EP1023043A2 - Cleansing compositions - Google Patents
Cleansing compositionsInfo
- Publication number
- EP1023043A2 EP1023043A2 EP98953292A EP98953292A EP1023043A2 EP 1023043 A2 EP1023043 A2 EP 1023043A2 EP 98953292 A EP98953292 A EP 98953292A EP 98953292 A EP98953292 A EP 98953292A EP 1023043 A2 EP1023043 A2 EP 1023043A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- water
- personal cleansing
- composition according
- cleansing composition
- 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- Withdrawn
Links
Classifications
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- 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
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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
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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
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
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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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- A61K8/8111—Homopolymers or copolymers of aliphatic olefines, e.g. polyethylene, polyisobutene; Compositions of derivatives of such polymers
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- 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
Definitions
- the present invention relates to cleansing compositions.
- mild personal cleansing compositions which display improved product stability and in combination with good rinse feel, good skin feel attributes, and foaming properties which are suitable for simultaneously cleansing and conditioning the skin and/or the hair and which may be used, for example, in the form of foam bath preparations, shower products, skin cleansers, hand, face and body cleansers, shampoos, etc.
- Mild cosmetic compositions must satisfy a number of criteria including cleansing power, foaming properties and mildness/low irritancy/good feel with respect to the skin, hair and the ocular mucosae.
- Skin is made up of several layers of cells which coat and protect the underlying tissue. The keratin and collagen fibrous proteins that form the skeleton of its structure. The outermost of these layers is referred to as the stratum corneum.
- Hair similarly has a protective outer coating enclosing the hair fibre which is called the cuticle.
- Anionic surfactants can penetrate the stratum corneum membrane and the cuticle and, by delipidization destroy membrane integrity and loss of barrier and water retention functions. This interference with skin and hair protective membranes can lead to a rough skin feel and eye irritation and may eventually permit the surfactant to trigger immune response creating irritation.
- Ideal cosmetic cleansers should cleanse the skin or hair gently, without defatting and/or drying the hair and skin and without irritating the ocular mucosae or leaving skin taut after frequent use. Most lathering soaps, shower and bath products, shampoos and bars fail in this respect.
- Certain synthetic surfactants are known to be mild.
- a major drawback of some mild synthetic surfactant systems when formulated for shampooing or personal cleansing is that they have what can be described as a "slippy" or “non-draggy” rinse feel which is not liked by some consumers.
- the use of certain surfactants such as potassium laurate, on the other hand, can yield a "draggy" rinse feel but at the expense of clinical skin mildness.
- Personal cleansing compositions having a "draggy" rinse feel at the same time as having excellent mildness characteristics are provided by the combination of certain water-insoluble oils, such as certain polyalphaoleftn oils, in combination with a mild, water-soluble surfactant system.
- Conventional personal cleansing compositions use materials such as Bentone gels and ethylene glycol distearate. Crystalline hydroxyl- containing stabilizer materials such as trihydroxystearin are known for use in liquid skin cleansers.
- WO 96/25144 discloses stress stable lathering skin cleansing compositions comprising a crystalline, hydroxy-containing stabilizer, lipid skin moisturising agent, surfactant and water.
- GB-A- 2297975 discloses personal cleansing compositions comprising surfactant, water-insoluble salt of a C14-C22 fatty acid, optionally a cationic or nonionic polymeric skin conditioning agent, trihydroxystearin and water.
- a rinse-off liquid personal cleansing composition comprising:
- Rl is H or C1-C20 alkyl
- R.4 is C1-C20 alkyl
- R2 is H or C ⁇ -C20» and R ⁇ is C1-C20 preferably from
- C5-C2O5 n is an integer from 0 to 3 and m is an integer of from 1 to 1000 and having a number average molecular weight of from about 1000 to about 25,000, and
- R2 is Rl or H
- R3 is Rl or H
- R4 is CO-20 alkyl
- R5 is C0-C20 alkyl
- R6 is C0-C20 alkyl
- R4+R5+R6 C 10-22 and wherein 1 ⁇ x+y ⁇ 4
- R7 is -R4(COH)xR5(COH)yR6, M is Na + , K + , or Mg , or H,
- compositions of the present invention provide an improvement in stability and rheology characteristics while at the same time providing an excellent rinse feel to the skin.
- liquid cleansing compositions herein comprise water, surfactant, crystalline hydroxy-containing stabilizer and a certain water-insoluble oil which will be described below.
- rinse feel means the feeling of the skin during the process of rinsing lather from the skin after cleansing with a cleansing composition.
- the type of rinse feel which is provided by the compositions of the present invention can be described by terms such as a “draggy” rinse feel, a “soap-like” rinse feel and a “non-slippery” or “non-slimy” rinse feel.
- Such a “draggy”, “soap-like”, “non-slippery” or “non-slimy” rinse feel can be detected by an increase in friction between the hand and skin during the process of rinsing lather from the skin.
- water-insoluble in relation to oils is a material which is substantially insoluble in distilled water at room temperature without the addition of other adjuncts and/or ingredients such as described herein.
- the water-insoluble oil for use herein is selected from (a) highly branched polyalphaolefins having the following formula:
- R 1 is H or C1-C20 alkyl
- R4 is C1-C20 alkyl
- R 2 is H or C1-C20
- R3 is C5-C2O 5 n 1S an integer from 0 to 3 and m is an integer of from 1 to 1000 and having a number average molecular weight of from about 1000 to about 25,000, preferably from about 2500 to about 6000, more preferably from about 2500 to about 4000.
- the polyalphaolefins of type (a) use herein have a viscosity of from about 300cst to about 50,000cst, preferably from about lOOOcst to about 12,000 cst, more preferably from about lOOOcst to about 4000cst at 40°C using the ASTM D-445 method for measuring viscosity.
- the oils of type (a) may also have a degree of unsaturation, but are preferably saturated.
- Suitable polyalphaolefins of type (a) as described above can be derived from 1-alkene monomers having from about 4 to about 20 carbon atoms, preferably from about 6 to about 12 carbon atoms, especially from about 8 to about 12 carbon atoms.
- the polyalphaolefins useful herein are preferably hydrogenated polyalphaolefm polymers.
- Non-limiting examples of 1-alkene monomers for use in preparing the polyalphaolefm polymers herein include 1-hexene, 1-octene, 1-decene, 1- dodecene, 1-tetradecene, branched chain isomers such as 4-methyl-l- pentene, and combinations thereof. Also suitable for preparing the polyolefm liquids are 1-hexene to 1-hexadecenes and combinations thereof, more preferably 1-octene to 1 -dodecene or combinations thereof.
- oils examples include polydecene oils such as those commercially available from Mobil Chemical Company, P.O. Box 3140, Edison, New Jersey 08818, USA, under the tradename Puresyn 40 and Puresyn 100.
- the number average particle diameter for the water-insoluble oil used herein lies in the range of from about 1 micron to about 500 microns, preferably from about 5 to about 200 microns, more preferably from about 5 to 50 microns, especially from about 5 to about 20 microns.
- compositions herein preferably comprise from about 0.1 % to about 20%), more preferably from about 0.5%) to about 10%, especially from about 1% to about 5%> by weight of water-insoluble oil.
- compositions of the present invention comprise a surfactant system of water-soluble surfactants.
- Water-soluble as defined herein, means a surfactant having a molecular weight of less than about 20,000 wherein the surfactant is capable of forming a clear isotropic solution when dissolved in water at 0.2 %> w/w under ambient conditions.
- Surfactants suitable for inclusion in compositions according to the present invention generally have a lipophilic chain length of from about 6 to about 22 carbon atoms and can be selected from anionic, nonionic, zwitterionic and amphoteric surfactants and mixtures thereof.
- the total level of surfactant is preferably from about 2%> to about 40%, more preferably from about 3% to about 20% by weight, and especially from about 5% to about 15%) by weight.
- the compositions preferably comprise a mixture of anionic with zwitterionic and/or amphoteric surfactants.
- the weight ratio of anionic surfactant: zwitterionic and/or amphoteric surfactant is in the range from about 1 :10 to about 10: 1, preferably from about 1 :5 to about 5:1, more preferably from about 1 :3 to about 3:1.
- Other suitable compositions within the scope of the invention comprise mixtures of anionic, zwitterionic and/or amphoteric surfactants with one or more nonionic surfactants.
- compositions of the invention can comprise a water-soluble anionic surfactant at levels from about 0.1 %> to about 20%), more preferably from about 0.1%) to about 15%>, and especially from about 1%> to about 10%> by weight.
- Water soluble anionic surfactants suitable for inclusion in the compositions of the invention include alkyl sulfates, ethoxylated alkyl sulfates, alkyl ethoxy carboxylates, alkyl glyceryl ether sulfonates, ethoxy ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alkyl ethoxysulphosuccinates, alpha-sulfonated fatty acids, their salts and/or their esters, alkyl phosphate esters, ethoxylated alkyl phosphate esters, acyl sarcosinates and fatty acid/protein condensates, soaps such as ammonium, magnesium, potassium, triethanolamine and sodium salts of lauric acid, myristic acid and palmitic acid,
- Alkyl and/or acyl chain lengths for these surfactants are C6-C22 * preferably Cj2- Ci8 more preferably C12-C14.
- Additional water-soluble anionic surfactants suitable for use in the compositions according to the present invention are the salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol and from about 1 to about 12 moles of ethylene oxide, with sodium, ammonium and magnesium being the preferred counterions.
- alkyl ethoxy sulfates containing from about 2 to 6, preferably 2 to 4 moles of ethylene oxide, such as sodium laureth-2 sulfate, sodium laureth-3 sulfate, ammonium laureth-3 sulfate and magnesium sodium laureth-3.6 sulfate.
- the anionic surfactant contains at least about 50%) especially at least about 75%> by weight of ethoxylated alkyl sulfate.
- ethoxylated alkyl sulfates obtained from narrow range ethoxylates are also suitable water-soluble anionic surfactants for use in the present compositions.
- Narrow range ethoxylated alkyl sulfates suitable for use herein are selected from sulphated alkyl ethoxylates containing on average from about 1 to about 6, preferably from about 2 to about 4 and especially about 3 moles of ethylene oxide such as NRE sodium laureth-3 sulfate.
- NRE materials suitable for use herein contain distributions of the desired ethylene oxide (EO n ) in the ranges of from 15% to about 30% by weight of EO n , from about 10%> to about 20%> by weight of EO n + ⁇ and from about 10% to about 20%) by weight of EO n _ ⁇ .
- Highly preferred NRE materials contain less than about 9% by weight of ethoxylated alkyl sulfate having 7 or more moles of ethylene oxide and less than about 13% by weight of non-ethoxylated alkyl sulfate.
- Suitable laureth 3 sulfate NRE materials are available from Hoechst under the trade names GENAPOL ZRO Narrow Range and GENAPOL Narrow Range.
- compositions of the present invention may contain, as a water-soluble anionic surfactant alkyl ethoxy carboxylate surfactant at a level of from about 0.5% to about 15%), preferably from about 1%> to about 10%>, more preferably from about 1%> to about 6%> and especially from about 1% to about 4%> by weight.
- alkyl ethoxy carboxylate surfactant is particularly valuable in the compositions according to the present invention for the delivery of excellent skin mildness attributes in combination with excellent rinsing performance and desirable lather characteristics.
- Alkyl ethoxy carboxylates suitable for use herein have the general formula (I):
- R ⁇ is a Cio to C ⁇ alkyl or alkenyl group, preferably a C ⁇ I-C15 , more preferably a C12-C14 alkyl or C12-C13 alkyl group
- k is an average value of ethoxylation ranging from 2 to about 7, preferably from about 3 to about 6, more preferably from about 3.5 to about 5.5, especially from about 4 to about 5, most preferably from about 4 to about 4.5
- M is a water- solubilizing cation, preferably an alkali metal, alkaline earth metal, ammonium, lower alkanol ammonium, and mono-, di-, and tri-ethanol ammonium, more preferably sodium, potassium and ammonium, most preferably sodium and ammonium and mixtures thereof with magnesium and calcium ions.
- alkyl ethoxy carboxylate surfactants suitable for use herein are alkyl ethoxy carboxylate surfactants having a selected distribution of alkyl chain length and/or ethoxylate.
- the alkyl ethoxy carboxylate surfactants suitable for use in the compositions according to the present invention may comprise a distribution of alkyl ethoxy carboxylates having different average values of R3 and/or k.
- the average value of k will generally fall in the range of from about 3 to about 6 when the average R ⁇ is C ⁇ ⁇ , C12, Cl3 or Cj
- Preferred water- soluble anionic alkyl ethoxy carboxylate surfactants suitable for use herein are the C12 to C14 (average EO 3-6) ethoxy carboxylates and the C12 to C13 (average EO 3-6) ethoxy carboxylates.
- Suitable materials include salts of NEODOX 23-4 (RTM) available from Shell Inc. (Houston, Texas, USA) and EMPICOL (RTM) CBCS (Albright & Wilson).
- alkyl ethoxy carboxylate surfactants wherein, when R- is a C12-C14 or C12-C13 alkyl group and the average value of k is in the range of from about 3 to about 6, more preferably from about 3.5 to about 5.5, especially from about 4 to about 5 and most preferably from about 4 to about 4.5.
- compositions are substantially free of soap, i.e. they contain less than about 5%», preferably less than about 1%>, preferably 0%, by weight, of soap.
- compositions according to the present invention may additionally comprise water-soluble nonionic surfactant at levels from about 0.1%) to about 20%), more preferably from about 0.1%) to about 10%>, and especially from about 1% to about 8%> by weight.
- surfactants of this class include sucrose polyester surfactants, Cjo-Cl8 alkyl polyglycosides and polyhydroxy fatty acid amide surfactants having the general formula (III).
- the preferred N-alkyl, N-alkoxy or N-aryloxy, polyhydroxy fatty acid amide surfactants according to formula (III) are those in which Rg is C5- C31 hydrocarbyl, preferably C ⁇ -Cio, hydrocarbyl, including straight-chain and branched chain alkyl and alkenyl, or mixtures thereof and R9 is typically, hydrogen, Ci-Cs alkyl or hydroxyalkyl, preferably methyl, or a group of formula -Rl-O-R 2 wherein Rl is C2-C8 hydrocarbyl including straight-chain, branched-chain and cyclic (including aryl), and is preferably C2-C4 alkylene, R 2 is Ci-Cs straight-chain, branched-chain and cyclic hydrocarbyl including aryl and oxyhydrocarbyl, and is preferably C1-C4 alkyl, especially methyl, or phenyl.
- Z2 is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
- Z2 preferably will be derived from a reducing sugar in a reductive ammination reaction, most preferably Z2 is a glycityl moiety.
- Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
- Z2 preferably will be selected from the group consisting of CH2-(CHOH) n -CH2 ⁇ H, CH(CH2 ⁇ H)-(CHOH) n _ 1 -CH2OH,
- n is an integer from 1 to 5, inclusive, and R is H or a cyclic mono- or poly-saccharide, and alkoxylated derivatives thereof.
- R is H or a cyclic mono- or poly-saccharide, and alkoxylated derivatives thereof.
- glycityls wherein n is 4, particularly CH2-(CHOH)4-CH2 ⁇ H.
- the most preferred polyhydroxy fatty acid amide has the formula R 8 (CO)N(CH )CH2(CHOH)4CH 2 OH wherein Rg is a C6-C19 straight chain alkyl or alkenyl group.
- Rg-CO- N ⁇ can be, for example, cocoamide, stearamide, oleamide, lauramide, myristamide, capricamide, caprylicamide, palmitamide, tallowamide, etc.
- non-ionic surfactants suitable for use in the compositions according to the present invention include primary amines such as cocamine (available as Adagen 160D (TM) from Witco) and alkanolamides such as cocamide MEA (available as Empilan CME (TM) from Albright and Wilson), PEG-3 cocamide, cocamide DEA (available as Empilan CDE (TM) from Albright and Wilson), lauramide MEA (available as Empilan LME (TM) from Albright and Wilson), lauramide MIPA, lauramide DEA, and mixtures thereof.
- cocamine available as Adagen 160D (TM) from Witco
- alkanolamides such as cocamide MEA (available as Empilan CME (TM) from Albright and Wilson), PEG-3 cocamide, cocamide DEA (available as Empilan CDE (TM) from Albright and Wilson), lauramide MEA (available as Empilan LME (TM) from Albright and Wilson), lauramide MIPA, laur
- Suitable amphoteric surfactants for use herein include (a) ammonium derivatives of formula [V] :
- R ⁇ is C5-C22 alkyl or alkenyl
- R2 is CH2CH2OH or CH2CO2M
- M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium and R3 is CH2CH2OH or H;
- n, m, p, and q are numbers from 1 to 4, and R ⁇ and M are independently selected from the groups specified above;
- Suitable amphoteric surfactants of type (a) include compounds of formula (V) in which Rj is CgHj ⁇ (especially isocapryl), C9H19 and C11H23 alkyl.
- Suitable amphoteric surfactants of type (a) are marketed under the trade name Miranol and Empigen.
- materials suitable for use in the present invention include cocoamphocarboxypropionate, cocoamphocarboxy propionic acid, cocoamphoacetate, cocoamphodiacetate (otherwise referred to as cocoamphocarboxyglycinate), sodium lauroamphoacetate (otherwise referred to as sodium lauroamphocarboxyglycinate).
- Specific commercial products include those sold under the trade names of Ampholak 7TX (sodium carboxy methyl tallow polypropyl amine), Empigen CDL60 and CDR 60 (Albright & Wilson), Miranol H2M Cone. Miranol C2M Cone. N.P., Miranol C2M Cone.
- Miranol C2M SF Miranol CM Special, Miranol Ultra L32 and C32 (Rh ⁇ ne-Poulenc); Alkateric 2CIB (Alkaril Chemicals); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Monateric CSH-32 (Mona Industries); Rewoteric AM-2C (Rewo Chemical Group); and Schercotic MS-2 (Scher Chemicals).
- amphoteric surfactants of this type are manufactured and sold in the form of electroneutral complexes with, for example, hydroxide counterions or with anionic sulfate or sulfonate surfactants, especially those of the sulfated Cg- Cig alcohol, Cg-Ci ethoxylated alcohol or Cg-Cig acyl glyceride types.
- anionic sulfate or sulfonate surfactants especially those of the sulfated Cg- Cig alcohol, Cg-Ci ethoxylated alcohol or Cg-Cig acyl glyceride types.
- compositions which are essentially free of (non-ethoxylated) sulfated alcohol surfactants are based herein on the uncomplexed forms of the surfactants, any anionic surfactant counterions being considered as part of the overall anionic surfactant component content.
- amphoteric surfactants of type (b) include N-alkyl polytrimethylene poly-, carboxymethylamines sold under the trade names Ampholak X07 and Ampholak 7CX by Berol Nobel and also salts, especially the triethanolammonium salts and salts of N-lauryl-beta-amino propionic acid and N-lauryl-imino-dipropionic acid.
- Such materials are sold under the trade name Deriphat by Henkel and Mirataine by Rh ⁇ ne- Poulenc.
- compositions herein can also contain from about 0.1 %> to about 20%), more preferably from about 0.1% to about 10%), and especially from about 1% to about 8%> by weight of a zwitterionic surfactant.
- Water-soluble betaine surfactants suitable for inclusion in the compositions of the present invention include alkyl betaines of the formula R5R6R ⁇ N + (CH2)nC ⁇ 2M and amido betaines of the formula (IX)
- R ⁇ is C5-C22 alkyl or alkenyl
- R and R7 are independently C ⁇ - C3 alkyl
- M is H
- n, m are each numbers from 1 to 4.
- Preferred betaines include cocoamidopropyldimethylcarboxymethyl betaine, commercially available from TH Goldschmidt under the tradename Tego betaine, and laurylamidopropyldimethylcarboxymethyl betaine, commercially available from Albright and Wilson under the tradename Empigen BR and from TH Goldschmidt under the tradename Tegobetaine L10S.
- Water-soluble sultaine surfactants suitable for inclusion in the compositions of the present invention include alkylamido sultaines of the formula;
- R ⁇ is C7 to C22 alkyl or alkenyl
- R2 and R3 are independently Ci to C3 alkyl
- M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium
- m and n are numbers from 1 to 4.
- Suitable for use herein is coco amido propylhydroxy sultaine which is commercially available under the tradename Mirataine CBS from Rhone-Poulenc.
- Water-soluble amine oxide surfactants suitable for inclusion in the compositions of the present invention include alkyl amine oxide R5R6R7NO and amido amine oxides of the formula
- R5 is C ⁇ to C22 alkyl or alkenyl
- R and R7 are independently C ⁇ to C3 alkyl
- M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium
- m is a number from 1 to 4.
- Preferred amine oxides include cocoamidopropylamine oxide, lauryl dimethyl amine oxide and myristyl dimethyl amine oxide.
- compositions according to the present invention can optionally include a polymeric cationic conditioning agent.
- Polymeric cationic conditioning agents are valuable in the compositions according to the present invention for provision of desirable skin feel attributes.
- the polymeric skin conditioning agent is preferably present at a level from about 0.01%> to about 5%>, preferably from about 0.01%) to about 3%> and especially from about 0.01%) to about 2% by weight.
- Suitable polymers are high molecular weight materials (mass-average molecular weight determined, for instance, by light scattering, being generally from about 2,000 to about 5,000,000, preferably from about 5,000 to about 3,000,000 more preferably from 100,000 to about 1,000,000).
- polymers include cationic guar gums, cationic polysaccharides; cationic homopolymers and copolymers derived from acrylic and/or methacrylic acid; cationic cellulose resins, quatemized hydroxy ethyl cellulose ethers; cationic copolymers of dimethyldiallylammonium chloride and acrylamide and/or acrylic acid; cationic homopolymers of dimethyldiallylammonium chloride; copolymers of dimethyl aminoethylmethacrylate and acrylamide, acrylic acid/dimethyldiallylammonium chloride/acrylamide copolymers, quatemised vinyl pyrrolidone acrylate or methacrylate copolymers of amino alcohol, quatemized copolymers of vinyl pyrrolidone and dimethylaminoethylmethacrylamide, vinyl pyrollidone/vinyl imidazolium methochloride copolymers and polyalkylene and ethoxy
- cationic polymers suitable for use herein include cationic guar gums such as hydroxypropyl trimethyl ammonium guar gum (d.s. of from 0.11 to 0.22) available commercially under the trade names Jaguar C-14-S(RTM) and Jaguar C-17(RTM) and also Jaguar C- 16(RTM), which contains hydroxypropyl substituents (d.s. of from 0.8-1.1) in addition to the above-specified cationic groups, and quatemized hydroxy ethyl cellulose ethers available commercially under the trade names Ucare Polymer JR-30M, JR-400, LR400, Catanal (RTM) and Celquat.
- cationic guar gums such as hydroxypropyl trimethyl ammonium guar gum (d.s. of from 0.11 to 0.22) available commercially under the trade names Jaguar C-14-S(RTM) and Jaguar C-17(RTM) and also Jaguar C- 16(RTM), which contains hydroxypropyl substituents
- Suitable cationic polymers are homopolymers of dimethyldiallylammonium chloride available commercially under the trade name Merquat 100, copolymers of dimethyl aminoethylmethacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, available commercially under the trade names Merquat 550 and Merquat S, acrylic acid/dimethyldiallylammonium chloride/acrylamide copolymers available under the trade name Merquat 3330, terpolymers of acrylic acid, methacrylamidopropyl trimethyl ammonium chloride and methyl acrylate commercially available under the tradename Merquat 2001, quatemized vinyl pyrrolidone acrylate or methacrylate copolymers of amino alcohol available commercially under the trade name Gafquat, for example Polyquatemium 11, 23 and 28 (quatemized copolymers of vinyl pyrrolidone and dimethyl aminoethylmethacrylate - Gafquat 755N
- compositions of the invention may also contain from about 0.1%) to about 20%), preferably from about 1% to about 15%, and more preferably from about 2%> to about 10% by weight of an oil derived nonionic surfactant or mixture of oil derived nonionic surfactants.
- Oil derived nonionic surfactants are valuable in compositions according to the invention for the provision of skin feel benefits both in use and after use.
- Suitable oil derived nonionic surfactants for use herein include water soluble vegetable and animal-derived emollients such as triglycerides with a polyethyleneglycol chain inserted; ethoxylated mono and di-glycerides, polyethoxylated lanolins and ethoxylated butter derivatives.
- One preferred class of oil-derived nonionic surfactants for use herein have the general formula (XII)
- n is from about 5 to about 200, preferably from about 20 to about 100, more preferably from about 30 to about 85, and wherein R comprises an aliphatic radical having on average from about 5 to 20 carbon atoms, preferably from about 7 to 18 carbon atoms.
- Suitable ethoxylated oils and fats of this class include polyethyleneglycol derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl tallowate, glyceryl palmate, glyceryl stearate, glyceryl laurate, glyceryl oleate, glyceryl ricinoleate, and glyceryl fatty esters derived from triglycerides, such as palm oil, almond oil, and com oil, preferably glyceryl tallowate and glyceryl cocoate.
- Suitable oil derived nonionic surfactants of this class are available from Croda Inc. (New York, USA) under their Crovol line of materials such as Crovol EP40 (PEG 20 evening primrose glyceride), Crovol EP 70 (PEG 60 evening primrose glyceride) Crovol A-40 (PEG 20 almond glyceride), Crovol A-70 (PEG 60 almond glyceride), Crovol M-40 (PEG 20 maize glyceride), Crovol M-70 (PEG 60 maize glyceride), Crovol PK-40 (PEG 12 palm kernel glyceride), and Crovol PK-70 (PEG 45 palm kernel glyceride) and under their Solan range of materials such as Solan E, E50 and X polyethoxylated lanolins and Aqualose L-20 (PEG 24 lanolin alcohol) and Aqualose W15 (PEG 15 lanolin alcohol) available from Westbrook Lanolin.
- Crovol EP40 PEG 20 evening primrose glyceride
- nonionic surfactants derived from composite vegetable fats extracted from the fruit of the Shea Tree (Butyrospermum Karkii Kotschy) and derivatives thereof.
- This vegetable fat known as Shea Butter is widely used in Central Africa for a variety of means such as soap making and as a barrier cream, it is marketed by Sederma (78610 Le Perray En Yvelines, France).
- Particularly suitable are ethoxylated derivatives of Shea butter available from Karlshamn Chemical Co. (Columbos, Ohio, USA) under their Lipex range of chemicals, such as Lipex 102 E-75 and Lipex 102 E-3 (ethoxylated mono, di-glycerides of Shea butter) and from Croda Inc.
- Crovol SB-70 ethoxylated mono, di-glycerides of Shea butter
- ethoxylated derivatives of Mango, Cocoa and Illipe butter may be used in compositions according to the invention. Although these are classified as ethoxylated nonionic surfactants it is understood that a certain proportion may remain as non-ethoxylated vegetable oil or fat.
- suitable oil-derived nonionic surfactants include ethoxylated derivatives of almond oil, peanut oil, rice bran oil, wheat germ oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, com oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grapeseed oil, and sunflower seed oil.
- Oil derived nonionic surfactants highly preferred for use herein from the viewpoint of optimum mildness and skin feel characteristics are Lipex 102- 3 (RTM) (PEG-3 ethoxylated derivatives of Shea Butter) and Softigen 767 (RTM) (PEG-6 caprylic/capric glycerides).
- the compositions according to the present invention can also comprise lipophilic emulsif ⁇ ers as skin care actives.
- Suitable lipophilic skin care actives include anionic food grade emulsifiers which comprise a di-acid mixed with a monoglyceride such as succinylated monoglycerides, monostearyl citrate, glyceryl monostearate diacetyl tartrate and mixtures thereof.
- compositions herein Another essential ingredient of the compositions herein is a crystalline, hydroxy-containing stabilizer.
- the crystalline, hydroxy-containing stabilizer is present in the compositions herein at a level of from about 0.5%) to about 10%), preferably from about 0.75%) to about 8%>, more preferably from about 1.25%) to about 5%> by weight.
- Suitable crystalline, hydroxy-containing stabilizer materials for use herein are hydroxy-containing fatty acids, fatty esters, fatty soap water-insoluble wax-like substances.
- Suitable crystalline, hydroxy-containing stabilizer materials for use herein are selected from:
- R2 is Rl or H
- R3 is Rl or H
- R4 is CO-20 alkyl
- R5 is C0-C20 alkyl
- R6 is C0-C20 alkyl
- R4+R5+R6 C 10-22 and wherein 1 ⁇ x+y ⁇ 4
- R7 is -R4(COH)xR5(COH)yR6, M is Na + , K + , or Mg , or H,
- hydroxy-containing stabilizers for use herein include 12-hydroxystearic acid, 9,10-dihydroxystearic acid, tri-9,10- dihydroxystearin and tri-12-hydroxystearin. Particularly preferred for use herein from the viewpoint of improving stability and rheology in combination with the polyalphaolefm oils is tri-12-hydroxy stearin.
- compositions herein can additionally comprise a wide variety of optional ingredients.
- optional ingredients are described below.
- water-insoluble polyalphaolefm oils in addition to the water-insoluble polyalphaolefm oils described above other water-insoluble oils can be used in the compositions of the present invetion.
- Additional water-insoluble oils for use in the personal cleansing compositions of the present invention those of type (b) which are branched alk(en)yl materials having the following formula:
- Rl is H or C1-C4 alkyl
- R 4 is C1-C4 alkyl
- R 2 is H or -C4 alkyl or C2-C4 alkenyl
- R3 is H or C1-C4 alkyl or C2-C4 alkenyl
- n is an integer from 0 to 3
- m is an integer of from 1 to 1000 and having a number average molecular weight of from about 600 to about 1000, preferably from about 750 to about 1000, especially from about 800 to about 1000.
- the branched alk(en)yl materials of type have a viscosity in the range of from about 500cst to about 50,000cst, preferably from about lOOOcst to about 10,000cst measured at 40°C using the ASTM method D-445 for measuring viscosity.
- Suitable alk(en)yl materials of type (b) for use herein are polymers of butene, isoprene, terpene, styrene or isobutene, preferably butene or isobutene.
- alk(en)yl oils of type (b) examples include polybutene oils such as those commercially available from Amoco under the tradename Indopol 40 and Indopol 100 and polyisobutene oils such as those commercially available from Presperse Inc. under the tradename Permethyl 104A and Parapol 950 from Exxon Chemicals Co..
- hydrophobically modified silicones having the following formula: hydrophobically modified silicones having the following formula:
- R is C1-C4 alkyl or phenyl
- R' is C1-C20 alkyl or phenyl
- z is 5 to 21
- x has a number average value in the range of from about 20 to 400
- y has a number average value in the range of from about 0 to about 10
- x + y lies in the range of 30 to 400.
- Preferred materials have values for x of from 40 to 200, preferably 60 to 100, values for y of from 0 to 5, preferably 0, and values for the sum of x and y of from 60 to 100.
- the alkylene chain z may be linear or branched.
- the silicone backbone may contain a small degree of branching to yield a resin (eg. MDQ or MDT resins).
- oils examples include those hydrophobically modified silicones available from GE Silicones under the tradename SF1632 (C16-C18 alkyl methicone), and octyl and decyl methicone.
- the number average particle diameter for the additional water-insoluble oil used herein lies in the range of from about 1 micron to about 500 microns, preferably from about 5 to about 200 microns, more preferably from about 5 to 50 microns, especially from about 5 to about 20 microns.
- compositions can also comprise an auxiliary nonionic or anionic polymeric thickening component, especially a water-soluble polymeric materials, having a molecular weight greater than about 20,000.
- auxiliary nonionic or anionic polymeric thickening component especially a water-soluble polymeric materials, having a molecular weight greater than about 20,000.
- water-soluble polymer is meant that the material will form a substantially clear solution in water at a 1%> concentration at 25 °C and the material will increase the viscosity of the water.
- water-soluble polymers which may desirably be used as an additional thickening component in the present compositions, are hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol (examples include PVA 217 from Kurary Chemical Co., Japan), polyvinyl pyrrolidone K-120, dextrans, for example Dextran purified crude Grade 2P, available from D&O Chemicals, carboxymethyl cellulose, plant exudates such as acacia, ghatti, and tragacanth, seaweed extracts such as sodium alginate, propylene glycol alginate and sodium carrageenan.
- Preferred as the additional thickeners for the present compositions are natural polysaccharide materials.
- examples of such materials are guar gum, locust bean gum, and xanthan gum.
- hydroxyethyl cellulose having a molecular weight of about 700,000.
- compositions according to the present invention may contain as an optional feature a hydrotrope.
- Suitable for use herein as hydrotropes are those well known in the art, including sodium xylene sulphonate, ammonium xylene sulphonate, sodium cumene sulphonate, short chain alkyl sulphate and mixtures thereof.
- Hydrotrope may be present in the compositions according to the invention at a level of from about 0.01%) to about 5%>, preferably from about 0.1%> to about 4%>, more preferably from about 0.5%) to about 3%> by weight.
- Hydrotrope, as defined herein means, a material which, when added to a non-dilute, water-soluble surfactant system can modify its viscosity and rheological profile.
- compositions of the invention may also include an insoluble perfume or cosmetic oil or wax or a mixture thereof at a level up to about 10%), preferably up to about 3%> by weight wherein the oil or wax is insoluble in the sense of being insoluble in the product matrix at a temperature of 25°C.
- Suitable insoluble cosmetic oils and waxes for use herein can be selected from water-insoluble silicones inclusive of non-volatile polyalkyl and polyaryl siloxane gums and fluids, volatile cyclic polydimethylsiloxanes, polyalkoxylated silicones, amino and quaternary ammonium modified silicones, rigid cross-linked and reinforced silicones and mixtures thereof, C1-C24 esters of C -C30 fatty acids such as isopropyl myristate, myristyl myristate and cetyl ricinoleate, Cg-C30 esters of benzoic acid, beeswax, saturated and unsaturated fatty alcohols such as behenyl alcohol, hydrocarbons such as mineral oils, petrolatum, squalane and squalene, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26th 1976), lanolin and oil-like lanolin derivatives, animal and vegetable trigly
- the viscosity of the final composition is preferably at least about 500 cps, more preferably from about 1,000 to about 50,000 cps, especially from about 1,000 to about 30,000 cps, more especially from about 1,000 to about 15,000 cps.
- the cleansing compositions can optionally include other hair or skin moisturizers which are soluble in the cleansing composition matrix.
- the preferred level of such moisturizers is from about 0.5%> to about 20%) by weight.
- the moisturizer is selected from essential amino acid compounds found naturally occurring in the stratum corneum of the skin and water-soluble nonpolyol nonocclusives and mixtures thereof.
- nonocclusive moisturizers are squalane, sodium pyrrolidone carboxylic acid, D-panthenol, lactic acid, L-proline, guanidine, pyrrolidone, hydrolyzed protein and other collagen-derived proteins, aloe vera gel, acetamide MEA and lactamide MEA and mixtures thereof.
- compositions herein may also include one or more suspending agents in addition to the crystalline, hydroxy-containing stabilizer.
- Suitable suspending agents for use herein include any of several long chain acyl derivative materials or mixtures of such materials. Included are ethylene glycol esters of fatty acids having from about 16 to about 22 carbon atoms. Preferred are the ethylene glycol stearates, both mono and distearate, but particularly the distearate containing less than about 7%> of the mono stearate.
- Other suspending agents found useful are alkanol amides of fatty acids, having from about 16 to 22 carbon atoms, preferably from about 16 to 18 carbon atoms. Preferred alkanol amides are stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate.
- compositions according to the present invention may also include an opacifier or pearlescing agent. Such materials may be included at a level of from about 0.01%> to about 5%, preferably from about 0.2%> to about 1.3% by weight.
- Opacifiers/pearlescers suitable for inclusion in the compositions of the present invention include: titanium dioxide, Ti ⁇ 2- EUPERLAN 810 (RTM); TEGO-PEARL (RTM); long chain (Ci6 - C22) acyl derivatives such as glycol or polyethylene glycol esters of fatty acid having from about 16 to about 22 carbon atoms and up to 7 ethyleneoxy units; alkanolamides of fatty acids, having from about 16 to about 22 carbon atoms, preferably about 16 to 18 carbon atoms such as stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide and alkyl (C ⁇ 6 - C22) dimethyl amine oxides such as stearyl dimethyl amine oxide.
- RTM Ti ⁇ 2- EUPERLAN 810
- RTM TEGO-PEARL
- long chain (Ci6 - C22) acyl derivatives such as glycol or polyethylene glycol esters
- the opacifier/pearlescer is present in the form of crystals.
- the opacifier/pearlescer is a particulate polystyrene dispersion having a particle size of from about 0.05 microns to about 0.45 microns, preferably from about 0.17 microns to about 0.3 microns, such dispersions being preferred from the viewpoint of providing optimum rheology and shear-thinning behaviour.
- Highly preferred is styrene acrylate copolymer and OPACFIER 680 (RTM) commercially available from Morton International.
- a number of additional optional materials can be added to the cleansing compositions each at a level of from about 0.1% to about 2%> by weight.
- Such materials include proteins and polypeptides and derivatives thereof; water-soluble or solubilizable preservatives such as DMDM Hydantoin, Germall 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, EDTA, Euxyl (RTM) K400, natural preservatives such as benzyl alcohol, potassium sorbate and bisabalol; sodium benzoate and 2-phenoxyethanol; other moisturizing agents such as hyaluronic acid, chitin , and starch- grafted sodium polyacrylates such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent Materials, Portsmith, VA, USA and described in US-A-4,076,663; solvents ; suitable anti- bacterial agents such as Oxeco (phen
- viscosity control agents such as magnesium sulfate and other electrolytes; colouring agents; Ti ⁇ 2 and Ti ⁇ 2-coated mica; perfumes and perfume solubilizers; and zeolites such as Valfour BV400 and derivatives thereof and Ca 2+ /Mg 2+ sequestrants such as polycarboxylates, amino polycarboxylates, polyphosphonates, amino polyphosphonates, EDTA etc, water softening agents such as sodium citrate and insoluble particulates such as zinc stearate and fumed silica. Water is also present at a level preferably of from about 20% to about 99.89%, preferably from about 40%> to about 90%>, more preferably at least about 75% by weight of the compositions herein.
- the pH of the compositions is preferably from about 3 to about 10, more preferably from about 5 to about 9, especially from about 5 to about 8 and most preferably from about 5 to 7.
- compositions of the present invention can be used for a variety of skin and hair care applications such as shower gels, body washes, hair shampoos, and the like.
- compositions of the present invention may be applied with the hand or preferably with a personal cleansing implement such as a puff.
- Suitable personal cleansing implements for use with the compositions of the present invention include those disclosed in the following patent documents which are incorporated herein by reference: US-A-5, 144,744 to Campagnoli, issued September 8,1992, US-A-3,343,196 to Barnhouse, W095/26671 to The Procter & Gamble Company, WO95/00116 to The Procter & Gamble Company and WO95/26670 to The Procter & Gamble Company.
- compositions according to the present invention are illustrated bythe following non-limiting examples.
- Compositions can be prepared by firstly making a premix of surfactants and a suspending agent. This is done by combining the surfactants, portion of the water, powder preservatives and the pH adjuster with mild agitation. This mixture is then heated up to about 90°C during which time, fatty alcohol/fatty acid and the Thixcin R are added with agitation.
- the mixture is held at high temperatures for five minutes to one hour before being cooled at a controlled rate to approximately 30-40°C via a heat exchanger causing the suspending agent to crystallize out.
- the products provide excellent rinse feel and mildness benefits together with excellent rheological attributes in storage, in dispensing and in-use, in combination with good efficacy benefits including skin conditioning, skin moisturising, good product stability, cleansing and lathering.
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Dermatology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Fats And Perfumes (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9722013.1A GB9722013D0 (en) | 1997-10-17 | 1997-10-17 | Cleansing compositions |
GB9722013 | 1997-10-17 | ||
PCT/US1998/021138 WO1999020243A2 (en) | 1997-10-17 | 1998-10-07 | Cleansing compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1023043A2 true EP1023043A2 (en) | 2000-08-02 |
Family
ID=10820722
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98953292A Withdrawn EP1023043A2 (en) | 1997-10-17 | 1998-10-07 | Cleansing compositions |
Country Status (12)
Country | Link |
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EP (1) | EP1023043A2 (zh) |
JP (1) | JP2001520182A (zh) |
KR (1) | KR20010024529A (zh) |
CN (1) | CN1278719A (zh) |
AR (1) | AR012526A1 (zh) |
AU (1) | AU1070299A (zh) |
BR (1) | BR9815224A (zh) |
CA (1) | CA2306402A1 (zh) |
CO (1) | CO4980894A1 (zh) |
GB (1) | GB9722013D0 (zh) |
WO (1) | WO1999020243A2 (zh) |
ZA (1) | ZA989321B (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19937813B4 (de) * | 1999-08-11 | 2006-04-13 | Kao Corp. | Wässriges Haarwaschmittel |
MXPA03003739A (es) † | 2000-10-27 | 2003-07-28 | Procter & Gamble | Composiciones liquidas estabilizadas. |
GB0027978D0 (en) | 2000-11-16 | 2001-01-03 | Ciba Sc Holding Ag | High solids solution of a cationic copolymer |
KR20050079711A (ko) * | 2004-02-06 | 2005-08-11 | 주식회사 태평양 | 불용성 입자를 안정하게 부유시킬 수 있는 전신 인체세정제 조성물 |
KR100834808B1 (ko) | 2006-11-02 | 2008-06-10 | (주)인비티 | 클렌징 조성물 |
KR101417030B1 (ko) * | 2007-11-30 | 2014-07-08 | (주)아모레퍼시픽 | 천연 식물성 오일이 안정하게 분산된 모발 화장료 조성물 |
EP2960322B1 (en) * | 2014-06-25 | 2021-01-13 | The Procter and Gamble Company | Structuring premixes comprising non-polymeric, crystalline, hydroxyl-containing structuring agents and a linear alkyl sulphate, and compositions comprising them |
CN116035952B (zh) * | 2022-12-12 | 2024-10-15 | 武汉芘芘薇莎生物科技有限公司 | 一种婴儿护臀膏及其制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5160739A (en) * | 1991-09-12 | 1992-11-03 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Cosmetic composition |
GB2297975B (en) * | 1995-01-14 | 1998-08-05 | Procter & Gamble | Cleansing compositions |
DE69615346T2 (de) * | 1995-02-15 | 2002-09-19 | Procter & Gamble | Kristalline hydroxywachse als öl-in-wasser stabilisatoren für flüssige hautreinigungszusammensetzungen |
BR9708281A (pt) * | 1996-03-27 | 1999-08-03 | Procter & Gamble | Condicionamento que contém condicionador de polialfaolefinas |
-
1997
- 1997-10-17 GB GBGB9722013.1A patent/GB9722013D0/en not_active Ceased
-
1998
- 1998-10-07 AU AU10702/99A patent/AU1070299A/en not_active Abandoned
- 1998-10-07 WO PCT/US1998/021138 patent/WO1999020243A2/en not_active Application Discontinuation
- 1998-10-07 BR BR9815224-6A patent/BR9815224A/pt not_active IP Right Cessation
- 1998-10-07 JP JP2000516646A patent/JP2001520182A/ja active Pending
- 1998-10-07 CA CA002306402A patent/CA2306402A1/en not_active Abandoned
- 1998-10-07 KR KR1020007004120A patent/KR20010024529A/ko not_active Application Discontinuation
- 1998-10-07 EP EP98953292A patent/EP1023043A2/en not_active Withdrawn
- 1998-10-07 CN CN98811035A patent/CN1278719A/zh active Pending
- 1998-10-13 ZA ZA989321A patent/ZA989321B/xx unknown
- 1998-10-16 CO CO98060363A patent/CO4980894A1/es unknown
- 1998-10-19 AR ARP980105195A patent/AR012526A1/es not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO9920243A3 * |
Also Published As
Publication number | Publication date |
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WO1999020243A3 (en) | 1999-07-01 |
CA2306402A1 (en) | 1999-04-29 |
ZA989321B (en) | 1999-04-20 |
WO1999020243A2 (en) | 1999-04-29 |
CO4980894A1 (es) | 2000-11-27 |
CN1278719A (zh) | 2001-01-03 |
GB9722013D0 (en) | 1997-12-17 |
KR20010024529A (ko) | 2001-03-26 |
JP2001520182A (ja) | 2001-10-30 |
AR012526A1 (es) | 2000-10-18 |
AU1070299A (en) | 1999-05-10 |
BR9815224A (pt) | 2000-10-17 |
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