CN1140260C - 含水清洁组合物 - Google Patents
含水清洁组合物 Download PDFInfo
- Publication number
- CN1140260C CN1140260C CNB971814015A CN97181401A CN1140260C CN 1140260 C CN1140260 C CN 1140260C CN B971814015 A CNB971814015 A CN B971814015A CN 97181401 A CN97181401 A CN 97181401A CN 1140260 C CN1140260 C CN 1140260C
- Authority
- CN
- China
- Prior art keywords
- acyl
- alkyl
- surfactant
- alkyl ether
- sulfate
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 96
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000004094 surface-active agent Substances 0.000 claims abstract description 85
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 31
- -1 acyl isethionates Chemical class 0.000 claims abstract description 28
- 239000000344 soap Substances 0.000 claims abstract description 21
- 239000000194 fatty acid Substances 0.000 claims abstract description 16
- 125000002252 acyl group Chemical group 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 65
- VKELSQNRSVJHGR-UHFFFAOYSA-N 4-oxo-4-sulfooxybutanoic acid Chemical compound OC(=O)CCC(=O)OS(O)(=O)=O VKELSQNRSVJHGR-UHFFFAOYSA-N 0.000 claims description 30
- 229940104261 taurate Drugs 0.000 claims description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 5
- 229930195729 fatty acid Natural products 0.000 abstract description 5
- 150000004665 fatty acids Chemical class 0.000 abstract description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 abstract 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract 2
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- 238000012360 testing method Methods 0.000 description 17
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- 235000013162 Cocos nucifera Nutrition 0.000 description 15
- 239000003921 oil Substances 0.000 description 15
- DHHFDKNIEVKVKS-FMOSSLLZSA-N Betanin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC(C(=C1)O)=CC(C[C@H]2C([O-])=O)=C1[N+]2=C\C=C\1C=C(C(O)=O)N[C@H](C(O)=O)C/1 DHHFDKNIEVKVKS-FMOSSLLZSA-N 0.000 description 13
- DHHFDKNIEVKVKS-MVUYWVKGSA-N Betanin Natural products O=C(O)[C@@H]1NC(C(=O)O)=C/C(=C\C=[N+]/2\[C@@H](C(=O)[O-])Cc3c\2cc(O)c(O[C@H]2[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O2)c3)/C1 DHHFDKNIEVKVKS-MVUYWVKGSA-N 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 13
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- 229910052757 nitrogen Inorganic materials 0.000 description 10
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- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 8
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 7
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- 125000004432 carbon atom Chemical group C* 0.000 description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000002453 shampoo Substances 0.000 description 5
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- 241001597008 Nomeidae Species 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
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- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 239000011780 sodium chloride Substances 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
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- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical class OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- QBKSIHCSDPPLJI-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]tetradecan-1-ol;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCC(CO)N(CCO)CCO QBKSIHCSDPPLJI-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
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- 241000208681 Hamamelis virginiana Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 208000028990 Skin injury Diseases 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
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- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 235000011399 aloe vera Nutrition 0.000 description 1
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- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
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- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical class CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 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 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
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- 229920001206 natural gum Polymers 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 125000001400 nonyl group Chemical group [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 1
- UKGRTCZMPQERFQ-UHFFFAOYSA-N octadecyl 2-hydroxypropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)O UKGRTCZMPQERFQ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([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 1
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- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 description 1
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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
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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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
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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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
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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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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Abstract
公开了高泡、温和的含水清洁组合物,其含短链阴离子表面活性剂和长链阴离子表面活性剂,长链和短链表面活性剂分别选自烷基醚硫酸盐、酰基甲基牛磺酸酯、酰基羟乙基磺酸盐、酰基肌氨酸盐、烷基磺基琥珀酸盐、烷基醚磺基琥珀酸盐和其混合物;短链表面活性剂也可以是或含有短链脂肪酸皂。
Description
技术领域
本发明涉及含水清洁组合物。特别是,本发明涉及适于清洁人体皮肤和头发的含水清洁组合物,该组合物是含有某些特定长链和短链表面活性剂的混合物。这些组合物不但温和而且表现出极佳的发泡性能。
背景技术
近来,高泡且温和的含水清洗组合物对于使用者来说愈来愈重要。如果该清洁组合物是用于局部涂敷在人体皮肤和头发上时,这些联合性质是十分有益的。所以,人们试图提供具有这两种性能的洗涤产品,例如洗发用香波、淋浴用凝胶和洗面泡沫体。但事实上,这些产品存在的主要问题是上述两种性质彼此不相容。虽然高泡表面活性剂通常极其粗糙,但温和的表面活性剂却无法提供足够的泡沫。
以往的尝试业已克服了上述问题,这是通过将可产生足量泡沫的粗糙表面活性剂与极柔和的辅助表面活性剂的合用来实现的。
US-A-3,728,447(C J Patterson)公开的洗发剂组合物含有脂肪酸乳酸盐或甘醇酸酯,虽然这些洗发剂的清洁作用令人满意,但其泡沫仍较少。为了获得较高的发泡作用,该专利在洗发剂组合物中掺入了发泡表面活性剂,例如十二烷基硫酸钠或十二烷基硫酸三乙醇胺盐。但是,这些发泡表面活性剂施用于人体皮肤时会引起高度刺激作用。
WO 91/09923描述了含有超温和表面活性剂和泡沫促进剂的组合物。所述超温和表面活性剂是具有疏水基团的烷基甘油醚磺酸盐(AGS),该疏水基团含有带有约7至9个碳原子的直链烷基链。常规泡沫促进剂如氧化胺类和水溶性卤化物盐均可被加入其中,用于提高泡沫的乳脂状、体积和稳定性。
EP-A-244 796(Kao)公开的洗涤剂组合物含有(a)磷酸盐表面活性剂和(b)酰基乳酸盐,其中的酰基含有12至18个碳原子。上述组合物的具体例子是十二烷基磷酸盐分别与硬脂酰基乳酸盐、异硬脂酰基乳酸盐和月桂酰基乳酸盐的混合物。
US-A-4,761,279(Eastman Kodak)公开的剃须膏制剂,含有C14-C22酰基乳酸盐的盐、饱和单甘油酯、丙二醇单酯和湿润剂。
已经发现,特定短链表面活性剂与特定长链表面活性剂的合用可提供具有附加特性的温和清洁组合物,这样的组合物在使用时可产生高度的泡沫。意外的是,极温和表面活性剂的合用可以获得上述性质,而它们在单独使用时却无法产生令人满意的泡沫也就是泡沫量。特定短链和特定长链表面活性剂的合用将在下文描述。
发明内容
因此,本发明提供一种含水清洁组合物,该组合物含有:
(a)短链阴离子表面活性剂,选自C6-C9烷基醚硫酸盐、C8-C11酰基乳酸盐、C6-C9酰基甲基牛磺酸酯、C6-C9酰基羟乙基磺酸盐、C6-C11脂肪酸皂、C6-C9烷基硫酸盐、C6-C11酰基肌氨酸盐、C6-C9烷基磺基琥珀酸盐、C6-C9烷基醚磺基琥珀酸盐,或其混合物;
(b)长链阴离子表面活性剂,选自C13-C18烷基醚硫酸盐、C13-C18酰基乳酸盐、C13-C16酰基甲基牛磺酸酯、C13-C15酰基羟乙基磺酸盐、C13-C16烷基硫酸盐、C13-C16酰基肌氨酸盐、C13-C16烷基磺基琥珀酸盐、C13-C16烷基醚磺基琥珀酸盐,或其混合物;
(c)任选的中链阴离子表面活性剂,选自C10-C12烷基醚硫酸盐、C12酰基乳酸盐、C10-C12酰基甲基牛磺酸酯、C10-C12酰基羟乙基磺酸盐、C10-C12烷基硫酸盐、C12酰基肌氨酸盐、C10-C12烷基磺基琥珀酸盐、C10-C12烷基醚磺基琥珀酸盐,或其混合物;
(d)水;
其中
(i)表面活性剂(a)和(b)的至少一种选自酰基乳酸盐、酰基肌氨酸盐、酰基甲基牛磺酸酯、烷基醚硫酸盐和酰基羟乙基磺酸盐;或短链阴离子表面活性剂(a)是C6-C11脂肪酸皂;
(ii)若存在表面活性剂(c),则表面活性剂(a)、(b)和(c)的含量应使(c)∶[(a)+(b)]的重量比小于1∶1。
短链阴离子表面活性剂(a)
本发明的含水清洁组合物含有0.1%至36%(重量)的短链表面活性剂,该短链表面活性剂选自C6-C9烷基醚硫酸盐、C8-C11酰基乳酸盐、C6-C9酰基甲基牛磺酸酯、C6-C9酰基羟乙基磺酸盐、C6-C11脂肪酸皂、C6-C9烷基硫酸盐、C6-C11酰基肌氨酸盐、C6-C9烷基磺基琥珀酸盐、C6-C9烷基醚磺基琥珀酸盐,或其混合物;
所述短链阴离子表面活性剂在本发明清洁组合物中的可取用量是0.5%至20%,优选1%至10%(重量)。
长链阴离子表面活性剂(b)
本发明所述含水清洁组合物含有0.1%至36%(重量)的长链表面活性剂,该长链表面活性剂选自:C13-C18烷基醚硫酸盐、C13-C18酰基乳酸盐、C13-C16酰基甲基牛磺酸酯、C13-C15酰基羟乙基磺酸盐、C13-C16烷基硫酸盐、C13-C16酰基肌氨酸盐、C13-C16烷基磺基琥珀酸盐、C13-C16烷基醚磺基琥珀酸盐,或其混合物;
所述长链阴离子表面活性剂(b)在本发明清洁组合物中的可取用量是0.5%至20%,优选1%至10%(重量)。
短链表面活性剂(a)和长链表面活性剂(b)的合用
上述短链表面活性剂和长链表面活性剂是以这样的方式合用:它们中至少一种选自如上所述的酰基乳酸盐、酰基肌氨酸盐、酰基甲基牛磺酸酯、烷基醚硫酸盐、酰基羟乙基磺酸盐和C6-C11脂肪酸皂。
这是指:
含有C6-C9烷基醚硫酸盐作为短链表面活性剂,或含有C13-C18烷基醚硫酸盐作为长链表面活性剂,或:
含有C8-C11酰基乳酸盐作为短链表面活性剂,或含有C13-C18酰基乳酸盐作为长链表面活性剂,或:
含有C6-C9酰基甲基牛磺酸酯作为短链表面活性剂,或含有C13-C16酰基甲基牛磺酸酯作为长链表面活性剂,或:
含有C6-C9酰基羟乙基磺酸盐作为短链表面活性剂,或含有C13-C15酰基羟乙基磺酸盐作为长链表面活性剂,或:
含有C6-C11酰基肌氨酸盐作为短链表面活性剂,或含有C13-C16酰基肌氨酸盐作为长链表面活性剂,或:
含有C6-C11脂肪酸皂作为短链表面活性剂。
令人惊奇的是,就本发明的效果来说,两种类型的表面活性剂(长链和短链表面活性剂)是否选自同一系列表面活性剂并不重要。
短链表面活性剂(a)相对于长链表面活性剂(b)的重量配比优选是1∶10-10∶1,更优选1∶3-6∶1,最优选1∶1-3∶1。
中链阴离子表面活性剂
本发明的清洁组合物任选地含有中链阴离子表面活性剂(c),该表面活性剂选自C10-C12烷基醚硫酸盐、C12酰基乳酸盐、C10-C12酰基甲基牛磺酸酯、C10-C12酰基羟乙基磺酸盐、C10-C12烷基硫酸盐、C12酰基肌氨酸盐、C10-C12烷基磺基琥珀酸盐、C10-C12烷基醚磺基琥珀酸盐,或其混合物;
已经发现,在每种同系表面活性剂中,上述特定系列的中链阴离子表面活性剂(c)在泡沫试验中产生最高程度的泡沫值(此后描述该泡沫试验)。另一方面,这些中链表面活性剂一般也是其分别所属同系列中刺激作用最强的表面活性剂。各同系列表面活性剂中均存在中链表面活性剂(c),并且其特定的链长或链长范围可以由下列所述泡沫试验测出。
例如,根据下述泡沫试验,在上文描述为中链阴离子表面活性剂(c)之一的C12酰基肌氨酸盐是中等链长的酰基肌氨酸盐。因此,它是一种在同系列酰基肌氨酸盐中产生最高程度泡沫值同时刺激性也最大的表面活性剂。
短链阴离子表面活性剂(a)、长链阴离子表面活性剂(b)和中链阴离子表面活性剂(c)以(c)∶(a)+(b)的重量比例小于1∶1的含量存在对于本发明的效果来说十分重要。
表面活性剂(a)、(b)和(c)的含量优选是使(c)∶(a)+(b)的重量比小于1∶1.5,更优选小于1∶2。而且,最优选在本发明所述组合物中不含有中链表面活性剂。
根据现有技术的建议,只有通过使用高泡同时具有严重皮肤刺激性缺陷的表面活性剂,尤其是中链表面活性剂才可获得高泡组合物。与这种建议相反的是,本发明提供了极其温和并且高泡的含水清洁组合物,它采用了十分温和的、在单独使用时无法产生足够泡沫的表面活性剂。意外的是,采用温和且低泡的表面活性剂组合物可以提供与中链表面活性剂等同的发泡性能,同时并不产生不利的皮肤刺激作用。
水
本发明所述组合物含有占组合物总重量60%至99%,优选96%至70%,最优选92%至78%(重量)的水。
组合物的应用
本发明还提供了含水组合物用作人体皮肤和头发的清洁剂,该组合物含有:
(a)短链阴离子表面活性剂,选自C6-C9烷基醚硫酸盐、C8-C11酰基乳酸盐、C6-C9酰基甲基牛磺酸酯、C6-C9酰基羟乙基磺酸盐、C6-C11脂肪酸皂、C6-C9烷基硫酸盐、C6-C11酰基肌氨酸盐、C6-C9烷基磺基琥珀酸盐、C6-C9烷基醚磺基琥珀酸盐,或其混合物;
(b)长链阴离子表面活性剂,选自C13-C18烷基醚硫酸盐、C13-C18酰基乳酸盐、C13-C16酰基甲基牛磺酸酯、C13-C15酰基羟乙基磺酸盐、C13-C16烷基硫酸盐、C13-C16酰基肌氨酸盐、C13-C16烷基磺基琥珀酸盐、C13-C16烷基醚磺基琥珀酸盐,或其混合物;
(c)任选的中链阴离子表面活性剂,选自C10-C12烷基醚硫酸盐、C12酰基乳酸盐、C10-C12酰基甲基牛磺酸酯、C10-C12酰基羟乙基磺酸盐、C10-C12烷基硫酸盐、C12酰基肌氨酸盐、C10-C12烷基磺基琥珀酸盐、C10-C12烷基醚磺基琥珀酸盐,或其混合物;
(d)水;
其中(i)表面活性剂(a)和(b)的至少一种选自酰基乳酸盐、酰基肌氨酸盐、酰基甲基牛磺酸酯、烷基醚硫酸盐和酰基羟乙基磺酸盐;或短链阴离子表面活性剂(a)是C6-C11脂肪酸皂;
(ii)若存在表面活性剂(c),则表面活性剂(a)、(b)和(c)的含量应是(c)∶[(a)+(b)]的重量比小于1∶1。
可将本发明组合物应用在头发或皮肤的洗涤,例如将其配制成洗发剂、漂去型护发产品、沐浴或淋浴用凝胶以及洗面组合物。
优选本发明组合物还含有辅助表面活性剂。该辅助表面活性剂可以选自任何已知的、适合局部涂敷在人体上的表面活性剂,并且可选自非离子、两性离子和阳离子表面活性剂或其混合物。特别优选的是温和表面活性剂,也就是不对角质层(最外层皮肤)产生刺激的表面活性剂。
适用的非离子表面活性剂包括:烷基多糖、乳糖酰胺(lactobionamide)、乙二醇酯、甘油单醚、多羟基酰胺(谷氨酰胺)、伯和仲脂肪醇乙氧基化物,尤其是每1摩尔醇由平均1至20摩尔环氧乙烷乙氧基化的C8-20脂肪醇。
优选的两性离子洗涤剂是具有含7至18个碳原子的烷基或链烯基并且其完整结构式如下的那些:
其中R1是含有7至18个碳原子的烷基或链烯基,R2和R3彼此独立地为烷基、羟烷基或羧基烷基,它们含有1至3个碳原子。
m为2至4
n为0或1
X是被羟基任选取代的、含有1至3个碳原子的亚烷基;和
Y是-CO2 -或-SO3 -。
其中m是2或3。
在上述两个通式中。R1、R2和R3如上述定义;特别是,R1可以是来自椰子的C12和C14烷基的混合物,由此至少半数,优选至少四分之三的R1基团含有10至14个碳原子。R2和R3优选为甲基。
或
这些结构式中的R1、R2和R3定义如前。
本发明的组合物可以含有结构剂(structurant),也就是提高低剪切(例如1s-1以下)粘度的附加材料。适用的材料包括:溶胀粘土,如合成锂皂石;脂肪酸及其衍生物,特别是脂肪酸单甘油酯聚乙二醇醚交联聚丙烯酸酯(例如Carbopol(TM))(Goodrich销售的聚合物);丙烯酸酯及其共聚物,聚乙烯吡咯烷酮及其共聚物;聚环乙亚胺;盐类,例如氯化钠和硫酸铵;蔗糖酯;胶凝剂;及其混合物。
在粘土中,更优选将合成水辉石(合成锂皂石)与能使粘土增稠的电解质盐相结合。适用的电解质包括:碱金属和碱土金属盐,例如卤化物、铵盐和硫酸盐。
本发明的组合物也可以含有增稠剂,也就是当使用中的剪切速率升高时用于维持组合物粘度的材料。适用的材料包括交联聚丙烯酰胺,例如Carbopol(TM)(Goodrich销售的聚合物);脂肪酸及其衍生物,尤其是脂肪酸单甘油酯聚乙二醇醚;天然树胶,包括藻酸盐、瓜耳胶、呫吨胶;和多糖衍生物,包括羟乙基纤维素、羧甲基纤维素和羟丙基瓜耳胶;丙二醇和丙二醇油酸酯;盐类,例如氯化钠和硫酸铵;甘油牛脂;及其混合物。
结构剂(structurant)和增稠剂的其它例子公开在国际化妆品学成分目录,第5版,1993,CTFA(化妆品、盥洗用品和香料协会)出版,该文献在此引入作为参考。
其它可以加入到本发明所述组合物中的辅料的例子包括:遮光剂;防腐剂,例如对羟基苯甲酸酯;抗微生物剂,例如抗氧剂,如丁羟基甲苯;杀菌剂;湿润剂,例如甘油和山梨糖醇;蜡;植物提取物,例如芦荟,北美金缕梅和接骨木花;着色剂;和香料。
具体实施方式
实施例
按照下列方案,评估每个具有实施例/参比实施例所定义的组成的表面活性剂混合物的皮肤温和性和发泡性能。
玉米蛋白试验(Zein test)(皮肤刺激性)
利用所谓的玉米蛋白试验来测定不同制剂对皮肤的刺激作用。这种体外试验法利用了表面活性剂和蛋白质的结合能力与表面活性剂所引起的皮肤损伤之间的相互关系。表皮蛋白质结构的变性在目测表面活性剂所致损伤的发展中是一个关键机制。将从玉米仁中提取出的不溶性蛋白质-玉米蛋白用作表皮蛋白质的模型,玉米蛋白在表面活性剂溶液中的溶解度是表面活性剂对皮肤刺激作用的一个可靠指标。该试验包括确定被表面活性剂溶解的玉米蛋白量。将5克玉米蛋白分散在40cm3表面活性剂溶液(2%)中。将该混合物在35℃振摇1小时,进而立刻离心除去未溶解的玉米蛋白。根据微量基耶达氏定氮法测出的溶液中的含氮量估算出溶解的玉米蛋白量(扣除表面活性剂中所含有的氮)。
泡沫量试验
用下列试验评定组合物的发泡能力。将25ml在蒸馏水中共含有10%表面活性剂的试验溶液和0.5g人造皮脂加入到250ml量筒内。用连在棒上的橡皮塞搅拌该溶液。该橡皮塞被调整到小于量筒内径5mm的最大直径。该橡皮塞在量筒内上下移动以穿过溶液和泡沫。活塞每1秒钟上下移动两次。在循环40次后取出橡皮塞,测量泡沫的体积。
实施例1和参比实施例A至C
醚硫酸盐
参比实施例A是Linevol 79醚硫酸盐3EO(壳牌产品(ex Shell)),它是C7、C8和C9烷基链的混合物,因此其烷基链长平均为8.2。
参比实施例B是Dobanol 23醚硫酸盐3EO(ex Shell),它是C12和C14烷基链的混合物,因此其烷基链长平均为12.5。
参比实施例C是Dobanol 45醚硫酸盐3EO(ex Shell),它是C14和C15烷基链的混合物,因此其烷基链长平均为14.5。
实施例1是Linevol 79醚硫酸盐3EO(ex shell)和Dobanol 45醚硫酸盐3E(ex Shell)的混合物,因此其烷基链长平均为11.4。
泡沫体积
玉米蛋白试验
(ml) (%N2)参比实施例A 70 0.15参比实施例B 100 0.45参比实施例C 75 0.32实施例1 105 0.22
由此看出,短链和长链的混合物(实施例1)给出与中链(参比实施例B)等量的泡沫,但具有很低的玉米蛋白试验评分。
实施例2和参比实施例D和E
在酰胺基甜菜碱存在下皂和醚硫酸盐混合
参比实施例D是10%椰油醚硫酸盐(3EO)[Empicol 0251,Albright & Wilson产品]+5%椰油酰胺基甜菜碱[Tegobetaine C,Goldschmidt出品]。
参比实施例E是10%辛酸钠皂+5%椰油酰胺基甜菜碱.
实施例2是8%椰油醚硫酸盐(3EO)+2%辛酸钠皂+5%椰油酰胺基甜菜碱。
泡沫体积
玉米蛋白试验
(ml) (%N2)参比实施例D 79 0.23参比实施例E 51 0.30实施例2 145 0.24
与典型的洗发制剂如参比实施例D相比,在实施例2的混合物中加入一定量的短链皂可以增加泡沫但对温和性(玉米蛋白)不产生不利影响。
实施例3和参比实施例F和G
在酰胺基甜菜碱存在下短链牛磺酸盐和醚硫酸盐混合
参比实施例F是10%椰油醚硫酸盐(3EO)[Empicol 0251,Albright & Wilson产品]+5%椰油酰胺基甜菜碱[Tegobetaine C,Goldschmidt产品]。
参比实施例G是10%C8辛酸盐+5%椰油酰胺基甜菜碱。
实施例3是7%椰油醚硫酸盐(3EO)+3%C8辛酸盐+5%椰油酰胺基甜菜碱。
泡沫体积
玉米蛋白试验
(ml) (%N2)参比实施例F 79 0.23参比实施例G 44 0.24实施例3 145 0.24
在实施例3的混合物中加入一定量的短链牛磺酸盐可以增加泡沫但不对温和性(玉米蛋白)产生不利影响。
实施例4和参比实施例H和I
在酰胺基甜菜碱存在下短链羟乙基磺酸盐和醚硫酸盐混合
参比实施例H是10%椰油醚硫酸盐(3EO)[Empicol 025l,Albright &Wilson产品]+5%椰油酰胺基甜菜碱[Tegobetaine C,Goldschmidt产品]。
参比实施例I是10%C8/10羟乙基磺酸盐[含有42%C8、45%C10、5%C16和5%C18的混合物]+5%椰油酰胺基甜菜碱。
实施例4是6%椰油醚硫酸盐(3EO)+4%C8/10羟乙基磺酸盐+5%椰油酰胺基甜菜碱。
泡沫体积
玉米蛋白试验
(ml) (%N2)参比实施例H 79 0.23参比实施例I 80 0.27实施例4 173 0.25
在实施例4的混合物中加入一定量的短链羟乙基磺酸盐可以增加泡沫但不对温和性(玉米蛋白)产生不利影响。
实施例5和参比实施例J和K
在酰胺基甜菜碱存在下短链肌氨酸盐和醚硫酸盐混合
参比实施例J是10%椰油醚硫酸盐(3EO)[Empicol 0251,Albright & Wilson产品]+5%椰油酰胺基甜菜碱[Tegobetaine C,Goldschmidt产品]。
参比实施例K是10%C8肌氨酸盐+5%椰油酰胺基甜菜碱。
实施例5是6%椰油醚硫酸盐(3EO)+4%C8肌氨酸盐+5%椰油酰胺基甜菜碱。
泡沫体积
玉米蛋白试验
(ml) (%N2)参比实施例J 79 0.23参比实施例K 42 0.30实施例5 111 0.26
在实施例5的混合物中加入一定量的短链肌氨酸盐可以增加泡沫但不对温和性(玉米蛋白)产生不利影响。
实施例6和参比实施例L至N
脂肪族羟乙基磺酸盐
参比实施例L是椰油羟乙基磺酸盐,它是C12、C14、C16和C18烷基链的混合物,因此其烷基链长平均为13.1。
参比实施例M是C8羟乙基磺酸盐。
参比实施例N是C14羟乙基磺酸盐。
实施例6是C8羟乙基磺酸盐和C14羟乙基磺酸盐的混合物。
泡沫体积
玉米蛋白试验
(ml) (%N2)参比实施例L 88 0.42参比实施例M 130 0.72参比实施例N 0 0.50实施例6 124 0.45
由此表明,短链和长链的混合物(实施例6)可以产生与中链(参比实施例M)相同的泡沫而且具有较低的玉米蛋白评分值。
实施例7和参比实施例O和P
在酰胺基甜菜碱存在下皂和椰油羟乙基磺酸盐混合
参比实施例O是10%椰油羟乙基磺酸盐(平均链长C13.1)+5%椰油酰胺基甜菜碱[Tegobetaine C,Goldschmidt产品]。
参比实施例P是10%辛酸钠皂+5%椰油酰胺基甜菜碱。
实施例7是7%椰油羟乙基磺酸盐+7%辛酸钠皂+5%椰油酰胺基甜菜碱。
泡沫体积
玉米蛋白试验
(ml) (%N2)参比实施例O 110 0.23参比实施例P 84 0.30实施例7 170 0.30
在实施例7的混合物中加入一定量的短链皂可以增加泡沫但不对温和性(玉米蛋白)产生不利影响。
实施例8和参比实施例Q和R
在酰胺基甜菜碱存在下短链肌氨酸盐和椰油羟乙基磺酸盐混合
参比实施例Q是10%椰油羟乙基磺酸盐+5%椰油酰胺基甜菜碱[Tegobetaine C,Goldschmidt产品]。
参比实施例R是10%C8肌氨酸盐+5%椰油酰胺基甜菜碱。
实施例8是7%椰油羟乙基磺酸盐+3%C8肌氨酸盐+5%椰油酰胺基甜菜碱。
泡沫体积
玉米蛋白试验
(ml) (%N2)参比实施例Q 110 0.23参比实施例R 44 0.30实施例8 140 0.27
在实施例8的混合物中加入一定量的短链肌氨酸盐可以增加泡沫但不对温和性(玉米蛋白)产生不利影响。
Claims (8)
1.一种高泡、温和的含水清洁组合物,该组合物含有:
(a)短链阴离子表面活性剂,选自C6-C9烷基醚硫酸盐、C6-C9酰基甲基牛磺酸酯、C6-C9酰基羟乙基磺酸盐、C6-C11脂肪酸皂、C6-C9烷基硫酸盐、C6-C11酰基肌氨酸盐、C6-C9烷基磺基琥珀酸盐、C6-C9烷基醚磺基琥珀酸盐,或其混合物;
(b)长链阴离子表面活性剂,选自C13-C18烷基醚硫酸盐、C13-C16酰基甲基牛磺酸酯、C13-C15酰基羟乙基磺酸盐、C13-C16烷基硫酸盐、C13-C16酰基肌氨酸盐、C13-C16烷基磺基琥珀酸盐、C13-C16烷基醚磺基琥珀酸盐,或其混合物;
(c)任选的中链阴离子表面活性剂,选自C10-C12烷基醚硫酸盐、C10-C12酰基甲基牛磺酸酯、C10-C12酰基羟乙基磺酸盐、C10-C12烷基硫酸盐、C12酰基肌氨酸盐、C10-C12烷基磺基琥珀酸盐、C10-C12烷基醚磺基琥珀酸盐,或其混合物;
(d)水;
其中(i)表面活性剂(a)和(b)的至少一种选自酰基肌氨酸盐、酰基甲基牛磺酸酯、烷基醚硫酸盐和酰基羟乙基磺酸盐;或短链阴离子表面活性剂(a)是C6-C11脂肪酸皂;
(ii)若存在表面活性剂(c),则表面活性剂(a)、(b)和(c)的含量应使(c)∶[(a)+(b)]的重量比小于1∶1。
2.权利要求1所述的清洁组合物,其中所述表面活性剂(a)、(b)和(c)的含量满足(c)∶[(a)+(b)]的重量比例低于1∶1.5。
3.权利要求1所述的清洁组合物,其中不含有中链表面活性剂(c)。
4.权利要求1所述的清洁组合物,其中表面活性剂(a)选自:C6-C8酰基甲基牛磺酸酯、C6-C8酰基羟乙基磺酸盐、C6-C8烷基醚硫酸盐和C8-C10酰基肌氨酸盐。
5.权利要求4所述的清洁组合物,其中表面活性剂(b)选自:C14-C16酰基甲基牛磺酸酯、C14-C16酰基羟乙基磺酸盐、C14-C16烷基醚硫酸盐和C14-C16酰基肌氨酸盐。
6.权利要求1所述的清洁组合物,其中短链表面活性剂(a)和长链表面活性剂(b)是选自相同系列的表面活性剂。
7.上述权利要求1至6任一项所述的清洁组合物,其中表面活性剂(a)∶(b)的重量比例是1∶10至10∶1。
8.含水组合物作为人体皮肤和头发清洁剂的应用,该组合物含有:
(a)短链阴离子表面活性剂,选自C6-C9烷基醚硫酸盐、C6-C9酰基甲基牛磺酸酯、C6-C9酰基羟乙基磺酸盐、C6-C11脂肪酸皂、C6-C9烷基硫酸盐、C6-C11酰基肌氨酸盐、C6-C9烷基磺基琥珀酸盐、C6-C9烷基醚磺基琥珀酸盐,或其混合物;
(b)长链阴离子表面活性剂,选自C13-C18烷基醚硫酸盐、C13-C16酰基甲基牛磺酸酯、C13-C15酰基羟乙基磺酸盐、C13-C16烷基硫酸盐、C13-C16酰基肌氨酸盐、C13-C16烷基磺基琥珀酸盐、C13-C16烷基醚磺基琥珀酸盐,或其混合物;
(c)任选的中链阴离子表面活性剂,选自C10-C12烷基醚硫酸盐、C10-C12酰基甲基牛磺酸酯、C10-C12酰基羟乙基磺酸盐、C10-C12烷基硫酸盐、C12酰基肌氨酸盐、C10-C12烷基磺基琥珀酸盐、C10-C12烷基醚磺基琥珀酸盐,或其混合物;
(d)水;
其中(i)表面活性剂(a)和(b)的至少一种选自酰基肌氨酸盐、酰基甲基牛磺酸酯、烷基醚硫酸盐和酰基羟乙基磺酸盐;或短链阴离子表面活性剂(a)是C6-C11脂肪酸皂;
(ii)若存在表面活性剂(c),则表面活性剂(a)、(b)和(c)的含量应使(c)∶[(a)+(b)]的重量比小于1∶1。
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GBGB9623935.5A GB9623935D0 (en) | 1996-11-18 | 1996-11-18 | Aqueous cleansing composition |
GB9623935.5 | 1996-11-18 |
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FR3010899B1 (fr) * | 2013-09-24 | 2017-02-17 | Oreal | Composition cosmetique comprenant une association d'agents tensioactifs anioniques de types carboxylate et acyl-isethionate. |
MX2020002112A (es) | 2017-08-25 | 2020-07-20 | Unilever Ip Holdings B V | Composicion de limpieza personal. |
EP3672566A1 (en) | 2017-08-25 | 2020-07-01 | Unilever PLC, a company registered in England and Wales under company no. 41424 of | Personal cleansing composition |
CA3086412C (en) * | 2018-01-19 | 2023-02-28 | The Procter & Gamble Company | Liquid detergent compositions comprising alkyl ethoxylated sulfate surfactant |
CN112136051B (zh) * | 2018-06-28 | 2024-09-27 | 联合利华知识产权控股有限公司 | 方法 |
WO2020229202A1 (en) | 2019-05-15 | 2020-11-19 | Purac Biochem B.V. | Lactylate blend for preservative/antimicrobial system |
CN111617428B (zh) * | 2020-04-07 | 2021-07-27 | 成都科宏达化学有限责任公司 | 一种无氯水成膜泡沫灭火剂及其制备方法 |
EP3957297A1 (en) * | 2020-08-21 | 2022-02-23 | PZ Cussons (International) Limited | Personal cleansing composition |
CN116270271B (zh) * | 2023-04-11 | 2023-10-20 | 佛山合德新材料有限公司 | 一种具有保湿修复调理性的复合氨基酸表面活性剂 |
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US3001944A (en) * | 1957-07-12 | 1961-09-26 | Colgate Palmolive Co | Controlling viscosity of synthetic detergent-soap shampoos |
US3728447A (en) * | 1970-03-03 | 1973-04-17 | Patterson Co C | Fatty acid lactylates and glycolates for conditioning hair |
US4758376A (en) * | 1985-11-28 | 1988-07-19 | Kao Corporation | Phosphate surfactant based detergent compositions |
US4761279A (en) * | 1987-03-31 | 1988-08-02 | Eastman Kodak Company | Shaving cream formulations |
US5726137A (en) * | 1989-06-21 | 1998-03-10 | Colgate-Palmolive Company | Low silicone hair conditioning shampoo and non-silicone hair conditioning/style control shampoo |
US4997641A (en) * | 1990-04-09 | 1991-03-05 | Colgate-Palmolive Company | Hair conditioning shampoo containing C6 -C10 alkyl sulfate or alkyl alkoxy sulfate |
US5084212A (en) * | 1989-12-29 | 1992-01-28 | The Procter & Gamble Company | Ultra mild surfactant with foam enhancer |
AU637668B2 (en) * | 1990-02-09 | 1993-06-03 | Unilever Plc | Detergent composition |
JP3079158B2 (ja) * | 1991-12-04 | 2000-08-21 | 味の素株式会社 | 洗浄剤組成物 |
GB9204175D0 (en) * | 1992-02-27 | 1992-04-08 | Unilever Plc | Cleansing composition |
MX9305745A (es) * | 1992-09-22 | 1994-05-31 | Colgate Palmolive Co | Champu o tratamiento de control de estilo acondicionador del cabello. |
AU671208B2 (en) * | 1993-06-30 | 1996-08-15 | Colgate-Palmolive Company, The | Anti-bacterial cleansing composition |
US5435933A (en) * | 1993-08-25 | 1995-07-25 | Colgate-Palmolive Company | Composition of synthetic detergents |
WO1995022311A1 (en) * | 1994-02-18 | 1995-08-24 | Unilever Plc | Personal washing compositions |
GB9509939D0 (en) * | 1995-05-17 | 1995-07-12 | Unilever Plc | Aqueous liquid cleansing composition containing fatty acid soaps |
WO1996037591A1 (en) * | 1995-05-27 | 1996-11-28 | The Procter & Gamble Company | Cleansing compositions |
-
1996
- 1996-11-18 GB GBGB9623935.5A patent/GB9623935D0/en active Pending
-
1997
- 1997-10-20 BR BR9713081-8A patent/BR9713081A/pt not_active Application Discontinuation
- 1997-10-20 WO PCT/EP1997/005918 patent/WO1998022086A1/en active IP Right Grant
- 1997-10-20 AU AU51212/98A patent/AU5121298A/en not_active Abandoned
- 1997-10-20 ES ES97945873T patent/ES2238732T3/es not_active Expired - Lifetime
- 1997-10-20 HU HU9904246A patent/HUP9904246A3/hu unknown
- 1997-10-20 DE DE69732787T patent/DE69732787T2/de not_active Expired - Lifetime
- 1997-10-20 JP JP52311898A patent/JP3675846B2/ja not_active Expired - Fee Related
- 1997-10-20 CN CNB971814015A patent/CN1140260C/zh not_active Expired - Fee Related
- 1997-10-20 EP EP97945873A patent/EP0946142B1/en not_active Revoked
- 1997-10-20 CA CA002269968A patent/CA2269968A1/en not_active Abandoned
- 1997-10-20 ID IDW990350A patent/ID21756A/id unknown
- 1997-11-06 US US08/965,519 patent/US6001787A/en not_active Expired - Lifetime
- 1997-11-10 IN IN651BO1997 patent/IN190004B/en unknown
- 1997-11-14 AR ARP970105333A patent/AR009611A1/es active IP Right Grant
-
1999
- 1999-11-09 US US09/437,885 patent/US6569825B1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE69732787D1 (de) | 2005-04-21 |
CN1244791A (zh) | 2000-02-16 |
GB9623935D0 (en) | 1997-01-08 |
EP0946142B1 (en) | 2005-03-16 |
IN190004B (zh) | 2003-05-31 |
JP2000509722A (ja) | 2000-08-02 |
BR9713081A (pt) | 2000-03-28 |
AR009611A1 (es) | 2000-04-26 |
US6001787A (en) | 1999-12-14 |
AU5121298A (en) | 1998-06-10 |
CA2269968A1 (en) | 1998-05-28 |
DE69732787T2 (de) | 2005-08-18 |
HUP9904246A2 (hu) | 2000-04-28 |
EP0946142A1 (en) | 1999-10-06 |
ES2238732T3 (es) | 2005-09-01 |
HUP9904246A3 (en) | 2001-11-28 |
ID21756A (id) | 1999-07-22 |
WO1998022086A1 (en) | 1998-05-28 |
US6569825B1 (en) | 2003-05-27 |
JP3675846B2 (ja) | 2005-07-27 |
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