EP0521893A4 - Foaming personal cleansing product with foam enhancing polymer. - Google Patents

Foaming personal cleansing product with foam enhancing polymer.

Info

Publication number
EP0521893A4
EP0521893A4 EP19910905607 EP91905607A EP0521893A4 EP 0521893 A4 EP0521893 A4 EP 0521893A4 EP 19910905607 EP19910905607 EP 19910905607 EP 91905607 A EP91905607 A EP 91905607A EP 0521893 A4 EP0521893 A4 EP 0521893A4
Authority
EP
European Patent Office
Prior art keywords
alkyl
acyl
personal cleansing
foam
polymer
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.)
Ceased
Application number
EP19910905607
Other languages
German (de)
French (fr)
Other versions
EP0521893A1 (en
Inventor
Scott William Syfert
Mary Louise Batt
Lawrence Harry Sanford
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0521893A4 publication Critical patent/EP0521893A4/en
Publication of EP0521893A1 publication Critical patent/EP0521893A1/en
Ceased legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/55Phosphorus compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/731Cellulose; Quaternized cellulose derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/737Galactomannans, e.g. guar; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular 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

  • This invention pertains to personal cleansing compositions for personal washing, especially of the face.
  • Liquid and solid bar compositions based on soap and/or synthetic surfactants are commonly used for cleansing the human body. To achieve adequate lather when diluted with water, these require a higher level of surfactant than is necessary for clean ⁇ ing. This excess surfactant can be irritating to the skin and is put into the environment unnecessarily.
  • foams for cleaning skin has usually been reserved for specialty products that are used without rinsing. See, e.g., U.S. Pat. No. 3,962,150, Viola, issued June 8, 1976, incorporated herein by reference. There has been little or no recognition of the mild ⁇ ness and environmental advantages that can be derived from the use of such products for general cleansing.
  • the level of surfactant actually required to provide good cleaning of the skin is quite low and the majority of the detergent surfactant in the usual toilet bar is wasted, either in the smear, that is left on the bar holder, or in detergent surfactant that is not fully dissolved and is therefore rinsed away without providing any benefit.
  • a mechanical foaming device When a mechanical foaming device is used, lower levels of surfactant can be used to achieve adequate lather. However, as the surfactant level is minimized, lather quality is also reduced and the foam quality can be of a poorer quality than that of better toilet bars.
  • the present invention relates to liquid personal cleansing products (compositions) containing low levels, e.g., from about 0.1% to about 16% of detergent surfactants, preferably mild detergent surfactants, and low level of foam enhancing polymer in an aqueous solvent system, said compositions being packaged in a container that can be manipulated by an individual to produce a foam (squeeze foamer container).
  • the compositions of this inven ⁇ tion preferably have a very low content of detergent surfactant to minimize adverse effects both to the skin and to the environment.
  • the quality of the foam can be enhanced, surprisingly, without adversely affecting the ability to dispense the product, by raising the viscosity by the addition of a small amount of a polymer. It is very surprising that foam quality and viscosity are so intimately related. Only very small differences of vis ⁇ cosity are required to make substantial differences in the foam quality. DETAILED DESCRIPTION OF THE INVENTION
  • the present invention comprises a personal cleansing composition in the form of an aqueous liquid comprising: (1) from about 0.1% to about 16%, preferably from about 1% to about 8%, more preferably from about 2% to about 6% of detergent surfactant, preferably mild detergent surfactant; and (2) from about 0.01% to about 5%, preferably from about 0.04% to about 2% of foam enhancing polymer.
  • the "delta viscosity" is the difference between the viscosity of a composition with and without the viscosity enhancing poly- mers.
  • the foam enhancing polymer accounts for a rise in the viscosity of the composition (without he polymer) of at least about 1 centipoise, preferably by from about 2 to about 10 centi- poise, more preferably by from about 2 to about 5 centipoise.
  • the increase in viscosity increases the composition's Foam Creamy Feel Rating as described in more detail hereinafter, so that said Foam Creamy Feel Rating is raised by at least about 0.5, preferably by at least about 1, more preferably by at least about 2.
  • the compositions's Foam Creamy Feel Rating without the polymer is at least 0.5 lower than the composition with the polymer.
  • the composition of this invention preferably has a viscosity of at least about 1.5, preferably from about 2 to about 15, more preferably from about 2 to about 12, and even more preferably from about 3 to about 10 centipoise at 21 * C when measured using a Brookfield LVT Viscometer with a UL adapter.
  • the lower viscosity limit is set by the quality of the foam and that varies with the surfactant system.
  • the upper viscosity limit is as high as can be tolerated as long as the product can be easily dispensed; thus viscosities of 20, 30, and even 40 cps are in ⁇ cluded within the scope of this invention.
  • the more preferred composition is made from a formulation which has a viscosity in the range of from about 1 to about 5 cps without the polymer.
  • the compositions of the present invention preferably have a Foam Creamy Feel Rating, as defined hereinafter, of at least about 5, preferably around or about 6. Foam Creamy Feel Ratings of about 7 and above are also desirable for some products.
  • Squeeze foam compositions without polymer can be formulated using higher levels of surfactant, 10-25%, preferably 15-20%, and achieve Foam Creamy Feel Ratings of 6, 7 or 8.
  • compositions of the present invention are extremely mild.
  • the use of less detergent surfactant makes any detergent surfactant milder and the use of a squeeze foamer package makes the resultant foam more acceptable to the consumer without the need to use more aggressive detergent surfactants for increased foam.
  • the invention uses less organic material and by using less material and no propellant, simplifies the use of concentrates by the eventual consumer to form the composition. This minimizes the need to continually sell the squeeze foam dispenser.
  • compositions of this invention comprise from about 60% to about 99% water, preferably at least about 75%, water, and a minor amount of other suitable solvents. Higher levels of water and lower levels of organic materials are desirable to minimize environmental concern.
  • the surfactant component of the present compositions com ⁇ prises water-soluble, e.g., alkali metal, ammonium, or substituted ammonium synthetic, or soap, detergent surfactant or mixtures thereof.
  • the compositions of this invention preferably contain up to about 15%, preferably from about 1% to about 8%, of synthetic detergent surfactant, preferably mild synthetic detergent surfac ⁇ tant.
  • the synthetic detergent surfactant is mild, as disclosed in commonly assigned U.S. Pat. No. 4,673,525, Small et al., issued June 16, 1987, incorporated herein by reference.
  • a mild synthetic detergent surfactant is defined therein, and herein, as one which does relatively little damage to the barrier function of the stratum corneum.
  • Synthetic detergents are the preferred detergent surfactants in the compositions herein.
  • Preferred types of synthetic deter ⁇ gent surfactants are of the anionic, a photeric, or zwitterionic types.
  • the detergent surfactants are those known to be mild to the skin. Many mild surfactants are low foaming. The present invention offers an advantage for such low foaming surfactants.
  • compositions herein contain a mixture of two amphoteric surfactants, a first amphoteric surfactant being selected from imidazolinium surfactants of Formula I:
  • R* is C8-C22 alkyl or alkenyl
  • R2 is hydrogen or CH2 CH 2M» Z s CO2M or CH2CO2M and M is H, alkali metal, ammonium or alkanolammonium
  • a second amphoteric surfactant being selected from amino- alkanoates of Formula II:
  • n and m are numbers from 1 to 4, and each Rl and M are independently selected from the groups specified i n ( I) above.
  • compositions comprise a premix or complex of the first amphoteric surfactant and anionic surfactant in an equivalent ratio of about 1.1 in order to provide approximate electroneutrality.
  • Some preferred mild synthetic detergent surfactants useful in this invention include alkyl glyceryl ether sulfonate (AGS); anionic acyl sarcosinates; methyl acyl taurates; fatty acyl glycinates; N-acyl glutamates; alkyl glucosides; acyl isethio- nates; alkyl sulfosuccinate; alpha-sulfonated fatty acids, their salts and/or their esters; alkyl phosphate esters; ethoxylated alkyl phosphate esters; alkyl ether sulfates; glucose esters and alkylated, e.g., methyl glucose esters; acylated and/or alkylated protein condensates; mixtures of alkyl ether sulfates and alkyl amine oxides; betaines; sultaines; and mixtures thereof.
  • AGS alkyl glyceryl ether
  • Alkyl and/or acyl chain lengths for these surfactants are C8-C22- preferably C10-C18-
  • Preferred mild synthetic detergent surfactants include: Cs-Cis monoalkyl phosphate salts, preferably at least partly in the form of their polyalkanol, e.g., N,N,N'N'-tetraethanol-(ethyl- enediamine) (Quadrol) salts; N-(Cs-Ci8 fatty acyl) glutamates; Cs-Cis alkyl imino acetates and/or imino propionates; preferably propionates; Cs-Cis fatty acyl glycinates and/or their mixtures with additional anionic synthetic detergent surfactant, and/or mixtures thereof.
  • each R24 is a straight or branched chain alkyl of from about 8 to about 24 carbon atoms; each G is a glyceryl ether moiety; each x is a number of from 1 to about 10; and each M is an alkali metal, ammonium, or substituted ammonium ion.
  • nonionic synthetic detergents are ethoxylated fatty alcohols (e.g., the reaction product of one mole of coconut fatty alcohol with from about 3 to about 30 moles of ethylene oxide) and fatty acid amides such as coconut fatty acid mono- ethanolamide and more pure cuts such as 1auric, myristic or stearic acid diethanolamides.
  • the nonionic surfactants disclosed in U.S. Pat. 3,962,150, supra, can be used in the compositions of the present invention.
  • One kind of preferred composition is substantially free of soap and has a pH of from about 4.5 to about 8.5, preferably from about 6 to about 8.
  • soap e.g., alkali metal soap
  • Such soap can be made by direct saponification of fats and oils or by the neutralization of free fatty acids which are prepared in a separate manufacturing pro ⁇ cess.
  • Particularly useful are sodium, potassium and alkanol- ammonium, e.g., triethanolammonium, salts of 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% Cj6, 23% Cis, 2% palmitoleic, 41.5% oleic and 3% linoleic. (The first three fatty acids listed are saturated.) Other mixtures with similar distributions can be used, 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% Cje, 2% Ci8, 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.
  • the preferred detergent surfactants are the mild synthetic surfactants disclosed in U.S. Pat. No. 4,673,525, Small et al . , issued June 16, 1987, incorporated herein by reference.
  • liquid cleansing compositions that are designed to be foamed in a squeeze foamer container, as described in detail hereinafter, can provide more acceptable foam without hurting other product properties.
  • the useful polymers should be either soluble or dispersible in water to a level that will give the desired viscosity increase.
  • Suitable polymers are high molecular weight materials (mass-average molecular weight deter ⁇ mined, for instance, by light scattering), being generally from about 2,000 to about 3,000,000, preferably from about 5,000 to about 2,500,000, and more preferably from about 7,000 to about 1,000,000).
  • the polymers Since the polymers apparently operate by raising the viscosity of the compositions, the polymers preferably have a thickening ability such that a 1% dispersion of the polymer in water at about 2TC (70 * F) exceeds about 1 centipoise, preferably about 2 centipoise.
  • Useful polymers are the cationic, nonionic, amphoteric, and anionic polymers useful in the cosmetic field. Preferred are cationic and nonionic resins and mixtures thereof, especially those that are beneficial to the skin. Also preferred are cellulose derivatives such as hydroxyethyl- and carboxymethyl- cellulose and guar gums such as hydroxypropyltrimethylammonium guar gum. Since the polymers are added to raise the viscosity, the compositions preferably should not contain large amounts of materials that reduce the viscosity and especially material that has no function except to reduce the viscosity.
  • the polymers useful herein are any of the typical polymers that provide an increase in viscosity.
  • the substituted cellulose materials preferred herein are commonly found in detergent compositions and are suitable for use in com ⁇ positions that come in contact with the skin.
  • the substituted cellulose polymers that are readily water-soluble or water-dispersible, and especially those that form clear solutions while raising the viscosity when used at low levels.
  • Examples of such polymers are the carboxymethyl- and ethoxylated cellulose polymers.
  • hydroxyethyl cellulose e.g., Natrosol 250MXR, Natrosol 250HR, etc.
  • cationic cellulose polymers e.g., Union Carbide's JR-400.
  • anionic, nonionic, and cationic polymeric skin con ⁇ ditioning 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:
  • (III) synthetic water-soluble polymers containing water- soluble groups e.g., quaternized silicones and quat- ernized polycarboxylates.
  • members of the cationic polysaccharide class include the cationic hydroxyethyl cellulose, e.g., JR-400 and LM-200 made by Union Carbide Corporation.
  • Copolymers of saccharides and synthetic monomers useful in the present invention encompass those containing the following saccharides: glucose, galactose, annose, arabinose, xylose, fucose, fructose, glucosamine, galactosamine, glucuronic acid, galacturonic acid, and 5 or 6 membered ring polyalcohols.
  • Xanthan gum e.g., Keltrol T, (molecular weight about 2,000,000) is also a suitable polymer.
  • hydroxymethyl , hydroxyethyl and hydroxypropyl derivatives of the above sugars are also desirable polymers.
  • Other desirable polymers are the bulky amine polymers as defined in the copending U.S. Patent Application of Robert G.
  • guar gum backbone Some examples of preferred bulky amine polymers are cationi guar gums having the following structures, wherein "guar” repre sents the guar gum backbone:
  • HEC bulky amine hydroxyethyl cellulose
  • the "x" in the above formulae is typically selected to provide a degree of substitution of from about 0.5 to about 4, preferably from about 1 to about 2.5.
  • These "bulky amine” groups have no odor problem and also have improved skin conditioning benefits.
  • the composition of this invention preferably comprises from about 0.01% to about 5%, preferably from about 0.04% to about 2%, of the polymer.
  • Some preferred cationic guars galactomannans are disclosed in U.S. Pat. No. 4,758,282, Stober et al., issued July 19, 1988, incorporated herein by reference.
  • the cationic guar gum polymers disclosed in commonly assigned U.S. Pat. Appli ⁇ cation Ser. No. 07/456,065, J.R. Knochel and P.E. Vest, filed Dec. 21, 1989, are suitable, especially when the cationic groups are substituted with bulky amine groups.
  • volatility of the amine which can be generated upon decomposition decreases with increasing molecular weight. Vola ⁇ tility is dependent, among other things, on the boiling point of the neat amine component. Odor impact also has a strong depen ⁇ dence on the amount of volatilized material that reaches the nose. Adding "bulky" amine groups has a desirable effect on volatility and, hence, odor impact of amines. For pure hydrocarbon substi- tution, the larger the alkyl chains (or the larger the degree of long chain substitution) the lower the odor impact.
  • the preferred bulky amine substituents have boiling points of greater than ambient temperature, and preferably at least about 30'C, more preferably more than about 80'C.
  • the preferred nonionic polymers have little detergent sur ⁇ factant activity.
  • the nonionic surfactant-polymers disclosed in the Examples of U.S. Pat. No. 3,962,150, supra, can be used as foam enhancers if they are used at a level which raises the viscosity of the composition by at least about 1 cps.
  • Suitable nonionic polymers include polyalkylene glycol, e.g., ethylene glycol polymers which include polymers having other groups such as alkyl or acyl groups present.
  • polyethyleneglycol (20-500) distearate can be used and can raise the viscosity the desired amount.
  • Some additional polymers include polyvinylpyrrolidone and copolymers of vinylpyrrolidone such as those containing vinyl acetate, dimethylaminoethylmethacrylate and quaternary versions of the same with methyl sulfates, and polymers and copolymers of vinyl alcohol and vinyl acetate.
  • Some acrylic polymers include polyacrylic acid, polyacrylamide, copolymers with esters of acrylic acid and methacrylic acid and copolymers of methylvinyl- ether and maleic anhydride.
  • the above containers do not use any propellant and are therefore safe for the consumer and the environment. They create a foam from almost any surfactant composition. Although there is no need to add foam boosters merely for the purpose of stabilizing the foam, such materials can be desirable. In some compositions the use of foam boosters can even be counterpro ⁇ ductive since the foam has to break in order for the container to work properly.
  • the composition is placed in the container reservoir (plastic squeeze bottle). Squeezing the container with the hand forces the composition through a foamer head, or other foam producing means, where the composition is mixed with air and then through a homogenizing means that makes the foam more homoge ⁇ neous and controls the consistency of the foam.
  • the foam is then discharged as a uniform, non-pressurized aerated foam.
  • the minimum pressure to activate the squeeze foamer is about 1 psig, typcally from about 2 psig to about 7 psig.
  • the minimum pressure is related to the size of the channels in the dispenser, the viscosity of the composition, etc.
  • the density of the foam should be between about 0.002 and about 0.25 g/cc, preferably between about 0.01 and about 0.12 g/cc, and more preferably between about 0.02 and about 0.07 g/cc.
  • Foam density is inversely related to the Creamy Feel Rating, so lower foam densities are preferred.
  • compositions of the present invention can contain option ⁇ al components such as those conventionally found in personal cleansing products.
  • Conventional antibacterial agents can be included in the present compositions at levels of from about 0.1% to about 4%, preferably from about 0.2% to about 1%.
  • Typical antibacterial agents which are suitable for use herein are 3,4-di- and 3,4',5-tribromosalicylanildes; 4,4'-dichloro-3-(trifluoro- methyl)carbanilide; 3,4,4'-trichlorocarbanilide; phenoxy ethanol or propanol; chlorhexidene salts; hexamidine salts; Irgasan DP 300 (Triclosan); salicylic acid; parachlorometaxylenol ; Octopirox; and mixtures of these materials.
  • Conventional nonionic emollients can be included as additional skin conditioning agents in the compo ⁇ sitions of the present invention at levels up to about 20%, preferably at levels of from about 1% to about 15%.
  • Such materials include, for example, mineral oils, fatty sorbitan esters (see U.S. Pat. No. 3,988,255, Seiden, issued Oct. 26, 1976, incorporated by reference herein), lanolin and lanolin deriva- tives, esters such as isopropyl myristate and triglycerides such as coconut oil .
  • Free fatty acid such as coconut fatty acid can be added to the compositions herein to improve the volume and quality (creami- ness) of the lather produced by the compositions herein.
  • Conventional perfumes, dyes, preservatives, and pigments can also be incorporated into compositions of the invention at levels up to about 1.5%.
  • Perfumes are preferably used at levels of from about 0.1% to about 1%, and dyes and pigments are preferably used at levels of from about 0.001% to about 0.5%.
  • a preferred composition of this invention also contains up to about 20% moisturizer, preferably one selected from glycerin and free fatty acid or mixtures thereof.
  • the more preferred compo ⁇ sitions contain from about 1% to about 15% moisturizer.
  • Foam Creamy Feel Rating Test The Foam Creamy Feel Rating test is used to measure the foam quality or creamy feel of foams produced from squeeze foamer packages. Foam Creamy Feel Rating is defined as a combined measurement of the firmness (body or substantivity) and lubricity of the foam in the hands. Foams are evaluated and graded on a 9 point scale relative to product standards which have assigned values.
  • the dispensing bottle should be filled with between 40 5 and 90 mis of foaming solution.
  • the foam is produced by squeezing the foamer package and dispensing -1.5 grams of foam onto the countertop.
  • Brookfield LVT Viscometer Brookfield UL Adaptor Measurement method
  • Step 8 The reading from Step 8 should be corrected and then multiplied by the factor appropriate for the spindle speed (see below); 10. Rinse the chamber and spindle well in 70 * F water, and test the next sample; and
  • Formula 1 is a good foaming composition without polymer having a viscosity of 2.4 and a Foam Creamy Feel Rating of 5.5.
  • Formula 2 is a preferred composition with polymer having a viscosity of 7.1 and a Foam Creamy Feel Rating of 6.4.
  • Formula 3 is another preferred composition with polymer having a viscosity of 5.3 and a Foam Creamy Feel Rating of 7.5.
  • Keltrol T is a polysaccharide made by Kelco, San Diego, Calif., and has a molecular weight of about 2,000,000.
  • Example II Formula A without polymer has a viscosity of
  • Formulas B, C and D each with a very small amount of polymer added, show increased viscosities and increased Foam Creamy Feel Ratings.
  • Formula E has three times the active detergent surfactant, but the same vis ⁇ cosity as Formulas B, C and D.
  • Formulas (% Active) are the active detergent surfactant, but the same vis ⁇ cosity as Formulas B, C and D.
  • Formulas 1-6 have from about 97% to about 99% water, and the Foam Creamy Feel Ratings of 2; 3; 5, and 6 are, respectively, 6.1; 7.0; 6.8; and 7.4.
  • Palm Kernel Oil Fatty Acid Sarco ⁇ 4.28 sinate Medialan KF, 40%
  • compositions of the present invention have improved Foam Creamy Feel Ratings as compared to the same compositions without the polymers.

Abstract

A liquid personal cleansing composition, packaged in a squeeze foamer container, which contains a low level of preferably mild surfactant and a low level of a foam enhancing polymer in an aqueous solvent. A rich, creamy foam is dispensed from the squeeze foamer for effectively cleansing the skin. The product is very mild. The composition can contain minimal amounts of organic materials so as to minimize effects on the environment and can be easily prepared from a concentrate by the ultimate consumer.

Description

FOAMING PERSONAL CLEANSING PRODUCT WITH FOAM ENHANCING POLYMER
FIELD OF THE INVENTION This invention pertains to personal cleansing compositions for personal washing, especially of the face.
BACKGROUND OF THE INVENTION Liquid and solid bar compositions based on soap and/or synthetic surfactants are commonly used for cleansing the human body. To achieve adequate lather when diluted with water, these require a higher level of surfactant than is necessary for clean¬ ing. This excess surfactant can be irritating to the skin and is put into the environment unnecessarily. The use of foams for cleaning skin has usually been reserved for specialty products that are used without rinsing. See, e.g., U.S. Pat. No. 3,962,150, Viola, issued June 8, 1976, incorporated herein by reference. There has been little or no recognition of the mild¬ ness and environmental advantages that can be derived from the use of such products for general cleansing. The level of surfactant actually required to provide good cleaning of the skin is quite low and the majority of the detergent surfactant in the usual toilet bar is wasted, either in the smear, that is left on the bar holder, or in detergent surfactant that is not fully dissolved and is therefore rinsed away without providing any benefit. When a mechanical foaming device is used, lower levels of surfactant can be used to achieve adequate lather. However, as the surfactant level is minimized, lather quality is also reduced and the foam quality can be of a poorer quality than that of better toilet bars.
SUMMARY OF THE INVENTION The present invention relates to liquid personal cleansing products (compositions) containing low levels, e.g., from about 0.1% to about 16% of detergent surfactants, preferably mild detergent surfactants, and low level of foam enhancing polymer in an aqueous solvent system, said compositions being packaged in a container that can be manipulated by an individual to produce a foam (squeeze foamer container). The compositions of this inven¬ tion preferably have a very low content of detergent surfactant to minimize adverse effects both to the skin and to the environment. The quality of the foam can be enhanced, surprisingly, without adversely affecting the ability to dispense the product, by raising the viscosity by the addition of a small amount of a polymer. It is very surprising that foam quality and viscosity are so intimately related. Only very small differences of vis¬ cosity are required to make substantial differences in the foam quality. DETAILED DESCRIPTION OF THE INVENTION
The present invention comprises a personal cleansing composition in the form of an aqueous liquid comprising: (1) from about 0.1% to about 16%, preferably from about 1% to about 8%, more preferably from about 2% to about 6% of detergent surfactant, preferably mild detergent surfactant; and (2) from about 0.01% to about 5%, preferably from about 0.04% to about 2% of foam enhancing polymer.
The "delta viscosity" is the difference between the viscosity of a composition with and without the viscosity enhancing poly- mers. The foam enhancing polymer accounts for a rise in the viscosity of the composition (without he polymer) of at least about 1 centipoise, preferably by from about 2 to about 10 centi- poise, more preferably by from about 2 to about 5 centipoise. The increase in viscosity increases the composition's Foam Creamy Feel Rating as described in more detail hereinafter, so that said Foam Creamy Feel Rating is raised by at least about 0.5, preferably by at least about 1, more preferably by at least about 2. In other words, the compositions's Foam Creamy Feel Rating without the polymer is at least 0.5 lower than the composition with the polymer.
The composition of this invention preferably has a viscosity of at least about 1.5, preferably from about 2 to about 15, more preferably from about 2 to about 12, and even more preferably from about 3 to about 10 centipoise at 21*C when measured using a Brookfield LVT Viscometer with a UL adapter. The lower viscosity limit is set by the quality of the foam and that varies with the surfactant system. In general, the upper viscosity limit is as high as can be tolerated as long as the product can be easily dispensed; thus viscosities of 20, 30, and even 40 cps are in¬ cluded within the scope of this invention. The more preferred composition is made from a formulation which has a viscosity in the range of from about 1 to about 5 cps without the polymer. The compositions of the present invention preferably have a Foam Creamy Feel Rating, as defined hereinafter, of at least about 5, preferably around or about 6. Foam Creamy Feel Ratings of about 7 and above are also desirable for some products.
Squeeze foam compositions without polymer can be formulated using higher levels of surfactant, 10-25%, preferably 15-20%, and achieve Foam Creamy Feel Ratings of 6, 7 or 8.
Compared to personal cleansing compositions that are in the form of toilet bars, the compositions of the present invention are extremely mild. The use of less detergent surfactant makes any detergent surfactant milder and the use of a squeeze foamer package makes the resultant foam more acceptable to the consumer without the need to use more aggressive detergent surfactants for increased foam.
From an environmental standpoint, as discussed hereinbefore, the invention uses less organic material and by using less material and no propellant, simplifies the use of concentrates by the eventual consumer to form the composition. This minimizes the need to continually sell the squeeze foam dispenser.
The compositions of this invention comprise from about 60% to about 99% water, preferably at least about 75%, water, and a minor amount of other suitable solvents. Higher levels of water and lower levels of organic materials are desirable to minimize environmental concern.
The Surfactant Component The surfactant component of the present compositions com¬ prises water-soluble, e.g., alkali metal, ammonium, or substituted ammonium synthetic, or soap, detergent surfactant or mixtures thereof. The compositions of this invention preferably contain up to about 15%, preferably from about 1% to about 8%, of synthetic detergent surfactant, preferably mild synthetic detergent surfac¬ tant. Preferably the synthetic detergent surfactant is mild, as disclosed in commonly assigned U.S. Pat. No. 4,673,525, Small et al., issued June 16, 1987, incorporated herein by reference. A mild synthetic detergent surfactant is defined therein, and herein, as one which does relatively little damage to the barrier function of the stratum corneum. Synthetic detergents are the preferred detergent surfactants in the compositions herein. Preferred types of synthetic deter¬ gent surfactants are of the anionic, a photeric, or zwitterionic types. Preferably, the detergent surfactants are those known to be mild to the skin. Many mild surfactants are low foaming. The present invention offers an advantage for such low foaming surfactants.
Preferred compositions herein contain a mixture of two amphoteric surfactants, a first amphoteric surfactant being selected from imidazolinium surfactants of Formula I:
N CH2 wherein R* is C8-C22 alkyl or alkenyl, R2 is hydrogen or CH2CH2M» Z s CO2M or CH2CO2M and M is H, alkali metal, ammonium or alkanolammonium; and a second amphoteric surfactant being selected from amino- alkanoates of Formula II:
iminodialkanoates of Formula III:
RlN[(CH2)mC02M]2 (III)
and mixtures thereof, wherein n and m are numbers from 1 to 4, and each Rl and M are independently selected from the groups specified i n ( I) above.
Examples of suitable amphoteric surfactants for use as the first amphoteric surfactant include compounds in which R is CgHjj (especially iso-capryl), CgHig and C11H23 alkyl. Especially preferred are the compounds in which R is C9H19, Z is CO2M and R2 is H; and the compounds in which R1 is C11H23, Z is COM and R2 is CH2CO2M.
It will be understood that a number of commercially available amphoteric surfactants of this type are manufactured and sold in the form of complexes with anionic surfactants, especially those of the sulfated Cs-Cis alcohol or Cs-Cis acyl glyceride types. In one aspect of the invention therefore, the compositions comprise a premix or complex of the first amphoteric surfactant and anionic surfactant in an equivalent ratio of about 1.1 in order to provide approximate electroneutrality.
Some preferred mild synthetic detergent surfactants useful in this invention include alkyl glyceryl ether sulfonate (AGS); anionic acyl sarcosinates; methyl acyl taurates; fatty acyl glycinates; N-acyl glutamates; alkyl glucosides; acyl isethio- nates; alkyl sulfosuccinate; alpha-sulfonated fatty acids, their salts and/or their esters; alkyl phosphate esters; ethoxylated alkyl phosphate esters; alkyl ether sulfates; glucose esters and alkylated, e.g., methyl glucose esters; acylated and/or alkylated protein condensates; mixtures of alkyl ether sulfates and alkyl amine oxides; betaines; sultaines; and mixtures thereof. Included in the surfactants are the alkyl ether, sulfates with 1 to 12 ethoxy groups, especially ammonium and sodium lauryl ether sul- fates. Alkyl and/or acyl chain lengths for these surfactants are C8-C22- preferably C10-C18- Preferred mild synthetic detergent surfactants include: Cs-Cis monoalkyl phosphate salts, preferably at least partly in the form of their polyalkanol, e.g., N,N,N'N'-tetraethanol-(ethyl- enediamine) (Quadrol) salts; N-(Cs-Ci8 fatty acyl) glutamates; Cs-Cis alkyl imino acetates and/or imino propionates; preferably propionates; Cs-Cis fatty acyl glycinates and/or their mixtures with additional anionic synthetic detergent surfactant, and/or mixtures thereof. Examples of anionic synthetic detergents are the salts of organic sulfuric reaction products such as
(a) alkyl sulfates having the formula R24OSO3M;
(b) alkyl sulfonates having the formula R24SO3M; (c) alkyl ether sulfates having the formula R2 (0C2H )X0S03M;
(d) alkyl monoglyceride sulfonates having the formula R24OG1-2-SO3M; and
(e) alkyl benzene sulfonates having the formula:
In the above formulae, each R24 is a straight or branched chain alkyl of from about 8 to about 24 carbon atoms; each G is a glyceryl ether moiety; each x is a number of from 1 to about 10; and each M is an alkali metal, ammonium, or substituted ammonium ion.
Examples of nonionic synthetic detergents are ethoxylated fatty alcohols (e.g., the reaction product of one mole of coconut fatty alcohol with from about 3 to about 30 moles of ethylene oxide) and fatty acid amides such as coconut fatty acid mono- ethanolamide and more pure cuts such as 1auric, myristic or stearic acid diethanolamides. The nonionic surfactants disclosed in U.S. Pat. 3,962,150, supra, can be used in the compositions of the present invention. One kind of preferred composition is substantially free of soap and has a pH of from about 4.5 to about 8.5, preferably from about 6 to about 8.
It may also be desirable to use soap, e.g., alkali metal soap as the detergent surfactant. Such soap can be made by direct saponification of fats and oils or by the neutralization of free fatty acids which are prepared in a separate manufacturing pro¬ cess. Particularly useful are sodium, potassium and alkanol- ammonium, e.g., triethanolammonium, salts of mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps.
The term "tallow" is used herein in connection with fatty acid mixtures which typically have an approximate carbon chain length distribution of 2.5% C14, 29% Cj6, 23% Cis, 2% palmitoleic, 41.5% oleic and 3% linoleic. (The first three fatty acids listed are saturated.) Other mixtures with similar distributions can be used, 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.
When the terms "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% Cje, 2% Ci8, 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.
As stated hereinbefore, the preferred detergent surfactants are the mild synthetic surfactants disclosed in U.S. Pat. No. 4,673,525, Small et al . , issued June 16, 1987, incorporated herein by reference. The Polymers
It has been discovered that the addition of certain polymeric materials to liquid cleansing compositions that are designed to be foamed in a squeeze foamer container, as described in detail hereinafter, can provide more acceptable foam without hurting other product properties. In general, the useful polymers should be either soluble or dispersible in water to a level that will give the desired viscosity increase. Suitable polymers are high molecular weight materials (mass-average molecular weight deter¬ mined, for instance, by light scattering), being generally from about 2,000 to about 3,000,000, preferably from about 5,000 to about 2,500,000, and more preferably from about 7,000 to about 1,000,000). Since the polymers apparently operate by raising the viscosity of the compositions, the polymers preferably have a thickening ability such that a 1% dispersion of the polymer in water at about 2TC (70*F) exceeds about 1 centipoise, preferably about 2 centipoise. Useful polymers are the cationic, nonionic, amphoteric, and anionic polymers useful in the cosmetic field. Preferred are cationic and nonionic resins and mixtures thereof, especially those that are beneficial to the skin. Also preferred are cellulose derivatives such as hydroxyethyl- and carboxymethyl- cellulose and guar gums such as hydroxypropyltrimethylammonium guar gum. Since the polymers are added to raise the viscosity, the compositions preferably should not contain large amounts of materials that reduce the viscosity and especially material that has no function except to reduce the viscosity.
Personal cleansing products containing quaternary amine polymers are disclosed in one or more of the following patents:
Pat. No. Date Inventor(s)
US 3,761,418 9/1973 Parran, Jr.;
US 4,234,464 11/1980 Morshauser;
US 4,061,602 12/1977 Oberstar et al . ; US 4,472,297 9/1984 Bolich et al . ;
US 4,491,539 1/1985 Hoskins et al . ;
US 4,540,507 9/1985 Grollier;
US 4,673,525 6/1987 Small et al . ;
US 4,704,224 11/1987 Saud; and Jap. J57105 6/30/82 Pola.
All of the above patents are incorporated herein by refer¬ ence, especially for their basic personal cleansing product and polymer disclosures.
As stated above, the polymers useful herein are any of the typical polymers that provide an increase in viscosity. The substituted cellulose materials preferred herein are commonly found in detergent compositions and are suitable for use in com¬ positions that come in contact with the skin. Especially pre¬ ferred are the substituted cellulose polymers that are readily water-soluble or water-dispersible, and especially those that form clear solutions while raising the viscosity when used at low levels. Examples of such polymers are the carboxymethyl- and ethoxylated cellulose polymers.
Specific examples include: hydroxyethyl cellulose (e.g., Natrosol 250MXR, Natrosol 250HR, etc.); and cationic cellulose polymers (e.g., Union Carbide's JR-400).
Other anionic, nonionic, and cationic polymeric skin con¬ ditioning 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:
(I) nonionic, anionic, and cationic polysaccharides; (II) copolymers of the saccharides of (I) and compatible synthetic monomers;
(III) synthetic water-soluble polymers containing water- soluble groups, e.g., quaternized silicones and quat- ernized polycarboxylates. Specific examples of members of the cationic polysaccharide class include the cationic hydroxyethyl cellulose, e.g., JR-400 and LM-200 made by Union Carbide Corporation.
Copolymers of saccharides and synthetic monomers useful in the present invention encompass those containing the following saccharides: glucose, galactose, annose, arabinose, xylose, fucose, fructose, glucosamine, galactosamine, glucuronic acid, galacturonic acid, and 5 or 6 membered ring polyalcohols. Xanthan gum, e.g., Keltrol T, (molecular weight about 2,000,000) is also a suitable polymer. Also included are hydroxymethyl , hydroxyethyl and hydroxypropyl derivatives of the above sugars. Other desirable polymers are the bulky amine polymers as defined in the copending U.S. Patent Application of Robert G. Bartolo and Louis F. Wong, Ser. No. 07/374,315 filed June 30, 1989, for "PERSONAL CLEANSING PRODUCT WITH ODOR COMPATIBLE BULK CATIONIC POLYMER," said application being incorporated herein b reference. Such polymers have the following generalized formul in which the backbone is represented by "POLYMER" and having th indicated non-labile cationic functional group:
(I) (POLYMER)-(CR1H-CR2R3-NR4R5 6)X wherein R1-R3 is H o any other substituent and R4, R5 and R6 combine with N to form a amine with less odor impact than trimethylamine, preferably a least one of R4, Rδ and R6 is alkyl having a chain length of fro about 2 to about 24 carbon atoms, or an alkoxy alkyl group con taining from about 2 to about 12 carbon atoms.
Some examples of preferred bulky amine polymers are cationi guar gums having the following structures, wherein "guar" repre sents the guar gum backbone:
An example of a bulky amine hydroxyethyl cellulose (HEC) polymer is:
(IV) C12H25
HEC- CH2-0-CH2-CH(0H)-CH2-N+CH3
CH3
The "x" in the above formulae is typically selected to provide a degree of substitution of from about 0.5 to about 4, preferably from about 1 to about 2.5. These "bulky amine" groups have no odor problem and also have improved skin conditioning benefits.
The composition of this invention preferably comprises from about 0.01% to about 5%, preferably from about 0.04% to about 2%, of the polymer. Some preferred cationic guars (galactomannans) are disclosed in U.S. Pat. No. 4,758,282, Stober et al., issued July 19, 1988, incorporated herein by reference. The cationic guar gum polymers disclosed in commonly assigned U.S. Pat. Appli¬ cation Ser. No. 07/456,065, J.R. Knochel and P.E. Vest, filed Dec. 21, 1989, are suitable, especially when the cationic groups are substituted with bulky amine groups.
For a homologous series of compounds (e.g., tri-substituted amines), volatility of the amine which can be generated upon decomposition decreases with increasing molecular weight. Vola¬ tility is dependent, among other things, on the boiling point of the neat amine component. Odor impact also has a strong depen¬ dence on the amount of volatilized material that reaches the nose. Adding "bulky" amine groups has a desirable effect on volatility and, hence, odor impact of amines. For pure hydrocarbon substi- tution, the larger the alkyl chains (or the larger the degree of long chain substitution) the lower the odor impact. Thus, the preferred bulky amine substituents have boiling points of greater than ambient temperature, and preferably at least about 30'C, more preferably more than about 80'C. The preferred nonionic polymers have little detergent sur¬ factant activity. The nonionic surfactant-polymers disclosed in the Examples of U.S. Pat. No. 3,962,150, supra, can be used as foam enhancers if they are used at a level which raises the viscosity of the composition by at least about 1 cps. Suitable nonionic polymers include polyalkylene glycol, e.g., ethylene glycol polymers which include polymers having other groups such as alkyl or acyl groups present. For example, polyethyleneglycol (20-500) distearate, or equivalent materials, can be used and can raise the viscosity the desired amount. Some additional polymers include polyvinylpyrrolidone and copolymers of vinylpyrrolidone such as those containing vinyl acetate, dimethylaminoethylmethacrylate and quaternary versions of the same with methyl sulfates, and polymers and copolymers of vinyl alcohol and vinyl acetate. Some acrylic polymers include polyacrylic acid, polyacrylamide, copolymers with esters of acrylic acid and methacrylic acid and copolymers of methylvinyl- ether and maleic anhydride.
The Squeeze Foamer Container Squeeze foamer packages are well known as exemplified by the disclosures in the following patents that are incorporated herein by reference. U.S. Pat. Nos.: 3,709,437, Wright, issued Jan. 9, 1973; 3,937,364, Wright, issued Feb. 10, 1976; 4,022,351, Wright, issued May 10, 1977; 4,147,306, Bennett, issued Apr. 3, 1979; 4,184,615, Wright, issued Jan. 22, 1980; 4,598,862, Rice, issued July 8, 1986; and 4,615,467, Grogan et al . , issued Oct. 7, 1986; and French Pat. 2,604,622, Verhulst, published Apr. 8, 1988. The above containers (packages) do not use any propellant and are therefore safe for the consumer and the environment. They create a foam from almost any surfactant composition. Although there is no need to add foam boosters merely for the purpose of stabilizing the foam, such materials can be desirable. In some compositions the use of foam boosters can even be counterpro¬ ductive since the foam has to break in order for the container to work properly. The composition is placed in the container reservoir (plastic squeeze bottle). Squeezing the container with the hand forces the composition through a foamer head, or other foam producing means, where the composition is mixed with air and then through a homogenizing means that makes the foam more homoge¬ neous and controls the consistency of the foam. The foam is then discharged as a uniform, non-pressurized aerated foam. The minimum pressure to activate the squeeze foamer is about 1 psig, typcally from about 2 psig to about 7 psig. The minimum pressure is related to the size of the channels in the dispenser, the viscosity of the composition, etc.
In general, the density of the foam should be between about 0.002 and about 0.25 g/cc, preferably between about 0.01 and about 0.12 g/cc, and more preferably between about 0.02 and about 0.07 g/cc. Foam density is inversely related to the Creamy Feel Rating, so lower foam densities are preferred.
Optional Components The compositions of the present invention can contain option¬ al components such as those conventionally found in personal cleansing products. Conventional antibacterial agents can be included in the present compositions at levels of from about 0.1% to about 4%, preferably from about 0.2% to about 1%. Typical antibacterial agents which are suitable for use herein are 3,4-di- and 3,4',5-tribromosalicylanildes; 4,4'-dichloro-3-(trifluoro- methyl)carbanilide; 3,4,4'-trichlorocarbanilide; phenoxy ethanol or propanol; chlorhexidene salts; hexamidine salts; Irgasan DP 300 (Triclosan); salicylic acid; parachlorometaxylenol ; Octopirox; and mixtures of these materials. Conventional nonionic emollients can be included as additional skin conditioning agents in the compo¬ sitions of the present invention at levels up to about 20%, preferably at levels of from about 1% to about 15%. Such materials include, for example, mineral oils, fatty sorbitan esters (see U.S. Pat. No. 3,988,255, Seiden, issued Oct. 26, 1976, incorporated by reference herein), lanolin and lanolin deriva- tives, esters such as isopropyl myristate and triglycerides such as coconut oil .
Free fatty acid such as coconut fatty acid can be added to the compositions herein to improve the volume and quality (creami- ness) of the lather produced by the compositions herein. Conventional perfumes, dyes, preservatives, and pigments can also be incorporated into compositions of the invention at levels up to about 1.5%. Perfumes are preferably used at levels of from about 0.1% to about 1%, and dyes and pigments are preferably used at levels of from about 0.001% to about 0.5%. A preferred composition of this invention also contains up to about 20% moisturizer, preferably one selected from glycerin and free fatty acid or mixtures thereof. The more preferred compo¬ sitions contain from about 1% to about 15% moisturizer.
Other optional components are disclosed in the patents incorporated herein by reference.
Foam Creamy Feel Rating Test The Foam Creamy Feel Rating test is used to measure the foam quality or creamy feel of foams produced from squeeze foamer packages. Foam Creamy Feel Rating is defined as a combined measurement of the firmness (body or substantivity) and lubricity of the foam in the hands. Foams are evaluated and graded on a 9 point scale relative to product standards which have assigned values.
I. Rating Scale ' A scale of "Foam Creamy Feel Ratings" of 1 to 9 is used for creamy feel with 1 being the least creamy and 9 the most creamy. Assigned values for creamy feel are: Foam Creamy
Feel Rating Standard 1.0 Hand lathered liquid hand soap (defined below) 5.5 Foaming solution out of commercial squeeze foamer package 7.0 Hand lathered bar soap I. Calibration: Composition of Standards and Foam Generation Prewash hands with liquid hand soap prior to calibration. A. Liquid Hand Soap
Composition % Active Potassium Soap (50 oleic/50 lauric) 26 Free Fatty Acid (50 oleic/50 lauric) 1.8 Potassium Acetate 4
Glycerin 2
Opacifier 0.4 EDTA 0.1
Water Balance
Foam Creamy Feel Rating = 1.0
Procedure 1. Wet hands.
2. Dispense 1 gram of liquid hand soap into hand.
3. Add a little water (0.5 cc) and rub both hands together in a circular motion 5 times.
4. Completely rotate hands 20 times, scrape lather onto a countertop.
5. Judge the firmness and lubricity of the foam by compressing it and rubbing it on the countertop and in your hands. This is a Foam Creamy Feel Rating of 1.
B. Foaming Solution/Foamer Package Composition % Active
Sodium Myristoyl Glutamate 5.0
Lauroyl Diethanolamide 5.0
Cocoamidopropyl Betaine 0.75
Sodium Lauroyl Sarcosinate 0.75 Foam Creamy Feel Rating = 5.5
Commercial Squeeze Foamer Package
Bottle manufactured by Kunstoff, Ltd., Uster, Switzerland, consisting of: l. 150 ml round HDPE/LDPE (High Density Polyethylene/Low Density Polyethylene) bottle 2. Standard push-pull, off-on, dispensing head 3. "White" mixing chamber
4. 11.5 mm long dip tube with 2.0 mm diameter Procedure
1. The dispensing bottle should be filled with between 40 5 and 90 mis of foaming solution.
2. Wet hands.
3. The foam is produced by squeezing the foamer package and dispensing -1.5 grams of foam onto the countertop.
4. Judge the firmness and lubricity of the foam by 10 compressing it and rubbing it on the countertop and in your hands. This is a Foam Creamy Feel Rating of 5.5.
15
20
Foam Creamy Feel Rating = 7.0
25 Procedure
1. Soak bar in 95*F water for 2 minutes prior to test to precondition it.
2. Wet hands with 95*F (about 35'C) water.
3. Rotate the bar of soap 6 complete times in your hand.
30 4. Add a little water (0.5 cc) and rub both hands together in a circular motion 5 times.
5. Completely rotate hands 20 times, scrape lather onto a countertop.
6. Judge the firmness and lubricity of the foam by co - 35 pressing it and rubbing it on the countertop and in your hands. This is a Foam Creamy Feel Rating of 7. III. Foam Rating Procedure
1. Wet hands.
2. Dispense -1.5 grams of foam from the foam generating package onto the countertop. 3. Judge the firmness and lubricity of the foam by com¬ pressing it and rubbing it on the countertop and in your hands. Assign the foam a rating relative to the stan¬ dards on the 9 point scale. The products of this invention should all have Foam Creamy Feel Ratings of at least about 5 or, preferably, higher as deter¬ mined by this test. More preferred Foam Creamy Feel Ratings of 6 and above have not been observed in any prior art compositions. The most preferred Foam Creamy Feel Ratings of 7 and above are normally only achieved with higher levels of surfactant and are not possible without the polymer in a squeeze foamer composition. Test Protocol for Measuring Low Viscosity Liquids Equipment needed:
Brookfield LVT Viscometer; and Brookfield UL Adaptor Measurement method:
1. Level viscometer;
2. Rinse sample chamber and spindle with 70*F (about 21°C) water and then dry;
3. Attach spindle; 4. Insure that sample to be tested is at 70*F;
5. Add 16 ml sample to test chamber pouring smoothly to insure bubbles are not formed (other model UL Adaptors may require 18.5 ml samples);
6. Slide test chamber over spindle and attach to viscometer;
7. Energize viscometer and rotate spindle at highest allowable speed (60 rpm for samples <10 cps);
8. Allow time for reading to stabilize -30 sec, then depress clutch and turn off the motor while the reading is in view;
9. The reading from Step 8 should be corrected and then multiplied by the factor appropriate for the spindle speed (see below); 10. Rinse the chamber and spindle well in 70*F water, and test the next sample; and
11. Occasionally check the accuracy of the viscometer with standards. Correction factors:
@ 60 rp viscosity cps ■ (spindle reading - 0.4) x 0.1 @ 30 rpm viscosity cps = spindle reading x 0.2 For more details refer to Brookfield's published instructions. The following examples are presented by way of illustration only.
In general, making procedures common to those used for conventional liquid detergent compositions are employed. The squeeze foamer package used was either a Kunstoff Supermatic® package, or a slightly modified one. Comparative results reported use the same type of package.
EXAMPLE I
Formula 1 is a good foaming composition without polymer having a viscosity of 2.4 and a Foam Creamy Feel Rating of 5.5. Formula 2 is a preferred composition with polymer having a viscosity of 7.1 and a Foam Creamy Feel Rating of 6.4. Formula 3 is another preferred composition with polymer having a viscosity of 5.3 and a Foam Creamy Feel Rating of 7.5.
Viscosity: 7.1
Foam Creamy Feel Rating: 6.4 Foam Density: 0.07
*Keltrol T is a polysaccharide made by Kelco, San Diego, Calif., and has a molecular weight of about 2,000,000.
Coco Amphocarboxyglycinate/ 0.56 (Active Level) Sodium Lauryl Sulfate (Miranol 2MCA mod., 39.5%)
Deriphat 160C 1.69 (Active Level)
Hydroxyethylcellulose (1% solution) 10.05
Glycerol 15.00
Ammonium Chloride 1.00
Euxyl K400 0.20
Fragrance 0.10
Citric Acid (10% solution) to pH 7.0
Water Balance
EXAMPLE II
In Example II, Formula A without polymer has a viscosity of
1.5 and a Foam Creamy Feel Rating of 5.2. Formulas B, C and D, each with a very small amount of polymer added, show increased viscosities and increased Foam Creamy Feel Ratings. Formula E has three times the active detergent surfactant, but the same vis¬ cosity as Formulas B, C and D. Formulas (% Active)
Ingredient A B C D E
Sodium Cocoyl Glutamate 7.3 7.3 7.3 7.3 22.6 HEC Gum (Natrosol
250MXR)* 0.14 PEG 150 Distearate** 1.85 JR400 Gum (Quatern- ized Cellulose)*** 0.27 Water Bal. Bal Bal Bal. Bal
Molecular Weight: -720,000
**Molecular Weight: - 7,000
***Molecular Weight: -400,000
EXAMPLE III In Example III, Formulas 1 and 2; 3 and 4; 5 and 6; 7 and 8; 9 and 10; 11 and 12; 13 and 14, are side-by-side comparisons, with and without polymer formulations. The balance of Formulas 1-22 is water.
Formulas (% Active)
N/A = Not available. Formulas (% Active)
Ingredient 13 14 15 16
Potassium Coco(hydrolysed Animal
Protein) (Lamepon S, 32%) 2.26 2.26 5.19 5.19 Coco Amphocarboxyglycinate/
Sodium Lauryl Sulfate
(Miranol 2MCA mod., 48%) Palm Kernel Oil Fatty Acid
Sarcosinate (Medialan KF, 40%) N-lauryl-iminopropionic acid
(Deriphat 160C, 28%)
Total Wt.% Active HEC Gum (Natrosol 250MXR)
Viscosity
Foam Creamy Feel Rating
Foam Density
EXAMPLE IV In Example IV, Formulas 1, 4, 7, 10, 13 and 16 have no polymer. Formulas (% Active)
F r u a % Active
Note that Formulas 1-6 have from about 97% to about 99% water, and the Foam Creamy Feel Ratings of 2; 3; 5, and 6 are, respectively, 6.1; 7.0; 6.8; and 7.4.
Formulas (% Active)
Ingredient 10 11 12 13 14
N-lauryl-iminopropionic acid
(Deriphat 160C, 28%) 0.5 0.5 0.5 1.5 1.5 Coco Amphocarboxyglycinate/ Sodium Lauryl Sulfate
(Miranol 2MCA mod., 39.5%)
Total Surfactant HEC Gum (Natrosol 250MXR) Water
Viscosity
Foam Creamy Feel Rating
Foam Density
Formulas (% Active)
Ingredient 15 16 17 18 N-lauryl-iminopropionic acid
(Deriphat 160C, 28%) 1.5 2.5 2.5 2.5 Coco Amphocarboxyglycinate/
Sodium Lauryl Sulfate
(Miranol 2MCA mod., 39.5%)
Total Surfactant HEC Gum (Natrosol 250MXR) Water
Viscosity
Foam Creamy Feel Rating
Foam Density
EXAMPLE V Rich Foam Quality Using High Surfactant Levels in Squeeze Foamer
Test Formulas (Wt.% Active)
Ingredient A
Sodium Cocoyl Glutamate 22.00
Coco Amphocarboxyglycinate/ 5.16 Sodium Lauryl Sulfate (Miranol 2MCA mod., 48%)
Palm Kernel Oil Fatty Acid Sarco¬ 4.28 sinate (Medialan KF, 40%)
N-lauryl-iminopropionic acid 4.32 (Deriphat 160*C, 28%)
Potassium Coco(hydrolysed Animal 11.39 Protein) (Lamepon S, 32%)
It is clear from the above Comparative Examples that the compositions of the present invention have improved Foam Creamy Feel Ratings as compared to the same compositions without the polymers.

Claims

Claims
1. A liquid personal cleansing composition, packaged in a squeeze foamer container, said composition comprising from about 0.1% to about 16% by weight of a surfactant selected from the group consisting of synthetic detergent surfactant, soap, and mixtures thereof; from about 60% to about 99% water; and from about 0.01% to about 5% by weight of viscosity enhancing polymer; wherein said viscosity enhancing polymer accounts for a rise in the viscosity of the composition (without the polymer) of at least about 1 centipoise.
2. The personal cleansing composition of Claim 1 wherein said sur¬ factant is essentially synthetic detergent surfactant and said water level is at least 75% water.
3. The personal cleansing composition of Claim 2 wherein said com¬ position contains from about 1% to about 8% of synthetic detergent sur¬ factant selected from the group consisting of: alkyl sulfates, alkyl glyceryl ether sulfonates, anionic acyl sarcosinates, methyl acyl taurates, fatty acyl glycinates, N-acyl glutamates, alkyl glucosides, acyl isethionates, alkyl sulfosuccinates, alpha-sulfonated fatty acid salts; alpha-sulfonated methyl ester salts, alkyl phosphate esters, ethoxylated alkyl phosphate esters, methyl glucose esters, acyl/protein condensates, betaines, sultaines, alkyl ether sulfates with 1 to 12 ethoxy groups or mixtures with trial ylamine • oxides, and mixtures thereof, wherein said synthetic detergent surfactant contains alkyl chains containing from about 8 to about 22 carbon atoms.
4. The personal cleansing composition of Claim 3 wherein said synthetic detergent surfactant is selected from the group consisting of: Cs-Cis monoalkyl phosphates, N-(Cs-Cιs acyl)glutamates, Cs-Cis fatty acyl glycinates, Cs-Cjs alkyl imino acetates and/or imino propionates, and mixtures thereof.
5. The personal cleansing composition of Claim 2 containing from about 1% to about 8% of said synthetic detergent surfactant and from about 80% to about 98% water; wherein said polymer raises the viscosity above the viscosity of said composition without said polymer by from about 2 to about 10 centipoise. 6. The personal cleansing composition of Claim 2 wherein said polymer is present at from about 0.04% to about 2% by weight.
7. The personal cleansing composition of Claim 2 wherein said pH is from about 4.5 to about 8.5.
8. The personal cleansing composition of Claim 1 wherein said polymer has a molecular weight of from 2,000 to 3,000,000 and is selected from the group consisting of:
(I) anionic, nonionic, and cationic polysaccharides; (II) copolymers of said saccharides (I) and synthetic monomers; (III) synthetic water-soluble and water-dispersible polymers; and (IV) mixtures thereof.
•**-
9. The personal cleansing composition of Claim 8 wherein said polymer is present at a level of from about 0.04% to about 2% and he viscosity is raised from abut 2 to about 10 centipoise; wherein said detergent surfactant is selected from soap, synthetic detergent surfactant, and mixtures thereof.
10. The personal cleansing composition of Claim 9 wherein said com¬ position contains from about 1% to about 8% of synthetic detergent sur¬ factant selected from the group consisting of: alkyl glyceryl ether sulfonates, anionic acyl sarcosinates, methyl acyl taurates, fatty acyl glycinates, N-acyl glutamates, alkyl glucosides, acyl isethionates, alkyl sulfosuccinates, alpha-sulfonated fatty acid salts; alpha-sulfo¬ nated methyl ester salts, alkyl phosphate esters, ethoxylated alkyl phosphate esters, methyl glucose esters, acyl/protein condensates, betaines, sultaines, alkyl ether sulfates with 1 to 12 ethoxy groups or mixtures with trial ylamine oxides, and mixtures thereof, wherein said synthetic detergent surfactant contains alkyl chains containing from about 8 to about 22 carbon atoms.
EP91905607A 1990-03-27 1991-03-01 Foaming personal cleansing product with foam enhancing polymer Ceased EP0521893A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US49992990A 1990-03-27 1990-03-27
US499929 1990-03-27

Publications (2)

Publication Number Publication Date
EP0521893A4 true EP0521893A4 (en) 1992-11-24
EP0521893A1 EP0521893A1 (en) 1993-01-13

Family

ID=23987331

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91905607A Ceased EP0521893A1 (en) 1990-03-27 1991-03-01 Foaming personal cleansing product with foam enhancing polymer

Country Status (11)

Country Link
EP (1) EP0521893A1 (en)
JP (1) JPH05506259A (en)
CN (1) CN1064013A (en)
AR (1) AR244999A1 (en)
AU (1) AU7457191A (en)
CA (1) CA2078443A1 (en)
IE (1) IE911001A1 (en)
MY (1) MY106392A (en)
NZ (1) NZ237582A (en)
PT (1) PT97097A (en)
WO (1) WO1991014759A1 (en)

Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5494533A (en) * 1991-12-12 1996-02-27 Richardson-Vicks, Inc. Method for personal cleansing
US5712232A (en) * 1994-09-20 1998-01-27 Kao Corporation Aqueous liquid cleansing composition
EP0728475A3 (en) * 1995-02-21 1997-03-19 Kao Corp Skin cleanser
CA2269809A1 (en) * 1996-10-30 1998-05-07 The Procter & Gamble Company Articles, methods for cleaning produce and edible animal protein
US6017549A (en) * 1997-09-30 2000-01-25 E-L Management Corp. Non-irritating cosmetic and pharmaceutical compositions
JP4040775B2 (en) 1998-12-11 2008-01-30 ジョンソン・エンド・ジョンソン株式会社 Cleaning composition
JP3815538B2 (en) * 1999-12-14 2006-08-30 ライオン株式会社 Liquid detergent composition
JP4613439B2 (en) 2001-04-24 2011-01-19 味の素株式会社 Cleaning composition
FR2839078B1 (en) * 2002-04-24 2006-01-06 Ajinomoto Kk DETERGENT COMPOSITION
US7651992B2 (en) 2003-02-28 2010-01-26 The Procter & Gamble Company Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant
JP2006515380A (en) * 2003-02-28 2006-05-25 ザ プロクター アンド ギャンブル カンパニー Foam generation dispenser containing foam generation dispenser and highly viscous composition
US7402554B2 (en) 2003-02-28 2008-07-22 The Procter & Gamble Company Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant
US8153108B2 (en) * 2003-04-25 2012-04-10 Kao Corporation Hair cosmetic product
JP5665261B2 (en) 2007-04-27 2015-02-04 花王株式会社 Hair dyeing or decoloring method
US8003594B2 (en) * 2007-04-30 2011-08-23 Kimberly-Clark Worldwide, Inc. Foamable moisturizing compositions
EP2196186A1 (en) 2008-12-15 2010-06-16 KPSS-Kao Professional Salon Services GmbH Cleansing composition
ES2397559T3 (en) * 2009-03-09 2013-03-07 Unilever Nv A cosmetic composition to lighten the skin
JP5630989B2 (en) 2009-03-11 2014-11-26 花王株式会社 Two-component hair dye
BR112012014641B1 (en) 2009-12-18 2020-09-01 Noxell Corporation PERSONAL CARE ARTICLE
CA2783473C (en) 2009-12-18 2015-11-17 The Procter & Gamble Company Foam oxidative hair colorant composition
US8387348B2 (en) 2009-12-22 2013-03-05 Cryovac, Inc. Aseptic packaging system, packaging process and package with internal fitment
ES2362774B2 (en) * 2009-12-28 2012-04-16 Coty Inc. BATH GEL WITH AN IMPROVED ENVIRONMENTAL PROFILE.
HUE032612T2 (en) 2011-06-24 2017-10-30 Sca Tissue France Personal cleaning composition comprising gelling and foaming agents for tissue impregnation
CN103841951A (en) 2011-09-30 2014-06-04 宝洁公司 Foam oxidative hair colorant composition with the free-base of 1, 4-diamino-2-methoxmethyl benzene
WO2016172409A1 (en) 2015-04-23 2016-10-27 The Procter & Gamble Company Delivery of surfactant soluble anti-dandruff agent
CA3014923C (en) 2016-03-03 2021-10-19 Sean Michael Renock Aerosol antidandruff composition
WO2018075847A1 (en) 2016-10-21 2018-04-26 The Procter & Gamble Company Concentrated shampoo dosage of foam designating hair volume benefits
US11154467B2 (en) 2016-10-21 2021-10-26 The Procter And Gamble Plaza Concentrated shampoo dosage of foam designating hair conditioning benefits
EP3528896A1 (en) 2016-10-21 2019-08-28 The Procter & Gamble Company Concentrated shampoo dosage of foam for providing hair care benefits
EP3528780A1 (en) 2016-10-21 2019-08-28 The Procter and Gamble Company Stable compact shampoo products with low viscosity and viscosity reducing agent
US11679073B2 (en) 2017-06-06 2023-06-20 The Procter & Gamble Company Hair compositions providing improved in-use wet feel
US11141370B2 (en) 2017-06-06 2021-10-12 The Procter And Gamble Company Hair compositions comprising a cationic polymer mixture and providing improved in-use wet feel
US11224567B2 (en) 2017-06-06 2022-01-18 The Procter And Gamble Company Hair compositions comprising a cationic polymer/silicone mixture providing improved in-use wet feel
MX2020003315A (en) * 2017-10-10 2021-12-06 Procter & Gamble A method of treating hair or skin with a personal care composition in a foam form.
WO2019074990A1 (en) 2017-10-10 2019-04-18 The Procter & Gamble Company Compact shampoo composition
US11116705B2 (en) 2017-10-10 2021-09-14 The Procter And Gamble Company Compact shampoo composition containing sulfate-free surfactants
WO2019074989A1 (en) 2017-10-10 2019-04-18 The Procter & Gamble Company Compact shampoo composition containing sulfate-free surfactants
WO2020005309A1 (en) 2018-06-29 2020-01-02 The Procter & Gamble Company Low surfactant aerosol antidandruff composition
US20220031599A1 (en) 2018-11-27 2022-02-03 Kao Corporation Cleanser
CN115151310A (en) 2020-02-27 2022-10-04 宝洁公司 Sulfur-containing anti-dandruff compositions with enhanced efficacy and aesthetics
CN111855095A (en) * 2020-09-02 2020-10-30 英德市东顺精细化工实业有限公司 Anti-freezing type gas leakage detection aerosol and preparation method thereof
JP2023549517A (en) 2020-12-04 2023-11-27 ザ プロクター アンド ギャンブル カンパニー Hair care composition containing malodor reducing substances
US20220378684A1 (en) 2021-05-14 2022-12-01 The Procter & Gamble Company Shampoo Compositions Containing a Sulfate-Free Surfactant System and Sclerotium Gum Thickener

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962150A (en) * 1974-04-10 1976-06-08 Richardson-Merrell Inc. Foam producing cleansing compositions
US4491539A (en) * 1981-06-04 1985-01-01 The Procter & Gamble Company Liquid cleansing product with skin feel additives
WO1991017237A1 (en) * 1990-04-27 1991-11-14 The Procter & Gamble Company Cleansing products

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4022351A (en) * 1975-04-03 1977-05-10 Hershel Earl Wright Foam dispenser
GB8416884D0 (en) * 1984-07-03 1984-08-08 Procter & Gamble Liquid cleansing composition
US4812253A (en) * 1985-05-13 1989-03-14 The Procter & Gamble Company Ultra mild skin cleansing composition
US4946618A (en) * 1988-11-02 1990-08-07 The Procter & Gamble Company Toilet bar composition containing cationic guar gum

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962150A (en) * 1974-04-10 1976-06-08 Richardson-Merrell Inc. Foam producing cleansing compositions
US4491539A (en) * 1981-06-04 1985-01-01 The Procter & Gamble Company Liquid cleansing product with skin feel additives
WO1991017237A1 (en) * 1990-04-27 1991-11-14 The Procter & Gamble Company Cleansing products

Also Published As

Publication number Publication date
PT97097A (en) 1991-12-31
WO1991014759A1 (en) 1991-10-03
AU7457191A (en) 1991-10-21
NZ237582A (en) 1994-09-27
CN1064013A (en) 1992-09-02
CA2078443A1 (en) 1991-09-28
IE911001A1 (en) 1991-10-09
JPH05506259A (en) 1993-09-16
MY106392A (en) 1995-05-30
AR244999A1 (en) 1993-12-30
EP0521893A1 (en) 1993-01-13

Similar Documents

Publication Publication Date Title
WO1991014759A1 (en) Foaming personal cleansing product with foam enhancing polymer
US4726944A (en) Instant lathering shampoo
US4668422A (en) Liquid hand-soap or bubble bath composition
US3590122A (en) Shampoo composition
JPH05506873A (en) cleansing products
US4556510A (en) Transparent liquid shower soap
GB2087919A (en) Anionic-amphoteric based antimicorbial shampoo
WO1992008444A1 (en) Mild skin cleansing toilet bar with silicone skin mildness/moisturizing aid
RU2211023C2 (en) Shaving non-aerosol gel composition
EP0133345A1 (en) Opaque liquid hand soap
CA1330924C (en) Liquid detergent containing taurate and sarcosinate surfactants
US4176176A (en) Hair shampoo and cleanser compositions
KR101444502B1 (en) Detergent for the skin and method for cleansing the skin with the same
US3697452A (en) Shampoo
AU666912B2 (en) Cosmetic composition
US3723360A (en) Shampoo of improved foaming and lathering power comprising higher fatty alcohol sulfate and substituted imidazoline
CA2019264C (en) Personal cleansing product with odor compatible bulky amine cationic polymer
WO1993000089A1 (en) Cleansing products
EP1000606B1 (en) Weak acid skin cleanser containing an alkali salt of N-acyl-amino acid
SA92120456B1 (en) cosmetic compounds
TW497975B (en) Paste-like cleansing compositions
JP2006169453A (en) Detergent composition
JPH05117138A (en) Liquid cleanser composition
JP2000204023A (en) Detergent composition
JPH05156288A (en) Detergent composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19920828

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17Q First examination report despatched

Effective date: 19930325

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 19950715