CN112513236A - 鼠李糖脂在表面活性剂体系中的用途 - Google Patents
鼠李糖脂在表面活性剂体系中的用途 Download PDFInfo
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- CN112513236A CN112513236A CN201980047655.5A CN201980047655A CN112513236A CN 112513236 A CN112513236 A CN 112513236A CN 201980047655 A CN201980047655 A CN 201980047655A CN 112513236 A CN112513236 A CN 112513236A
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- ABHHITAVUODQNA-UHFFFAOYSA-M potassium;benzenesulfonate Chemical class [K+].[O-]S(=O)(=O)C1=CC=CC=C1 ABHHITAVUODQNA-UHFFFAOYSA-M 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- WBPFVHVTNAEJCX-UHFFFAOYSA-M sodium;2-[[4-(dimethylamino)phenyl]-(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)methyl]-5-[ethyl-[(3-sulfonatophenyl)methyl]amino]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(C)C)C(S([O-])(=O)=O)=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 WBPFVHVTNAEJCX-UHFFFAOYSA-M 0.000 description 1
- NETSNTQRMHVIEK-UHFFFAOYSA-M sodium;2-[n-butyl-4-[[4-[butyl(2-sulfonatoethyl)azaniumylidene]cyclohexa-2,5-dien-1-ylidene]-[4-(4-ethoxyanilino)phenyl]methyl]anilino]ethanesulfonate Chemical compound [Na+].C1=CC(N(CCS([O-])(=O)=O)CCCC)=CC=C1C(C=1C=CC(NC=2C=CC(OCC)=CC=2)=CC=1)=C1C=CC(=[N+](CCCC)CCS([O-])(=O)=O)C=C1 NETSNTQRMHVIEK-UHFFFAOYSA-M 0.000 description 1
- FLOMHNPVJPAASA-UHFFFAOYSA-M sodium;3-[[4-(dimethylamino)phenyl]-[4-[methyl-[(3-sulfonatophenyl)methyl]amino]phenyl]methylidene]-6-dimethylazaniumylidenecyclohexa-1,4-diene-1-sulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1C(\C=1C=CC(=CC=1)N(C)CC=1C=C(C=CC=1)S([O-])(=O)=O)=C\1C=C(S([O-])(=O)=O)C(=[N+](C)C)C=C/1 FLOMHNPVJPAASA-UHFFFAOYSA-M 0.000 description 1
- IXNUVCLIRYUKFB-UHFFFAOYSA-M sodium;3-[[4-[[4-(diethylamino)-2-methylphenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].CC1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC=1C=C(C=CC=1)S([O-])(=O)=O)=C(C=C1)C=CC1=[N+](CC)CC1=CC=CC(S([O-])(=O)=O)=C1 IXNUVCLIRYUKFB-UHFFFAOYSA-M 0.000 description 1
- KQRZWHVIXVADGL-UHFFFAOYSA-M sodium;4-[[4-(dibenzylamino)phenyl]-(4-dibenzylazaniumylidenecyclohexa-2,5-dien-1-ylidene)methyl]benzene-1,3-disulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC(S(=O)(=O)[O-])=CC=C1C(C=1C=CC(=CC=1)N(CC=1C=CC=CC=1)CC=1C=CC=CC=1)=C(C=C1)C=CC1=[N+](CC=1C=CC=CC=1)CC1=CC=CC=C1 KQRZWHVIXVADGL-UHFFFAOYSA-M 0.000 description 1
- FTUYQIPAPWPHNC-UHFFFAOYSA-M sodium;4-[[4-[benzyl(ethyl)amino]phenyl]-[4-[benzyl(ethyl)azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]benzene-1,3-disulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=CC=CC=2)C=2C(=CC(=CC=2)S([O-])(=O)=O)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC=C1 FTUYQIPAPWPHNC-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- 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
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- A61K8/60—Sugars; Derivatives thereof
- A61K8/602—Glycosides, e.g. rutin
-
- 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
-
- 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
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- 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
- C11D1/04—Carboxylic acids or salts thereof
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/667—Neutral esters, e.g. sorbitan esters
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dermatology (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Molecular Biology (AREA)
- Detergent Compositions (AREA)
Abstract
本发明涉及鼠李糖脂在用于手洗洗涤剂的表面活性剂体系中向消费者赋予在手上的温和性的感觉的用途。
Description
技术领域
本发明涉及鼠李糖脂在用于手洗洗涤剂的表面活性剂体系中的用途。
背景技术
手洗洗涤剂是指涉及消费者用他们的手洗涤基质的洗涤剂。使用领域主要包括洗衣用途(即衣物的手洗)和手动洗碗(HDW)(即餐具等的手洗)。手洗洗涤剂涉及在洗涤过程中洗涤剂液体与手的密切接触,无论是在洗衣还是在HDW中。虽然制剂功效是恢复消费者使用的重要属性,但制剂的感觉体验及其在制剂使用期间和之后由消费者在洗涤期间的使用留下了消费者是否对产品具有良好或不良体验的持久印象。
感觉体验可以包括例如产品本身或使用过程中的令人愉快的颜色或香味。消费者使用手洗洗涤剂的另一个重要感觉体验是在手上留下的持久感觉。这一点很重要,因为手洗过程涉及消费者的手接触制剂和产生的洗涤液,并且制剂可能对皮肤造成刺激。
需要在手上留下改善的感觉的改进的手洗洗涤剂。尤其是,在洗涤过程中留下在手上的温和性的改善的感觉,以及在手洗过程结束后留下在手上的温和性的持久改善的感觉的那些。
解决这个的一种方法是包含增强温和性的成分,例如聚乙二醇成分。
发明内容
我们发现,在用于手洗洗涤剂的表面活性剂体系中使用鼠李糖脂向消费者赋予在手上的温和性的感觉。通过使用鼠李糖脂,减少或消除了使用聚乙二醇等成分的必要性。
本发明在第一方面涉及鼠李糖脂在用于手洗洗涤剂的表面活性剂体系中向消费者赋予在手上的温和性的感觉的用途。
优选地,在手洗过程结束后,手随后变干后,在手上的温和性的感觉持续存在。
优选地,在使用方面,鼠李糖脂在表面活性剂体系中以表面活性剂体系的5-100重量%,优选10-90重量%,更优选15-80重量%,最优选15-50重量%的含量存在。
优选地,手洗洗涤剂是流体洗涤剂组合物,优选水性洗涤剂组合物。
优选地,鼠李糖脂在组合物中以1-20重量%,优选1.25-15重量%,更优选1.5-12.5重量%,最优选2-10重量%的含量存在。
优选地,手洗洗涤剂为手动洗碗组合物,或用于手洗的液体洗衣洗涤剂组合物。
优选地,鼠李糖脂包含至少50重量%的二鼠李糖脂,更优选至少60重量%的二鼠李糖脂,甚至更优选70重量%的二鼠李糖脂,最优选至少80重量%的二鼠李糖脂。
优选地,鼠李糖脂为式Rha2C8-12C8-12的二鼠李糖脂。
本文中描述的任何优选主题内容可以与任何其他主题内容相结合,特别是结合两个或更多个优选主题内容。
具体实施方式
手洗
手洗洗涤剂是指涉及消费者用他们的手洗涤基质的洗涤剂。优选的手洗用途主要包括洗衣用途(即衣物的手洗)和手动洗碗(HDW)(即餐具等的手洗)。手洗洗涤剂涉及在洗涤过程中洗涤剂液体与手紧密接触,无论是在洗衣过程中还是在手动洗碗过程中。
鼠李糖脂
鼠李糖脂是一类糖脂。它们由鼠李糖结合β-羟基脂肪酸组成。鼠李糖是一种糖。脂肪酸在动植物中无处不在。
鼠李糖脂在E.Deziel等的Applied Microbiology and Biotechnology(2010)86:1323-1336中有讨论。鼠李糖脂由Glycosurf,AGAE Technologies和Urumqi Unite Bio-Technology Co.,Ltd.生产。鼠李糖脂可由铜绿假单胞菌细菌的菌株产生。鼠李糖脂也可由恋臭假单胞菌的重组细胞产生,其中重组细胞与该细胞的野生型相比,包含酶a/P水解酶、鼠李糖基转移酶I或鼠李糖基转移酶II中的至少一种的增加的活性。
鼠李糖脂有两大类;单鼠李糖脂和二鼠李糖脂。
单鼠李糖脂具有单个鼠李糖糖环。铜绿假单胞菌产生的典型单鼠李糖脂是L-鼠李糖基-β-羟基癸酰基-β-羟基癸酸酯(RhaC10C10)。其可称为Rha-C10-C10,具有式为C26H48O9。单鼠李糖脂具有单个鼠李糖糖环。
IUPAC名称为3-[3-[(2R,3R,4R,5R,6S)-3,4,5-三羟基-6-甲基环氧乙烷-2-基]氧癸酰氧基]癸酸。
二鼠李糖脂具有两个鼠李糖糖环。典型的二鼠李糖脂是L-鼠李糖基-L-鼠李糖基-β-羟基癸酰基-β-羟基癸酸酯(Rha2C10C10)。其可称为Rha-Rha-C-10-C-10,具有式C32H58O13。
IUPAC名称为3-[3-[4,5-二羟基-6-甲基-3-(3,4,5-三羟基-6-甲基环氧乙烷-2-基)氧环氧乙烷-2-基]氧癸酰氧基]癸酸。
在实践中,取决于碳源和细菌菌株,具有不同烷基链长度组合的多种多样其他次要组分与上述更常见的鼠李糖脂组合存在。单鼠李糖脂和二鼠李糖脂的比率可通过生产方法控制。一些细菌仅产生单鼠李糖脂,参见US5767090:实施例1,一些酶可将单鼠李糖脂转化为二鼠李糖脂。
在各种公布文件中,单鼠李糖脂具有符号Rha-,其可缩写为Rh或RL2。类似地,二鼠李糖脂具有符号Rha-Rha或Rh-Rh-或RL1。出于历史原因,“鼠李糖脂2”是单鼠李糖脂,“鼠李糖脂1”是二鼠李糖脂。这导致文献中“RL1”和“RL2”的用法的一些歧义。
在本专利说明书中,我们使用了术语单鼠李糖脂和二鼠李糖脂,以避免这种可能的混淆。然而如果使用缩写,R1是单鼠李糖脂,R2是二鼠李糖脂。有关现有技术中术语混淆的更多信息,请参见对US4814272的介绍。
已经检测到由以下细菌产生的下列鼠李糖脂:(C12:1,C14:1表示具有双键的脂肪酰基链)。
铜绿假单胞菌产生的鼠李糖脂(单鼠李糖脂):
Rha-C8”C10、Rha-C10-C8、Rha-C10-C10、Rha-C10-C12、Rha-C10-C12:1、Rha-C12-C10、Rha-C12:1-C10
铜绿假单胞菌产生的鼠李糖脂(二鼠李糖脂):
Rha-Rha-C8-C10、Rha-Rha-C8-C12:1、Rha-Rha-C10-C8、Rha-Rha-C10-C10、Rha-Rha-C10-C12:1、Rha-Rha-C10-C12、Rha-Rha-C12-C10、Rha-Rha-C12:1-C12、Rha-Rha-C10-C14:1
铜绿假单胞菌产生的鼠李糖脂(未被鉴定为单鼠李糖脂或二鼠李糖脂):
C8-C8、C8-C10、C10-C8、C8”C12:1、C12:1-C8、C10-C10、C12-C10、C12:1-C10、C12-C12、C12:1-C12、C14-C10、C14:1-C10、C14-C14。
绿叶假单胞菌产生的鼠李糖脂(仅单鼠李糖脂):
Rha-C10-C8、Rha-C10-C10、Rha-C12-C10、Rha-C12:1-C10、Rha-C12-C12、Rha-C12:1-C12、Rha-C14-C10、Rha-C14:1-C10
类鼻疽伯克氏菌产生的鼠李糖脂(仅二鼠李糖脂):
Rha-Rha-C14-C14。
Burkholdera(Pseudomonas)plantarii产生的鼠李糖脂(仅二鼠李糖脂):
Rha-Rha-C14-C14。
美国典型培养物保藏中心(ATCC)有超过100个菌株的铜绿假单胞菌在记录中。还有一些菌株是仅商业鼠李糖脂的制造商可得的。此外,世界各地的各种研究机构分离了可能上千种的菌株。有些工作已经进入将它们分组。每个菌株都具有不同的特征,包括有多少鼠李糖脂产生、产生的鼠李糖脂是什么类型、其代谢什么、以及其生长的条件。只有低百分比的菌株被广泛研究。
通过评估和筛选,可以分离出铜绿假单胞菌的菌株以以更高浓度和更有效地产生鼠李糖脂。也可以选择产生较少副产物和代谢不同原料或污染物的菌株。这种生产受到细菌在其中生长的环境的极大影响。
典型的二鼠李糖脂是L-鼠李糖基-L-鼠李糖基-β-羟基癸酰基-β-羟基癸酸酯(式为C32H58O13的Rha2C10C10)。
在实践中,取决于碳源和细菌菌株,具有不同烷基链长度组合的多种多样其他次要组分与上述更常见的鼠李糖脂组合存在。单鼠李糖脂和二鼠李糖脂的比率可通过生产方法控制。一些细菌仅产生单鼠李糖脂,参见US5767090:实施例1,一些酶可将单鼠李糖脂转化为二鼠李糖脂。
优选地,鼠李糖脂在组合物中以1-20重量%,优选1.25-15重量%,更优选1.5-12.5重量%,最优选2-10重量%的含量存在。
鼠李糖脂优选选自:
-铜绿假单胞菌产生的鼠李糖脂(单鼠李糖脂):
Rha-C8-C10、Rha-C10-C8、Rha-C10-C10、Rha-C10-C12、Rha-C10-C12:1、Rha-C12-C10、Rha-C12:1-C10
-绿叶假单胞菌产生的鼠李糖脂(仅单鼠李糖脂):
Rha-C10-C8、Rha-C10-C10、Rha-C12-C10、Rha-C12:1-C10、Rha-C12-C12、Rha-C12:1-C12、Rha-C14-C10、Rha-C14:1-C10
-通过引入铜绿假单胞菌的rhlA和rhlB基因,也可以从恋臭假单胞菌生产的单鼠李糖脂[Cha等,Bioresour Technol.2008.99(7):2192-9]
-铜绿假单胞菌产生的鼠李糖脂(二鼠李糖脂):
Rha-Rha-C8-C10、Rha-Rha-C8-C12:1、Rha-Rha-C10-C8、Rha-Rha-C10-C10、Rha-Rha-C10-C12:1、Rha-Rha-C10-C12、Rha-Rha-C12-C10、Rha-Rha-C12:1-C12、Rha-Rha-C10-C14:1
-类鼻疽伯克氏菌产生的鼠李糖脂(仅二鼠李糖脂):
Rha-Rha-C14-C14。
-Burkholdera(Pseudomonas)plantarii产生的鼠李糖脂(仅二鼠李糖脂):
Rha-Rha-C14-C14。
-铜绿假单胞菌产生的鼠李糖脂,最初未被鉴定为单鼠李糖脂或二鼠李糖脂:
C8-C8、C8-C10、C10-C8、C8-C12:1、C12:1-C8、C10-C10、C12-C10、C12:1-C10、C12-C12、C12:1-C12、C14-C10、C14:1-C10、C14-C14。
鼠李糖脂优选为L-鼠李糖基-β-羟基癸酰基-β-羟基癸酸酯(式为C26H48O9的RhaC10C10)。
优选地,鼠李糖脂包含至少50重量%的二鼠李糖脂,更优选至少60重量%的二鼠李糖脂,甚至更优选70重量%的二鼠李糖脂,最优选至少80重量%的二鼠李糖脂。
优选地,鼠李糖脂为式Rha2C8-12C8-12的二鼠李糖脂。优选的烷基链长度为C8-C12。烷基链可以是饱和的或不饱和的。
最优选的二鼠李糖脂是式Rha2C8-12C8-12的二鼠李糖脂的实例,本文中称为鼠李糖脂R2,可供应自Evonik。
手洗洗涤剂组合物
手洗洗涤剂组合物是清洁组合物,可用于清洁一种或多种基质。
该组合物优选为流体洗涤剂组合物,更优选为水性洗涤剂组合物。
优选地,手洗洗涤剂为手动洗碗组合物,或用于手洗的液体洗衣洗涤剂组合物。
优选地,当液体洗衣洗涤剂,当以4g/L在293K下溶解于去矿物质水中时,手动洗碗组合物的pH为4-8,更优选4.5-7.5。
优选地,当液体洗衣洗涤剂,当以4g/L在293K下溶解于去矿物质水中时,液体洗衣洗涤剂组合物的pH为6-11,更优选7-9。
第二阴离子表面活性剂
在本发明的第二方面的手洗组合物中,该组合物包含第二不同阴离子表面活性剂。
该组合物包含1至20重量%,优选1.5-17.5重量%,更优选2-15重量%,最优选5-15重量%的第二不同阴离子表面活性剂。
在本发明的第二方面的手洗组合物中,优选地,鼠李糖脂在表面活性剂体系中以表面活性剂体系的10-90重量%,更优选15-80重量%,最优选15-50重量%的含量存在。
优选地,在本发明的第一方面的用途方面,该组合物包含第二不同阴离子表面活性剂。
当使用第二不同阴离子表面活性剂时,优选地,鼠李糖脂在表面活性剂体系中以表面活性剂体系的10-90重量%,更优选15-80重量%,最优选15-50重量%的含量存在。
在本发明的所有方面,优选地,第二阴离子表面活性剂选自C10至C20直链烷基苯磺酸盐、C10至C20烷基硫酸盐、C10至C20烷基醚硫酸盐及其混合物。更优选地,第二不同阴离子表面活性剂是前述阴离子表面活性剂的混合物。更优选地,第二不同阴离子表面活性剂(b)是C10至C20直链烷基苯磺酸盐和C10至C20烷基醚硫酸盐的混合物。最优选地,C10至C20直链烷基苯磺酸盐和C10至C20烷基醚硫酸盐的混合物是比率为10:90至90:10、优选20:80至80:20、更优选30:70至70:30的混合物。
额外的表面活性剂
组合物中可存在额外的表面活性剂。
优选地,清洁组合物包含0-20重量%,更优选0-10重量%的额外表面活性剂。
这些优选选自另外的阴离子、非离子和两性离子表面活性剂。
通常,表面活性剂体系的非离子和阴离子表面活性剂可以选自“Surface ActiveAgents”,卷1,Schwartz&Perry,Interscience 1949;卷2,Schwartz,Perry&Berch,Interscience 1958;Manufacturing Confectioners Company出版的“McCutcheon'sEmulsifiers and Detergents”的当前版本,或“Tenside Taschenbuch”,H.Stache,第2版,Carl Hauser Verlag,1981中描述的表面活性剂。优选地,所用表面活性剂是饱和的。
可以使用的优选的非离子洗涤剂化合物包括具有疏水基团和反应性氢原子的化合物,例如脂族醇、酸、酰胺,与环氧烷,特别是环氧乙烷单独或与环氧丙烷一起的反应产物。具体的非离子洗涤剂化合物是脂族直链或支链伯或仲醇与环氧乙烷的缩合产物,通常为5至40EO,优选为7EO至9EO。
可以使用的优选的阴离子洗涤剂化合物通常是具有含约8至约22个碳原子的烷基的有机硫酸和磺酸的水溶性碱金属盐,术语烷基用于包括较高级酰基的烷基部分。
合适的合成阴离子洗涤剂化合物的实例是烷基硫酸钠和烷基硫酸钾,特别是通过使例如由牛油或椰油制得的醇硫酸化而获得的那些,烷基C10至C20苯磺酸钠和钾,特别是直链仲烷基C10至C15苯磺酸钠;以及烷基甘油醚硫酸钠,特别是衍生自牛油或椰油的较高级醇和衍生自石油的合成醇的那些醚。优选的阴离子洗涤剂化合物是C11-C15烷基苯磺酸钠和C12-C14烷基硫酸钠。同样适用的是表面活性剂例如显示抗盐析的在EP-A-328 177(Unilever)中描述的那些、EP-A-070 074中描述的烷基聚糖苷表面活性剂、和烷基单糖苷。
优选的表面活性剂体系是阴离子与非离子洗涤剂活性材料的混合物,特别是EP-A-346 995(Unilever)中指出的阴离子和非离子表面活性剂的分组和例子。特别优选的是表面活性剂体系,其为前述阴离子表面活性剂与C12-C16伯醇3-7EO乙氧基化物一起的混合物。
优选的两性离子表面活性剂包括椰油酰胺丙基甜菜碱。两性离子表面活性剂的优选含量为0.1-5重量%,优选0.5-4重量%。
另外的成分
取决于手洗组合物是手动洗碗组合物还是用于手洗的液体洗衣洗涤剂组合物,手洗组合物可包含任何这些进一步的优选成分。
助洗剂或络合剂
助洗剂材料可以在用于手洗的液体洗衣洗涤剂组合物中特别有用。
助洗剂材料可选自1)钙螯合剂材料,2)沉积材料,3)钙离子交换材料,和4)其混合物。
钙螯合剂助洗剂材料的实例包括碱金属多磷酸盐,例如三磷酸钠,和有机螯合剂,例如乙二胺四乙酸。
沉淀助洗剂材料的实例包括正磷酸钠和碳酸钠。
钙离子交换助洗剂材料的实例包括各种类型的水不溶性结晶或无定形铝硅酸盐,其中沸石是最熟知的代表,例如沸石A、沸石B(也称为沸石P)、沸石C、沸石X、沸石Y以及在EP-A-0,384,070中描述的P型沸石。
组合物也可以包含0-65重量%的助洗剂或络合剂,例如乙二胺四乙酸、二亚乙基三胺五乙酸、烷基或烯基琥珀酸、次氮基三乙酸或下文提到的其它助洗剂。依靠其络合金属离子的能力,许多助洗剂也是漂白稳定剂。
沸石和碳酸盐(包括碳酸氢盐和倍半碳酸盐)是优选的助洗剂。
组合物可以含有作为助洗剂的结晶铝硅酸盐,优选碱金属铝硅酸盐,更优选铝硅酸钠。这通常以小于15重量%的含量存在。铝硅酸盐是具有以下通式的材料:
0.8-1.5M2O·Al2O3·0.8-6SiO2
其中M是一价阳离子,优选钠。这些材料含有一些结合水,且要求具有至少50mgCaO/g的钙离子交换能力。在上式中,优选的铝硅酸钠含有1.5-3.5个SiO2单元。它们可以容易地通过硅酸钠和铝酸钠之间的反应制备,如文献中详细描述的。表面活性剂与铝硅酸盐(存在时)的比率优选大于5:2,更优选大于3:1。
替代地,或者在铝硅酸盐助洗剂之外,可以使用磷酸盐助洗剂。在本领域中,术语“磷酸盐”包括二磷酸盐、三磷酸盐、和膦酸盐种类。其它形式的助洗剂包括硅酸盐,例如可溶性硅酸盐、偏硅酸盐、层状硅酸盐(例如来自Hoechst的SKS-6)。
当洗衣组合物时,优选地,洗衣洗涤剂制剂为非磷酸盐助洗的洗衣洗涤剂制剂,即包含少于1重量%的磷酸盐。优选地,如果包含助洗剂,洗衣洗涤剂制剂为碳酸盐助洗的。
荧光剂
这些材料可以在用于手洗的液体洗衣洗涤剂组合物中特别有用。
组合物优选地包含荧光剂(光学增亮剂)。
组合物中使用的一种或多种荧光剂的总量通常为0.005-2重量%,更优选0.01-0.1重量%。优选的荧光剂类别是:二苯乙烯基联苯化合物,如Tinopal(商标)CBS-X;二胺二苯乙烯二磺酸化合物,如Tinopal DMS pure Xtra和Blankophor(商标)HRH;以及吡唑啉化合物,如Blankophor SN。优选的荧光剂为:2(4-苯乙烯基-3-磺苯基)-2H-萘酚[1,2-d]三唑钠、4,4'-双{[(4-苯胺基-6-(N甲基-N-2羟乙基)氨基1,3,5-三嗪-2-基)]氨基}二苯乙烯-2,2'二磺酸二钠、4,4'-双{[(4-苯胺基-6-吗啉基-1,3,5-三嗪-2-基)]氨基}二苯乙烯-2-2'二磺酸二钠,和4,4'-双(2-磺苯乙烯基)联苯二钠。
优选的是方法中使用的水溶液具有荧光剂。当荧光剂存在于方法中使用的水溶液中时,其优选在0.0001g/L-0.1g/L、优选0.001g/L-0.02g/L的范围内。
染料
组合物优选包含染料。染料为在K.Hunger(ed).Industrial Dyes:Chemistry,Properties,Applications(Weinheim:Wiley-VCH 2003)中讨论的。以颜色指数(Societyof Dyers and Colourists and the American Association of Textile Chemists andColorists)列出有机染料。
优选的染料发色团是偶氮、吖嗪、蒽醌、酞菁和三苯甲烷。
偶氮、蒽醌、酞菁和三苯甲烷染料优选带有带电荷或不带电荷的净阴离子。吖嗪染料优选带有净阴离子或阳离子电荷。
优选的非调色染料选自蓝色染料,最优选带有磺酸根基团的蒽醌染料和带有磺酸根基团的三苯甲烷染料。优选的化合物是酸性蓝80、酸性蓝1、酸性蓝3;酸性蓝5、酸性蓝7、酸性蓝9、酸性蓝11、酸性蓝13、酸性蓝15、酸性蓝17、酸性蓝24、酸性蓝34、酸性蓝38、酸性蓝75、酸性蓝83、酸性蓝91、酸性蓝97、酸性蓝93、酸性蓝93:1、酸性蓝97、酸性蓝100、酸性蓝103、酸性蓝104、酸性蓝108、酸性蓝109、酸性蓝110和酸性蓝213。当溶解时,具有非调色染料的颗粒为洗涤液提供有吸引力的颜色。
蓝色或紫色调色染料是最优选的。调色染料在洗涤过程的洗涤或漂洗步骤期间沉积到织物,为织物提供可见的色度(hue)。在这方面,染料赋予白色衣物蓝色或紫色,色调角为240至345,更优选260至320,最优选270至300。在该试验中使用的白色衣物为漂白的非丝光处理的(non-mercerised)编织棉片。
调色染料为在WO2005/003274、WO2006/032327(Unilever)、WO2006/032397(Unilever)、WO2006/045275(Unilever)、WO2006/027086(Unilever)、WO2008/017570(Unilever)、WO2008/141880(Unilever)、WO2009/132870(Unilever)、WO2009/141173(Unilever)、WO2010/099997(Unilever)、WO2010/102861(Unilever)、WO2010/148624(Unilever)、WO2008/087497(P&G)、WO2011/011799(P&G)、WO2012/054820(P&G)、WO2013/142495(P&G)和WO2013/151970(P&G)中讨论的。
可以使用调色染料的混合物。
调色染料发色团最优选地选自单偶氮、二偶氮、蒽醌和吖嗪。
单偶氮染料优选含有杂环,最优选为噻吩染料。单偶氮染料优选被烷氧基化,并且优选在pH=7时不带电荷或带阴离子电荷。WO 2013/142495和WO 2008/087497中讨论了烷氧基化噻吩染料。
最优选的调色染料选自直接紫9、直接紫99、直接紫35、溶剂紫13、分散紫28,具有以下结构的染料
香料
优选地,组合物包含香料。香料优选地以0.001至3重量%,最优选0.1至1重量%的范围存在。许多适合的香料的实例在CFTA Publications出版的CTFA(Cosmetic,Toiletryand Fragrance Association)1992International Buyers Guide和Schnell PublishingCo出版的OPD 1993Chemicals Buyers Directory,80年版中提供。
在制剂中存在多种香料组分是常见的。在本发明的组合物中,设想存在四种或更多种,优选五种或更多种,更优选六种或更多种、或甚至七种或更多种不同的香料组分。
在香料混合物中,优选15至25重量%是头香。头香是由Poucher(Journal of theSociety of Cosmetic Chemists 6(2):80[1955])定义。优选的头香选自柑橘油、芳樟醇、乙酸芳樟酯、薰衣草、二氢月桂烯醇、玫瑰醚和顺式-3-己醇。
优选的是洗衣处理组合物不含过氧漂白剂,例如过碳酸钠、过硼酸钠和过酸。
聚合物
组合物可包含一种或多种另外的聚合物。例子是羧甲基纤维素、聚(乙二醇)、聚(乙烯醇)、聚羧酸酯如聚丙烯酸酯、马来/丙烯酸共聚物和甲基丙烯酸月桂酯/丙烯酸共聚物。防止染料沉积的聚合物,例如聚(乙烯基吡咯烷酮)、聚(乙烯基吡啶-N-氧化物)和聚(乙烯基咪唑),可以存在于制剂中。
可以包含增稠聚合物如阴离子丙烯酸聚合物,实例包括Acusol820。
酶
这些材料可以在用于手洗的液体洗衣洗涤剂组合物中特别有用。
在实施本发明的方法时,本发明的清洁组合物中优选存在一种或多种酶。
优选地,本发明的洗衣组合物中每种酶的含量为0.0001重量%-0.1重量%蛋白质。
特别设想的酶包括蛋白酶、α-淀粉酶、纤维素酶、脂肪酶、过氧化物酶/氧化酶、果胶酸裂解酶和甘露聚糖酶或其混合物。
合适的脂肪酶包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。有用的脂肪酶的实例包括来自以下的脂肪酶:腐质霉(Humicola)(同义词嗜热真菌(Thermomyces)),例如来自EP 258 068和EP 305 216中所述的H.lanuginosa(T.lanuginosus)或来自WO 96/13580中所述的H.insolens;假单胞菌脂肪酶,例如来自产碱假单胞菌(P.alcaligenes)或假产碱假单胞菌(P.pseudoalcaligenes)(EP 218 272)、洋葱假单胞菌(P.cepacia)(EP 331 376)、施氏假单胞菌(P.stutzeri)(GB 1,372,034)、荧光假单胞菌(P.fluorescens),假单胞菌菌株SD 705(WO 95/06720和WO 96/27002)、P.wisconsinensis(WO 96/12012);芽孢杆菌脂肪酶,例如来自枯草芽孢杆菌(B.subtilis)(Dartois等(1993),Biochemica et Biophysica Acta,1131,253-360)、嗜热脂肪芽孢杆菌(B.stearothermophilus)(JP 64/744992)或短小芽孢杆菌(B.pumilus)(WO 91/16422)。
其他实例是脂肪酶变体,例如在WO 92/05249、WO 94/01541、EP 407 225、EP 260105、WO 95/35381、WO 96/00292、WO 95/30744、WO 94/25578、WO 95/14783、WO 95/22615、WO 97/04079和WO 97/07202、WO 00/60063中描述的那些。
优选的可商购脂肪酶包括LipolaseTM和Lipolase UltraTM、LipexTM和LipocleanTM(Novozymes A/S)。
本发明的方法可以在分类为EC 3.1.1.4和/或EC 3.1.1.32的磷脂酶的存在下进行。如本文所用,术语磷脂酶是对磷脂具有活性的酶。
磷脂,例如卵磷脂或磷脂酰胆碱,由在外部(sn-1)和中间(sn-2)位置被两个脂肪酸酯化,并在第三位置被磷酸酯化的甘油组成;磷酸反过来可以被酯化成氨基醇。磷脂酶是参与磷脂水解的酶。可以区分磷脂酶活性的多种类型,包括磷脂酶A1和A2,其水解一个脂肪酰基(分别在sn-1和sn-2位置)以形成溶血磷脂;和溶血磷脂酶(或磷脂酶B),其可以水解溶血磷脂中剩余的脂肪酰基。
磷脂酶C和磷脂酶D(磷酸二酯酶)分别释放二酰基甘油或磷脂酸。
酶和光漂白剂可以表现出一些相互作用,并且应选择为使得这种相互作用不是负面的。通过在产品内包封一种或另一种酶或光漂白剂和/或其他隔离,可以避免某些负面相互作用。
合适的蛋白酶包括具有动物、植物或微生物来源的那些。微生物来源是优选的。包括化学修饰的或蛋白质工程化的突变体。蛋白酶可以是丝氨酸蛋白酶或金属蛋白酶,优选碱性微生物蛋白酶或胰蛋白酶样蛋白酶。优选的可商购蛋白酶包括AlcalaseTM、SavinaseTM、PrimaseTM、DuralaseTM、DyrazymTM、EsperaseTM、EverlaseTM、PolarzymeTM和KannaseTM(Novozymes A/S)、MaxataseTM、MaxacalTM、MaxapemTM、ProperaseTM、PurafectTM、Purafect OxPTM、FN2TM和FN3TM(Genencor International Inc.)。
本发明的方法可在分类为EC 3.1.1.74的角质酶的存在下进行。根据本发明使用的角质酶可以具有任何来源。
优选地,角质酶具有微生物来源,特别是细菌、真菌或酵母来源。
合适的淀粉酶(α和/或β)包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。淀粉酶包括例如获自芽孢杆菌,如在GB 1,296,839中更详细描述的地衣芽孢杆菌的特殊菌株,或在WO 95/026397或WO 00/060060中公开的芽孢杆菌菌株的α-淀粉酶。可商购的淀粉酶是DuramylTM、TermamylTM、Termamyl UltraTM、NatalaseTM、StainzymeTM、FungamylTM和BANTM(Novozymes A/S)、RapidaseTM和PurastarTM(来自GenencorInternational Inc.)。
合适的纤维素酶包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。合适的纤维素酶包括来自以下的纤维素酶:芽孢杆菌属、假单胞菌属、腐质霉属、镰刀菌属、梭孢壳属、支顶孢属,例如从公开于US 4,435,307、US 5,648,263、US 5,691,178、US 5,776,757、WO 89/09259、WO 96/029397和WO 98/012307的特异腐质霉、太瑞斯梭孢壳霉、嗜热毁丝霉和尖孢镰刀菌产生的真菌纤维素酶。可商购的纤维素酶包括CelluzymeTM、CarezymeTM、CellucleanTM、EndolaseTM、RenozymeTM(Novozymes A/S)、ClazinaseTM和Puradax HATM(Genencor International Inc.)和KAC-500(B)TM(KaoCorporation)。
合适的过氧化物酶/氧化酶包括具有植物、细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。有用的过氧化物酶的实例包括来自鬼伞属,例如来自灰盖鬼伞的过氧化物酶,及其变体,如在WO 93/24618、WO 95/10602和WO 98/15257中所述的那些。可商购的过氧化物酶包括GuardzymeTM和NovozymTM51004(Novozymes A/S)。
另外的适用的酶在WO2009/087524、WO2009/090576、WO2009/107091、WO2009/111258和WO2009/148983中讨论。
酶稳定剂
存在于组合物中的任何酶可以使用常规的稳定剂稳定化,例如多元醇,如丙二醇或甘油;糖或糖醇;乳酸;硼酸或硼酸衍生物,例如芳族硼酸酯,或苯基硼酸衍生物,如4-甲酰基苯基硼酸,并且组合物可以如例如WO 92/19709和WO 92/19708中所述配制。
当烷基足够长以形成支链或环状链时,烷基包括支链的、环状的和直链的烷基链。烷基优选为直链或支链的,最优选为直链的。
除非另有说明,本文中使用的不定冠词“一个/种(a/an)”及其对应的定冠词“该/所述(the)”是指至少一个/种、一个/种或多个/种。
将通过以下非限制性实施例进一步描述本发明。
实施例
进行专家小组评估的目的是确定和测量产品与对照制剂相比在特定感官特性方面的差异。这是通过产品的盲测进行的。开展的研究确保所有小组成员均以随机顺序看到并评估所有原型和对照产品。小组成员是经过培训的小组成员:这些是筛选了感官敏锐度和经过培训的分析技术的小组成员,其中有12-15名小组成员。
小组成员以0-10量表工作,有两个定位点,1为不是非常温和,9为非常温和。
在洗涤过程后,小组成员等待10分钟,同时他们的手滴干。然后他们评估他们的手的温和感觉。
对于温和性属性,测量以下感觉属性:
干燥手后在手上的温和感是指干燥手后在手上感觉到的乳脂状/层状印象;通过用手指在手表面之间滑动和用大姆指在其他手指上感觉来进行评估,并且再次按照在根本不温和和非常温和之间的等级量表进行测量。
使用的制剂——对照
对照制剂均具有1180至1610厘泊(cP)的可接受粘度。
使用Anton Paar ASC流变仪在25℃下测量粘度——使用Bob设置并报告在23s-1剪切速率下测量的粘度
使用的制剂——根据本发明
鼠李糖脂R2是Evonik提供的二鼠李糖脂。
根据本发明的制剂均具有1350至1520厘泊(cP)之间的可接受粘度。
使用Anton Paar ASC流变仪在25℃下测量粘度——使用Bob设置并报告在23s-1剪切速率下测量的粘度。
长期持久温和属性的结果表
1相比于对照1至3的长期持久温和性
制剂1与对照1至3相比给出了该属性的统计学显著性改善(Tukey’s HSD检验,95%置信区间)。
2相比于对照1至3的长期持久温和性
制剂2与对照1至3相比给出了该属性的统计学显著性改善(Tukey’s HSD检验,95%置信区间)。
3相比于对照1至3的长期持久温和性
制剂3与对照1至3相比给出了该属性的统计学显著性改善(Tukey’s HSD检验,95%置信区间)。
4相比于对照1至3的长期持久温和性
制剂4与对照1至3相比给出了该属性的统计学显著性改善(Tukey’s HSD检验,95%置信区间)。
5相比于对照1至3的长期持久温和性
制剂5与对照1至3相比给出了该属性的统计学显著性改善(Tukey’s HSD检验,95%置信区间)。
从该数据可以看出,在用于手洗洗涤剂的表面活性剂体系中使用鼠李糖脂向消费者赋予在手上的温和性的感觉。尤其是在手洗过程结束后,在手随后干燥后,在手上的温和感持续存在的情况下看到这种感觉。
Claims (8)
1.鼠李糖脂在用于手洗洗涤剂的表面活性剂体系中向消费者赋予在手上的温和性的感觉的用途。
2.根据权利要求1所述的用途,其中在手洗过程结束后,手随后变干后,在手上的温和性的感觉持续存在。
3.根据权利要求1或权利要求2所述的用途,其中所述鼠李糖脂在所述表面活性剂体系中以所述表面活性剂体系的5-100重量%,优选10-90重量%,更优选15-80重量%,最优选15-50重量%的含量存在。
4.根据前述权利要求中任一项所述的用途,其中所述手洗洗涤剂是流体洗涤剂组合物,优选水性洗涤剂组合物。
5.根据前述权利要求中任一项所述的用途,其中所述手洗洗涤剂是手动洗碗组合物,或用于手洗的液体洗衣洗涤剂组合物。
6.根据权利要求5所述的用途,其中所述鼠李糖脂在所述组合物中以1-20重量%,优选1.25-15重量%,更优选1.5-12.5重量%,最优选2-10重量%的含量存在。
7.根据前述权利要求中任一项所述的用途,其中所述鼠李糖脂包含至少50重量%的二鼠李糖脂,更优选至少60重量%的二鼠李糖脂,甚至更优选70重量%的二鼠李糖脂,最优选至少80重量%的二鼠李糖脂。
8.根据前述权利要求中任一项所述的用途,其中所述鼠李糖脂为式Rha2C8-12C8-12的二鼠李糖脂。
Applications Claiming Priority (3)
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EP4204526B1 (en) | 2020-08-28 | 2024-04-24 | Unilever IP Holdings B.V. | Surfactant and detergent composition |
EP4204396B1 (en) | 2020-08-28 | 2024-05-29 | Unilever IP Holdings B.V. | Surfactant and detergent composition |
EP4392522A1 (en) * | 2021-08-26 | 2024-07-03 | Unilever IP Holdings B.V. | A concentrated cleaning composition |
WO2023200753A1 (en) | 2022-04-11 | 2023-10-19 | The Procter & Gamble Company | Personal care composition containing a biosurfactant |
WO2024097599A1 (en) | 2022-10-31 | 2024-05-10 | The Procter & Gamble Company | Personal care composition containing a biosurfactant |
WO2024167985A1 (en) | 2023-02-10 | 2024-08-15 | The Procter & Gamble Company | Silicone-free conditioning shampoo composition |
US20240299285A1 (en) | 2023-03-08 | 2024-09-12 | The Procter & Gamble Company | Personal care composition |
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US20210283036A1 (en) | 2021-09-16 |
WO2020016097A1 (en) | 2020-01-23 |
CL2021000115A1 (es) | 2021-08-20 |
BR112021000774A2 (pt) | 2021-04-13 |
AR117610A1 (es) | 2021-08-18 |
EP3824057B1 (en) | 2023-10-18 |
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