WO1995013349A1 - Produit de nettoyage automoussant multifonctionnel - Google Patents

Produit de nettoyage automoussant multifonctionnel Download PDF

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Publication number
WO1995013349A1
WO1995013349A1 PCT/US1994/012965 US9412965W WO9513349A1 WO 1995013349 A1 WO1995013349 A1 WO 1995013349A1 US 9412965 W US9412965 W US 9412965W WO 9513349 A1 WO9513349 A1 WO 9513349A1
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WIPO (PCT)
Prior art keywords
composition
percent
surfactant
self
amount
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PCT/US1994/012965
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English (en)
Inventor
Dawn T. Anderson
James M. Wilmott
Joseph I. Kravitz
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Dowbrands Inc.
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Priority to AU10934/95A priority Critical patent/AU1093495A/en
Publication of WO1995013349A1 publication Critical patent/WO1995013349A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/044—Suspensions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/046—Aerosols; Foams
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0043—For use with aerosol devices
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons

Definitions

  • This invention relates to a novel stable, aqueous self-foaming cleansing composition More particularly, this invention relates to a stable self-foaming cleansing composition incorporating a self-foaming agent, an active suspensate and low levels of a surface active agent
  • cleansing products for personal and home use for example shampoos, skin cleansers, soaps and hard surface cleaners
  • the products can take the form of a liquid, a gel or paste of various viscosities
  • These products have various amounts of various essential and optional ingredients or components selected for their intended function or use
  • One of the principal components in most cleansing products is a surfactant
  • Surfactants are used to remove dirt and debris and also to impart a foaming characteristic to the cleansing product which gives the consumer a perceived indication that the product is functioning as a cleanser
  • some cleansing products may contain an active ingredient, to impart a secondary function to the product
  • these additional ingredients tend to suppress the foaming action of surfactants
  • the problem with trying to combine an active component into a surfactant-based formulation has to do with competing functions of ingredients, that is, the use of one or more actives in a formulation may suppress the foaming characteristic of the surfactant
  • a hydrophobic auxiliary active such as a hydrophobe
  • the amount of surfactant in the formulation is increased so that the formulation will provide a level of foaming and cleansing which is acceptable to the consumer
  • the beneficial effect of the active is lost Converse . , if the level of surfactant is maintained then the level of the active component must be lowered and the beneficial effects of the auxiliary active is lost
  • auxiliary active ingredient in a surfactant-based formulation which translates to maximum deposition of the active ingredient on a surface to be cleaned while maintaining the required amount of surfactant necessary to obtain an acceptable foaming and cleansing product for a consumer
  • a self-foaming cleansing composition including a surfactant, a compatible suspending agent a suspensate adapted to be deposited onto a surface to be cleaned, a lather-generating agent to provide self-lathering; and water
  • the present composition enables the use of low surfactant levels thereby lowering irritation yet maximizing the deposition of the suspensate and its contents to maximize functionality While the present invention is not limited to any specific theory of action, it should be of interest and may be helpful in understanding the present invention, if the following explanation is offered for the surprising discovery that reduced levels of surfactant are possible for surfactant-based formulation and still maintaining acceptable levels of foam and cleansing
  • the foam is generated by the entrapment of air from the surrounding atmosphere This is accomplished by creating sites of nucleation for the air in the surfactant-based liquid
  • the mechanical action of rubbing the hands together, or rubbing the hands on the hair, or rubbing a sponge or brush on a surface will provide suitable sites of nucleation and consequently will generate a foam
  • the quality and quantity of the foam produced is dependent on the nature and dilution of the surfactant, the type and amount of mechanical action and the presence of dirt, oil or other matter on the surface that can modify the foam.
  • a foam-generating agent is added to the surfactant base little or no mechanical action is needed to produce an acceptable foam.
  • the release of the entrapped foaming agent results in self-nucleation of a bubble in the surfactant solution.
  • the lather forming abilities of a system with a self-foaming agent is so efficient that the level of surfactant can be greatly reduced without affecting the quality or quantity of foam produced.
  • a auxiliary active component is added, the presence of the self- foaming agent can overcome the foam suppressing effect of the auxiliary active component on the primary surfactant or blend of surfactants.
  • higher levels of auxiliary active can be incorporated into the cleansing system without reducing the quality or quantity of lather produced.
  • the level of primary surfactant can be greatly reduced without adversely affecting foaming resulting in a greater deposition of the auxiliary active component or components.
  • the composition of the present invention delivers more functional materials than conventional 2-in- 1 products due to the lower surfactant levels.
  • the lower surfactant levels are also less harsh to skin and hair and other surfaces.
  • Figure 1 is a graphical illustration of the amount of deposition of peanut oil on a surface using certain formulations of the present invention.
  • Figure 2 is a graphical illustration of the amount of deposition of peanut oil on a surface using certain formulations of the present invention.
  • Figure 3 is a graphical illustration of the amount of deposition of silicone oil on a surface using certain formulations of the present invention.
  • Figure 4 is a graphical illustration of the cleaning efficacy of certain formulations of the present invention.
  • Figure 5 is a graphical illustration of the foaming height of certain comparative formulations.
  • Figure 6 is a graphical illustration of the foaming height of certain formulations of the present invention.
  • the present invention is a stable, homogeneous, self- foaming composition which includes, as essential components, water; an effective amount of a suitable surfactant adapted to provide the required cleansing and foaming properties to the composition; an effective amount of a selective suspending agent adapted to suspend an active suspensate which is to be deposited on a surface to be cleaned; an effective amount o ⁇ a selective suspensate adapted to function as its intended use and an effective amount of a selective self-foaming agent adapted to provide the resultant composition with self-lathering properties.
  • stable it is meant that the composition of the present invention remains suitably homogeneous, that is, free from separation, flocculation, creaming or syneresis, to deliver the desired performance properties for at least a two year period of time under normal use conditions.
  • Water is an essential component of the composition of the present invention because it serves as a diluent and a solvent for the entire matrix, and allows the suspending agent to stabilize the suspensate(s) of the composition
  • Water from any source including, for example, tap water, distilled water, deionized water is suitable for use in the present invention 5
  • the amount of watenn the total composition ultimately is determined by the amount of the other essential and optional ingredients included in the composition
  • Preferably demineralized water is used.
  • the water used is from 1.0 percent to 99 percent by weight.
  • from 35 percent to 95 percent by weight of the composition should be water and, more preferably, from 60 percent to 90 percent by weight of the total composition 0 should be water.
  • the composition of the present invention includes as an essential constituent at least one or more surface active agents (surfactants). These materials reduce the surface tension of water and create a suitable interfacial tension between the water and particulate matter, oil and gases having a positive absolute vapor pressure at use conditions so as to 5 generate foam and remove dirt and debris from the surface
  • surfactant used in the composition of the present invention can be for example an anionic, nonionic, amphote ⁇ c (zwitterionic), cationic or mixtures thereof.
  • Suitable anionic surfactants include alkyl and aikyl ether sulfates, or combinations thereof. These surfactants have the respective formula OSO3M and RO(C 2 H 4 0) x S ⁇ 3M 0 wherein R is an alkyl or alkenyl radical or preferably 8 to 22 and, more preferably 10 to 18 carbon atoms, x is O to 10 and M is a water-soluble cation sue*" * as ammonium, sodium, potassium, and triethanolamine
  • Suitable anionic surfactants include acyl sarcosines derived from natural fatty acids and amino acid sarcos ⁇ ne (N-methyl glycine) of the following formula
  • R is a fatty acid hydrocarbon chain from 10 to 20 carbon atoms
  • M is a water-soiuble cation such as ammonium sodium, potassium triethanolamine, etc.
  • Common derivatives include lauroyl, myristoyl, oleoyl, and stearoyl sarcosinates.
  • Suitable anionic surfactants include alkyl and alkylbenzene sulfonate, succinates, sulfoacetates, and sulfosuccinates having from 8 to 24 carbon atoms.
  • Suitable derivatives include the ammonium, sodium, potassium, and triethanolamine salts thereof.
  • Nonionic synthetic detergents can be broadly defined as compounds produced by the condensation of aikylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Another class has semi-polar characteristics. Classes of nonionic synthetic detergents are as follows:
  • the monoethanol, diethanol, and ammonia amides of fatty acids having an acyl moiety of from 8 to 18 carbon atoms are normally derived from naturally occurring glycerides, for example, coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, for example, by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.
  • a class of nonionic synthetic detergents under the trade name of Pluronic ® are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the hydrophobic portion of the molecule which, or course, exhibits water insolubility, has a molecular weight of from 1500 to 1800.
  • the addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where the polyethylene content is about 50 percent of the total weight of the condensation product.
  • the polyethylene oxide condensates of alkyl phenols for example, the condensation products of alkyl phenols, having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • the alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.
  • nonionic synthetic detergents derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine.
  • R3 wherein R is an alkyl radical of from about 8 to about 24 carbon atoms, R 2 and R 3 are each methyl, ethyl or hydroxyethyl radical, R 4 is ethylene, and n equal from 0 to about 10.
  • the arrow in the formula is a conventional representation of a semi-polar bond.
  • Specific examples of amine oxide detergents include dimethyldodecylamine oxide; cetyldimethylamine oxide; bis-
  • (2-hydroxyethyl) dodecylamine oxide (2-hydroxyethyl) dodecylamine oxide; and bis-(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropyl amine oxide.
  • R5 is an alkyl radical containing from 10 to 28 carbon atoms, from O to 5 ether linkages and from O to about 2 hydroxyl substituents, at least one moiety of R 5 being an alkyl radical containing 0 ether linkages and containing from 10 to 18 carbon atoms
  • R6 is an alkyl radical containing from 1 to 3 carbon atoms and from one to two hydroxyl groups.
  • Specific examples of these sulfoxides are: dodecyl methyl sulfoxide; 3-hydroxy tridecyl methyl sulfoxide; 3-methoxytridecyl methyl sulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.
  • Amphoteric synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing groups, for example, carboxy, sulfo, suifato, phosphato, or phosphono Examples of compounds falling within this definition are sod ⁇ um-3-dodecylam ⁇ no-prop ⁇ onate and sod ⁇ um-3-dodecylammopropane sulfonate Zwitte ⁇ onic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radical may oe straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water so
  • Cationic detergents include those having the formula R-N(R 2 ) 3 ( + ) x (-) wherein R is an alkyl chain containing from 8 to 20 carbon atoms, each R 2 is selected from the group consisting of alkyl and alkanol groups containing from 1 to 4 carbon atoms and benzyl groups 5 there being normally no more than one benzyl group and two R 2 groups can be joined by either a carbon-carbon ether, or imino linkage to form a ring structure, and X represents a halogen atom, sulfate group, nitrate group or other pseudohalogen group.
  • the surfactant is present in the composition of the present invention in an effective amount to reduce the surface tension of water and to create a suitable interfacial tension so as to cleanse the surface of materials not normally removed by water alone and to generate a suitable foam.
  • the amount of surfactant used in the composition of the present invention should be sufficient to provide the desired cleansing and foaming. Below the 5 preferred amounts discussed herein below, the composition will not provide adequate cleaning and foaming. Above the preferred amounts, the amount of surfactant will be too high and the deposition of the active ingredient will not be sufficient. Furthermore, too high levels of surfactant will irritate the skin of a consumer or degrade the surface the composition is applied to. In addition, use of any of the ingredients in the present invention above the 0 preferred amounts would not be economical
  • the surfactant is present in the composition in an amount of from 0 001 percentto 50 percent by weight of the comDosition Preferaoly, the surfactant is present in an amount of from 0.01 percent to 10 percent by weight based on the weight of the composition.
  • the surfactant is present in an amount o * f from 0.1 percent to 5 5 percent by weight based on the total weight of the composition It has been found that even at the above low levels the formulation generates sufficient foam acceptable to the consumer
  • a nonionic, anionic, cationic or amphote ⁇ c surfactant may be used alone, * n the composition of the present invention; or one or more surfactant may be used as a mixture, the surfactants selected from anionic, nonionic, cationic, and amphote ⁇ c surfactants to provide * ⁇ composition of the invention
  • Numerous surface active agents or surfactants, suitable for use in the present composition are described in detail in McCutcheon's "Emulsifiers and Detergents", 1991 and in U S Patent Nos 3,723,357, 3,964,500, 4,788,006, 4,364,837, 4,491 ,539, and 4,678,606
  • Preferred examples of anionic surfactants useful in the present invention include ammonium lauryl sulf
  • the composition of the present invention includes at least one or more suspensates because the suspensate is the active ingredient which is insoluble and suspended in the formulation and is to be deposited onto a surface and provides the auxiliary benefit
  • the composition of the present invention is referred to as "multifunctional " because a plurality of active ingredients can be incorporated into the composition to provide several benefits to a surface
  • the suspensate is generally an ingredient selected to provide a certain beneficial property to the surface such as conditioning, shine, etc
  • the suspensate generally is a hydrophobe
  • the hydrophobe used in the present invention can be, but is not limited to, for example a low to non-polar material that serves as an "active" (suspensate)
  • the hydrophobe is a dispersed oil, wax, solid or paste
  • Suitable materials that can be suspended in the current composition can be described by the following formula C n H ( n + 2 - ⁇ ) where n is an integer from 6 to greater than 1 million x is 0 or an even integer no greater than n
  • These materials include saturated, unsaturated, branched and cyclic hydrocarbon chains Examples include: mineral oil, petrolatum, PERMETHYL * " fluids, and polybutylenes
  • suspensates are the mono, d ⁇ , tr ⁇ or poly alkyl esters or ethers of di, tn or polyhydroxy compounds such as ethylene glycol, propylene glycol, glycerin, sorbitol or polyol
  • These agents include, but are not limited to the following branched, saturated or unsaturated vegetable oils such as soybean oil, babassu oil, castor oil, cottonseed oil, Chinese tallow oil, crambe oil, pe ⁇ lla oil, Danisn rapeseed oil, rice bran oil, palm oil, palm kernel oil, olive oil, linseed oil, coconut oil, sunflower oil safflower oil peanut oil, and corn oil
  • Preferred saturated and unsaturated vegetable oils are those having fatty acid components with 6 to 24 carbon atoms
  • An example of a preferred suspensate is peanut oil
  • Additional oily suspensate include esters of the type
  • and R 2 are saturated or unsaturated branched or cyclic alkyl radicals of 2 to 24 carbon atoms and n is an integor from O to 20 Suitable esters include isopropyl palmitate and dnsopropyl adipate
  • the present composition may also comprise a silicone material to deliver some measure of auxiliary benefit such as lubrication or shine
  • the silicone material are preferably insoluble in water Suitable water-insoluble silicone materials include polyalkyisiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polysiloxane gums, and polyethersiioxane copolymers Teachings directed to suitable silicone materials are found in U S 4,788,006, U S 4,341 ,799, 4,152,416, 3,964,500, 3,208,91 1 , 4,364,837 and U S 4,465,619
  • R-i is a saturated, unsaturated, branched or cyclic alkyl radical from C2 to C24, M (* * ⁇ s defined by
  • R 2 , R 3 and R 4 are hydrogen or a saturated, unsaturated or branched alkyl or hydroxyalkyi radical from C-* to C-io, R 4 is a saturated, unsaturated, branched or cyclic alkyl or substituted alkyl radical from C 2 to C 24
  • R 4 is a saturated, unsaturated, branched or cyclic alkyl or substituted alkyl radical from C 2 to C 24
  • These materials can be either a homogeneous polymer or a cooolymer of two or more monomers
  • homogeneous polymers include polypropylene oxide and polybutylene oxide Typically, the molecular weights of these materials is between 100 and 10,000 daltons Additionally, these materials can be condensed with a mono or polyhydroxyalkyl alcohol as exemplified by the UCON fluids fromthe Union Carbide Chemical
  • Particulate solids can also be supended in the current composition
  • a nonlimiting example includes the antidandruff agents selenium disulfide, sulfur, and compounds of pynthione, especially zinc py ⁇ thione
  • the amount of suspensate used in the composition should not be so low that no deposition of the active suspensate is obtained Too high levels of suspensate may also provide an unstable composition or suppress the foaming characteristic of the composition
  • a hydrophobe suspensate is inherently a foam depressor as known in the prior art
  • the hydrophobe functions so as to not suppress the foam at the preferred levels of use
  • the suspensate is present in the composition in an amount of from
  • the hydrophobe is present in an amount of from 0 01 percent to 30 percent by weight based on the weight of the composition More preferably, the hydrophobe is present in an amount of from 0 1 percent to
  • the composition of the present invention includes at least one or more suspending agents which serves to stabilize the suspensate in the surfactant solution It also serves, as a secondary function, to modify viscosity of the system to improve the flow and spreading properties of the compositon
  • the suspending agent used in the composition of the present invention can be, but is not limited to, for example, a modified polysaccharide, synthetic polymer or inorganic
  • Suitable polysaccharide or polysaccharide derived suspending agents include, for example, those of cellulosic polymers, guar gums, xanthan gums, locust bean gums, gum arabic starches, starch amyloses and alginates Excellentteachings directed to useful polysaccharides and polysaccharide derivatives are seen in The Encyclopedia of Polymer Science and
  • Useful polysaccharide or polysaccharide derivatives are those of the guar gums and guar gum derivatives
  • Guar gums include those of high molecular weight carbohydrates or polysaccharides made up of linked mannose and galactose units The molecule may be a straight chain of mannose units linked to each other by means of beta (1-4) glycosidic linkages
  • Galactose units may branch from alternate mannose units through alpha (1-6) linkages with the mannose units
  • Useful guar gums include derivatives of hydroxypropyl, hydroxyethyl, sodium carboxymethyl, and carboxymethylhydroxypropyi guar gums Teachings directed to guar gums are seen in U S Patent Nos 4,678,606 and 4,491 ,539
  • polysaccharide or polysaccharide derivatives include those of the cellulosic polymers such as methyl, ethyl, hydroxypropyl, hydroxyethyl, carboxymethyl, and carboxymethylhydroxypropyi cellulose
  • a particularly useful polysaccharide is xanthan gum This biosynthetic gum material is commercially available and is a heteropolysaccha ⁇ de with a molecular weight of greater than 1 million It is believed to contain D-glucose, D-mannose and D-glucuronate It is partially acetylated with approximately 5 0 percent acetyl This information and other is found in Whisler, Roy L , Editer, Industrial Gums - Polysaccharides and Their Denvaties, New York Academic Press, 1973
  • Suitable polymeric suspending agents for the current composition are carboxyl vinyl polymers
  • Carboxyvinyl polymers useful in the present invention have carboxy c acid monomer units derived from olefmically unsaturated carboxylic acid monomers containing at least one activated carbon-to-carbon olefmic double bond, and at least one carboxyl group
  • the olefmic double bond readily functions in polymerization because of its presence in the monomer molecule either in the alpha-beta position with respect to a carboxyl group or as a part of a terminal methylene grouping, that is, CH 2 ⁇
  • Olefmically unsaturated acids in this group include acrylic acids typified by the acrylic acid itself, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-acrylic acid, beta methylacrylic acid (crotonic acid), alpha-phenyl acrylic acid, beta-acryloxy propionic acid, sorbic acid, alpha-chloro sorbic acid, angelic acid, cinnamic acid, p-chlor
  • Preferred carboxyhc acid monomeric units are derived from acrylic acid monomers having the general structure
  • C N
  • monovalent alkyl radicals of 1 to 4 carbons monovalent aryl radicals of 6 to 14 carbons, monovalent alkaryl radicals of 7 to 12 carbons
  • acrylic, methacryhc and ethacry c acids are more preferred with acrylic acid being the most preferred
  • Another useful carboxyhc monomer is maleic anhydride or the acid
  • Suitable acrylic ester monomeric units are derived from acrylic ester monomers having the formula
  • acrylic esters include decyl acrylate, isodecyl acrylate, lauryl acrylate, dodecyl acrylate, stearyl acrylate, and the corresponding methacrylates Mixtures of two or more of the long chain acrylic esters can be successfully polymerized with one or more of the carboxyhc acids
  • the carboxyvinyl polymers have crosslinking monomeric units derived from polyfunctional vinyhdene monomers containing at least two terminal CH 2 -C ⁇ groups
  • Particularly useful crosslinking monomers are those polyalkenyl polyethers having more than one alkenyl ether group per molecule, and the most useful monomers have alkenyl groups in which an olefmic double bond is attached to a terminal methylene CH 2 -C ⁇
  • Such monomers can be prepared by the ethe ⁇ fication of a polyhyd ⁇ c alcohol containing at least four carbon atoms and at least two hydroxyl groups Products of such reactions are complex mixtures of polyethers with varying number of ether groups It is preferred to use polyethers containing an average of two or more alkenyl ether groups per molecule
  • Other crosslinking monomers can also be used Allyl pentaerythritol, t ⁇ methyolpropane diallylether, and allyl sucrose are exceptional crosslinking mono
  • the carboxyvinyl polymer preferably comprises * * * rom 95 to 99, and more preferably 96 to 98 weight percent of one or more of the carboxyhc acid monomeric units and preferably 5 to 1 , and more preferably 4 to 2 weight percent of one or more of the acrylic ester monomeric units
  • the carboxyvinyl polymer further preferably comprises a small proportion of the polyethylenically unsaturated crosslinking monomeric unit
  • the crosslinking monomeric unit is preferably from 0 1 to 1 and more preferably from 0 1 to 0 6 weight percent of the carboxyvinyl polymer
  • Preferred carboxyvinyl polymers useful to the present composition are Carbopol ® 1342 and 1352, Pemulen ® TR1 and TR2 (all of B F Goodrich & Co ) Carbopol ® 1342 is most preferred
  • vinyhdene monomers can be used in place of the carboxyhc acid in small amounts so long as the basic properties of the carboxyvinyl polymer such as thickening or a suspending are not adversely affected
  • Examples include acrylonit ⁇ le, methacrylonit ⁇ le, acrylamide, methacrylamide, styrene, vinyl toluene, vinyl methyl ether, vinyl ethyl ketone, Dutadiene, vinyl acetate, methyl acrylate, butyl acrylate, cyanopropyl acrylate, methoxyetnyl acrylate, chloroethyl acrylate, chloroethyl acrylate, vinyl chlo ⁇ e, vinyhdene chloride, esters of maleic and fumaric acid, bis (B-chloroethyl) vinyl phosphonates, and the like, monomers that are known to those skilled in the art.
  • the carboxyvinyl polymers described herein have weight average molecular weights greater than about 500 to as high as several million. Molecular weight of such polymers is preferably in the range of 100,000 to 5 million.
  • Polymerization of the monomers may be carried out in the presence of a free radical catalyst in an inert atmosphere under pressure with proper agitation.
  • Polymerization temperature may be varied from 0° to 125°Cw ⁇ th polymerization between 25° to 90°C ⁇ n presence of a free radical catalyst generally resulting in polymer yields of 75 to 100 percent.
  • the monomers can be charged continuously or in batch during the course of polymerization or in any other conventional manner.
  • Useful free radical forming catalysts include, for example, peroxygen compounds such as sodium, potassium and ammonium persulfates, caprylyl peroxide, benzoyl peroxide, hydrogen peroxide, pelargonyl peroxide, cumene hydroperoxides, tertiary butyl diperphthalate, tertiary butyl perbenzoate, sodium peracetate, di(2-ethylhexyl)- peroxydicarbonate, as well as azo catalysts such as axodiisobutyryl nitrile
  • Other useful catalysts include the so-called "redox" type of catalyst and the heavy-metal activated catalyst systems Ultra-violet light may also be utilized as a source of free radicals. Although some systems polymerize solely by heat, catalysts generally provide better control.
  • the polymerization medium can be a mixture of suitable organic liquids or solvents.
  • the product is preferably obtained as a very fine friable or fluffy precipitate
  • Typical solvents include hydrocarbons containing 6 to 8 carbon atoms such as benzene, tetraline hexane, heptane, and cyclohexane; chlorinated solvents such as carbon tetrachlo ⁇ de, chloroform, t ⁇ chloroethylene, methyl chloride ethyl chloride, and methylene chloride; chlorofluoroalkanes such as chlorofluorome thane and chlorofluoroe thane containing at least 4 halogen atoms; esters such as methyl acetate and ethyl acetate; and alcohols including, for example, methanol, ethanol and butanol Amount of organic medium
  • the carboxyvinyl polymer preferably comprises between 0.1 to 1.5, more preferably between 0.8 and 1 0, and most preferably about 0 9 weight percent of the composition.
  • the carboxyvinyl polymer may function as both a thickener for the composition and as a suspending agent for the oily conditioning agent.
  • the carboxyvinyl polymer is present in an amount sufficient to suspend and stabilize the oily conditioning agent.
  • the carboxyvinyl polymer is further preferably present in an amount and the carboxyl groups thereof are
  • the carboxyvinyl polymer is preferably 30 to 100 and more preferably 70 to 80 percent neutralized.
  • Suitable neutralizing agents for the carboxyvinyl polymer include those known in art as well asalkali anionic surfactants which provide the additional desired neutralizing effect.
  • the neutralizing agent may be an organic or inorganic substance having a basic moiety capable of partially or substantially neutralizing the carboxyvinyl polymer.
  • Useful neutralizing agents are seen in U.S. Patent Nos. 3,330,731 and 3,590,005.
  • Useful neutralizing agents include alkali and alkaline earth metal hydroxides; mono-, di-, and tri-aliphatic amines containing from 1 to 20 carbon atoms in the aliphatic carbon chain with the same or different substituent groups in
  • alkanolamines containing from 1 to 12 carbon atoms in the alkyl group.
  • Suitable alkali metal hydroxides include, for example, those of sodium, potassium, and lithium.
  • Suitable alkanolamines include mono-, di-, and tri-ethanolamines, ethanolamines, propanolamines, isopropanolamines.
  • a most preferred neutralizing agent is triethanolamine. Also useful as neutralizing agents are the anionic acyl sarcosine surfactants described above,
  • suspending agents include alkali-soluble polymer emulsions such as Acrylates/Steareth-20 Methacrylate Copolymer, available as Aculyn'" 22 Thickener (Rohm and Haas Company). The use of this material is described in the Aculyn Personal Care polymers formulation bulletin, FC- 116, issued in 1990, available from Rohm and Haas. Other possible alkali-soluble polymer emulsions such as Acrylates/Steareth-20 Methacrylate Copolymer, available as Aculyn'" 22 Thickener (Rohm and Haas Company). The use of this material is described in the Aculyn Personal Care polymers formulation bulletin, FC- 116, issued in 1990, available from Rohm and Haas. Other possible
  • suspending agents include Di(Hydrogentated) Tallow Phthalic Acid Amide, avialble as Stepan TAB T "-2 (Stepan Company). The use of this material is described in the TAB-2 product bulletin, avialable from Stepan.
  • Other possible suspending agents include liquid dipsersions of sodium polyacrylate such as Sodium Polyacrylate Copolymer and Mineral Oil and PPG-1 Trideceth-6 available as Salcare SC91 (Allied Colloids). The use of this material is described in the Salcare SC-
  • a suitable inorganic suspending agent can be, but is not limited to, magnesium aluminum silicate marketed as EEGUMTM by the anderbilt Chemical Company.
  • the amount of suspending agent used in the composition should not be so low that no suspension of the suspensate is obtained. Too high levels of suspending agent would be so low that no suspension of the suspensate is obtained. Too high levels of suspending agent would be so low that no suspension of the suspensate is obtained. Too high levels of suspending agent would be so low that no suspension of the suspensate is obtained. Too high levels of suspending agent would be so low that no suspension of the suspensate is obtained. Too high levels of suspending agent would be so low that no suspension of the suspensate is obtained. Too high levels of suspending agent would be so low that no suspension of the suspensate is obtained. Too high levels of suspending agent would be so low that no suspension of the suspensate is obtained. Too high levels of suspending agent would be so low that no suspension of the suspensate is obtained. Too high levels of suspending agent would be so low that no suspension of the suspensate is obtained. Too high levels of suspending agent would be so low that no suspension of the suspensate is obtained. Too high levels of suspending agent would
  • the suspending agent is present in the composition in an amount of from 0.001 percent to lO perce ⁇ t by weight of the composition.
  • the suspending agent is present in an amount of from 0.01 percent to 5 percent by weight based on the weight of the composition. More preferably, the suspending agent is present in a amount of from 0.1 percent to 2 percent by weight based on the weight of the composition.
  • the composition of the present invention includes at least one or more self- foaming or lathering-generating agents because, the self-foaming agent imparts to the composition a foam property with minimal outside mechanical energy required.
  • the self- foaming agent can provide the ultimate composition with positive pressure for ease of dispensing or may have no positive pressure for greater versatility in choice of packaging materials.
  • the lather-generating agent useful in the present invention can be for example a hydrocarbon or other suitable materials.
  • the self-foaming agent comprises at least one aliphatic hydrocarbon fluid which is a liquefiable gas or a gaseous hydrocarbon at room temperature.
  • the gaseous hydrocarbon is preferably selected from propane, isobutane, butane, and neopentane.
  • the self-foaming agent may further comprise at least one non-polar liquid which is substantially insoluble in water. Numerous water-insoluble non-polar liquids are described in detail in McCutcheon's "Functional Ingredients", 1991.
  • substantially insoluble as used herein means liquids which are less than about 0.1 percent by weight soluble in water.
  • the water-insoluble non-polar liquid may be a substantially water insoluble nonvolatile silicone oil.
  • the silicone oil includes polyalkylsiloxanes, polyarylsiloxanes, polyalkyarylsiloxanes, polysioxane gums, dihydroxypolysiloxane, and polyethersiloxane copolymers.
  • the water-insoluble non-polar liquid is preferably an aliphatic hydrocarbon which exists as a liquid at room temperature, or is a liquid hydrocarbon.
  • Illustrative but not limiting of the liquid hydrocarbons include: isopentane, pentane, n-hexane, isohexane, 2, 3- dimethylbutane, and mineral oil.
  • the vapor pressure of the aliphatic hydrocarbon fluids is primarily responsible for the vapor pressure of the composition. It has been found that higher the vapor pressure of the composition, the more rapidly the lather develops, but the composition may also be dispensed as a foam. It is useful forthe purposes of this invention that the composition be substantially free from foaming, and is a liquid before and at the time of dispensation.
  • the hydrocarbons may be so selected as to provide a composition exerting a positive pressure at least at about 1.6°C. It is preferred that the compositions exert a positive pressure at least at about 13°C (55°F). Most preferred compositions are those that exert a positive pressure at least at about 22°C.
  • the choice of suitable hydrocarbons, alone or in combination; the concentration of hydrocarbons in the composition; and the relative ratios of component hydrocarbons if more than one hydrocarbon is used, are therefore, very critical to obtain the composition of the invention.
  • the weight ratio of the gaseous hydrocarbon to water-insoluble liquid generally varies in range from 5:95 to 50:50.
  • the weight ratio of the gaseous hydrocarbon to water-insoluble liquid varies in range from 10:90 to 20:80.
  • the self-foaming agent typically comprises from 1 percent to 20 percent by weight of the composition.
  • the self-foaming agent is a single gaseous hydrocarbon, which is neopentane. It is suitably present in an amount from 1 percent to 5 percent by weight, based on the weight of the composition.
  • the self-foaming agent is a mixture of iso-butane or n-butane and a nonvolatile silicone oil.
  • the nonvolatile silicone oil is preferably dimethicone.
  • the self- foaming agent is a mixture of at least one gaseous hydrocarbon selected from n-butane and iso-butane and at least one liquid hydrocarbon selected from iso-pentane, n-pentane, 2-3, dimethyl butane, n-hexane, isohexane, and mineral oil.
  • the weight ratio of the gaseous hydrocarbon to liquid hydrocarbon typically varies in range from 0.5:99.5 to 99.5:0.5.
  • the weight ratio of the gaseous hydrocarbon to liquid hydrocarbon is in the range from 10:90 to 20:80. The most preferred ratio is 20:80.
  • the self-foaming agent can also be a volatile organic liquid of such a nature and in such amount that, although in liquid form at ambient temperature and having a vapor pressure substantially below atmospheric pressure, its volatilization is capable of being promoted by the combination of the aqueous soap solution and the surface active agent to an extent that a lather is generated in a practical period of time.
  • the volatile organic liquid is a water-insoluble organic liquid boiling in the range from 25°C to 70°C, but preferably in the range from 35°C to 50°C.
  • Those liquids include saturated aliphatic hydrocarbons having 5 or 6 carbon atoms, such as n-pentane, iso-pentane, n-hexane, iso-hexane, 2,2-dimethyl-butane, 2,3-dimethyl-butane, and 3-methyl-pentane, and completely halogenated hydrocarbons containing 2 carbon atoms such as 1 ,1 ,2-trichloro- trifluoroethane.
  • Other organic liquid compounds useful here are described in U.S. Patent No. 4,744,979 incorporated herein by reference.
  • the amount of self-foaming agent used in the composition should not be so low that no foaming effect is obtained yet not be so high that the composition becomes "unstable” that is, the composition should not become a multiphase system or nonhomogeneous. Also, too much of self-foaming agent can provide an unstable foam. High levels of self-foaming agent can also result in a composition that is "harsh", that is, that irritates the skin of consumer or discolors or damages a surface. If a hydrocarbon is used as a self-foaming agent, for example, too much hydrocarbon can make the composition flammable.
  • the self-foaming agent is present in the composition in an amount of from 0.01 percent to 35 percent by weight of the composition.
  • the lather- generating agent is present in an amount of from 0.1 percent to 20 percent by weight based on the weight of the composition More preferably, the self-foaming agent in the composition is from 1 percent to 10 percent by weight
  • composition of the present invention may also contain minor amounts, such as from O to 10 percent by weight, of one or more conventional additional ingredients to impart desired characteristics to the composition.
  • suitable additives include for example foam supplements, auxiliary thickening agents, humectants, coloring agents, opacifiers, perfumes, dyes, germicidal agents, preservatives, antiseptic agents, antibacterial agents, disinfectants, emollients, humectants, skin conditioners and pacifying agents
  • composition of the present invention may be prepared by simply mixing all ingredients together, and stirring them thoroughly
  • the present composition is prepared by using an in-line intimate mixing process using, for example, a static mixer and metering one stream of self- foaming agent into another stream comprising the remaining ingredients of the composition
  • the present composition is prepared by mixing all the components by shaking mechanically in well known shaking apparatus While the ingredients of the present invention may be mixed in any suitable order, it is preferred that the self- foaming agent be contacted with the other ingredients in a final step to prevent premature foaming of the compositions
  • the steps include admixing the suspending agent with water, then adding the surfactant to the mixture followed by adding the hydrophobe to the mixture and then adding the self-foaming agent
  • the ingredients used in the present invention can be in any useful form such as liquids, solids, pastes, flake, powder, etc
  • the self-foaming agent can also be introduced into the composition as a gas
  • the resultant composition can take the form of a liquid, gel, paste, cream or lotion
  • composition of the present invention is useful for a variety of topical applications including personal cleaning, household cleaning, industrial cleaning as well as shaving preparations
  • the composition of the present invention is particularly useful in a shower to be used in lieu of bar soaps and shampoos
  • the composition of the present invention is also useful in many other types of cleansing applications for example shining such as wood cleaner, shoe polish, car wash and shine; deodorizing such as carpet cleaner, upholstery cleaner, pet wash; disinfecting such as toilet bowl cleaner, bathroom surface cleaner, and kitchen countertops, protecting such as upholstery, shoe/boot/leather polish, and car protectant, conditioning such as leather cleaner/conditioner, coloring such as car wash and color and shoe polish
  • Other applications in which the present composition can be used includes auto wash, surgical scrub, shave preparation, abrasive cleaners, oven cleaners, mildew cleaners, leatner cleaner/protector, pet care and industrial cleaners
  • the corriDOSition may be packaged in a pressurized or non-pressurized container depending on the nature of the ingredients used in the composition.
  • Example 1 The formulations of Examples 1-47 are described in Tables I - VIII below and were prepared as follows: Water was first added to a beaker. Carbopol (available from B. F. Goodrich) and an oil were premixed to make sure to completely disperse Carbopol. The mixture of Carbopol/oil was added to water with high shear propeller mixing and mixed until homogeneous. A surfactant was added to the water with reduced speed mixing and mixed until homogeneous. Nuocept C (available from Nuodex) was then added to the mixture. The viscosity and pH of the mixture was adjusted with TEA. The finished base was cooled to 5°C. The hydrocarbon blend was also cooled to 5°C. The specified amounts in Tables l-VIII were poured into a bottle with a leakproof closure and shaken until homogeneous.
  • Carbopol available from B. F. Goodrich
  • An oil were premixed to make sure to completely disperse Carbopol.
  • Ammonium cocoyi isethionate (ACI) 15.72 7.86 6.3 4.7 3.1 1.6
  • Nuocept C Polymethoxy Bicyclic Oxazolidine 0 0..22 0.2 0.2 0.2 0.2 0.2 I Water qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100
  • Propylene Glycol Isostearate 2.31 2.31 2.31 2.31 2.31 2.31 Carbopol 0.69 0.69 0.69 0.69 0.69 ALS 20 10 8 6 4 2 ACI 15.72 7.86 6.3 4.7 3.1 1.6 TEA ⁇ .3 ⁇ .3 ⁇ .3 ⁇ .3 ⁇ .3 ⁇ .3 ⁇ .3 ⁇ .3 ⁇ .3
  • Carbopol 1342 0.69 0.69 0.69 0.69 0.69 0.69 0.69 0.69 0.69 0.69 0.69 0.69
  • Examples 48-59 are described in Tables IX and X and were prepared as follows: Water was first added to a beaker. With maximum agitation, Xanthan gum, or Salcare was added to water and mixed until hydrated Then the remaining ingredients were added. The hydrocarbon was added as in the previous Examples 1-47.
  • Examples60-77 The formulations of Examples 60-77 are described in Tables XI - XIII and were prepared as described in Examples 1-47 except that the hydrocarbon blends and levels as described in Tables XI - XIII were used. TABLE XI - Various level s and bl ends of post-foamer Exampl e s - weight percent
  • the substrate used for the determination of the deposition of emollients was 100% worsted flannel (Style 526, Testfabrics, Middlesex, NJ) Worsted flannel, or wool, was chosen, because it has a keratin structure and exhibits similar affinity for emollients as human skin Approximately 2 x 2 inch wool swatches were saturated with water The wet swatches were centered in a custom sample holder The sample holder suspended the swatch such that only a defined area (9 6 cm 2 ) was treated Approximately 0 25 g of the cleanser was applied to the swatch and rubbed with an angled end Teflon spatula for 30 seconds The sample was allowed to rest for 30 seconds, then removed from the sample holder and rinsed with water (temperature 35 5 ⁇ 0 5°C, flow rate. 6 L mm ') for 30 seconds The swatch was finally suspended and dried overnight B Hexane Extraction of Treated Swatch
  • the treated wool swatch was centered, treated side down, over the opening of a 30 mL jar With the rounded end of a spatula, the swatch was pushed into the jar To the jar was added 15 mL of hexane The jar was capped tightly and placed on a Gyrotory shaker for 5 minutes at 350 rpm. After shaking, 5 mL of the extract was removed and transferred to a sample vial Exactly 5 mL of fresh hexane was added to the jar that contained the swatch and the sample was shaken for an additional five minutes.
  • Figure 3 is dimethicone deposition on wool swatches after washing with examples 1-6 TABLE XIV - Deposition test results
  • Binder clips 1 inch size
  • TEA lauryl sulfate 30 percent, available from Henkel Corporation, Hoboken, New Jersey
  • Latex examination gloves must be worn during this section of the method to minimize contamination of skin oils to the swatches.
  • Latex examination gloves must be worn during this section of the method to minimize contamination of skin oils to the swatches.
  • the foam height for some of the examples above was evaluated according to the following methods: (1) Foam Height measurement for "5-second" foam height when using products without self- foaming agent (that is, for the examples shown in Figure 5) a. Weigh 100 gms soft water into a 250 mL graduated cylinder with stopper. b. Weight in 10 gms of product. c. Invert (shake) cylinder 10 times with moderate action. d. Set cylinder on bench and record level of foam in mLs after 5 seconds, e. Repeat (2) Foam height measurement for "5-second” foam height when using products with self- foaming agent (for example, the example shown in Figure 6) a. Dispense 10 grams of product into 150 mL beakerthat has a stir bar mixing at lowest speed. b. Record foam height in mLs on the graduated beaker after 5 seconds. c. Repeat.

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Abstract

Produit de nettoyage automoussant et stable comportant un tensioactif, un agent de suspension compatible, un liquide faiblement polaire à non polaire servant d'auxiliaire (suspensat), un agent moussant assurant l'autoproduction de mousse, et de l'eau.
PCT/US1994/012965 1993-11-10 1994-11-09 Produit de nettoyage automoussant multifonctionnel WO1995013349A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997003646A1 (fr) * 1995-07-21 1997-02-06 Cussons (International) Limited Composition lavante
DE10012492A1 (de) * 2000-03-15 2001-09-27 Henkel Kgaa Reinigungsmittel
US6407044B2 (en) * 1998-01-28 2002-06-18 The Proctor & Gamble Company Aerosol personal cleansing emulsion compositions which contain low vapor pressure propellants
US7939480B2 (en) * 1995-07-21 2011-05-10 Pz Cussons (International) Limited Cleaning composition
KR101474722B1 (ko) * 2013-05-13 2014-12-22 코스맥스 주식회사 피부 쿨링 및 클렌징 겸용 조성물
WO2017187125A1 (fr) * 2016-04-26 2017-11-02 Pz Cussons (International) Ltd Composition de gel d'aérosol
WO2017187124A1 (fr) * 2016-04-26 2017-11-02 Pz Cussons (International) Ltd Composition de nettoyage douce post-moussage
JP2019515037A (ja) * 2016-04-26 2019-06-06 ピーゼット カッソンズ（インターナショナル）リミテッド パーソナルクレンジング組成物
CN111088005A (zh) * 2018-10-23 2020-05-01 中国石油化工股份有限公司 增强驱油用表面活性剂组合物注入性能的方法及组合物及其制备方法和应用

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GB858544A (en) * 1956-05-24 1961-01-11 Jean Jacques Estignard Bluard Improvements in foam producing compositions
FR2161068A1 (fr) * 1971-11-26 1973-07-06 Johnson & Son Inc S C Compositions de traitement de surface
EP0247766A2 (fr) * 1986-05-28 1987-12-02 Lloyd I. Osipow Shampooing moussant instantanément
WO1990011343A1 (fr) * 1989-03-21 1990-10-04 Imaginative Research Associates, Inc. Compositions auto-moussantes a base d'huile et procede de production et d'utilisation
WO1994002109A2 (fr) * 1992-07-28 1994-02-03 Dowbrands Inc. Composition liquide de nettoyage moussant instantanement et distributeur associe
EP0586295A1 (fr) * 1992-08-31 1994-03-09 Nln Compositions fluides, rapidement moussantes, exemptes de savons, contenant un hydrocarbure inférieur et propulsées en récipient sous pression de gaz comprimé

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB858544A (en) * 1956-05-24 1961-01-11 Jean Jacques Estignard Bluard Improvements in foam producing compositions
FR2161068A1 (fr) * 1971-11-26 1973-07-06 Johnson & Son Inc S C Compositions de traitement de surface
EP0247766A2 (fr) * 1986-05-28 1987-12-02 Lloyd I. Osipow Shampooing moussant instantanément
WO1990011343A1 (fr) * 1989-03-21 1990-10-04 Imaginative Research Associates, Inc. Compositions auto-moussantes a base d'huile et procede de production et d'utilisation
WO1994002109A2 (fr) * 1992-07-28 1994-02-03 Dowbrands Inc. Composition liquide de nettoyage moussant instantanement et distributeur associe
EP0586295A1 (fr) * 1992-08-31 1994-03-09 Nln Compositions fluides, rapidement moussantes, exemptes de savons, contenant un hydrocarbure inférieur et propulsées en récipient sous pression de gaz comprimé

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997003646A1 (fr) * 1995-07-21 1997-02-06 Cussons (International) Limited Composition lavante
AU717722B2 (en) * 1995-07-21 2000-03-30 Pz Cussons (International) Limited Cleaning composition
US7939480B2 (en) * 1995-07-21 2011-05-10 Pz Cussons (International) Limited Cleaning composition
US6407044B2 (en) * 1998-01-28 2002-06-18 The Proctor & Gamble Company Aerosol personal cleansing emulsion compositions which contain low vapor pressure propellants
DE10012492A1 (de) * 2000-03-15 2001-09-27 Henkel Kgaa Reinigungsmittel
KR101474722B1 (ko) * 2013-05-13 2014-12-22 코스맥스 주식회사 피부 쿨링 및 클렌징 겸용 조성물
WO2017187125A1 (fr) * 2016-04-26 2017-11-02 Pz Cussons (International) Ltd Composition de gel d'aérosol
WO2017187124A1 (fr) * 2016-04-26 2017-11-02 Pz Cussons (International) Ltd Composition de nettoyage douce post-moussage
GB2552864A (en) * 2016-04-26 2018-02-14 Pz Cussons (International) Ltd Aerosol gel composition
JP2019515037A (ja) * 2016-04-26 2019-06-06 ピーゼット カッソンズ（インターナショナル）リミテッド パーソナルクレンジング組成物
JP2019515959A (ja) * 2016-04-26 2019-06-13 ピーゼット カッソンズ（インターナショナル）リミテッド エアゾールジェル組成物
JP2019515958A (ja) * 2016-04-26 2019-06-13 ピーゼット カッソンズ（インターナショナル）リミテッド 後発泡低刺激性クレンジング組成物
AU2017256895B2 (en) * 2016-04-26 2022-03-03 Pz Cussons (International) Ltd Post-foaming mild cleansing composition
CN111088005A (zh) * 2018-10-23 2020-05-01 中国石油化工股份有限公司 增强驱油用表面活性剂组合物注入性能的方法及组合物及其制备方法和应用
CN111088005B (zh) * 2018-10-23 2022-10-11 中国石油化工股份有限公司 增强驱油用表面活性剂组合物注入性能的方法及组合物及其制备方法和应用

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