EP1656337A1 - Esters d'acide citrique - Google Patents

Esters d'acide citrique

Info

Publication number
EP1656337A1
EP1656337A1 EP04728546A EP04728546A EP1656337A1 EP 1656337 A1 EP1656337 A1 EP 1656337A1 EP 04728546 A EP04728546 A EP 04728546A EP 04728546 A EP04728546 A EP 04728546A EP 1656337 A1 EP1656337 A1 EP 1656337A1
Authority
EP
European Patent Office
Prior art keywords
weight
citric acid
alcohol
acid ester
ester mixtures
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.)
Withdrawn
Application number
EP04728546A
Other languages
German (de)
English (en)
Inventor
Ansgar Behler
Werner Seipel
Norbert Boyxen
Daniela Prinz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cognis IP Management GmbH
Original Assignee
Cognis IP Management GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cognis IP Management GmbH filed Critical Cognis IP Management GmbH
Publication of EP1656337A1 publication Critical patent/EP1656337A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
    • C07C69/704—Citric acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

Definitions

  • the present invention relates to selected citric acid ester mixtures of selected ethoxylated alcohols and with a special content of monoester to diester, a process for their preparation and their use, if appropriate, in a mixture with other surfactants for the production of cosmetic agents with high foaming power and low irritation potential.
  • Citric acid esters which are also known as alkyl ether citrates, have been known compounds for a long time and have also found their way into cosmetic products.
  • European patent application EP 282 289 A1 cosmetic compositions which contain monoalkyl citric acid salts of alcohols having 1 to 7 moles of ethoxylated alcohols having 10 to 18 carbon atoms.
  • particularly high monoester contents of over 95% of the citric acid esters are desirable and can be obtained by reacting citric anhydride with the corresponding ethoxylated alcohols.
  • the international application WO 94/10970 describes a solubilizer, the monoalkyl citrates with alkyl groups containing 7 to 10 carbon atoms, as an ingredient in perfumes, cosmetic compositions, such as cleaning and care products for body and textiles.
  • European published patent application EP 199 131 A discloses citric acid esters of alcohols containing 1 to 20 moles of ethoxylated alcohols having 8 to 20 carbon atoms, which can be mono-, di- or triesters. According to this document, citric acid esters produced from 1 mol of citric acid and 2 mol with 7 mol of ethoxylated alcohol mixture of C11, C12 and C13 alcohols show low irritation potential and acceptable foaming power.
  • citric acid esters are esters of alcohols having 5 to 30 mol of ethoxylated alcohols having 12 to 18 carbon atoms. These can be mono-, di- and / or triesters. According to the examples, the mono- or diesters of 7 or 9 moles of ethoxylated coconut alcohol, which always also contains unsaturated alcohols, are particularly suitable. According to US Pat. No. 6,413,527, nanoemulsions with citric acid esters of C8-22 alcohols ethoxylated with 3 to 9 moles have good moisturizing properties for skin and hair, mono-, di- and / or triesters being equally suitable. •
  • the esters for example, have a moderate foaming behavior, the monoesters of lauryl alcohol ethoxylated with 3 and 6 moles of ethylene oxide showing better foaming behavior than the diesters, while the esters with 9 moles of ethylene oxide as diesters are better than the monoesters.
  • the citric acid esters known from the prior art often do not meet the foaming behavior desired by the users of cosmetic products, especially in the case of shampoos and bath additives, in particular in combination with other surfactants.
  • the object of the present invention was therefore to provide citric acid esters which show very good foaming behavior, both with regard to the foaming kinetics and in the foaming behavior after a long time.
  • the citric acid esters should have practically no irritation potential.
  • citric acid esters were sought, which themselves have a high surface activity.
  • a first object of the present invention relates to citric acid ester mixtures of ethoxylated alcohols of the general formula (I)
  • R 1 is an alkyl radical and n is the degree of ethoxylation, characterized in that R 1 is a linear alkyl radical derived from a fatty alcohol mixture containing 45-75% by weight of C12-, 15-35% by weight of C14-, 0-15 %
  • R 1 stands for numbers from 5 to 9, with the proviso that the weight ratio of monoester: diester in the citric acid ester mixtures is in the range from 3: 1 to 10: 1
  • the present invention further relates to a process for the preparation of the citric acid ester mixtures according to the invention from ethoxylated alcohols of the general formula (I)
  • the weight ratio of monoester: diester in the citric acid ester mixtures is in the range from 3: 1 to 10: 1, characterized in that the citric acid with the alcohol ethoxyates of the formula (I) in a molar ratio of 0.9: 1 to 1.1: 1, in particular 1: 1 are esterified.
  • Another object of the present invention relates to the use of citric acid ester mixtures of ethoxylated alcohols of the general formula (I) - optionally in a mixture with other surfactants for the production of foaming, skin-friendly cosmetic products.
  • citric acid ester mixtures selected according to the invention surprisingly show both a distinctly good foaming behavior and no irritation potential to the skin, a behavior which is retained even in mixtures with other surfactants.
  • the irritation potential which is better than diesters of citric acid is surprising, since surfactants having anionic groups (carboxylate group) normally have worse irritation potentials than surfactants having nonionic groups (ester group).
  • citric acid ester mixtures according to the invention are derived from ethoxylated alcohols of the general formula (I)
  • the alcohol mixtures are mixtures mainly of capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol and / or stearyl alcohol in the stated weight ratios.
  • the mixtures are accessible either by mixing the individual alcohols or by mixing appropriate alcohol mixtures.
  • citric acid ester mixtures of alcohols of the formula (I) are preferred, where R 1 is a linear alkyl radical, derived from a fatty alcohol mixture containing 65-75 % By weight of C12, 20 to 30% by weight of C14, 0-5% by weight of C16 and 0 to 5% by weight of C18 alcohol.
  • the fatty alcohol mixture has the following chain distribution in% by weight: C10: 0-2%; C12: 70-75%; C14: 24-30%; C16: 0-2% and can be obtained from palm kernel or coconut oil, for example.
  • R 1 is a linear alkyl radical, derived from a fatty alcohol mixture containing 45-60% by weight of C12, 15 to 30% by weight. % C14, 5-15% by weight C16 and 8 to 20% by weight C18 alcohol.
  • These alcohol mixtures on which the citric acid ester mixtures are based are commercially available alcohol mixtures, for example Dehydol LT TM, a commercial product from Cognis Deutschland GmbH & Co. KG.
  • the fatty alcohol mixture has the following chain distribution in% by weight: ⁇ C12: 0-3%; C12: 48-58%; C14: 18-24%; C16: 8-12%; C18: 11-15%; > C18: 0-1% and is accessible, for example, from palm kernel or coconut oil.
  • the degree of ethoxylation n is preferably a number from 6 to 8, it being possible for the number to be whole or fractional.
  • the (fat) alcohol mixtures may also contain small amounts of short-chain or longer-chain alcohols, preferably below 10% by weight, in particular 5% by weight, based on alcohol mixtures.
  • citric acid ester mixtures according to the invention are mixtures of isomeric compounds of the general formula (II)
  • the citric acid ester mixtures according to the invention thus necessarily contain mono- and diesters, preferably in amounts of 50 to 90% by weight, in particular from 60 to 80% by weight - calculated as mono- and diesters and based on the mixture).
  • the mixtures may contain triester and free citric acid as the remainder, which is missing by 100% by weight.
  • the mixtures preferably contain little free citric acid, with less than 10% by weight, based on mixtures, being preferred.
  • the citric acid esters according to the invention are mainly partial esters of citric acid which still contain at least one free carboxyl group. Accordingly, they can also be acidic esters or their neutralization products, and X in formula (II) can be hydrogen or a cation.
  • the partial esters are then preferably located. in the form of alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and / or glucammonium salts (i.e. X stands for alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and / or glucammonium ion).
  • citric acid esters it is essential that the citric acid be esterified with the alcohol ethoxylates of the formula (I) in a molar ratio of 0.9: 1 to 1.1: 1, in particular 1: 1.
  • the process conditions as such correspond to the prior art, and it may be essential that the reaction takes place in a nitrogen atmosphere. It may furthermore be advantageous to set the temperatures in the reaction in the range from 150 to 170 and preferably from 160.degree.
  • the citric acid ester mixtures according to the invention are obtained as the end product.
  • the esters can be free or in the form of salts.
  • a small proportion of unesterified citric acid usually results, preferably less than 10% by weight.
  • Reaction products which contain a maximum of 8% and in particular a maximum of 5% of unesterified citric acid are particularly preferred.
  • the acid number of the products obtained according to the invention is preferably 120 to 180, the saponification number is preferably in the range from 200 to 280. All measurements according to DIN.
  • citric acid ester mixtures according to the invention can be formulated with further surfactants, advantageously with anionic and / or nonionic surfactants.
  • surfactants advantageously with anionic and / or nonionic surfactants.
  • Nonionic, anionic, cationic and / or amphoteric or amphoteric surfactants can be contained as surface-active substances.
  • anionic surfactants are soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates (fatty ether amide sulfates, fatty ether amide sulfates, hydroxymate ether sulfates, hydroxymate ether sulfates, hydroxymate ether sulfates, hydroxymate ether sulfates, hydroxymate ether sulfates, hydroxy
  • anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably, a narrow homolog distribution.
  • Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkyl phenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosidic acid, alkyl glucose amides, and glucuric acid fatty acid (glucuric acid) glucoronic acid (glucoric acid) glucoronic acid (glucuric acid) glucoronic acid (glucoronic acid), especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternized fatty acid trialkanolamine ester salts.
  • Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds.
  • the most preferred nonionic surfactants include called the alkyl polyglycosides. Reference is made to the alkyl and / or alkenyl sulfates and to the alkyl ether sulfates as particularly suitable anionic surfactants, without any restriction in relation to the selection of the nonionic and / or anionic surfactants.
  • Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (III)
  • R 2 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and M is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates that Can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristic alcohol, cetyl alcohol, palm oleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, arachyl alcohol, petroselyl alcohol, petroselyl alcohol Erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts.
  • Alkyl sulfates based on Ci6 / i8 tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts are particularly preferred.
  • ether sulfates are known anionic surfactants which are produced on an industrial scale by SO3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
  • CSA chlorosulfonic acid
  • ether sulfates which follow the formula (IV) are suitable
  • R 3 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms
  • m represents numbers from 1 to 10
  • Z represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 1 to 5 moles of ethylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristic alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostyl alcohol, ela-alcohol alcohol, ela-alcohol alcohol, ela-alcohol alcohol, ela-alcohol alcohol, Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and.
  • the ether sulfates can have both a conventional and a narrow homolog distribution. It is particularly preferred to use ether sulfates based on adducts of an average of 1.5 to 2.5 moles of ethylene oxide with technical C12 / 14 or C12 / 18 coconut oil alcohol fractions in the form of their sodium and / or magnesium salts.
  • Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (V)
  • R 4 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 4 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 4 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above.
  • Alkyl oligoglucosides based on hardened C12 / 14 coconut alcohol with a DP of 1 to 3 are preferred.
  • citric acid ester mixtures according to the invention can be used alone, but in particular in a mixture with one or more of the aforementioned surfactants for the production of foaming, skin-friendly cosmetic products.
  • the cosmetic products can be water-free or water-containing formulations.
  • the compounds are used in hair shampoos, hair lotions, foam baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat masses, stick preparations, powders or ointments.
  • the citric acid ester mixtures of the present invention can also be used in combination with other auxiliaries and additives customary in cosmetics, such as, for example, oil bodies, emulsifiers, superfatting agents, pearlescent waxes, consistency enhancers, thickening agents, polymers, silicone compounds, fats, waxes, lecithins, phosphorus lipids, stabilizers, biogenic Active ingredients, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents, UV light protection factors and the like. ⁇ . can be combined.
  • the citric acid ester mixtures are preferably used in amounts of 0.1 to 20% by weight, in particular 0.5 to 10% by weight, based on the cosmetic agent.
  • mixtures of APG compounds of the formula (V) ' and the citric acid ester mixtures according to the invention show particularly advantageous properties in which the weight ratio of the APGs to the citric acid ester mixtures is in the range from 3: 1 to 1: 3.
  • Aqueous formulations are particularly preferred, especially if they are slightly acidic and preferably have a pH between 5 and 6.5.
  • Dehydol LT 7 TM is a fatty alcohol mixture, ethoxylated with 7 moles of ethylene oxide.
  • the fatty alcohol mixture has the following chain distribution in% by weight: ⁇ C12: 0-3%; C12: 48-58%; C14: 18-24%; C16: 8-12%; C18: 11-15%; > C18: 0-1%
  • Dehydol LS 6 TM a commercial product from Cognis Deutschland GmbH & Co. KG, is a fatty alcohol mixture, ethoxylated with 6 moles of ethylene oxide.
  • the fatty alcohol mixture has the following chain distribution in% by weight: C10: 0-2%; C12: 70-75%; C14: 24-30%; C16: 0-2%
  • a fatty alcohol mixture ethoxylated with 10 moles of ethylene oxide.
  • the fatty alcohol mixture has the following chain distribution in% by weight: ⁇ C12: 0-3%; C12: 48-58%; C14: 18-24%; C16: 8-12%; C18: 11-15%; > C18: 0-1%
  • Dehydol 04 TM a commercial product of Cognis Deutschland GmbH & Co. KG, is an octanol, ethoxylated with 4 moles of ethylene oxide.
  • the saponification number (VZ) was determined in accordance with DGF CV 3.
  • the acid number (SZ) was determined in accordance with DIN 53402
  • the foaming kinetics were measured after 30 seconds and the foam potential after 60, 90, 120, 150 s and after 180 s using the rotor-foam method (DIN 13996 in preparation).
  • the rotor foam test device consists of a temperature-controlled, double-walled cylindrical glass vessel with an inner diameter of 17.5 cm. A scale with mm graduation for reading the foam height and the liquid level is attached to the cylindrical glass vessel.
  • the glass jar is also provided with a styrofoam lid, which serves to cover and insulate the jar.
  • the mixer consists of a special mixer head with a 28 cm long mixer shaft with a 1 cm diameter and a JK mixer with digital speed display. In addition, a thermostat, a stop watch and a thermometer (digital) are required.
  • the first value of the foam height was determined after 30 seconds, the agitator was switched off for a maximum of 10 seconds. The amount of foam was then determined after 60 and 180 seconds.
  • Citric acid ester of a C12 / 14 0.5 g / l 30 s 265 ml
  • citric acid esters according to the invention with the selected mono: diester contents show a significantly better foaming behavior than those citric acid esters with higher diester contents (example 1 in comparison to comparison example).
  • the citric acid esters according to the invention with the selected degrees of ethoxylation have better foaming behavior than those with higher degrees of ethoxylation (example 1 in comparison with comparative example 2) or with shorter alcohol chains (examples 1 and 2 in comparison with comparative example 3), both with regard to the foaming kinetics and after longer times.
  • citric acid esters according to the invention are not irritating to the eyes and are therefore better tolerated than comparable citric acid esters with higher diester contents (Comparative Example 1) or with shorter alkyl chains (Comparative Example 3).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des mélanges d'esters d'acide citrique sélectionnés, d'alcools éthoxylés et présentant une teneur particulière en constituants allant des monoesters aux diesters. L'invention concerne un procédé permettant de préparer lesdits mélanges, ainsi que leur utilisation, éventuellement en mélange avec d'autres tensioactifs pour produire des agents cosmétiques à haut pouvoir moussant et à faible potentiel irritant.
EP04728546A 2003-04-30 2004-04-21 Esters d'acide citrique Withdrawn EP1656337A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10319401A DE10319401A1 (de) 2003-04-30 2003-04-30 Citronensäureester
PCT/EP2004/004209 WO2004096749A1 (fr) 2003-04-30 2004-04-21 Esters d'acide citrique

Publications (1)

Publication Number Publication Date
EP1656337A1 true EP1656337A1 (fr) 2006-05-17

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP04728546A Withdrawn EP1656337A1 (fr) 2003-04-30 2004-04-21 Esters d'acide citrique

Country Status (5)

Country Link
US (1) US20070098666A1 (fr)
EP (1) EP1656337A1 (fr)
JP (1) JP2006525253A (fr)
DE (1) DE10319401A1 (fr)
WO (1) WO2004096749A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004054842A1 (de) * 2004-11-12 2006-05-24 Cognis Ip Management Gmbh Ölhaltige Tensidgele
DE102005060733A1 (de) * 2005-12-16 2007-06-28 Cognis Ip Management Gmbh Reinigungstücher
DE102006044618A1 (de) * 2006-09-19 2008-03-27 Cognis Ip Management Gmbh Alkylethercitrate für die selektive Reinigung der Haut
US8623342B1 (en) * 2009-07-20 2014-01-07 Surfatech Corporation Naturally derived citrate polyesters
US20120002405A1 (en) * 2010-07-02 2012-01-05 Sol-Light, Llc. Illuminating book light with attachable heads
CN106278885A (zh) * 2016-08-23 2017-01-04 成都米特瑞新材料科技有限公司 一种柠檬酸三棕榈酯的改进增塑剂
CN106316842A (zh) * 2016-08-23 2017-01-11 成都米特瑞新材料科技有限公司 一种柠檬酸三棕榈酯的改进增塑剂的制备方法
EP3752481A1 (fr) 2018-02-14 2020-12-23 Basf Se Procédé de production de condensats tensioactifs d'acide citrique et produits obtenus par ce procédé

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IT1201411B (it) * 1985-03-26 1989-02-02 Rol Raffineria Olii Lubrifican Tesnioattivi derivati dall'acido citrico
DE4025925A1 (de) * 1990-08-16 1992-02-20 Henkel Kgaa Salze von polycarbonsaeurepartialestern
DE4111811A1 (de) * 1991-04-11 1992-10-15 Rewo Chemische Werke Gmbh Citronensaeurefettalkoholesterpolyglykolether- sulfosuccinate, verfahren zu ihrer herstellung und ihre verwendung
DE4131878A1 (de) * 1991-09-25 1993-04-01 Henkel Kgaa Verfahren zur herstellung von liposomen
US6284230B1 (en) * 1996-12-30 2001-09-04 The Procter & Gamble Company Hair conditioning shampoo compositions comprising primary anionic surfactant
FR2758261A1 (fr) * 1997-01-10 1998-07-17 Oreal Compositions cosmetiques presentant une rincabilite amelioree
DE19856555A1 (de) * 1998-12-08 2000-06-15 Cognis Deutschland Gmbh Ölbäder
FR2788449B1 (fr) * 1999-01-14 2001-02-16 Oreal Nanoemulsion a base de citrates d'alkylether, et ses utilisations dans les domaines cosmetique, dermatologique, pharmaceutique et/ou ophtalmologique

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Title
See references of WO2004096749A1 *

Also Published As

Publication number Publication date
US20070098666A1 (en) 2007-05-03
JP2006525253A (ja) 2006-11-09
DE10319401A1 (de) 2004-11-18
WO2004096749A1 (fr) 2004-11-11

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