A46(异丁烷和丙烷),Diversified Cpc International(ChannahonUS)
21.发泡剂HF0(反式1,3,3,3四氟丙1烯),得自Honey Well
表2-附加实施例组合物
1.月桂基聚氧乙烯醚-1硫酸钠,得自Stepan Company
2.十一烷基硫酸钠(C11,Isachem 123S)70%活性物质,供应商:P&G
3.LAPB(Mackam DAB),35%活性物质含量,供应商:Rhodia
4.双丙二醇,得自陶氏化学公司
5.Amphosol HCA,得自Stepan Company
6.乙二醇二硬脂酸酯,得自Golschmidt化学公司
7.羟甲辛吡酮,得自Clariant
8.U2 ZPT,得自Lonza
9.碳酸锌,得自Bruggeman Group
10.芳香剂,得自P&G
11.Jaguar C500,得自Solvay,具有500,000g/mol的M.Wt和0.8meq/g的电荷密度12.聚二甲基硅氧烷DM5500,Wacker Silicone
13.盐酸,得自Mallinckrodt Baker Inc.
14.防腐剂Kathon CG,得自Akzo Nobel
15.二甲苯磺酸钠,得自Stepan Company
16.氯化钠USP(食品级),供应商为Morton
17.柠檬酸,得自Cargill Inc.
18.苯甲酸钠,得自Kalama Chemical
19.水,得自Misty Mountain Spring Water
20.发泡剂A46(异丁烷和丙烷),Diversified Cpc International(ChannahonUS)
21.发泡剂HF0(反式1,3,3,3四氟丙1烯),得自Honey Well
测试方法
光泽度单位(GU)
通过使用由BYK-Gardner,USA提供的Micro-TriGlossmeter测量泡沫的光泽/光泽度。将泡沫分配到称为“圆盘-G”的样品架中。将光泽计放置在含有泡沫的样品架上,并在样品架中分配和制备泡沫的10秒内施加操作按钮。进行60度测量。Micro-TriGloss计提供的测量单位为“GU”,代表“光泽度单位”。GU测量值越高,泡沫越光泽,消费者越有可能将毛发调理有益效果归因于泡沫。
泡沫密度和泡沫体积
通过将100ml烧杯放在质量平衡器上,对烧杯的质量量皮重,然后将产品从气溶胶容器分配到100ml烧杯中直到泡沫体积在容器边缘上方来测量泡沫密度。通过在将泡沫分配到容器边缘上方10秒内刮擦刮刀,使泡沫与烧杯顶部齐平。然后将得到的100ml泡沫的质量除以体积(100),以确定以g/ml为单位的泡沫密度。
通过将称重皿放置在质量平衡器上,对称重皿的质量量皮重,然后从气溶胶容器中分配所需量的产物来测量泡沫体积。测定分配的泡沫克数,然后除以泡沫密度法测定的泡沫密度,得到泡沫体积,单位为ml或cm3。
粘度锥/板粘度测量
制剂的粘度通过Brookfield Engineering Laboratories,Stoughton,MA的锥/板控制应力布鲁克菲尔德流变仪R/S Plus测量。使用的锥体(主轴C-75-1)具有75mm的直径和1°的角度。粘度使用稳态流动实验在2s-1的恒定剪切速率和26.5℃的温度下测定。样品尺寸为2.5ml,并且总测量读数时间为3分钟。
泡沫流变学方法(屈服点)
将泡沫洗发剂施用于AR1000流变仪,用于泡沫振荡应力扫描。60mm光滑的丙烯酸板用于剪切应力测量。测量在25℃下进行。将板头降低至1200微米并用刮刀除去多余的泡沫,以便在测量期间不会发生阻力。然后将测量间隙高度降低1000微米。扫描发生在0.1Pa至400Pa之间。通过TA Rheology Advantage Data Analysis软件分析数据。屈服点在振荡剪切应力开始偏离其切线的点处确定。屈服点测量以Pa单位报告。
Kruss Lather分析仪(气泡尺寸)
由Kruss提供的市售Kruss泡沫分析仪DFA100用于分析初始Sauter平均半径R32(气泡尺寸)的泡沫洗发剂。将洗发剂泡沫分配到含有棱镜的CY4571柱中。将内部塞子从室顶部放入约100ml的柱子中。相机高度设置为244mm,并且相机位置放在3个插槽中。结构发泡以每秒2帧的速度捕获120秒。数据分析在Kruss Advance1.5.1.0软件应用程序版本上执行。
实施方案
A.一种泡沫剂型,包含:
a.约5cm3至约70cm3的泡沫;
其中泡沫包含:
i.按泡沫的重量计约0.5g至约4g的去污表面活性剂;
ii.按泡沫的重量计约0.001g至约4g的推进剂,其中推进剂选自氢氟烃(HFC)、氢氟烯烃(HFO)、以及它们的混合物;
iii.约0.05g/cm3至约0.35g/cm3的泡沫密度;
iv.包含约5μm至约100μm的R32的气泡尺寸分布;以及
v.约4GU至约40GU的光泽度单位测量值。
B.段落A所述的泡沫剂型,其中推进剂选自1,3,3,3-四氟丙-1-烯、1,1-二氟乙烷、以及它们的混合物。
C.段落A或B所述的泡沫剂型,其中光泽度单位测量值为约5GU至约30GU。
D.段落A至C中任一段所述的泡沫剂型,其中光泽度单位测量值为约5GU至约20GU。
E.段落A至D中任一段所述的泡沫剂型,其中光泽度单位测量值为约5GU至约15GU。
F.段落A至E中任一段所述的泡沫剂型,其中气泡尺寸分布包含约10μm至约60μm的R32。
G.段落A至F中任一段所述的泡沫剂型,其中气泡尺寸分布包含约20μm至约50μm的R32。
H.段落A至G中任一段所述的泡沫剂型,其中屈服点为约15Pa至约100Pa。
I.段落A至H中任一段所述的泡沫剂型,其中泡沫剂型的体积为约10g/cm3至约70g/cm3。
J.段落A至I中任一段所述的泡沫剂型,其中泡沫剂型的体积为约20g/cm3至约70g/cm3。
K.段落A至J中任一段所述的泡沫剂型,其中泡沫密度为约0.08g/cm3至约0.25g/cm3。
L.段落A至K中任一段所述的泡沫剂型,其中去污表面活性剂是阴离子表面活性剂。
M.段落A至L中任一段所述的泡沫剂型,其中泡沫剂型还包含按泡沫的重量计约0.0035g至约0.7g的去头皮屑剂。
N.段落M所述的泡沫剂型,其中去头皮屑剂选自羟甲辛吡酮、吡啶硫酮锌、以及它们的混合物。
O.段落A至N中任一段所述的泡沫剂型,其中推进剂是1,3,3,3-四氟丙-1-烯。
P.一种泡沫剂型,包含:
a.约5cm3至约70cm3的泡沫;
其中泡沫包含:
i.按泡沫的重量计约0.5g至约4g的去污表面活性剂;
ii.按泡沫的重量计约0.001g至约4g的推进剂,其中推进剂选自氢氟烃(HFC)、氢氟烯烃(HFO)、以及它们的混合物;
iii.约0.05g/cm3至约0.35g/cm3的泡沫密度;
iv.按泡沫的重量计约0.00005g至约0.25g阳离子沉积聚合物;
v.包含约5μm至约100μm的R32的气泡尺寸分布;以及
vi.约4GU至约40GU的光泽度单位测量值。
Q.段落P所述的泡沫剂型,其中光泽度单位测量值为约5GU至约30GU。
R.段落P或Q所述的泡沫剂型,其中光泽度单位测量值为约5GU至约20GU。
S.段落P至R中任一段所述的泡沫剂型,其中光泽度单位测量值为约5GU至约15GU。
T.段落P至S中任一段所述的泡沫剂型,其中推进剂选自1,3,3,3-四氟丙-1-烯、1,1-二氟乙烷、以及它们的混合物。
本文所公开的量纲和值不应理解为严格限于所引用的精确数值。相反,除非另外指明,否则每个此类量纲旨在表示所述值以及围绕该值功能上等同的范围。例如,公开为“40mm”的量纲旨在表示“约40mm”。
除非明确排除或以其它方式限制,本文中引用的每一篇文献,包括任何交叉引用或相关专利或专利申请以及本申请对其要求优先权或其有益效果的任何专利申请或专利,均据此全文以引用方式并入本文。对任何文献的引用不是对其作为与本发明的任何所公开或本文受权利要求书保护的现有技术的认可,或不是对其自身或与任何一个或多个参考文献的组合提出、建议或公开任何此类发明的认可。此外,当本发明中术语的任何含义或定义与以引用方式并入的文献中相同术语的任何含义或定义矛盾时,应当服从在本发明中赋予该术语的含义或定义。
虽然已举例说明和描述了本发明的具体实施方案,但是对于本领域技术人员来说显而易见的是,在不脱离本发明的实质和范围的情况下可作出多个其它变化和修改。因此,本文旨在于所附权利要求中涵盖属于本发明范围内的所有此类变化和修改。
Claims (11)
1.一种泡沫剂型,包含:
a.5cm3至70cm3的泡沫;
其中所述泡沫包含:
i.按所述泡沫的重量计0.5g至4g的去污表面活性剂;
ii.按所述泡沫的重量计0.001g至4g的推进剂,其中所述推进剂选自氢氟烃(HFC)、氢氟烯烃(HFO)、以及它们的混合物;
iii.0.05g/cm3至0.35g/cm3的泡沫密度;
iv.包含5μm至100μm的R32的气泡尺寸分布;以及
v.4GU至40GU的光泽度单位测量值。
2.根据前述权利要求所述的泡沫剂型,其中所述推进剂选自1,3,3,3-四氟丙-1-烯、1,1-二氟乙烷、以及它们的混合物。
3.根据前述权利要求中任一项所述的泡沫剂型,其中所述光泽度单位测量值为5GU至30GU,优选5GU至20GU,并且更优选5GU至15GU。
4.根据前述权利要求中任一项所述的泡沫剂型,其中所述气泡尺寸分布包含10μm至60μm,并且优选20μm至50μm的R32。
5.根据前述权利要求中任一项所述的泡沫剂型,其中屈服点为15Pa至100Pa。
6.根据前述权利要求中任一项所述的泡沫剂型,其中所述泡沫剂型的体积为10g/cm3至70g/cm3;优选20g/cm3至70g/cm3,并且更优选0.08g/cm3至0.25g/cm3。
7.根据前述权利要求中任一项所述的泡沫剂型,其中所述去污表面活性剂是阴离子表面活性剂。
8.根据前述权利要求中任一项所述的泡沫剂型,其中所述泡沫剂型还包含按所述泡沫的重量计0.0035g至0.7g的去头皮屑剂。
9.根据前述权利要求中任一项所述的泡沫剂型,其中所述泡沫剂型还包含选自羟甲辛吡酮、吡啶硫酮锌、以及它们的混合物的去头皮屑剂。
10.根据前述权利要求中任一项所述的泡沫剂型,其中所述推进剂是1,3,3,3-四氟丙-1-烯。
11.根据前述权利要求中任一项所述的泡沫剂型,其中所述泡沫剂型还包含按所述泡沫的重量计0.00005g至0.25g的阳离子沉积聚合物。
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WO2018075846A1 (en) | 2018-04-26 |
US11154467B2 (en) | 2021-10-26 |
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