EP0405664B1 - Körperwaschmittel mit geruchsverträglichem kationischem Polymer auf der Basis sperriger Amine - Google Patents

Körperwaschmittel mit geruchsverträglichem kationischem Polymer auf der Basis sperriger Amine Download PDF

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Publication number
EP0405664B1
EP0405664B1 EP90201638A EP90201638A EP0405664B1 EP 0405664 B1 EP0405664 B1 EP 0405664B1 EP 90201638 A EP90201638 A EP 90201638A EP 90201638 A EP90201638 A EP 90201638A EP 0405664 B1 EP0405664 B1 EP 0405664B1
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alkyl
cationic
weight
personal cleansing
polymer
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French (fr)
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EP0405664A2 (de
EP0405664A3 (de
Inventor
Robert Gregory Bartolo
Louis Fay Wong
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • compositions for personal washing which compositions comprise quaternary amine polymers.
  • Liquid and solid bar compositions based on soap and/or synthetic surfactants are commonly used for cleansing the human body.
  • a wide variety of additives have been suggested for inclusion in said compositions. Some enhance the physical properties, e.g., bar hardness, wear rate, resistance to water. Others enhance the in-use properties such as lather characteristics and some impact on the impression the composition has on the skin both during washing (bar feel) and afterwards.
  • the useful polymers should be soluble or dispersible in water to a level of at least 1% by weight, preferably at least 5% by weight at 25°C.
  • Suitable polymers are high molecular weight materials (mass-average molecular weight determined, for instance, by light scattering, being generally from 20,000 to 5,000,000, preferably from 50,000 to 4,000,000, and more preferably from 500,000 to 3,000,000) and preferably have a thickening ability such that a 1% dispersion of the polymer in water at 20°C exceeds 1 Pa ⁇ S (10 poise) at a shear rate of 10 ⁇ sec-1.
  • Useful polymers are the cationic, nonionic, amphoteric, and anionic polymers useful in the cosmetic field. Preferred are cationic and nonionic resins and mixtures thereof. Highly preferred are the cationic resins.
  • the preferred cationic polymers include cationic guar gums such as hydroxyproxyltrimethylammonium guar gum.
  • cationic guar gums such as hydroxyproxyltrimethylammonium guar gum.
  • cationic trimethylamine quaternized polymers in compositions having a pH of 7.5 or above. They break down and release odoriferous labile amines.
  • the present invention relates to a personal cleansing product in the form of a toilet bar made with a selected quaternized cationic polymer wherein each quaternary ammonium moiety is derived from a bulky amine.
  • An object of the present invention is to provide an improved toilet soap bar comprising a cationic polymeric skin conditioning agent which does not comprise a potential odoriferous amine moiety.
  • the present invention comprises basic personal cleansing compositions comprising from 0.2% to 5% by weight selected cationic polymer wherein each cationic group is derived from a "bulky” amine.
  • each cationic group is derived from a "bulky” amine.
  • the compositions of this invention consistently exhibit superior odor stability due to the selected "bulky amine" cationic polymers.
  • basic personal cleansing compositions as used herein means that the composition has a pH of at least 8.5.
  • illustrations A and B show the theoretical degradation of labile amine containing cationic polymers in a basic environment.
  • R1-R3 is H or any other substituent and R4, R5 and R6 combine with N to form an amine with less odor impact than trimethylamine, at least one of R4, R5 and R6 is alkyl having a chain length of from 2 to 24 carbon atoms, or an alkoxy alkyl group containing from 2 to 12 carbon atoms or a hydroxy ethyl group.
  • cationic guar gums having the following structures:
  • HEC bulky amine hydroxyethyl cellulose
  • the composition of this invention comprises from 0.2% to 5%, preferably from 0.5% to 2% by weight, of the cationic polymer.
  • the average molecular weight of the preferred cationic guar gum is from 50,000 to 1,000,000, preferably from 100,000 to 500,000, and more preferably from 250,000 to 400,000 and the degree of substitution is from 0.5 to 4, preferably from 1 to 2.5.
  • Some preferred cationic guars (galactomannans) are disclosed in US-A-4,758,282, Stober et al., issued July 19, 1988.
  • bulky amine cationic polymeric skin conditioning agents useful in the present invention have molecular weights of from 1,000 to 3,000,000.
  • Useful polymers are selected from the group consisting of:
  • members of the bulky amine cationic polysaccharide class include the cationic hydroxyethyl cellulose, e.g., LM-200 (RTM) made by Union Carbide Corporation.
  • the cationic copolymers of saccharides and synthetic cationic monomers useful in the present invention encompass those containing the following saccharides: glucose, galactose, mannose, arabinose, xylose, fucose, fructose, glucosamine, galactosamine, glucuronic acid, galacturonic acid, and 5 or 6 membered ring polyalcohols. Also included are hydroxymethyl, hydroxyethyl and hydroxypropyl derivatives of the above sugars.
  • volatility decreases with increasing molecular weight. Volatility is dependent, among other things on the boiling point of the neat component. Odor impact also has a strong dependence on the amount of volatilized material that reaches the nose. Table 1 demonstrates the significant effect which adding "bulky” groups has on volatility and, hence, odor impact of amines. For pure hydrocarbon substitution, the larger the alkyl chains (or the larger the degree of long chain substitution) the lower the odor impact.
  • the quaternised cationic polymers used in the present invention have an ammonium moiety derived from bulky amines having boiling points of greater than 80°C.
  • the surfactant component of the present compositions comprises alkali metal soap or mixtures of alkali metal soap and synthetic surfactant.
  • Alkali metal soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps.
  • tallow is used herein in connection with fatty acid mixtures which typically have an approximate carbon chain length distribution of 2.5% C14, 29% C16, 23% C18, 2% palmitoleic, 41.5% oleic and 3% linoleic. (The first three fatty acids listed are saturated.) Other mixtures with similar distribution, such as the fatty acids derived from various animal tallows. The tallow can also be hardened (i.e., hydrogenated) to convert part or all of the unsaturated fatty acid moieties to saturated fatty acid moieties.
  • coconut oil and “coconut fatty acid” (CNFA) are used herein, they refer to fatty acid mixtures which typically have an approximate carbon chain length distribution of about 8% C7, 7% C10, 48% C12, 17% C14, 9% C16, 2% C18, 7% oleic, and 2% linoleic. (The first six fatty acids listed are saturated.) Other sources having similar carbon chain length distribution such as palm kernel oil and babassu kernel oil are included with the terms coconut oil and coconut fatty acid.
  • a preferred soap bar of this invention comprises soap as its primary or sole surfactant. It also contains as an essential ingredient a skin conditioning amount of a hydrated, cationic guar gum provided by a cationic guar gum polymer. This polymer is uniformly distributed in the soap bar matrix without affecting the smooth feel of the dry or wet bar.
  • Another preferred toilet bar is based on mild synthetic surfactants as disclosed in US-A-4,673,525, Small et al., issued June 16, 1987.
  • Synthetic detergents can also be present in compositions herein.
  • Preferred types of synthetic detergents are of the anionic or nonionic type.
  • anionic synthetic detergents are the salts of organic sulfuric reaction products such as
  • R24 is a straight or branched chain alkyl of from 8 to 24 carbon atoms; M is an alkali metal or ammonium ion; x is a number of from 1 to 10; y is a number of from 1 to 4; and X is selected from the group consisting of chlorine, hydroxyl, and -SO3M, at least one X in each molecule being -SO3M.
  • nonionic synthetic detergents are ethoxylated fatty alcohols (e.g., the reaction product of one mole of coconut fatty alcohol with from 3 to 30 moles of ethylene oxide) and fatty acid amides such as coconut fatty acid monoethanolamide and stearic acid diethanolamide.
  • compositions herein can be free of synthetic detergents.
  • synthetic detergents include the mild synthetic surfactants disclosed in US-A-4,673,525, Small et al., issued June 16, 1987.
  • Insoluble alkaline earth metal soaps such as calcium stearate and magnesium stearate can also be incorporated into compositions of the present invention at levels up to 30% by weight. These materials are particularly useful in toilet bars in which synthetic detergents are present in that they tend to reduce the relatively high solubility which such bars normally have. These alkaline earth metal soaps are not included within the term “soap” as otherwise used in this specification.
  • the term “soap” as used herein refers to the alkali metal soaps.
  • compositions of the present invention can contain optional components such as those conventionally found in personal cleansing products.
  • Conventional antibacterial agents can be included in the present compositions at levels of from 0.5% to 4% by weight.
  • Typical antibacterial agents which are suitable for use herein are 3,4-di- and 3,4',5-tribromosalicylanilides; 4,4'-dichloro-3-(trifluoromethyl)carbanilide; 3,4,4'-trichlorocarbanilide and mixtures of these materials.
  • Conventional nonionic emollients can be included as additional skin conditioning agents in the compositions of the present invention at levels up to 40%, preferably at levels of from 1% to 25% by weight.
  • Such materials include, for example mineral oils, paraffin wax having a melting point of from about 37.8°C (about 100°F.), fatty sorbitan esters (see US-A-3,988,255, Seiden, issued Oct. 26, 1976 , lanolin and lanolin derivatives, esters such as isopropyl myristate and triglycerides such as coconut oil or hydrogenated tallow.
  • Free fatty acid such as coconut fatty acid can be added to the compositions herein to improve the volume and quality (creaminess) of the lather produced by the compositions herein.
  • perfumes, dyes and pigments can also be incorporated into compositions of the invention at levels up to 5% by weight.
  • Perfumes are preferably used at levels of from 0.5% to 3% by weight and dyes and pigments are preferably used at levels of from 0.001% to 0.5% by weight.
  • Toilet bars of the present invention can be prepared in any conventional manner.
  • the bulky amine cationic polymer can be added to noodles of the base soap mixture containing from 10% to 22% moisture in an amalgamator. Any optional ingredients such as perfumes, dyes, etc., are also added to the amalgamator.
  • the mixture is processed in the amalgamator and milled in the conventional manner under conventional conditions. It is then extruded (plodded) into logs for cutting and stamping into toilet bars.
  • the bulky amine cationic polymer is added to soap noodle and mixed in the soap mixing steps of the soap bar making process.
  • the soap bars of this invention contain up to 15% by weight of a synthetic surfactant. If a synthetic surfactant is included, a mild one is preferred.
  • a mild synthetic surfactant is defined herein as one which does relatively little damage to the barrier function of the stratum corneum.
  • the mild surfactant is preferably used at a level of 2-15% by weight.
  • the fatty acid soap and mild surfactant mixture preferably has a ratio of 2.5:1 to 37:1, preferably from 2.5:1 to 14:1, and most preferably from 6.5:1 to 14:1, soap:synthetic.
  • a preferred soap bar of this invention also contains from 2% to 17% by weight moisturizer, preferably one selected from glycerin and free fatty acid or mixtures thereof.
  • the more preferred bar of this invention contains at least 4% by weight moisturizer.
  • Some preferred mild synthetic surfactants useful in this invention include alkyl glyceryl ether sulfonate (AGS), anionic acyl sarcosinates, methyl acyl taurates, N-acyl glutamates, alkyl glucosides, acyl isethionates, alkyl sulfosuccinate, alkyl phosphate esters, ethoxylated alkyl phosphate esters, alkyl ether sulfates, methyl glucose esters, protein condensates, mixtures of alkyl ether sulfates and alkyl amine oxides, betaines, sultaines, and mixtures thereof.
  • AGS alkyl glyceryl ether sulfonate
  • anionic acyl sarcosinates methyl acyl taurates
  • N-acyl glutamates N-acyl glutamates
  • alkyl glucosides acyl isethionates
  • alkyl ether sulfates with 1 to 12 ethoxy groups especially ammonium and sodium lauryl ether sulfates.
  • Alkyl chain lengths for these surfactants are C8-C22, preferably C10-C18.
  • the most preferred mild surfactant is sodium CN AGS.
  • Plodded soap noodles are conveyed to a continuous mixer (CM) where approximately 1.0 part of cationic polymer is introduced, mixed, and plodded with the soap noodles. Uniform distribution during this addition and mixing step is important for acceptable bar feel performance.
  • the polymer/soap noodles (generic noodles) are conveyed to milling.
  • Two four-roll soap mills feed, stationary, middle, and top rolls are used in this step. This is a split milling (two set of mills are used in parallel) process to obtain a homogeneous mix. Efficient milling is needed in this intimate mixing step.
  • CM continuous mixer
  • CM wet mixing
  • the mixture is milled using a four-roll mill, plodded, and then stamped into toilet bars of any convenient size and shape.
  • the resulting bars are tested for odor.
  • the bars have a pH of 9.5 in a 1% aqueous solution.
  • the pH buffers are commercially available buffers:
  • JR-400 made by Union Carbide Corporation and JAGUAR C-15 (RTM) made by Hi-Tek Polymers, Inc., are outside the selected polymers of this invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Claims (8)

  1. Körperreinigungszusammensetzung in der Form eines Toilettenriegels, umfassend 5 Gew.-% bis 90 Gew.-% von einem grenzflächenaktiven Mittel, welches unter Alkalimetallseife und Gemischen aus Alkalimetallseife und synthetischem grenzflächenaktivem Mittel ausgewählt ist, wobei das synthetische grenzflächenaktive Mittel in einer Menge bis zu 15 Gew.-% vorhanden ist; und 0,2 Gew.-% bis 5 Gew.-% von einem quaternierten kationischen Polymer, wobei jeder Ammoniumrest die Formel:

            -CR¹H-CRR³-NR⁴R⁵R⁶

    besitzt, worin R¹ bis R³ für H oder jeden beliebigen anderen Substituenten stehen und mindestens einer der Reste R⁴, R⁵ und R⁶ Alkyl mit einer Kettenlänge von 2 bis 24 Kohlenstoffatomen oder eine Alkoxyalkylgruppe mit 2 bis 12 Kohlenstoffatomen oder eine Hydroxyethylgruppe darstellt; und wobei sich jeder quaternäre Ammoniumrest aus einem sperrigen Amin mit einem Siedepunkt von mehr als 80°C herleitet, wodurch das kationische Polymer im wesentlichen von Gruppen frei ist, welche in einer basischen Umgebung Amine ausbilden, die einen Geruch aufweisen; und wobei die genannte Zusammensetzung in 1%iger wäßriger Lösung einen pH-Wert von mindestens 8,5 aufweist.
  2. Körperreinigungszusammensetzung nach Anspruch 1, worin das genannte kationische Polymer ein kationisches Guargummi ist.
  3. Körperreinigungszusammensetzung nach Anspruch 1, worin das genannte kationische Polymer von der Gruppe ausgewählt ist, welche aus:
    Figure imgb0011
    Figure imgb0012
     und Gemischen hievon besteht; und wobei das genannte Polymer ein Molekulargewicht von 50.000 bis 1,000.000 aufweist.
  4. Körperreinigungszusammensetzung nach Anspruch 1, wobei das genannte kationische Polymer in Mengen von 0,5 Gew.-% bis 4 Gew.-% vorhanden ist.
  5. Körperreinigungszusammensetzung nach Anspruch 1, wobei das genannte kationische Polymer ein Molekulargewicht von 1.000 bis 3,000.000 aufweist und von der Gruppe ausgewählt ist, welche aus:
    (I) kationischen Polysacchariden;
    (II) kationischen Copolymeren von Sacchariden und synthetischen kationischen Monomeren; und
    (III) synthetischen Polymeren, welche von der aus:
    (A) quaternierten Siliconen,
    (B) quaternierten Methacrylaten bestehenden Gruppe ausgewählt ist; und
    (IV) Gemischen hievon besteht.
  6. Verfahren zur Herstellung der Körperreinigungszusammensetzung nach Anspruch 1, umfassend die Schritte von:
    (a) Ausbilden eines Gemisches aus dem genannten kationischen Polymer und Alkalimetallseifengemischnudeln, wobei das genannte Polymer im genannten Gemisch in einer Menge vorhanden ist, um 0,2 Gew.-% bis 5 Gew.-% des genannten Polymers in der genannten Zusammensetzung zu gewährleisten; welches Gemisch 6% bis 15% Feuchtigkeit aufweist;
    (b) Pilieren des genannten Gemisches zu einem einheitlichen Gemisch;
    (c) Strangpressen des genannten einheitlichen Gemisches;
    (d) Extrudieren des genannten pilierten und stranggepreßten Gemisches; und
    (e) Prägen des genannten extrudierten Gemisches zu Toilettenriegeln.
  7. Körperreinigungszusammensetzung nach Anspruch 1, wobei die genannte Zusammensetzung 2 Gew.-% bis 15 Gew.-% an synthetischem grenzflächenaktivem Mittel enthält, welches unter Alkylglycerylethersulfonaten, anionischen Acylsarcosinaten, Methylacyltauraten, N-Acylglutamaten, Alkylglucosiden, Acylisethionaten, Alkylsulfosuccinaten, Alkylphosphatestern, ethoxylierten Alkylphosphatestern, Methylglucoseestern, Proteinkondensaten, Gemischen von ethoxylierten Alkylsulfaten und Alkylaminoxiden, Betainen, Sultainen, den Alkylethersulfaten mit 1 bis 12 Ethoxygruppen und Gemischen hievon ausgewählt ist, wobei das genannte synthetische grenzflächenaktive Mittel Alkylketten mit 8 bis 22 Kohlenstoffatomen aufweist.
  8. Verfahren nach Anspruch 7, wobei die genannte Zusammensetzung 5 Gew.-% bis 10 Gew.-% eines C₈-C₁₈-Alkylglycerylethersulfonates enthält.
EP90201638A 1989-06-30 1990-06-22 Körperwaschmittel mit geruchsverträglichem kationischem Polymer auf der Basis sperriger Amine Expired - Lifetime EP0405664B1 (de)

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AR (1) AR243596A1 (de)
AT (1) ATE137260T1 (de)
AU (1) AU620999B2 (de)
BR (1) BR9003038A (de)
CA (1) CA2019264C (de)
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US5154849A (en) * 1990-11-16 1992-10-13 The Procter & Gamble Company Mild skin cleansing toilet bar with silicone skin mildness/moisturizing aid
US5387675A (en) * 1993-03-10 1995-02-07 Rhone-Poulenc Specialty Chemicals Co. Modified hydrophobic cationic thickening compositions
US5849280A (en) † 1996-08-06 1998-12-15 A-Veda Corporation Hair conditioning solid
US5858939A (en) * 1997-03-21 1999-01-12 Lever Brothers Company, Division Of Conopco, Inc. Method for preparing bars comprising use of separate bar adjuvant compositions comprising benefit agent and deposition polymer
EP1791871B1 (de) * 2004-08-31 2012-02-15 Hercules Incorporated Verfahren zur herstellung von niedermolekularem kationischem polygalactomannan mit verringertem geruch
IT1391979B1 (it) * 2008-07-18 2012-02-02 Lamberti Spa Eteri di galattomannani modificati
JP5367494B2 (ja) * 2009-08-06 2013-12-11 花王株式会社 枠練り石鹸の製造方法

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EP0337354A1 (de) * 1988-04-12 1989-10-18 Kao Corporation Waschmittelzusammensetzung mit geringer Reizung
WO1990015589A1 (de) * 1989-06-16 1990-12-27 Wella Aktiengesellschaft Klares haar- und körperreinigungsmittel

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Publication number Priority date Publication date Assignee Title
EP0308189A2 (de) * 1987-09-17 1989-03-22 The Procter & Gamble Company Hautreinigungsstück mit niedrigem Feuchtegehalt
EP0337354A1 (de) * 1988-04-12 1989-10-18 Kao Corporation Waschmittelzusammensetzung mit geringer Reizung
WO1990015589A1 (de) * 1989-06-16 1990-12-27 Wella Aktiengesellschaft Klares haar- und körperreinigungsmittel

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ATE137260T1 (de) 1996-05-15
TR24531A (tr) 1991-11-01
CA2019264A1 (en) 1990-12-31
EP0405664A2 (de) 1991-01-02
DK0405664T3 (da) 1996-08-12
DE69026651T2 (de) 1996-11-21
EP0405664A3 (de) 1991-01-16
AU620999B2 (en) 1992-02-27
MY107250A (en) 1995-10-31
CA2019264C (en) 1995-07-18
ES2086362T3 (es) 1996-07-01
DE69026651D1 (de) 1996-05-30
BR9003038A (pt) 1991-08-20
AU5805590A (en) 1991-01-03
JPH03115210A (ja) 1991-05-16
AR243596A1 (es) 1993-08-31
EG19777A (en) 1996-03-31
JP2930671B2 (ja) 1999-08-03
MA21897A1 (fr) 1991-04-01
PE13191A1 (es) 1991-04-05

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