AU1775501A - Personal care articles comprising cationic polymer coacervate compositions - Google Patents
Personal care articles comprising cationic polymer coacervate compositions Download PDFInfo
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- AU1775501A AU1775501A AU17755/01A AU1775501A AU1775501A AU 1775501 A AU1775501 A AU 1775501A AU 17755/01 A AU17755/01 A AU 17755/01A AU 1775501 A AU1775501 A AU 1775501A AU 1775501 A AU1775501 A AU 1775501A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0208—Tissues; Wipes; Patches
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
- A61K8/442—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/60—Sugars; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/731—Cellulose; Quaternized cellulose derivatives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/16—Emollients or protectives, e.g. against radiation
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/54—Polymers characterized by specific structures/properties
- A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
- A61K2800/5426—Polymers characterized by specific structures/properties characterized by the charge cationic
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Dermatology (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Toxicology (AREA)
- Biomedical Technology (AREA)
- Cosmetics (AREA)
- Medicinal Preparation (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
- Detergent Compositions (AREA)
Description
WO 01/35905 PCT/USOO/31679 PERSONAL CARE ARTICLES COMPRISING CATIONIC POLYMER COACERVATE COMPOSITIONS TECHNICAL FIELD 5 The present invention relates to disposable, personal care articles suitable for cleansing and/or therapeutically treating the skin, hair and any other sites in need of such treatment. These articles each comprise a water insoluble substrate comprising a nonwoven layer; and a therapeutic benefit component, disposed adjacent to said water insoluble substrate, wherein said component comprises from about 10% to about 1000%, by weight of the water insoluble substrate, of a therapeutic benefit composition comprising a 10 safe and effective amount of a cationic polymer and a safe and effective amount of an anionic surfactant wherein said composition forms a coacervate when said article is exposed to water. Consumers use the articles by wetting them with water and rubbing them on the area to be cleansed and/or therapeutically treated (e.g. conditioned). The invention also encompasses methods for cleansing and/or conditioning the skin and hair using 15 the articles of the present invention. BACKGROUND OF THE INVENTION Personal care products, particularly cleansing and conditioning products, have traditionally been marketed in a variety of forms such as bar soaps, creams, lotions, and gels. Typically, these products have attempted to satisfy a number of criteria to be acceptable to consumers. These criteria include cleansing 20 effectiveness, skin feel, mildness to skin, hair, and ocular mucosae, and lather volume. Ideal personal cleansers should gently cleanse the skin or hair, cause little or no irritation, and should not leave the skin or hair with a heavy buildup or overly dry when used frequently. It is also highly desirable to deliver such cleansing and conditioning benefits from a disposable product. Disposable products are convenient because they obviate the need to carry or store cumbersome 25 bottles, bars, jars, tubes, and other forms of clutter including cleansing products and other products capable of providing therapeutic or aesthetic benefits. Disposable products are also a more sanitary alternative to the use of a sponge, washcloth, or other cleansing implement intended for extensive reuse, because such implements can develop bacterial growth, unpleasant odors, and other undesirable characteristics related to repeated use. 30 The articles of the present invention surprisingly provide effective cleansing and/or therapeutic benefits to the skin and hair in a convenient, inexpensive, and sanitary manner. The present invention provides the convenience of not needing to carry, store, or use a separate implement (such as a washcloth or sponge), a cleanser and/or a therapeutic benefit product. These articles are convenient to use because they are in the form of either a single, disposable personal care article or multiple disposable articles useful 35 for cleansing as well as application of a therapeutic or aesthetic benefit agent. Moreover, these articles are suitable for use within or in conjunction with another personal care implement that is designed for more extensive use. In this instance, the articles of the present invention are disposed within or attached to a WO 01/35905 PCTIUSOO/31679 separate personal care implement that is not readily disposable, e.g., a bath towel or washcloth. In addition, the disposable articles of the present invention may be removeably attached to a handle or grip suitable for moving the article over the surface to be cleansed and/or therapeutically treated (e.g., conditioned). Although in preferred embodiments the articles of the present invention are suitable for personal 5 care applications, they may also be useful in a variety of other industries such as the automotive care, marine vehicle care, household care, animal care, etc. where surfaces or areas are in need of cleansing and/or application of a benefit agent, e.g., wax, conditioner, UV protectant, etc.. In preferred embodiments of the present invention, the articles are suitable for personal care applications and are useful for cleansing and/or conditioning the skin, hair, and similar keratinous surfaces 10 in need of such treatment. Consumers use these articles by wetting them with water and rubbing them on the area to be treated. The article consists of a water insoluble substrate and a therapeutic benefit component. Without being limited by theory, it is believed that the nonwoven layer of the substrate, particularly, enhances cleansing and exfoliation, and optimizes delivery and deposition of a therapeutic or aesthetic benefit agent that might be contained within the article. 15 SUMMARY OF THE INVENTION The present invention relates to a substantially dry, disposable personal care article comprising: a) a water insoluble substrate comprising a nonwoven layer; and b) a therapeutic benefit component, disposed adjacent to said water insoluble substrate, wherein said component comprises from about 10% to about 1000%, by weight of the water insoluble substrate, 20 of a therapeutic benefit composition comprising: 1) a safe and effective amount of a cationic polymer; 2) a safe and effective amount of an anionic surfactant; wherein said composition forms a coacervate when said article is exposed to water. The present invention also relates to a method of cleansing and/or conditioning the skin and hair 25 which comprises the steps of: a) wetting such articles with water and b) contacting the skin or hair with the wetted articles. All percentages and ratios used herein, unless otherwise indicated, are by weight and all measurements made are at 25'C, unless otherwise designated. The invention hereof can comprise, consist of, or consist essentially of, the essential as well as optional ingredients and components described therein. 30 In the description of the invention various embodiments and/or individual features are disclosed. As will be apparent for the skilled practitioner all combinations of such embodiments and features are possible and can result in preferred executions of the invention. All documents referred to herein, including patents, patent applications, and printed publications, are hereby incorporated by reference in their entirety in this disclosure. 35 DETAILED DESCRIPTION OF THE INVENTION 2 WO 01/35905 PCT/USOO/31679 As used herein, "disposable" is used in its ordinary sense to mean an article that is disposed or discarded after a limited number of usage events, preferably less than 25, more preferably less than about 10, and most preferably less than about 2 entire usage events. As used herein, "substantially dry" means that the articles of the present invention exhibit a 5 Moisture Retention of less than about 0.95 gms, preferably less than about 0.75 gms, even more preferably, less than about 0.5 gms, even more preferably less than about 0.25 gms, even still more preferably less than about 0.15 gms, and most preferably, less than about 0.1 gms. The determination of the Moisture Retention is discussed later. The personal care articles of the present invention comprise the following essential components. 10 WATER INSOLUBLE SUBSTRATE The articles of the present invention comprise a water insoluble substrate comprising at least one nonwoven layer or ply. Preferably, this nonwoven layer is non-scouring. As used herein, "non-scouring" means that the layer exhibits an Abrasive Value of greater than about 15, preferably greater than about 30, more preferably greater than about 50, even more preferably greater than about 70, and most preferably 15 greater than about 80 as determined by the Abrasiveness Value Methodology described below. Preferably, the substrate layers are soft yet invigorating to the skin of the consumer when used. Without being limited by theory, the water insoluble substrate enhances cleansing and/or therapeutic treatment. The substrate can have the same or differing textures on each side such that the gripping side of the article is the same or a different texture as the skin/site contact side. The substrate may 20 act as an efficient lathering and exfoliating implement. By physically coming into contact with the skin or hair, the substrate significantly aids in cleansing and removal of dirt, makeup, dead skin, and other debris. In preferred embodiments, however, the substrate is non-scouring or nonabrasive to the skin. Materials suitable for the nonwoven layer are selected from the group consisting of cellulosic nonwovens, sponges (i.e., both natural and synthetic), formed films, battings, and combinations thereof. 25 Preferably, the layer comprises materials selected from the group consisting of cellulosic nonwovens, formed films, lofty battings, foams, sponges, reticulated foams, vacuum-formed laminates, scrims, polymeric nets, and combinations thereof. More preferably, the nonwoven layer comprises materials selected from the group consisting of cellulosic nonwovens, non-lofty nonwovens, formed films, lofty battings, and combinations thereof. As used herein, "nonwoven" means that the layer does not comprise 30 fibers which are woven into a fabric but the layer need not comprise fibers at all, e.g., formed films, sponges, foams, scrims, etc.. When the layer comprises fiber, the fibers can either be random (i.e., randomly aligned) or they can be carded (i.e., combed to be oriented in primarily one direction). Furthermore, the layer can be a composite material composed of a combination of additional layers, i.e., plies, of random and carded fibers. 35 In one embodiment, the nonwoven layer of the substrate comprises batting. Preferably, the nonwoven layer is lofty, non-scouring, and is of low-density. As used herein, "lofty" means that the layer has density of from about 0.00005 g/cm 3 to about 0.1 g/cm 3 , preferably from about 0.001 g/cm 3 to about 3 WO 01/35905 PCT/USOO/31679 0.09 g/cm 3 and a thickness of from about 0.04 inches to about 2 inches at 5 gms/in 2 . The nonwoven layer which comprises batting preferably comprises synthetic materials. As used herein, "synthetic" means that the materials are obtained primarily from various man-made materials or from natural materials which have been further altered. Suitable synthetic materials include, but are not limited to, acetate fibers, acrylic 5 fibers, cellulose ester fibers, modacrylic fibers, polyamide fibers, polyester fibers, polyolefin fibers, polyvinyl alcohol fibers, rayon fibers, polyethylene foam, polyurethane foam, and combinations thereof. Preferred synthetic materials, particularly fibers, may be selected from the group consisting of nylon fibers, rayon fibers, polyolefin fibers, polyester fibers, and combinations thereof Preferred polyolefin fibers are fibers selected from the group consisting of polyethylene, polypropylene, polybutylene, polypentene, and 10 combinations and copolymers thereof. More preferred polyolefin fibers are fibers selected from the group consisting of polyethylene, polypropylene, and combinations and copolymers thereof. Preferred polyester fibers are fibers selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polycyclohexylenedimethylene terephthalate, and combinations and copolymers thereof. More preferred polyester fibers are fibers selected from the group consisting of polyethylene terephthalate, 15 polybutylene terephthalate, and combinations and copolymers thereof. Most preferred synthetic fibers comprise solid staple polyester fibers which comprise polyethylene terephthalate homopolymers. . Suitable synthetic materials may include solid single component (i.e., chemically homogeneous) fibers, multiconstituent fibers (i.e., more than one type of material making up each fiber), and multicomponent fibers (i.e., synthetic fibers which comprise two or more distinct filament types which are somehow 20 intertwined to produce a larger fiber), and combinations thereof. Preferred fibers include bicomponent fibers, multiconstituent fibers, and combinations thereof. Such bicomponent fibers may have a core-sheath configuration or a side-by-side configuration. In either instance, the nonwoven layer may comprise either a combination of fibers comprising the above-listed materials or fibers which themselves comprise a combination of the above-listed materials. 25 For the core-sheath fibers, preferably, the cores comprise materials selected from the group consisting of polyesters, polyolefins having a Tg of at least about I 0*C higher than the sheath material, and combinations thereof. Conversely, the sheaths of the bicomponent fibers preferably comprise materials selected from the group consisting of polyolefins having a Tg of at least about 10'C lower than the core material, polyesters polyolefins having a Tg of at least about I0*C lower than the core material, and 30 combinations thereof In any instance, side-by side configuration, core-sheath configuration, or solid single component configuration, the fibers of the nonwoven layer may exhibit a helical or spiral or crimped configuration, particularly the bicomponent type fibers. The batting nonwoven layer may also comprise natural fibers. 35 Furthermore, the fibers of the batting nonwoven layer preferably have an average thickness of from about 0.5 microns to about 150 microns. More preferably, the average thickness of the fibers are from about 5 microns to about 75 microns. In an even more preferred embodiment, the average thickness of the 4 WO 01/35905 PCTUSOO/31679 fibers are from about 8 microns to about 40 microns. Furthermore, the fibers of the nonwoven layer may be of varying sizes, i.e., the fibers of the nonwoven layer may comprise fibers having different average thicknesses. Also, the cross section of the fibers can be round, flat, oval, elliptical or otherwise shaped. In another embodiment, the nonwoven layer of the present invention may comprise a composite 5 material, i.e., a material having one or more plies of the same or different suitable materials merely superimposed physically, joined together continuously (e.g., laminated, etc.) or in a discontinuous pattern, or by bonding at the external edges (or periphery) of the layer and/or at discrete loci. For instance, the nonwoven layer may further comprise composite materials selected from the group consisting of fibrous nonwovens, sponges, foams, reticulated foams, polymeric nets, scrims, vacuum-formed laminates, formed 10 films and formed film composite materials. It is preferred that the nonwoven layer comprise a formed film composite material comprising at least one formed film and at least one nonwoven wherein the layer is vacuum formed. A suitable formed film composite material includes, but is not limited to, a vacuum laminated composite formed film material formed by combining a carded polypropylene nonwoven having a basis weight of 30 gsm with a formed film. 15 In another embodiment, the nonwoven layer is apertured. The apertures in the nonwoven layer of the water insoluble substrate will generally range in average diameter between about 0.5 mm and 5 mm. More preferably, the apertures will range in size between about 1 mm to 4 mm in average diameter. Preferably, no more than about 10% of the apertures in the nonwoven layer of the substrate will fall outside these size ranges. More preferably, no more than about 5% of the apertures in the nonwoven layer will fall 20 outside these size ranges. For apertures which are not circular in shape, the "diameter" of the aperture refers to the diameter of a circular opening having the same surface area as the opening of the non-circular shaped aperture. Within the nonwoven layer, the apertures will generally occur at a frequency of from about 0.5 to 12 apertures per straight linear centimeter. More preferably, the apertures in the surface of the layer will 25 occur at a frequency of from about 1.5 to 6 apertures per straight linear centimeter. The apertures must at least be placed within the nonwoven layer. Such apertures need not protrude completely through one surface of the nonwoven layer to the other. They, however, may do so. Additionally, apertures may or may not be placed in the nonwoven layer of the substrate such that the entire article is apertured through it's entire volume. 30 Apertures may be formed in the nonwoven layer of the water insoluble substrate as such a substrate, or layer thereof, is being formed or fabricated. Alternatively, apertures may be formed in the nonwoven layer after the substrate comprising the layer has been completely formed. The nonwoven layer may comprise a variety of both natural and synthetic fibers or materials. As used herein, "natural" means that the materials are derived from plants, animals, insects or byproducts of 35 plants, animals, and insects. The conventional base starting material is usually a fibrous web comprising any of the common synthetic or natural textile-length fibers, or combinations thereof. 5 WO 01/35905 PCTIUSOO/31679 Nonlimiting examples of natural materials useful in the present invention include, but are not limited to, silk fibers, keratin fibers and cellulosic fibers. Nonlimiting examples of keratin fibers include those selected from the group consisting of wool fibers, camel hair fibers, and the like. Nonlimiting examples of cellulosic fibers include those selected from the group consisting of wood pulp fibers, cotton 5 fibers, hemp fibers, jute fibers, flax fibers, and combinations thereof. Cellulosic fiber materials are preferred in the present invention. Nonlimiting examples of synthetic materials useful in the present invention include those selected from the group consisting of acetate fibers, acrylic fibers, cellulose ester fibers, modacrylic fibers, polyamide fibers, polyester fibers, polyolefin fibers, polyvinyl alcohol fibers, rayon fibers, polyethylene 10 foam, polyurethane foam, and combinations thereof. Examples of suitable synthetic materials include acrylics such as acrilan, creslan, and the acrylonitrile-based fiber, orlon; cellulose ester fibers such as cellulose acetate, amel, and acele; polyamides such as nylons (e.g., nylon 6, nylon 66, nylon 610, and the like); polyesters such as fortrel, kodel, and the polyethylene terephthalate fiber, polybutylene terephalate fiber, dacron; polyolefins such as polypropylene, polyethylene; polyvinyl acetate fibers; polyurethane 15 foams and combinations thereof. These and other suitable fibers and the nonwovens prepared therefrom are generally described in Riedel, "Nonwoven Bonding Methods and Materials," Nonwoven World (1987); The Encyclopedia Americana, vol. 11, pp. 147-153, and vol. 26, pp. 566-581 (1984); U. S. Patent No. 4,891,227, to Thaman et al., issued January 2, 1990; and U. S. Patent No. 4,891,228, each of which is incorporated by reference herein in its entirety. 20 Nonwovens made from natural materials consist of webs or sheets most commonly formed on a fine wire screen from a liquid suspension of the fibers. See C.A. Hampel et al., The Encyclopedia of Chemistry, third edition, 1973, pp. 793-795 (1973); The Encyclopedia Americana, vol. 21, pp. 376-383 (1984); and G.A. Smook, Handbook of Pulp and Paper Technologies, Technical Association for the Pulp and Paper Industry (1986); which are incorporated by reference herein in their entirety. 25 Natural material nonwovens useful in the present invention may be obtained from a wide variety of commercial sources. Nonlimiting examples of suitable commercially available paper layers useful herein include Airtex@, an embossed airlaid cellulosic layer having a base weight of about 71 gsy, available from James River, Green Bay, WI; and Walkisoft@, an embossed airlaid cellulosic having a base weight of about 75 gsy, available from Walkisoft U.S.A., Mount Holly, NC. 30 Additional suitable nonwoven materials include, but are not limited to, those disclosed in U. S. Patent Nos. 4,447,294, issued to Osborn on May 8, 1984; 4,603,176 issued to Bjorkquist on July 29, 1986; 4,981,557 issued to Bjorkquist on January 1, 1991; 5,085,736 issued to Bjorkquist on February 4, 1992; 5,138,002 issued to Bjorkquist on August 8, 1992; 5,262,007 issued to Phan et al. on November 16, 1993; 5,264,082, issued to Phan et al. on November 23, 1993; 4,637,859 issued to Trokhan on January 20, 1987; 35 4,529,480 issued to Trokhan on July 16, 1985; 4,687,153 issued to McNeil on August 18, 1987; 5,223,096 issued to Phan et al. on June 29, 1993 and 5,679,222, issued to Rasch et al. on October 21, 1997, each of which is incorporated by reference herein in its entirety. 6 WO 01/35905 PCT/USOO/31679 Methods of making nonwovens are well known in the art. Generally, these nonwovens can be made by air-laying, water-laying, meltblowing, coforming, spunbonding, or carding processes in which the fibers or filaments are first cut to desired lengths from long strands, passed into a water or air stream, and then deposited onto a screen through which the fiber-laden air or water is passed. The resulting layer, 5 regardless of its method of production or composition, is then subjected to at least one of several types of bonding operations to anchor the individual fibers together to form a self-sustaining web. In the present invention the nonwoven layer can be prepared, by a variety of processes including, but not limited to, air entanglement, hydroentanglement, thermal bonding, and combinations of these processes. Nonwovens made from synthetic materials useful in the present invention can be obtained from a 10 wide variety of commercial sources. Nonlimiting examples of suitable nonwoven layer materials useful herein include HEF 40-047, an apertured hydroentangled material containing about 50% rayon and 50% polyester, and having a basis weight of about 61 grams per square meter (gsm), available from Veratec, Inc., Walpole, MA; HEF 140-102, an apertured hydroentangled material containing about 50% rayon and 50% polyester, and having a basis weight of about 67 gsm, available from Veratec, Inc., Walpole, MA; 15 Novonet@ 149-616, a thermo-bonded grid patterned material containing about 100% polypropylene, and having a basis weight of about 60 gsm available from Veratec, Inc., Walpole, MA; Novonet® 149-801, a thermo-bonded grid patterned material containing about 69% rayon, about 25% polypropylene, and about 6% cotton, and having a basis weight of about 90 gsm, available from Veratec, Inc. Walpole, MA; Novonet@ 149-191, a thermo-bonded grid patterned material containing about 69% rayon, about 25% 20 polypropylene, and about 6% cotton, and having a basis weight of about 120 gsm, available from Veratec, Inc. Walpole, MA; HEF Nubtex@ 149-801, a nubbed, apertured hydroentangled material, containing about 100% polyester, and having a basis weight of about 84 gsm, available from Veratec, Inc. Walpole, MA; Keybak® 951V, a dry formed apertured material, containing about 75% rayon, about 25% acrylic fibers, and having a basis weight of about 51 gsm, available from Chicopee, New Brunswick, NJ; Keybak® 1368, 25 an apertured material, containing about 75% rayon, about 25% polyester, and having a basis weight of about 47 gsm, available from Chicopee, New Brunswick, NJ; Duralace® 1236, an apertured, hydroentangled material, containing about 100% rayon, and having a basis weight from about 48 gsm to about 138 gsm, available from Chicopee, New Brunswick, NJ; Duralace@ 5904, an apertured, hydroentangled material, containing about 100% polyester, and having a basis weight from about 48 gsm to 30 about 138 gsm, available from Chicopee, New Brunswick, NJ; Chicopee® 5763, a carded hydroapertured material (8x6 apertures per inch, 3X2 apertures per cm), containing about 70% rayon, about 30% polyester, and a optionally a latex binder (Acrylate or EVA based) of up to about 5% w/w, and having a basis weight from about 60 gsm to about 90 gsm, available form Chicopee, New Brunswick, NJ; Chicopee® 9900 series (e.g., Chicopee 9931, 62 gsm, 50/50 rayon/polyester, and Chicopee 9950 50 gsm, 50/50 rayon/polyester), a 35 carded, hydroentangled material, containing a fiber composition of from 50% rayon/50% polyester to 0% 7 WO 01/35905 PCT/USOO/31679 rayon/100% polyester or 100% rayon/0% polyester, and having a basis weight of from about 36 gsm to about 84 gsm, available form Chicopee, New Brunswick, NJ; Sontara 8868, a hydroentangled material, containing about 50% cellulose and about 50% polyester, and having a basis weight of about 72 gsm, available from Dupont Chemical Corp. Preferred non-woven substrate materials have a basis weight of 5 about from 24 gsm to about 96 gsm, more preferably from about 36 gsm to about 84 gsm, and most preferably from about 42 gsm to about 78 gsm. The nonwoven layer may also be a polymeric mesh sponge as described in European Patent Application No. EP 702550A1 published March 27, 1996, which is incorporated by reference herein in its entirety. Such polymeric mesh sponges comprise a plurality of plies of an extruded tubular netting mesh 10 prepared from nylon or a strong flexible polymer, such as addition polymers of olefin monomers and polyamides of polycarboxylic acids. The nonwoven layer may also comprise formed films and composite materials, i.e., multiply materials containing formed films. Preferably, such formed films comprise plastics which tend to be soft to the skin. Suitable soft plastic formed films include, but are not limited to, polyolefins such as low density 15 polyethylenes (LDPE). In such cases where the nonwoven layer comprises a plastic formed film, it is preferred that the nonwoven layer be apertured, e.g., macroapertured or microapertured, such that the layer is fluid permeable. In one embodiment, the nonwoven layer comprises a plastic formed film which is only microapertured. The surface aberrations of the microapertures, i.e., the male side, are preferably located on the interior surface of the second layer and preferably face toward the inside of the substrate, i.e., toward 20 the therapeutic benefit component. In certain embodiments which include apertures having petal-like edged surface aberrations, without being limited by theory, it is believed that when the surface aberrations of the apertures face toward the therapeutic benefit component, the application of pressure by the hand to the article allows the petal-like edges of the surface aberrations to fold inward thereby creating numerous valves on the interior surface of the layer which in effect meter out the therapeutic benefit component 25 contained within the article thereby extending the article's useful life. In another embodiment, the nonwoven layer comprises a plastic formed film which is both microapertured and macroapertured. In such embodiments, the nonwoven layer is well-suited to contact the area to be therapeutically treated given the cloth-like feel of such microapertured films. Preferably, in such an embodiment, the surface aberrations of the microapertures face opposite of the surface aberrations 30 of the macroapertures on the nonwoven layer. In such an instance, it is believed that the macroapertures maximize the overall wetting/lathering of the article by the three-dimensional thickness formed from the surface aberrations which are under constant compression and decompression during the use of the article thereby creating lathering bellows. In any case, the nonwoven layer comprising a formed film preferably has at least about 100 35 apertures/cm 2 , more preferably at least 500 apertures/cm 2, even still more preferably at least about 1000 apertures/cm 2 , and most preferably at least about 1500 apertures/cm 2 of the substrate. More preferred embodiments of the present invention include a nonwoven layer which has water flux rate of from about 5 8 WO 01/35905 PCT/USOO/31679 cm 3 /cm 2 -s to about 70 cm 3 /cm 2 -s, more preferably from about 10 cm 3 /cm 2 -s to about 50 cm 3 /cm 2 -s and most preferably from about 15 cm 3 /cm 2 -s to about 40 cm 3 /cm 2 -s. Suitable formed films and formed film-containing composite materials useful in the nonwoven layer of the present invention include, but are not limited to, those disclosed in U. S. Patent No. 4,342,314 5 issued to Radel et al. on August 3, 1982, commonly assigned co-pending application U. S. Serial No. 08/326,571 and PCT Application No. US95/07435, filed June 12, 1995 and published January 11, 1996, and U. S. Patent No. 4,629,643, issued to Curro et al. on December 16, 1986, each of which is incorporated by reference herein in its entirety. Furthermore, the nonwoven layer may be a formed film composite material comprising at least one formed film and at least one nonwoven wherein the layer is vacuum 10 formed. A suitable formed film composite material includes, but is not limited to, a vacuum laminated composite formed film material formed by combining a carded polypropylene nonwoven having a basis weight of 30 gsm with a formed film. Additionally, the nonwoven layer and any additional layers are preferably bonded to one another in order to maintain the integrity of the article. This bonding may consist of spot bonding (e.g., hot point 15 bonding), continuous joining (e.g., laminated, etc.) in a discontinuous pattern, or by bonding at the external edges (or periphery) of the layers and/or at discrete loci or combinations thereof. When spot bonding is used in the present articles, it is preferred that the spot bonds are separated by a distance of not less than about 1 cm. In any instance, however, the bonding may be arranged such that geometric shapes and patterns, e.g. diamonds, circles, squares, etc., are created on the exterior surfaces of the layers and the 20 resulting article. It is also envisioned in the articles of the present invention that the nonwoven layer and any additional layers may be surface modified to form single composite layer having 2 sides with different textures. Thus, in effect, the water insoluble substrate can be construed as comprising a single composite layer with dual textured sides or surfaces. 25 In any event, it is preferred that the bonded area present between the nonwoven layer and any additional layers be not greater than about 50% of the total surface area of the layers, preferably not greater than about 15%, more preferably not greater than about 10%, and most preferably not greater than about 8%. Each of the layers discussed herein comprises at least two surfaces, namely an interior surface and 30 an exterior surface, each of which may have the same or different texture and abrasiveness. Preferably, the articles of the present invention comprise substrates and therefore layers which are soft to the skin. However, differing texture substrates can result from the use of different combinations of materials or from the use of different manufacturing processes or a combination thereof. For instance, a dual textured water insoluble substrate can be made to provide a personal care article with the advantage of having a more 35 abrasive side for exfoliation and a softer, absorbent side for gentle cleansing and/or therapeutic treatment. In addition, the separate layers of the substrate can be manufactured to have different colors, thereby helping the user to further distinguish the surfaces. 9 WO 01/35905 PCT/USOO/31679 Furthermore, each of the layers of the articles as well as the articles themselves may be made into a wide variety of shapes and forms including flat pads, thick pads, thin sheets, ball-shaped implements, irregularly shaped implements. The exact size of the layers will depend upon the desired use and characteristics of the article and may range in surface area size from about a square inch to about hundreds 5 of square inches. Especially convenient layer and article shapes include, but are not limited to, square, circular, rectangular, hourglass, mitt-type or oval shapes having a surface area of from about 5 in 2 to about 200 in 2 , preferably from about 6 in 2 to about 120 in 2 , and more preferably from about 15 in 2 to about 100 in 2, and a thickness of from about 0.5 mm to about 50 mm, preferably from about 1 mm to about 25 mm, and more preferably from about 2 mm to about 20 mm. 10 Abrasiveness Value Methodology The Abrasiveness Value indicates the "non-scouring" property of the nonwoven layer of the present articles. The nonwoven layers of the present invention are mildly exfoliating but are not rough to the skin. Therefore, the Abrasiveness Value determination involves rubbing the substrate along a test surface using a mechanical device and then examining the resulting scratch marks produced on the test 15 surface using different analysis techniques. The following equipment is needed for the methodology. 1. Martindale Toothbrush Wear and Abrasion Tester: Model 103, serial nos. 103-1386/2 upwards. Martindale 07-01-88 made by James H. Heal and Co. Ltd. Textile Testing and QC Equipment. Foot area: 43x44mm. 1Kg weight. 20 2. Capped Polystyrene strips 1 lx8cm. Clear general purpose polystyrene layer on white High Impact Polystyrene, e. g., EMA Model Supplies SS-20201L. 3. Substrates to be tested. 4. Glossmeter, e.g. Sheen Tri-Microgloss 20-60-85 Prepare the polystyrene strips for scratching by removing plastic protective coating from the side 25 to be scratched and rinsing with ethanol (do not use tissue). Place the strip onto non abrasive surface and allow strip to dry in the air. Then, attach the polystyrene strip to the base of a Martindale wear tester with tape along the edges. Align the strip centrally under the path of the scrubbing device, with the length of the strip in the direction of movement. Cut a 2.5" x 2.5" substrate sample. Attach the substrate sample to the scrubbing foot of the Martindale wear tester, with double sided tape, aligning the machine direction of the 30 substrate with the direction of travel. Secure the scrubbing foot assembly into the instrument with the screws supplied. Slot 1Kg weight on to the top of the scrubbing foot assembly and ensure the scrubbing foot moves only in one direction (forward and backwards). Cover the entire Martindale wear tester with a safety screen. Set the machine to perform 50 cycles in 1 minute and allow to run. (Frequency = 0.833Hz). Once the machine has stopped take off the footer assembly and lift the polystyrene strip off the base of the 35 machine. Label the polystyrene indicating the substrate used and store in a plastic bag. Next, the strips are analyzed. The strips are placed on a black construction paper background and at least 5 samples of the same substrate are analyzed to get a reproducible average. The Glossmeter is 10 WO 01/35905 PCT/USOO/31679 placed orthogonally (such that light beam is at right angles to scratches) and centrally over scratched side of the polystyrene strip. A 200 angle is selected and the sample is measured yielding the Abrasiveness Value. As the Abrasiveness Value decreases the scratchiness or scouring property of a substrate increases. THERAPEUTIC BENEFIT COMPONENT 5 The articles of the present invention further comprise a safe and effective amount of a therapeutic benefit component. The benefit component is disposed adjacent to the water insoluble substrate and comprises from about 10% to about 1000%, by weight of the water insoluble substrate, of a therapeutic benefit composition. The benefit composition further comprises a safe and effective amount of a cationic polymer and a safe and effective amount of an anionic surfactant wherein said composition forms a 10 coacervate when the article is exposed to water. Cationic Polymer The personal care compositions of the present invention comprise a safe and effective amount of cationic polymer. The cationic polymer may be selected from the group consisting of natural backbone quaternary ammonium polymers, synthetic backbone quaternary ammonium polymers, natural backbone 15 amphoteric type polymers, synthetic backbone amphoteric type polymers, and combinations thereof. The cationic polymer preferably exhibits a charge density of greater than about 0.05 meq/gm, more preferably, greater than about 0.1 meq/gm, even more preferably, greater than about 0.2 meq/gm, even more preferably, greater than about 0.5 meq/gm, and most preferably, greater than about 1 meq/gm. The molecular weight of the cationic polymer is preferably greater than about 250, more 20 preferably, greater than about 350, even more preferably greater than about 450, and most preferably, greater than about 500. More preferably, the cationic polymer is selected from the group consisting of natural backbone quaternary ammonium polymers selected from the group consisting of Polyquaternium-4, Polyquaternium 10, Polyquaternium-24, PG-hydroxyethylcellulose alkyldimonium chlorides, guar hydroxypropyltrimonium 25 chloride, hydroxypropylguar hydroxypropyltrimonium chloride, and combinations thereof; synthetic backbone quaternary ammonium polymers selected from the group consisting of Polyquaternium-2, Polyquaternium-6, Polyquaternium-7, Polyquaternium-11, Polyquaternium-16, Polyquaternium-17, Polyquaternium-18, Polyquaternium-28, Polyquaternium-32, Polyquaternium-37, Polyquaternium-43, Polyquaternium-44, Polyquaternium-46, polymethacylamidopropyl trimonium chloride, acrylamidopropyl 30 trimonium chloride/acrylamide copolymer, and combinations thereof; natural backbone amphoteric type polymers selected from the group consisting of chitosan, quaternized proteins, hydrolyzed proteins, and combinations thereof; synthetic backbone amphoteric type polymers selected from the group consisting of Polyquaternium-22, Polyquaternium-39, Polyquaternium-47, adipic acid/dimethylaminohydroxypropyl diethylenetriamine copolymer, polyvinylpyrrolidone/dimethylyaminoethyl methacyrlate copolymer, 35 vinylcaprolactam/ polyvinylpyrrolidone/dimethylaminoethylmethacrylate copolymer, vinaylcaprolactam/ polyvinylpyrrolidone/dimethylaminopropylmethacrylamide terpolymer, polyvinylpyrrolidone/dimethylaminopropylmethacrylamide copolymer, polyamine, and combinations 11 WO 01/35905 PCT/USOO/31679 thereof; and combinations thereof. Even more preferably, the cationic polymer is a synthetic backbone amphoteric type polymer. Even still more preferably, the cationic polymer is a polyamine. When the cationic polymer is a polyamine, it is preferred that the cationic polyamine polymer be selected from the group consisting of polyethyleneimines, polyvinylamines, polypropyleneimines, 5 polylysines and combinations thereof. Even more preferably, the cationic polyamine polymer is a polyethyleneimine. In certain embodiments in which the cationic polymer is a polyamine, the polyamine may be hydrophobically or hydrophilically modified. In this instance, the cationic polyamine polymer is selected from the group consisting of benzylated polyamines, ethoxylated polyamines, propoxylated polyamines, 10 alkylated polyamines, amidated polyamines, esterified polyamines and combinations thereof. The coacervate-forming composition comprises from about 0.01% to about 20%, more preferably from about 0.05% to about 10%, and most preferably from about 0.1% to about 5%, by weight of the coacervate forming composition, of the cationic polymer. Anionic Surfactant 15 The coacervate compositions of the present invention also comprise an anionic surfactant. Without being limited by theory, it is believed that the anionic surfactant interacts with the cationic polymer to partially reduce cationic charge density, decreasing solubility and enhancing deposition on skin. The compositions preferably comprise from about 10% to about 1,000%, preferably from about 50% to about 600%, and more preferably from about 100% to about 250%, based on the weight of the water insoluble 20 substrate, of the anionic surfactant. A wide variety of anionic surfactants are suitable for use in the compositions of the present invention. See, e.g., U. S. Patent 2,929,678, issued to Laughlin et al. on December 30, 1975. Nonlimiting examples of anionic surfactants include the acyl isethionates (e.g., C 12
-C
30 ), alkyl and alkyl ether sulfates and salts thereof, alkyl and alkyl ether phosphates and salts thereof, alkyl methyl taurates (e.g., C 12
-C
30 ), 25 monoalkanol amine phosphates.and soaps (e.g., alkali metal salts like sodium or potassium salts) of fatty acids. Preferably, for the coacervate-forming composition, the anionic surfactant is selected from the group consisting of sarcosinates, glutamates, sodium alkyl sulfates, ammonium alkyl sulfates, sodium alkyleth sulfates, ammonium alkyleth sulfates, ammonium laureth-n-sulfates, sodium laureth-n-sulfates, isethionates, glycerylether sulfonates, sulfosuccinates, monoalkanol amine phosphates and combinations 30 thereof. More preferably, the anionic surfactant is selected from the group consisting of sodium lauroyl sarcosinate, monosodium lauroyl glutamate, sodium alkyl sulfates, ammonium alkyl sulfates, sodium alkyleth sulfates, ammonium alkyleth sulfates, monoalkanol amine phosphates, and combinations thereof. Without being limited by theory, it is believed that the cationic polymer and anionic surfactant coexist in the form of a coacervate when exposed to an aqueous medium. As used herein, "coacervate" 35 means an associative phase separation of oppositely charged polymer and surfactant or polymer and polymer caused by product dilution. The result is an aqueous gel-like material which is formed, the coacervate. Once formed, the coacervates alone in the present compositions may improve the appearance 12 WO 01/35905 PCT/US00/31679 of dry skin once applied. Furthermore, such coacervates may also serve as mechanisms for deposition of a therapeutic benefit agents thereby facilitating the substantivity of such agents to the skin. As the substantivity of the agent to the skin and/or hair is increased the effectiveness of the agent is increased. pH1 5 When the article is exposed to water, the therapeutic benefit compositions of the present invention exhibit a pH of from about 4 to about 10. Preferably, the pH is from about 4.5 to 9.5 and more preferably from about 5 to 9. Surface to Saturation Ratio Methodology The articles of the present invention comprise a therapeutic benefit component which is 10 substantially on the surface of the substrate. By "substantially on the surface of the substrate" is meant that the surface to saturation ratio is greater than about 1.25, preferably greater than about 1.5, more preferably greater than about 2.0, even more preferably greater than about 2.25, and most preferably greater than 2.5. The surface to saturation ratio is a ratio of the measurement of benefit agent on the surface of the substrate. These measurements are obtained from Attenuated Total Reflectance (ATR) FT-IR Spectroscopy the use of 15 which is well known to one skilled in the art of analytical chemistry. Many conventional methods of application of conditioning agents to substrates employ processes and/or product rheologies unsuitable for the purposes of the present invention. For example, a process to dip the substrate web in a fluid bath of conditioning agent and then squeeze the substrate web through metering rolls, so called "dip and nip" processing, applies conditioning agent through the entire substrate 20 and therefore does not afford opportunity for effective direct transfer of the composition off the cloth and onto another surface during use. Furthermore, many of the articles of the present invention utilize sufficient loadings of conditioning agent onto substrates to provide an effective whole body benefit, usually requiring about 100-200% loading rates based on the weight of the dry substrate. Known personal care implements that use these high loading levels essentially avoid dealing with aesthetic issues that can result 25 from these high loadings by distributing the loading evenly throughout the substrate, including the substrate interior. Applicants have surprisingly found that high loadings of conditioning agent can be maintained on the surface of the article, thus advantageously affording opportunity for direct transfer of the benefit agents from the substrate to the surface to be treated during use, while delivering improved aesthetics by the compositions of the present invention. 30 The procedure to obtain the measurements is as follows: Instrumental Setup: A BioRad FTS-7 spectrometer, manufactured by Bio Rad Labs, Digital Laboratory Division, located in Cambridge, MA, is used to collect the infrared spectra. Typically, the measurements consist of 100 scans at 4 cm" resolution. The collection optics consist of a flat 60 deg ZnSe ATR crystal, manufactured by Graseby Specac, Inc., located in Fairfield, CT. Data is collected at 25'C and 35 analyzed using Grams 386 software, distributed by Galactic Industries Corp., located in Salem, NH. Prior to measurement the crystal is cleaned with a suitable solvent. The sample is placed onto the ATR crystal and held under constant 4 kilogram weight. 13 WO 01/35905 PCT/USOO/31679 Experimental Procedure: (1) Measure the reference (background) spectrum of the cleaned, air dried cell. (2) First, select a substrate with no benefit agents applied to it, the substrate selected comprising the external surface of the article. Place substrate on top of the ATR crystal., external surface 5 against the crystal. First lay the substrate flat on the measuring platform. Then place a 4 kg. weight on top of the substrate. Then, measure the spectrum (typically 100 scans at 4 cm" resolution). The substrate acts as an internal standard because the absorbancy of the substrate alone is thus identified. Identify the main substrate peaks and wavenumbers. (3) Repeat the procedure for the substrate of the article with benefit agent applied to it. Identify 10 the primary benefit agent's peak heights, which are the highest observed peaks that either do not correspond to a substrate peak as observed previously; or which may correspond to a previously observed substrate peak but which exhibit the greatest percentage increase in absorbance due to presence of the conditioning agent. Record the wavenumber and absorbance of several benefit agent peaks. 15 (4) Select the substrate peak from the spectra determined in step 3 which occurs at a wavenumber determined in step 2, but which does not correspond to one of the primary benefit agent peaks selected in step 3. Record the wavenumber selected and the absorbance from the absorbance spectrum in step 3. (5) Calculate the ratio of each benefit agent's peak height determined in step 3 to the substrate's 20 peak height determined in step 4. The highest number of the group represents the surface to saturation ratio for the article. The following contain some examples: Substrate* Substrate Peak and Conditioner Conditioner Peak Ht. Ratio Peak Ht. Batting (blend of Glycerin polyester heat bonded 0.0865 (C-O Peak at 0.181 2.09 with 70% PET/PE (C=O Peak at 1710 1030 cm") bicomponent fiber) cm, 1 ) Batting (blend of Hydrocarbon polyester heat bonded 0.0865 (C-H Peak at 0.160 1.85 with 70% PET/PE (C=O Peak at 1710 2923 cm') bicomponent fiber) cm1) 70% Rayon/30% 0.0333 Glycerin Polyester, (C=O Peak at 1710 (C-O Peak at 0.0684 2.05 hydroentangled cm 1) 1030 cm') *Substrates of these types are readily available, for example from PGI Nonwovens, Benson, NC Moisture Retention Methodology 14 WO 01/35905 PCTUSOO/31679 As described above, the articles of the present invention are considered to be "substantially dry". As used herein, "substantially dry" means that the articles of the present invention exhibit a Moisture Retention of less than about 0.95 gins, preferably less than about 0.75 gins, even more preferably, less than about 0.5 gins, even more preferably less than about 0.25 gins, even still more preferably less than about 5 0.15 gms, and most preferably, less than about 0.1 gins. The Moisture Retention is indicative of the dry feel that users perceive upon touching the articles of the present invention as opposed to the feel of "wet" wipes. In order to determine the Moisture Retention of the present articles and other disposable substrate based products, the following equipment and materials are needed. 10 Bounty White Paper Towel Procter & Gamble SKU 37000 63037 Basis Weight = 42.14gsm Balance Accurate to 0.Og Lexan 0.5" thickness large enough to cover samples completely and weighs 10OOg Weight A 2000g weight or combination to equal 2000g Next, weigh two paper towels separately and record each weight. Place one paper towel on flat surface (e.g. lab bench). Place the sample article on top of that towel. Place the other paper towel on top of sample article. Next, place the Lexan and then the 2000g weight(s) on top of the sandwiched sample article. Wait 1 minute. After the minute, remove weight(s) and Lexan. Weigh the top and bottom paper 15 towel and record the weight. Calculate the Moisture Retention by subtracting the initial paper towel weight from the final weight (after 1 minute) for both the top and bottom paper towels. Add the weight differences obtained for the top and bottom paper towels. Assuming multiple articles are tested, average the total weight differences to obtain the Moisture Retention. 20 MULTIPLE ARTICLE EMBODIMENT The articles of the present invention may also be packaged individually or with additional articles suitable for providing separate benefits not provided by the primary article, e.g., aesthetic, therapeutic, functional, or otherwise, thereby forming a personal care kit. The additional article of this personal care kit preferably comprises a water insoluble substrate comprising at least one layer and either a cleansing 25 component containing a lathering surfactant or a therapeutic benefit component disposed onto or impregnated into that layer of the substrate of the additional article. The additional article of the present invention may also serve a functional benefit in addition to or in lieu of a therapeutic or aesthetic benefit. For instance, the additional article may be useful as a drying 15 WO 01/35905 PCTIUS0O/31679 implement suitable for use to aid in the removal of water from the skin or hair upon completion of a showering or bathing experience. MULTIPLE CHAMBERED EMBODIMENT The articles of the present invention may also comprise one or more chambers. Such chambers or 5 compartments result from the connection (e.g., bonding) of the substrate layers to one another at various loci to define enclosed areas. These chambers are useful, e.g., for separating various article components from one another, e.g., the surfactant-containing cleansing component from a conditioning agent. The separated article components which provide a therapeutic or aesthetic or cleansing benefit may be released from the chambers in a variety of ways including, but not limited to, solubilization, emulsification, 10 mechanical transfer, puncturing, popping, bursting, squeezing of the chamber or even peeling away a substrate layer which composes a portion of the chamber. OPTIONAL COMPONENTS The articles of the present invention may contain a variety of other components such as are conventionally used in a given product type provided that they do not unacceptably alter the benefits of the 15 invention. These optional components should be suitable for application to human skin and hair, that is, when incorporated into the article they are suitable for use in contact with human skin without undue toxicity, incompatibility, instability, allergic response, and the like, within the scope of sound medical or formulator's judgment. The CTFA Cosmetic Ingredient Handbook, Second Edition (1992) describes a wide variety of nonlimiting cosmetic and pharmaceutical ingredients commonly used in the skin care industry, 20 which are suitable for use in the articles of the present invention. Examples of these ingredient classes include: enzymes, abrasives, skin exfoliating agents, absorbents, aesthetic components such as fragrances, pigments, colorings/colorants, essential oils, skin sensates, astringents, etc. (e.g., clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazel distillate), anti-acne agents (e.g., resorcinol, sulfur, salicylic acid, erythromycin, zinc, etc.), anti-caking agents, antifoaming agents, additional 25 antimicrobial agents (e.g., iodopropyl butylcarbamate), antioxidants, binders, biological additives, buffering agents, bulking agents, chelating agents, chemical additives, colorants, cosmetic astringents, cosmetic biocides, denaturants, drug astringents, external analgesics, film formers or materials, e.g., polymers, for aiding the film-forming properties and substantivity of the composition (e.g., copolymer of eicosene and vinyl pyrrolidone), humectants, opacifying agents, pH adjusters, propellants, reducing agents, sequestrants, 30 skin bleaching agents (or lightening agents) (e.g., hydroquinone, kojic acid, ascorbic acid, magnesium ascorbyl phosphate, ascorbyl glucosamine), skin soothing and/or healing agents (e.g., panthenol and derivatives (e.g., ethyl panthenol), aloe vera, pantothenic acid and its derivatives, allantoin, bisabolol, and dipotassium glycyrrhizinate), skin treating agents, including agents for preventing, retarding, arresting, and/or reversing skin wrinkles (e.g., alpha-hydroxy acids such as lactic acid and glycolic acid and beta 35 hydroxy acids such as salicylic acid), thickeners, hydrocolloids, particular zeolites, and vitamins and derivatives thereof (e.g. tocopherol, tocopherol acetate, beta carotene, retinoic acid, retinol, retinoids, retinyl palmitate, niacin, niacinamide, and the like). The articles of the present invention may include 16 WO 01/35905 PCT/USOO/31679 carrier components such as are known in the art. Such carriers can include one or more compatible liquid or solid filler diluents or vehicles which are suitable for application to skin or hair. The articles of the present invention may optionally contain one or more of such optional components. Preferred articles optionally contain a safe and effective amount of therapeutic benefit 5 component comprising a therapeutic benefit agent selected from the group consisting of vitamin compounds, skin treating agents, anti-acne actives, anti-wrinkle actives, anti-skin atrophy actives, anti inflammatory actives, topical anesthetics, artificial tanning actives and accelerators, anti-microbial actives, anti-fungal actives, anti-viral agents, enzymes, sunscreen actives, anti-oxidants, skin exfoliating agents, and combinations thereof. As used herein, "a safe and effective amount" means an amount of a compound or 10 component sufficient to significantly induce a positive effect or benefit, but low enough to avoid serious side effects, (e.g., undue toxicity or allergic reaction), i.e., to provide a reasonable benefit to risk ratio, within the scope of sound medical judgment. The optional components useful herein can be categorized by their therapeutic or aesthetic benefit or their postulated mode of action. However, it is to be understood that the optional components useful 15 herein can in some instances provide more than one therapeutic or aesthetic benefit or operate via more than one mode of action. Therefore, classifications herein are made for the sake of convenience and are not intended to limit the component to that particular application or applications listed. Also, when applicable, the pharmaceutically-acceptable salts of the components are useful herein. Anionic Polymers 20 The articles of the present invention may optionally comprise an anionic polymer. Suitable anionic polymers may be selected from the group consisting of polyacrylic acid polymers, polyacrylamide polymers, copolymers of acrylic acid, acrylamide, and other natural or synthetic polymers (e.g., polystyrene, polybutene, polyurethane, etc.), naturally derived gums, and combinations thereof. Suitable gums include alginates (e.g., propylene glycol alginate), pectins, chitosans (e.g., chitosan lactate), and 25 modified gums (e.g., starch octenyl succinate), and combinations thereof. More preferably, the anionic polymer is selected from the group consisting of polyacrylic acid polymers, polyacrylamide polymers, pectins, chitosans, and combinations thereof. Preferred articles of the present invention comprise from about 0.01% to about 20%, more preferably from about 0.05% to about 10%, and most preferably from about 0.1% to about 5%, by weight of the coacervate-forming composition, of the anionic polymer. 30 Vitamin Compounds The present articles may comprise vitamin compounds, precursors, and derivatives thereof. These vitamin compounds may be in either natural or synthetic form. Suitable vitamin compounds include, but are not limited to, Vitamin A (e.g., beta carotene, retinoic acid, retinol, retinoids, retinyl palmitate, retinyl proprionate, etc.), Vitamin B (e.g., niacin, niacinamide, riboflavin, pantothenic acid, etc.), Vitamin C (e.g., 35 ascorbic acid, etc.), Vitamin D (e.g., ergosterol, ergocalciferol, cholecalciferol, etc.), Vitamin E (e.g., tocopherol acetate, etc.), and Vitamin K (e.g., phytonadione, menadione, phthiocol, etc.) compounds. 17 WO 01/35905 PCT/USOO/31679 In particular, the articles of the present invention may comprise a safe and effective amount of a vitamin B 3 compound. Vitamin B 3 compounds are particularly useful for regulating skin condition as described in co-pending U. S. Application Serial No. 08/834,010, filed April 11, 1997 (corresponding to international publication WO 97/39733 Al, published October 30, 1997) which is incorporated by 5 reference herein in its entirety. The therapeutic component of the present invention preferably comprise from about 0.01% to about 50%, more preferably from about 0.1% to about 10%, even more preferably from about 0.5% to about 10%, and still more preferably from about 1% to about 5%, most preferably from about 2% to about 5%, of the vitamin B 3 compound. As used herein, "vitamin B 3 compound" means a compound having the formula: OR N 10 wherein R is - CONH 2 (i.e., niacinamide), - COOH (i.e., nicotinic acid) or - CH 2 OH (i.e., nicotinyl alcohol); derivatives thereof; and salts of any of the foregoing. Exemplary derivatives of the foregoing vitamin B 3 compounds include nicotinic acid esters, including non-vasodilating esters of nicotinic acid, nicotinyl amino acids, nicotinyl alcohol esters of 15 carboxylic acids, nicotinic acid N-oxide and niacinamide N-oxide. Examples of suitable vitamin B 3 compounds are well known in the art and are commercially available from a number of sources, e.g., the Sigma Chemical Company (St. Louis, MO); ICN Biomedicals, Inc. (Irvin, CA) and Aldrich Chemical Company (Milwaukee, WI). The vitamin compounds may be included as the substantially pure material, or as an extract 20 obtained by suitable physical and/or chemical isolation from natural (e.g., plant) sources. Skin Treating Agents The articles of the present invention may contain one or more skin treating agents. Suitable skin treating agents include those effective for preventing, retarding, arresting, and/or reversing skin wrinkles. Examples of suitable skin treating agents include, but are not limited to, alpha-hydroxy acids such as lactic 25 acid and glycolic acid and beta-hydroxy acids such as salicylic acid. Anti-Acne Actives Examples of useful anti-acne actives for the articles of the present invention include, but are not limited to, the keratolytics such as salicylic acid (o-hydroxybenzoic acid), derivatives of salicylic acid such as 5-octanoyl salicylic acid, and resorcinol; retinoids such as retinoic acid and its derivatives (e.g., cis and 30 trans); sulfur-containing D and L amino acids and their derivatives and salts, particularly their N-acetyl derivatives, a preferred example of which is N-acetyl-L-cysteine; lipoic acid; antibiotics and antimicrobials such as benzoyl peroxide, octopirox, tetracycline, 2,4,4'-trichloro-2'-hydroxy diphenyl ether, 3,4,4' trichlorobanilide, azelaic acid and its derivatives, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, 18 WO 01/35905 PCT/USOO/31679 ethyl acetate, clindamycin and meclocycline; sebostats such as flavonoids; and bile salts such as scymnol sulfate and its derivatives, deoxycholate, and cholate. Anti-Wrinkle and Anti-Skin Atrophy Actives Examples of anti-wrinkle and anti-skin atrophy actives useful for the articles of the present 5 invention include, but are not limited to, retinoic acid and its derivatives (e.g., cis and trans); retinol; retinyl esters; niacinamide, salicylic acid and derivatives thereof; sulfur-containing D and L amino acids and their derivatives and salts, particularly the N-acetyl derivatives, a preferred example of which is N-acetyl-L cysteine; thiols, e.g., ethane thiol; hydroxy acids, phytic acid, lipoic acid; lysophosphatidic acid, and skin peel agents (e.g., phenol and the like). 10 Non-Steroidal Anti-Inflammatory Actives (NSAIDS) Examples of NSAIDS useful for the articles of the present invention include, but are not limited to, the following categories: propionic acid derivatives; acetic acid derivatives; fenamic acid derivatives; biphenylcarboxylic acid derivatives; and oxicams. All of these NSAIDS are fully described in U. S. Patent 4,985,459 to Sunshine et al., issued January 15, 1991, incorporated by reference herein in its entirety. 15 Examples of useful NSAIDS include acetyl salicylic acid, ibuprofen, naproxen, benoxaprofen, flurbiprofen, fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, carprofen, oxaprozin, pranoprofen, miroprofen, tioxaprofen, suprofen, alminoprofen, tiaprofenic acid, fluprofen and bucloxic acid. Also useful are the steroidal anti-inflammatory drugs including hydrocortisone and the like. Topical Anesthetics 20 Examples of topical anesthetic drugs useful for the articles of the present invention include, but are not limited to, benzocaine, lidocaine, bupivacaine, chlorprocaine, dibucaine, etidocaine, mepivacaine, tetracaine, dyclonine, hexylcaine, procaine, cocaine, ketamine, pramoxine, phenol, and pharmaceutically acceptable salts thereof. Artificial Tanning Actives and Accelerators 25 Examples of artificial tanning actives and accelerators useful for the articles of the present invention include, but are not limited to, dihydroxyacetaone, tyrosine, tyrosine esters such as ethyl tyrosinate, and phospho-DOPA. Antimicrobial and Antifungal Actives Examples of antimicrobial and antifungal actives useful for the articles of the present invention 30 include, but are not limited to, B-lactam drugs, quinolone drugs, ciprofloxacin, norfloxacin, tetracycline, erythromycin, amikacin, 2,4,4'-trichloro-2'-hydroxy diphenyl ether, 3,4,4'-trichlorocarbanilide, phenoxyethanol, phenoxy propanol, phenoxyisopropanol, doxycycline, capreomycin, chlorhexidine, chlortetracycline, oxytetracycline, clindamycin, ethambutol, hexamidine isethionate, metronidazole, pentamidine, gentamicin, kanamycin, lineomycin, methacycline, methenamine, minocycline, neomycin, 35 netilmicin, paromomycin, streptomycin, tobramycin, miconazole, tetracycline hydrochloride, erythromycin, zinc erythromycin, erythromycin estolate, erythromycin stearate, amikacin sulfate, doxycycline hydrochloride, capreomycin sulfate, chlorhexidine gluconate, chlorhexidine hydrochloride, 19 WO 01/35905 PCT/USOO/31679 chlortetracycline hydrochloride, oxytetracycline hydrochloride, clindamycin hydrochloride, ethambutol hydrochloride, metronidazole hydrochloride, pentamidine hydrochloride, gentamicin sulfate, kanamycin sulfate, lineomycin hydrochloride, methacycline hydrochloride, methenamine hippurate, methenamine mandelate, minocycline hydrochloride, neomycin sulfate, netilmicin sulfate, paromomycin sulfate, 5 streptomycin sulfate, tobramycin sulfate, miconazole hydrochloride, amanfadine hydrochloride, amanfadine sulfate, octopirox, parachlorometa xylenol, nystatin, tolnaftate, zinc pyrithione and clotrimazole. Anti-viral Agents The articles of the present invention may further comprise one or more anti-viral agents. Suitable 10 anti-viral agents include, but are not limited to, metal salts (e.g., silver nitrate, copper sulfate, iron chloride, etc.) and organic acids (e.g., malic acid, salicylic acid, succinic acid, benzoic acid, etc.). In particular compositions which contain additional suitable anti-viral agents include those described in copending U. S. patent applications Serial Nos. 09/421,084 (Beerse et al.) ; 09/421,131 (Biedermann et al.); 09/420,646 (Morgan et al.); and 09/421,179 (Page et al.), which were each filed on October 19, 1999. 15 Enzymes The article of the present invention may optionally include one or more enzymes. Preferably, such enzymes are dermatologically acceptable. Suitable enzymes include, but are not limited to, keratinase, protease, amylase, subtilisin, etc.. Sunscreen Actives 20 Also useful herein are sunscreening actives. A wide variety of sunscreening agents are described in U.S. Patent No. 5,087,445, to Haffey et al., issued February 11, 1992; U.S. Patent No. 5,073,372, to Turner et al., issued December 17, 1991; U.S. Patent No. 5,073,371, to Turner et al. issued December 17, 1991; and Segarin, et al., at Chapter VIII, pages 189 et seq., of Cosmetics Science and Technology, all of which are incorporated herein by reference in their entirety. Nonlimiting examples of sunscreens which are 25 useful in the compositions of the present invention are those selected from the group consisting of 2 ethylhexyl p-methoxycinnamate, 2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2 phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-t-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4 methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, and mixtures thereof. Still 30 other useful sunscreens are those disclosed in U.S. Patent No. 4,937,370, to Sabatelli, issued June 26, 1990; and U.S. Patent No. 4,999,186, to Sabatelli et al., issued March 12, 1991; these two references are incorporated by reference herein in their entirety. Especially preferred examples of these sunscreens include those selected from the group consisting of 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester of 2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester with 4 35 hydroxydibenzoylmethane, 4-N,N- (2-ethylhexyl)-methylaminobenzoic acid ester of 2-hydroxy-4-(2 hydroxyethoxy)benzophenone, 4-N,N-(2-ethylhexyl)-methylaminobenzoic acid ester of 4-(2 hydroxyethoxy)dibenzoylmethane, and mixtures thereof. Exact amounts of sunscreens which can be 20 WO 01/35905 PCT/USOO/31679 employed will vary depending upon the sunscreen chosen and the desired Sun Protection Factor (SPF) to be achieved. SPF is a commonly used measure of photoprotection of a sunscreen against erythema. See Federal Register, Vol. 43, No. 166, pp. 38206-38269, August 25, 1978, which is incorporated herein by reference in its entirety. 5 Hydrocolloids Hydrocolloids may also be optionally included in the articles of the present invention. Hydrocolloids are well known in the art and are helpful in extending the useful life of the surfactants contained in the cleansing component of the present invention such that the articles may last throughout at least one entire showering or bathing experience. Suitable hydrocolloids include, but are not limited to, 10 xanthan gum, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxylpropyl cellulose, methyl and ethyl cellulose, natural gums, gudras guar gum, bean gum, natural starches, deionitized starches (e.g., starch octenyl succinate) and the like. Exothermic Zeolites Zeolites and other compounds which react exothermically when combined with water may also be 15 optionally included in the articles of the present invention. Structured Conditioning Agents The articles of the present invention may optionally comprise structured conditioning agents. Suitable structured conditioning agents include, but are not limited to, vesicular structures such as ceramides, liposomes, and the like. 20 Hydrogel Forming Polymeric Gelling Agents In certain embodiments of the present invention, the articles may optionally comprise an aqueous gel, i.e., a hydrogenl", formed from a hydrogel forming polymeric gelling agent and water. More specifically, the hydrogel is contained within the cleansing component or the therapeutic benefit component of the article. When an aqueous gel is present, the articles preferably comprise from about 0.1% to about 25 100%, by weight of the water insoluble substrate, more preferably from about 3% to about 50%, and most preferably from about 5% to about 35%, of a hydrogel forming polymeric gelling agent, calculated based on the dry weight of the hydrogel forming polymeric gelling agent. In general, the hydrogel forming polymeric gelling agent materials of the present invention are at least partially crosslinked polymers prepared from polymerizable, unsaturated acid-containing monomers 30 which are water-soluble or become water-soluble upon hydrolysis. These include monoethylenically unsaturated compounds having at least one hydrophilic radical, including (but not limited to) olefinically unsaturated acids and anhydrides which contain at least one carbon-carbon olefinic double bond. With respect to these monomers, water-soluble means that the monomer is soluble in deionized water at 25*C at a level of at least 0.2%, preferably at least 1.0%. 35 Upon polymerization, monomeric units as described above will generally constitute from about 25 mole percent to 99.99 mole percent, more preferably from about 50 mole percent to 99.99 mole percent, 21 WO 01/35905 PCT/USOO/31679 most preferably at least about 75 mole percent of the polymeric gelling agent material (dry polymer weight basis), of acid-containing monomers. The hydrogel forming polymeric gelling agent herein is partially crosslinked to a sufficient degree preferably that is high enough such that the resulting polymer does not exhibit a glass transition 5 temperature (Tg) below about 140'C, and accordingly, the term "hydrogel forming polymeric gelling agent," as used herein, shall mean polymers meeting this parameter. Preferably the hydrogel forming polymeric gelling agent does not have a Tg below about 180*C, and more preferably does not have a Tg prior to decomposition of the polymer, at temperatures of about 300*C or higher. The Tg can be determined by differential scanning calorimetry (DSC) conducted at a heating rate of 20.0 C 0 /minute with 5 10 mg or smaller samples. The Tg is calculated as the midpoint between the onset and endset of heat flow change corresponding to the glass transition on the DSC heat capacity heating curve. The use of DSC to determine Tg is well known in the art, and is described by B. Cassel and M. P. DiVito in "Use of DSC To Obtain Accurate Thermodynamic and Kinetic Data", American Laboratory, January 1994, pp 14-19, and by B. Wunderlich in Thermal Analysis, Academic Press, Inc., 1990. 15 The hydrogel forming polymeric material is characterized as highly absorbent and able to retain water in its absorbed or "gel" state. Preferred hydrogel forming polymeric gelling agent hereof will be able to absorb at least about 40 g water (deionized) per gram of gelling agent, preferably at least about 60 g/g, more preferably at least about 80 g/g. These values, referred to as "Absorptive Capacity" herein can be determined according to the procedure in the Absorptive Capacity "Tea Bag" test described above. 20 The hydrogel forming polymeric gelling agent hereof will, in general, be at least partially crosslinked. Suitable cross-linking agents are well know in the art and include, for example, (1) compounds having at least two polymerizable double bonds; (2) compounds having at least one polymerizable double bond and at least one functional group reactive with the acid-containing monomer material; (3) compounds having at least two functional groups reactive with the acid-containing monomer 25 material; and (4) polyvalent metal compounds which can form ionic cross-linkages. Cross-linking agents having at least two polymerizable double bonds include (i) di- or polyvinyl compounds such as divinylbenzene and divinyltoluene; (ii) di- or poly-esters of unsaturated mono- or poly carboxylic acids with polyols including, for example, di- or triacrylic acid esters of polyols such as ethylene glycol, trimethylol propane, glycerine, or polyoxyethylene glycols; (iii) bisacrylamides such as N,N 30 methylenebisacrylamide; (iv) carbamyl esters that can be obtained by reacting polyisocyanates with hydroxyl group-containing monomers; (v) di- or poly-allyl ethers of polyols; (vi) di- or poly-allyl esters of polycarboxylic acids such as diallyl phthalate, diallyl adipate, and the like; (vii) esters of unsaturated mono or poly-carboxylic acids with mono-allyl esters of polyols such as acrylic acid ester of polyethylene glycol monoallyl ether; and (viii) di- or tri-allyl amine. 35 Cross-linking agents having at least one polymerizable double bond and at least one functional group reactive with the acid-containing monomer material include N-methylol acrylamide, glycidyl acrylate, and the like. Suitable cross-linking agents having at least two functional groups reactive with the 22 WO 01/35905 PCTIUSOO/31679 acid-containing monomer material include glyoxal; polyols such as ethylene glycol and glycerol; polyamines such as alkylene diamines (e.g., ethylene diamine), polyalkylene polyamines, polyepoxides, di or polyglycidyl ethers and the like. Suitable polyvalent metal cross-linking agents which can form ionic cross-linkages include oxides, hydroxides and weak acid salts (e.g., carbonate, acetate and the like) of 5 alkaline earth metals (e.g., calcium, magnesium) and zinc, including, for example, calcium oxide and zinc diacetate. Cross-linking agents of many of the foregoing types are described in greater detail in Masuda et al., U. S. Patent 4,076,663, issued February 28, 1978, and Allen et al., U. S. Patent 4,861,539, issued August 29, 1989, both incorporated herein by reference. Preferred cross-linking agents include the di- or 10 polyesters of unsaturated mono- or polycarboxylic acids mono-allyl esters of polyols, the bisacrylamides, and the di- or tri-allyl amines. Specific examples of especially preferred cross-linking agents include N,N' methylenebisacrylamide and trimethylol propane triacrylate. The cross-linking agent will generally constitute from about 0.001 mole percent to 5 mole percent of the resulting hydrogel-forming polymeric material. More generally, the cross-linking agent will 15 constitute from about 0.01 mole percent to 3 mole percent of the hydrogel-forming polymeric gelling agent used herein. The hydrogel forming polymeric gelling hereof may be employed in their partially neutralized form. For purposes of this invention, such materials are considered partially neutralized when at least 25 mole percent, and preferably at least 50 mole percent of monomers used to form the polymer are acid 20 group-containing monomers which have been neutralized with a base. Suitable neutralizing bases cations include hydroxides of alkali and alkaline earth metal (e.g. KOH, NaOH), ammonium, substituted ammonium, and amines such as amino alcohols (e.g., 2-amino-2-methyl-1,3-propanediol, diethanolamine, and 2-amino-2-methyl-I-propanol. This percentage of the total monomers utilized which are neutralized acid group-containing monomers is referred to herein as the "degree of neutralization." The degree of 25 neutralization will preferably not exceed 98%. Hydrogel forming polymeric gelling agents suitable for use herein are well known in the art, and are described, for example, in U. S. Patent 4,076,663, Masuda et al., issued February 28, 1978; U. S. Patent 4,062,817, Westerman, issued December 13, 1977; U. S. Patent 4,286,082, Tsubakimoto et al., issued August 25, 1981; U. S. Patent 5,061,259, Goldman et al., issued October 29, 1991, and U. S. Patent 30 4,654,039, Brandt et al., issued March 31, 1987 each of which is incorporated herein in its entirety. Hydrogel forming polymeric gelling agents suitable for use herein are also described in U. S. Patent 4,731,067, Le-Khac, issued March 15, 1988, U. S. Patent 4,743,244, Le-Khac, issued May 10, 1988, U. S. Patent 4,813,945, Le-Khac, issued March 21, 1989, U. S. Patent 4,880,868, Le-Khac, issued November 14, 1989, U. S. Patent 4,892,533, Le-Khac, issued January 9, 1990, U. S. Patent 5,026,784, Le 35 Khac, issued June 25, 1991, U. S. Patent 5,079,306, Le-Khac, issued January 7, 1992, U. S. Patent 5,151,465, Le-Khac, issued September 29, 1992, U. S. Patent 4,861,539, Allen, Farrer, and Flesher, issued 23 WO 01/35905 PCTUSOO/31679 August 29, 1989, and U. S. Patent 4,962,172, Allen, Farrer, and Flesher, issued October 9, 1990, each of which is incorporated herein by reference in its entirety. Suitable hydrogel forming polymeric gelling agents in the form of particles are commercially available from Hoechst Celanese Corporation, Portsmouth, VA, USA (SanwetTM Superabsorbent Polymers) 5 Nippon Shokubai, Japan (Aqualic T M , e.g., L-75, L-76) and Dow Chemical Company, Midland, MI, USA (Dry Tech
TM
). Hydrogel forming polymeric gelling agents in the form of fibers are commercially available from Camelot Technologies Inc., Leominster, MA, USA (Fibersorb
TM
, e.g., SA 7200H, SA 7200M, SA 7000L, SA 7000, and SA 7300). 10 The articles of the present invention may also contain other hydrophilic gelling agents. These include carboxylic acid-containing polymers as otherwise described above, except which have relatively lower degrees of crosslinking, such that they exhibit a Tg below 140'C, as well as a variety of other water soluble or colloidally water soluble polymers, such as cellulose ethers (e.g. hydroxyethyl cellulose, methyl cellulose, hydroxy propylmethyl cellulose), polyvinylpyrrolidone, polyvinylalcohol, guar gum, 15 hydroxypropyl guar gum and xanthan gum. Preferred among these additional hydrophilic gelling agents are the acid-containing polymers, particularly carboxylic acid-containing polymers. Especially preferred are those that comprise water-soluble polymer of acrylic acid crosslinked with a polyalkenyl polyether of a polyhydric alcohol, and optionally an acrylate ester or a polyfunctional vinylidene monomer. Preferred copolymers useful in the present invention are polymers of a monomeric mixture 20 containing 95 to 99 weight percent of an olefinically unsaturated carboxylic monomer selected from the group consisting of acrylic, methacrylic and ethacrylic acids; about 1 to about 3.5 weight percent of an acrylate ester of the formula:
R
1 O I l1
CH
2 =C-C-O-R wherein R is an alkyl radical containing 10 to 30 carbon atoms and R 1 is hydrogen, methyl or ethyl; and 25 0.1 to 0.6 weight percent of a polymerizable cross-linking polyalkenyl polyether of a polyhydric alcohol containing more than one alkenyl ether group per molecule wherein the parent polyhydric alcohol contains at least 3 carbon atoms and at least 3 hydroxyl groups. Preferably, these polymers contain from about 96 to about 97.9 weight percent of acrylic acid and from about 2.5 to about 3.5 weight percent of acrylic esters wherein the alkyl group contains 12 to 22 30 carbon atoms, and R 1 is methyl, most preferably the acrylate ester is stearyl methacrylate. Preferably, the amount of crosslinking polyalkenyl polyether monomer is from about 0.2 to 0.4 weight percent. The preferred crosslinking polyalkenyl polyether monomers are allyl pentaerythritol, trimethylolpropane diallylether or allyl sucrose. These polymers are fully described in U. S. Patent No. 4,509,949, to Huang et al., issued April 5, 1985, this patent being incorporated herein by reference. 24 WO 01/35905 PCT/USOO/31679 Other preferred copolymers useful in the present invention are the polymers which contain at least two monomeric ingredients, one being a monomeric olefinically-unsaturated carboxylic acid, and the other being a polyalkenyl, polyether of a polyhydric alcohol. Additional monomeric materials may be present in the monomeric mixture if desired, even in predominant proportion. 5 The first monomeric ingredient useful in the production of these carboxylic polymers are the olefinically-unsaturated carboxylic acids containing at least one activated carbon-to-carbon olefinic double bond, and at least one carboxyl group. The preferred carboxylic monomers are the acrylic acids having the general structure R2
CH
2 =C-COOH 10 wherein R 2 is a substituent selected from the class consisting of hydrogen, halogen, and the cyanogen (-C=N) groups, monovalent alkyl radicals, monovalent alkaryl radicals and monovalent cycloaliphatic radicals. Of this class, acrylic, methacrylic, and ethacrylic acid are most preferred. Another useful carboxylic monomer is maleic anhydride or the acid. The amount of acid used will be from about 95.5 to about 98.9 weight percent. 15 The second monomeric ingredient useful in the production of these carboxylic polymers are the polyalkenyl polyethers having more than one alkenyl ether grouping per molecule, such as alkenyl groups in which an olefinic double bond is present attached to a terminal methylene grouping, CH 2 =C<. The additional monomeric materials which may be present in the polymers include polyfunctional vinylidene monomers containing at least two terminal CH 2 < groups, including for example, butadiene, 20 isoprene, divinyl benzene, divinyl napbthlene, allyl acrylates, and the like. These polymers are fully described in U. S. Patent No. 2,798,053, to Brown, issued July 2, 1957, which is incorporated herein by reference in its entirety. Examples of carboxylic acid copolymers useful in the present invention include Carbomer 934, Carbomer 941, Carbomer 950, Carbomer 951, Carbomer 954, Carbomer 980, Carbomer 981, Carbomer 25 1342, acrylates/C10-30 alkyl acrylate cross polymer (available as Carbopol 934, Carbopol 941, Carbopol 950, Carbopol 951, Carbopol 954, Carbopol 980, Carbopol 981, Carbopol 1342, and the Pemulen series, respectively, from B. F. Goodrich). Other carboxylic acid copolymers useful in the present invention include sodium salts of acrylic acid/acrylamide copolymers sold by the Hoechst Celanese Corporation under the trademark of Hostaceren 30 PN73. Also included are the hydrogel polymers sold by Lipo Chemicals Inc. under the trademark of HYPAN hydrogels. These hydrogels consist of crystalline plicks of nitrates on a C-C backbone with various other pendant groups such as carboxyls, amides, and amidines. An example would include HYPAN SA 100 H, a polymer powder available from Lipo Chemical. 25 WO 01/35905 PCT/USOO/31679 Neutralizing agents for use in neutralizing the acidic groups of these polymers include those previously described. Hydrophobic Conditioning Agents The articles of the present invention may comprise one or more hydrophobic conditioning agents 5 which are useful for providing a conditioning benefit to the skin or hair during the use of the article. The articles of present invention preferably comprise from about 0.5% to about 1,000%, more preferably from about 1% to about 200%, and most preferably from about 25% to about 100%, by weight of the water insoluble substrate, of a hydrophobic conditioning agent. The hydrophobic conditioning agent may be selected from one or more hydrophobic conditioning 10 agents such that the weighted arithmetic mean solubility parameter of the hydrophobic conditioning agent is less than or equal to 10.5. It is recognized, based on this mathematical definition of solubility parameters, that it is possible, for example, to achieve the required weighted arithmetic mean solubility parameter, i.e., less than or equal to 10.5, for a hydrophobic conditioning agent comprising two or more compounds if one of the compounds has an individual solubility parameter greater than 10.5. 15 Solubility parameters are well known to the formulation chemist of ordinary skill in the art and are routinely used as a guide for determining compatibility's and solubilities of materials in the formulation process. The solubility parameter of a chemical compound, 6, is defined as the square root of the cohesive energy density for that compound. Typically, a solubility parameter for a compound is calculated from 20 tabulated values of the additive group contributions for the heat of vaporization and molar volume of the components of that compound, using the following equation: 1/2 Ej SZ = i wherein Yi; Ei = the sum of the heat of vaporization additive group contributions, and 25 Y_ m= the sum of the molar volume additive group contributions Standard tabulations of heat of vaporization and molar volume additive group contributions for a wide variety of atoms and groups of atoms are collected in Barton, A.F.M. Handbook of Solubility Parameters, CRC Press, Chapter 6, Table 3, pp. 64-66 (1985), which is incorporated by reference herein in its entirety. The above solubility parameter equation is described in Fedors, R.F., "A Method for Estimating Both the 26 WO 01/35905 PCT/US0O/31679 Solubility Parameters and Molar Volumes of Liquids", Polymer Engineering and Science, vol. 14, no. 2, pp. 147-154 (February 1974), which is incorporated by reference herein in its entirety. Solubility parameters obey the law of mixtures such that the solubility parameter for a mixture of materials is given by the weighted arithmetic mean (i.e. the weighted average) of the solubility parameters 5 for each component of that mixture. See, Handbook of Chemistry and Physics, 57th edition, CRC Press, p. C-726 (1976-1977), which is incorporated by reference herein in its entirety. Formulation chemists typically report and use solubility parameters in units of (cal/cm 3 )1/ 2 . The tabulated values of additive group contributions for heat of vaporization in the Handbook of Solubility Parameters are reported in units of kJ/mol. However, these tabulated heat of vaporization values are readily 10 converted to cal/mol using the following well-known relationships: I J/mol = 0.239006 cal/mol and 1000 J= l k. See Gordon, A.J. et al., The Chemist's Companion, John Wiley & Sons, pp. 456-463, (1972), which is incorporated by reference herein in its entirety. Solubility parameters have also been tabulated for a wide variety of chemical materials. 15 Tabulations of solubility parameters are found in the above-cited Handbook of Solubility Parameters. Also, see "Solubility Effects In Product, Package, Penetration, And Preservation", C.D. Vaughan, Cosmetics and Toiletries, vol. 103, October 1988, pp. 47-69, which is incorporated by reference herein in its entirety. Nonlimiting examples of hydrophobic conditioning agents include those selected from the group 20 consisting of mineral oil, petrolatum, lecithin, hydrogenated lecithin, lanolin, lanolin derivatives, C7-C40 branched chain hydrocarbons, Cl-C30 alcohol esters of Cl-C30 carboxylic acids, Cl-C30 alcohol esters of C2-C30 dicarboxylic acids, monoglycerides of Cl-C30 carboxylic acids, diglycerides of Cl-C30 carboxylic acids, triglycerides of Cl-C30 carboxylic acids, ethylene glycol monoesters of C1-C30 carboxylic acids, ethylene glycol diesters of Cl-C30 carboxylic acids, propylene glycol monoesters of Cl 25 C30 carboxylic acids, propylene glycol diesters of Cl-C30 carboxylic acids, Cl-C30 carboxylic acid monoesters and polyesters of sugars, polydialkylsiloxanes, polydiarylsiloxanes, polyalkarylsiloxanes, cylcomethicones having 3 to 9 silicon atoms, vegetable oils, hydrogenated vegetable oils, polypropylene glycol C4-C20 alkyl ethers, di C8-C30 alkyl ethers, and combinations thereof. Mineral oil, which is also known as petrolatum liquid, is a mixture of liquid hydrocarbons 30 obtained from petroleum. See The Merck Index, Tenth Edition, Entry 7048, p. 1033 (1983) and International Cosmetic Ingredient Dictionary, Fifth Edition, vol. 1, p.
4 15
-
4 17 (1993), which are incorporated by reference herein in their entirety. Petrolatum, which is also known as petroleum jelly, is a colloidal system of nonstraight-chain solid hydrocarbons and high-boiling liquid hydrocarbons, in which most of the liquid hydrocarbons are 35 held inside the micelles. See The Merck Index, Tenth Edition, Entry 7047, p. 1033 (1983); Schindler, 27 WO 01/35905 PCT/USOO/31679 Drug. Cosmet. Ind., 89, 36-37, 76, 78-80, 82 (1961); and International Cosmetic Ingredient Dictionary, Fifth Edition, vol. 1, p. 537 (1993), which are incorporated by reference herein in their entirety. Lecithin is also useful as a hydrophobic conditioning agent. It is a naturally occurring mixture of the diglycerides of certain fatty acids, linked to the choline ester of phosphoric acid. 5 Straight and branched chain hydrocarbons having from about 7 to about 40 carbon atoms are useful herein. Nonlimiting examples of these hydrocarbon materials include dodecane, isododecane, squalane, cholesterol, hydrogenated polyisobutylene, docosane (i.e. a C 2 2 hydrocarbon), hexadecane, isohexadecane (a commercially available hydrocarbon sold as Permethyl® 101A by Presperse, South Plainfield, NJ). Also useful are the C7-C40 isoparaffins, which are C7-C40 branched hydrocarbons. 10 Polydecene, a branched liquid hydrocarbon, is also useful herein and is commercially available under the tradenames Puresyn 100@ and Puresyn 3000@ from Mobile Chemical (Edison, NJ). Also useful are Cl-C30 alcohol esters of Cl-C30 carboxylic acids and of C2-C30 dicarboxylic acids, including straight and branched chain materials as well as aromatic derivatives. Also useful are esters such as monoglycerides of Cl-C30 carboxylic acids, diglycerides of Cl-C30 carboxylic acids, 15 triglycerides of Cl-C30 carboxylic acids, ethylene glycol monoesters of Cl-C30 carboxylic acids, ethylene glycol diesters of Cl-C30 carboxylic acids, propylene glycol monoesters of Cl-C30 carboxylic acids, and propylene glycol diesters of Cl-C30 carboxylic acids. Straight chain, branched chain and aryl carboxylic acids are included herein. Also useful are propoxylated and ethoxylated derivatives of these materials. Nonlimiting examples include diisopropyl sebacate, diisopropyl adipate, isopropyl myristate, isopropyl 20 palmitate, myristyl propionate, ethylene glycol distearate, 2-ethylhexyl palmitate, isodecyl neopentanoate, di-2-ethylhexyl maleate, cetyl palmitate, myristyl myristate, stearyl stearate, cetyl stearate, behenyl behenrate, dioctyl maleate, dioctyl sebacate, diisopropyl adipate, cetyl octanoate, diisopropyl dilinoleate, carpylic/capric triglyceride, PEG-6 caprylic/capric triglyceride, PEG-8 caprylic/capric triglyceride, and combinations thereof. 25 Also useful are various Cl-C30 monoesters and polyesters of sugars and related materials. These esters are derived from a sugar or polyol moiety and one or more carboxylic acid moieties. Depending on the constituent acid and sugar, these esters can be in either liquid or solid form at room temperature. Examples of liquid esters include: glucose tetraoleate, the glucose tetraesters of soybean oil fatty acids (unsaturated), the mannose tetraesters of mixed soybean oil fatty acids, the galactose tetraesters of oleic 30 acid, the arabinose tetraesters of linoleic acid, xylose tetralinoleate, galactose pentaoleate, sorbitol tetraoleate, the sorbitol hexaesters of unsaturated soybean oil fatty acids, xylitol pentaoleate, sucrose tetraoleate, sucrose pentaoletate, sucrose hexaoleate, sucrose hepatoleate, sucrose octaoleate, and mixtures thereof. Examples of solid esters include: sorbitol hexaester in which the carboxylic acid ester moieties are palmitoleate and arachidate in a 1:2 molar ratio; the octaester of raffinose in which the carboxylic acid ester 35 moieties are linoleate and behenate in a 1:3 molar ratio; the heptaester of maltose wherein the esterifying carboxylic acid moieties are sunflower seed oil fatty acids and lignocerate in a 3:4 molar ratio; the octaester 28 WO 01/35905 PCTIUSOO/31679 of sucrose wherein the esterifying carboxylic acid moieties are oleate and behenate in a 2:6 molar ratio; and the octaester of sucrose wherein the esterifying carboxylic acid moieties are laurate, linoleate and behenate in a 1:3:4 molar ratio. A preferred solid material is sucrose polyester in which the degree of esterification is 7-8, and in which the fatty acid moieties are C18 mono- and/or di-unsaturated and behenic, in a molar ratio 5 of unsaturates: behenic of 1:7 to 3:5. A particularly preferred solid sugar polyester is the octaester of sucrose in which there are about 7 behenic fatty acid moieties and about 1 oleic acid moiety in the molecule. Other materials include cottonseed oil or soybean oil fatty acid esters of sucrose. The ester materials are further described in, U. S. Patent No. 2,831,854, U. S. Patent No. 4,005,196, to Jandacek, issued January 25, 1977; U. S. Patent No. 4,005,195, to Jandacek, issued January 25, 1977, U. S. Patent 10 No. 5,306,516, to Letton et al., issued April 26, 1994; U. S. Patent No. 5,306,515, to Letton et al., issued April 26, 1994; U. S. Patent No. 5,305,514, to Letton et al., issued April 26, 1994; U. S. Patent No. 4,797,300, to Jandacek et al., issued January 10, 1989; U. S. Patent No. 3,963,699, to Rizzi et al, issued June 15, 1976; U. S. Patent No. 4,518,772, to Volpenhein, issued May 21, 1985; and U. S. Patent No. 4,517,360, to Volpenhein, issued May 21, 1985; each of which is incorporated by reference herein in its 15 entirety. Nonvolatile silicones such as polydialkylsiloxanes, polydiarylsiloxanes, and polyalkarylsiloxanes are also useful oils. These silicones are disclosed in U. S. Patent No. 5,069,897, to Orr, issued December 3, 1991, which is incorporated by reference herein in its entirety. The polyalkylsiloxanes correspond to the general chemical formula R 3 SiO[R 2 SiO],SiR 3 wherein R is an alkyl group (preferably R is methyl or 20 ethyl, more preferably methyl) and x is an integer up to about 500, chosen to achieve the desired molecular weight. Commercially available polyalkylsiloxanes include the polydimethylsiloxanes, which are also known as dimethicones, nonlimiting examples of which include the Vicasil® series sold by General Electric Company and the Dow Coming® 200 series sold by Dow Coming Corporation. Specific examples of polydimethylsiloxanes useful herein include Dow Coming® 225 fluid having a viscosity of 25 10 centistokes and a boiling point greater than 200'C, and Dow Coming® 200 fluids having viscosities of 50, 350, and 12,500 centistokes, respectively, and boiling points greater than 200'C. Also useful are materials such as trimethylsiloxysilicate, which is a polymeric material corresponding to the general chemical formula [(CH 2
)
3 SiOl/ 2 ]x[SiO 2 ]y, wherein x is an integer from about 1 to about 500 and y is an integer from about 1 to about 500. A commercially available trimethylsiloxysilicate is sold as a mixture 30 with dimethicone as Dow Coming® 593 fluid. Also useful herein are dimethiconols, which are hydroxy terminated dimethyl silicones. These materials can be represented by the general chemical formulas
R
3 SiO[R 2 SiO]xSiR 2 OH and HOR 2 SiO[R 2 SiO1xSiR 2 OH wherein R is an alkyl group (preferably R is methyl or ethyl, more preferably methyl) and x is an integer up to about 500, chosen to achieve the desired molecular weight. Commercially available dimethiconols are typically sold as mixtures with dimethicone 35 or cyclomethicone (e.g. Dow Coming® 1401, 1402, and 1403 fluids). Also useful herein are polyalkylaryl 29 WO 01/35905 PCT/USOO/31679 siloxanes, with polymethylphenyl siloxanes having viscosities from about 15 to about 65 centistokes at 25 0 C being preferred. These materials are available, for example, as SF 1075 methylphenyl fluid (sold by General Electric Company) and 556 Cosmetic Grade phenyl trimethicone fluid (sold by Dow Coming Corporation). Alkylated silicones such as methyldecyl silicone and methyloctyl silicone are useful herein 5 and are commercially available from General Electric Company. Also useful herein are alkyl modified siloxanes such as alkyl methicones and alkyl dimethicones wherein the alkyl chain contains 10 to 50 carbons. Such siloxanes are commercially available under the tradenames ABIL WAX 9810 (C 24
-C
28 alkyl methicone) (sold by Goldschmidt) and SF1632 (cetearyl methicone)(sold by General Electric Company). Vegetable oils and hydrogenated vegetable oils are also useful herein. Examples of vegetable oils 10 and hydrogenated vegetable oils include safflower oil, castor oil, coconut oil, cottonseed oil, menhaden oil, palm kernel oil, palm oil, peanut oil, soybean oil, rapeseed oil, linseed oil, rice bran oil, pine oil, sesame oil, sunflower seed oil, hydrogenated safflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated cottonseed oil, hydrogenated menhaden oil, hydrogenated palm kernel oil, hydrogenated palm oil, hydrogenated peanut oil, hydrogenated soybean oil, hydrogenated rapeseed oil, hydrogenated 15 linseed oil, hydrogenated rice bran oil, hydrogenated sesame oil, hydrogenated sunflower seed oil, and mixtures thereof Also useful are C4-C20 alkyl ethers of polypropylene glycols, CI-C20 carboxylic acid esters of polypropylene glycols, and di-C8-C30 alkyl ethers. Nonlimiting examples of these materials include PPG 14 butyl ether, PPG- 15 stearyl ether, dioctyl ether, dodecyl octyl ether, and mixtures thereof. 20 Hydrophilic Conditioning Agents The articles of the present invention may optionally comprise one or more hydrophilic conditioning agents. Nonlimiting examples of hydrophilic conditioning agents include those selected from the group consisting of polyhydric alcohols, polypropylene glycols, polyethylene glycols, ureas, pyrolidone carboxylic acids, ethoxylated and/or propoxylated C3-C6 diols and triols, alpha-hydroxy C2-C6 carboxylic 25 acids, ethoxylated and/or propoxylated sugars, polyacrylic acid copolymers, sugars having up to about 12 carbons atoms, sugar alcohols having up to about 12 carbon atoms, and mixtures thereof. Specific examples of useful hydrophilic conditioning agents include materials such as urea; guanidine; glycolic acid and glycolate salts (e.g., ammonium and quaternary alkyl ammonium); lactic acid and lactate salts (e.g., ammonium and quaternary alkyl ammonium); sucrose, fructose, glucose, eruthrose, erythritol, sorbitol, 30 mannitol, glycerol, hexanetriol, propylene glycol, butylene glycol, hexylene glycol, and the like; polyethylene glycols such as PEG-2, PEG-3, PEG-30, PEG-50, polypropylene glycols such as PPG-9, PPG-12, PPG-15, PPG-17, PPG-20, PPG-26, PPG-30, PPG-34; alkoxylated glucose; hyaluronic acid; cationic skin conditioning polymers (e.g., quaternary ammonium polymers such as Polyquaternium polymers); and mixtures thereof. Glycerol, in particular, is a preferred hydrophilic conditioning agent in 35 the articles of the present invention. Also useful are materials such as aloe vera in any of its variety of forms (e.g., aloe vera gel), chitosan and chitosan derivatives, e.g., chitosan lactate, lactamide monoethanolamine; acetamide monoethanolamine; and mixtures thereof. Also useful are propoxylated 30 WO 01/35905 PCT/USOO/31679 glycerols as described in propoxylated glycerols described in U. S. Patent No. 4,976,953, to Orr et al., issued December 11, 1990, which is incorporated by reference herein in its entirety. When the therapeutic benefit component comprises such conditioning agents, the benefit component may be made to include a variety of forms in addition to the coacervate that is formed when the 5 article is exposed to water. In one embodiment of the present invention, the conditioning agents are in the form of an emulsion. For instance, oil-in-water, water-in-oil, water-in-oil-in-water, and oil-in-water-in silicone emulsions are useful herein. As used in the context of emulsions, "water" may refer not only to water but also water soluble or water miscible agents like glycerin. In one embodiment, the conditioning agents comprise an emulsion which further comprises an 10 aqueous phase and an oil phase. As will be understood by the skilled artisan, a given component will distribute primarily into either the aqueous or oil phase, depending on the water solubility/dispersibility of the therapeutic benefit agent in the component. In one embodiment, the oil phase comprises one or more hydrophobic conditioning agents. In another embodiment, the aqueous phase comprises one or more hydrophilic conditioning agents. 15 When the conditioning agents of the therapeutic benefit are emulsion form, the emulsion generally contains an aqueous phase and an oil or lipid phase. Suitable oils or lipids may be derived from animals, plants, or petroleum and may be natural or synthetic (i.e., man-made). Such oils are discussed above in the Hydrophobic Conditioning Agents section. Additionally, preferred emulsions also contain a hydrophilic conditioning agent such as glycerin such that a glycerin-in-oil emulsion results. 20 Therapeutic benefit component which contains an emulsion will preferably further contain from about 1% to about 10%, more preferably from about 2% to about 5%, of an emulsifier, based on the weight of therapeutic benefit component. Emulsifiers may be nonionic, anionic or cationic. Suitable emulsifiers are disclosed in, for example, U.S. Patent 3,755,560, issued August 28, 1973, Dickert et al.; U.S. Patent 4,421,769, issued December 20, 1983, Dixon et al.; and McCutcheon's Detergents and Emulsifiers, North 25 American Edition, pages 317-324 (1986). Therapeutic benefit components in emulsion form may also contain an anti-foaming agent to minimize foaming upon application to the skin. Anti-foaming agents include high molecular weight silicones and other materials well known in the art for such use. The therapeutic benefit component may also be in the form of a microemulsion. As used herein, "microemulsion" refers to thermodynamic stable mixtures of two immiscible solvents (one apolar and the 30 other polar) stabilized by an amphiphilic molecule, a surfactant. Preferred microemulsions include water in-oil microemulsions. Cleansing Component The articles of the present invention may optionally comprise a cleansing component which further comprises one or more surfactants. The cleansing component is disposed adjacent to the nonwoven 35 layer of the water insoluble substrate. The articles of the present invention comprise from about 10% to about 1,000%, preferably from about 50% to about 600%, and more preferably from about 100% to about 250%, based on the weight of the water insoluble substrate, of the surfactant. Also, the articles of the 31 WO 01/35905 PCT/USOO/31679 present invention preferably comprise at least about 1 gram, by weight of the water insoluble substrate, of a surfactant. Thus, the cleansing component may be added to the substrate without requiring a drying process. The surfactants of the cleansing component are preferably lathering surfactants. As used herein, 5 "lathering surfactant" means a surfactant, which when combined with water and mechanically agitated generates a foam or lather. Such surfactants are preferred since increased lather is important to consumers as an indication of cleansing effectiveness. In certain embodiments, the surfactants or combinations of surfactants are mild. As used herein, "mild" means that the surfactants as well as to the articles of the present invention demonstrate skin mildness at least milder than common bar soap matrices which typically 10 comprise a combination of natural soap and synthetic surfactant (e.g., Lever 2000@ and Zest@). Methods for measuring mildness, or inversely the irritancy, of surfactant containing articles, are based on a skin barrier destruction test. In this test, the milder the surfactant, the lesser the skin barrier is destroyed. Skin barrier destruction is measured by the relative amount of radio-labeled (tritium labeled) water (3H-H 2 0) which passes from the test solution through the skin epidermis into the physiological buffer contained in 15 the diffusate chamber. This test is described by T.J. Franz in the J. Invest. Dermatol., 1975, 64, pp. 190 195; and in U. S. Patent No. 4,673,525, to Small et al., issued June 16, 1987, which are both incorporated by reference herein in their entirety. Other testing methodologies for determining surfactant mildness well known to one skilled in the art can also be used. A wide variety of lathering surfactants are useful herein and include those selected from the group 20 consisting of anionic lathering surfactants, nonionic lathering surfactants, cationic lathering surfactants, amphoteric lathering surfactants, and mixtures thereof. Anionic Lathering Surfactants Nonlimiting examples of anionic lathering surfactants useful in the compositions of the present invention are disclosed in McCutcheon's, Detergents and Emulsifiers, North American edition (1986), 25 published by Allured Publishing Corporation; McCutcheon's, Functional Materials, North American Edition (1992); and U. S. Patent No. 3,929,678, to Laughlin et al., issued December 30, 1975, each of which is incorporated by reference herein in their entirety. A wide variety of anionic surfactants are potentially useful herein. Nonlimiting examples of anionic lathering surfactants include those selected from the group consisting of alkyl and alkyl ether 30 sulfates, sulfated monoglycerides, sulfonated olefins, alkyl aryl sulfonates, primary or secondary alkane sulfonates, alkyl sulfosuccinates, acyl taurates, acyl isethionates, alkyl glycerylether sulfonate, sulfonated methyl esters, sulfonated fatty acids, alkyl phosphates, acyl glutamates, acyl sarcosinates, alkyl sulfoacetates, acylated peptides, alkyl ether carboxylates, acyl lactylates, anionic fluorosurfactants, and combinations thereof. Combinations of anionic surfactants can be used effectively in the present invention. 35 Anionic surfactants for use in the cleansing component include alkyl and alkyl ether sulfates. These materials have the respective formulae RIO-SO3M and R1(CH2H4O)x-O-SO3M, wherein RI is a saturated or unsaturated, branched or unbranched alkyl group from about 8 to about 24 carbon atoms, x is 1 32 WO 01/35905 PCTUSOO/31679 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine. The alkyl sulfates are typically made by the sulfation of monohydric alcohols (having from about 8 to about 24 carbon atoms) using sulfur trioxide or other known sulfation technique. The alkyl ether sulfates are typically made as condensation products of 5 ethylene oxide and monohydric alcohols (having from about 8 to about 24 carbon atoms) and then sulfated. These alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Specific examples of alkyl sulfates which may be used in the cleansing component are sodium, ammonium, potassium, magnesium, or TEA salts of lauryl or myristyl sulfate. Examples of alkyl ether sulfates which may be used include ammonium, sodium, magnesium, or TEA laureth-3 sulfate. 10 Another suitable class of anionic surfactants are the sulfated monoglycerides of the form RICO O-CH2-C(OH)H-CH2-O-SO3M, wherein RI is a saturated or unsaturated, branched or unbranched alkyl group from about 8 to about 24 carbon atoms, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine. These are typically made by the reaction of glycerin with fatty acids (having from about 8 to about 24 carbon atoms) to form a 15 monoglyceride and the subsequent sulfation of this monoglyceride with sulfur trioxide. An example of a sulfated monoglyceride is sodium cocomonoglyceride sulfate. Other suitable anionic surfactants include olefin sulfonates of the form R1SO3M, wherein RI is a mono-olefin having from about 12 to about 24 carbon atoms, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine. 20 These compounds can be produced by the sulfonation of alpha olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sultones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxyalkanesulfonate. An example of a sulfonated olefin is sodium C14/C16 alpha olefin sulfonate. Other suitable anionic surfactants are the linear alkylbenzene sulfonates of the form Rl-C6H4 25 S03M, wherein RI is a saturated or unsaturated, branched or unbranched alkyl group from about 8 to about 24 carbon atoms, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine. These are formed by the sulfonation of linear alkyl benzene with sulfur trioxide. An example of this anionic surfactant is sodium dodecylbenzene sulfonate. 30 Still other anionic surfactants suitable for this cleansing component include the primary or secondary alkane sulfonates of the form RISO3M, wherein RI is a saturated or unsaturated, branched or unbranched alkyl chain from about 8 to about 24 carbon atoms, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine. These are commonly formed by the sulfonation of paraffins using sulfur dioxide in the presence of chlorine 35 and ultraviolet light or another known sulfonation method. The sulfonation can occur in either the secondary or primary positions of the alkyl chain. An example of an alkane sulfonate useful herein is alkali metal or ammonium C13-C17 paraffin sulfonates. 33 WO 01/35905 PCT/USOO/31679 Still other suitable anionic surfactants are the alkyl sulfosuccinates, which include disodium N octadecylsulfosuccinamate; diammonium lauryl sulfosuccinate; tetrasodium N-(1,2-dicarboxyethyl)-N octadecylsulfosuccinate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic acid. 5 Also useful are taurates which are based on taurine, which is also known as 2 aminoethanesulfonic acid. Examples of taurates include N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate as detailed in U.S. Patent No. 2,658,072 which is incorporated herein by reference in its entirety. Other examples based of taurine include the acyl taurines formed by the reaction of n-methyl taurine with fatty acids (having from about 8 to about 24 carbon 10 atoms). Another class of anionic surfactants suitable for use in the cleansing component are the acyl isethionates. The acyl isethionates typically have the formula RlCO-0-CH2CH2SO3M wherein RI is a saturated or unsaturated, branched or unbranched alkyl group having from about 10 to about 30 carbon atoms, and M is a cation. These are typically formed by the reaction of fatty acids (having from about 8 to 15 about 30 carbon atoms) with an alkali metal isethionate. Nonlimiting examples of these acyl isethionates include ammonium cocoyl isethionate, sodium cocoyl isethionate, sodium lauroyl isethionate, and mixtures thereof. Still other suitable anionic surfactants are the alkylglyceryl ether sulfonates of the form RI OCH2-C(OH)H-CH2-SO3M, wherein RI is a saturated or unsaturated, branched or unbranched alkyl 20 group from about 8 to about 24 carbon atoms, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine. These can be formed by the reaction of epichlorohydrin and sodium bisulfite with fatty alcohols (having from about 8 to about 24 carbon atoms) or other known methods. One example is sodium cocoglyceryl ether sulfonate. Other suitable anionic surfactants include the sulfonated fatty acids of the form R1-CH(SO4) 25 COOH and sulfonated methyl esters of the from Rl-CH(S04)-CO-0-CH3, where RI is a saturated or unsaturated, branched or unbranched alkyl group from about 8 to about 24 carbon atoms. These can be formed by the sulfonation of fatty acids or alkyl methyl esters (having from about 8 to about 24 carbon atoms) with sulfur trioxide or by another known sulfonation technique. Examples include alpha sulphonated coconut fatty acid and lauryl methyl ester. 30 Other anionic materials include phosphates such as monoalkyl, dialkyl, and trialkylphosphate salts formed by the reaction of phosphorous pentoxide with monohydric branched or unbranched alcohols having from about 8 to about 24 carbon atoms. These could also be formed by other known phosphation methods. An example from this class of surfactants is sodium mono or dilaurylphosphate. Other anionic materials include acyl glutamates corresponding to the formula RICO-N(COOH) 35 CH2CH2-CO2M wherein RI is a saturated or unsaturated, branched or unbranched alkyl or alkenyl group of about 8 to about 24 carbon atoms, and M is a water-soluble cation. Nonlimiting examples of which include sodium lauroyl glutamate and sodium cocoyl glutamate. 34 WO 01/35905 PCT/USOO/31679 Other anionic materials include alkanoyl sarcosinates corresponding to the formula RlCON(CH3)-CH2CH2-CO2M wherein RI is a saturated or unsaturated, branched or unbranched alkyl or alkenyl group of about 10 to about 20 carbon atoms, and M is a water-soluble cation. Nonlimiting examples of which include sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, and ammonium lauroyl 5 sarcosinate. Other anionic materials include alkyl ether carboxylates corresponding to the formula RI (OCH2CH2)x-OCH2-CO2M wherein RI is a saturated or unsaturated, branched or unbranched alkyl or alkenyl group of about 8 to about 24 carbon atoms, x is 1 to 10, and M is a water-soluble cation. Nonlimiting examples of which include sodium laureth carboxylate. 10 Other anionic materials include acyl lactylates corresponding to the formula RICO-[O-CH(CH3) CO]x-CO2M wherein RI is a saturated or unsaturated, branched or unbranched alkyl or alkenyl group of about 8 to about 24 carbon atoms, x is 3, and M is a water-soluble cation. Nonlimiting examples of which include sodium cocoyl lactylate. Other anionic materials include the carboxylates, nonlimiting examples of which include sodium 15 lauroyl carboxylate, sodium cocoyl carboxylate, and ammonium lauroyl carboxylate. Anionic flourosurfactants can also be used. Other anionic materials include natural soaps derived from the saponification of vegetable and/or animal fats & oils exmaples of which include sodium laurate, sodium myristate, palmitate, stearate, tallowate, cocoate. 20 Any counter cation, M, can be used on the anionic surfactant. Preferably, the counter cation is selected from the group consisting of sodium, potassium, ammonium, monoethanolamine, diethanolamine, and triethanolamine. More preferably, the counter cation is ammonium. Nonionic Lathering Surfactants Nonlimiting examples of nonionic lathering surfactants for use in the compositions of the present 25 invention are disclosed in McCutcheon's, Detergents and Emulsifiers, North American edition (1986), published by allured Publishing Corporation; and McCutcheon's, Functional Materials, North American Edition (1992); both of which are incorporated by reference herein in their entirety. Nonionic lathering surfactants useful herein include those selected from the group consisting of alkyl glucosides, alkyl polyglucosides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, 30 sucrose esters, amine oxides, and mixtures thereof. Alkyl glucosides and alkyl polyglucosides are useful herein, and can be broadly defined as condensation products of long chain alcohols, e.g., C8-30 alcohols, with sugars or starches or sugar or starch polymers, i.e., glycosides or polyglycosides. These compounds can be represented by the formula (S)n-O-R wherein S is a sugar moiety such as glucose, fructose, mannose, and galactose; n is an integer of 35 from about 1 to about 1000, and R is a C8-30 alkyl group. Examples of long chain alcohols from which the alkyl group can be derived include decyl alcohol, cetyl alcohol, stearyl alcohol, lauryl alcohol, myristyl alcohol, oleyl alcohol, and the like. Preferred examples of these surfactants include those wherein S is a 35 WO 01/35905 PCT/USOO/31679 glucose moiety, R is a C8-20 alkyl group, and n is an integer of from about I to about 9. Commercially available examples of these surfactants include decyl polyglucoside (available as APG 325 CS from Henkel) and lauryl polyglucoside (available as APG 600CS and 625 CS from Henkel). Also useful are sucrose ester surfactants such as sucrose cocoate and sucrose laurate. 5 Other useful nonionic surfactants include polyhydroxy fatty acid amide surfactants, more specific examples of which include glucosamides, corresponding to the structural formula: 0 R1 R2-C -N-Z wherein: R is H, C -C4 alkyl, 2-hydroxyethyl, 2-hydroxy- propyl, preferably C -C alkyl, more preferably methyl or ethyl, most preferably methyl; R2 is C 5
-C
3 1 alkyl or alkenyl, preferably C -C 10 alkyl or alkenyl, more preferably C 9 -C 1 7 alkyl or alkenyl, most preferably C I-C 1 5 alkyl or alkenyl; and Z is a polhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with a least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably is a sugar moiety selected from the group consisting of glucose, fructose, maltose, lactose, galactose, mannose, xylose, and mixtures thereof. An especially preferred surfactant corresponding to the 15 above structure is coconut alkyl N-methyl glucoside amide (i.e., wherein the R 2CO- moiety is derived from coconut oil fatty acids). Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd.; U. S. Patent No. 2,965,576, to E.R. Wilson, issued December 20, 1960; U. S. Patent No. 2,703,798, to A.M. Schwartz, issued March 8, 1955; and U. S. Patent No. 1,985,424, to Piggott, 20 issued December 25, 1934; each of which are incorporated herein by reference in their entirety. Other examples of nonionic surfactants include amine oxides. Amine oxides correspond to the general formula R 1
R
2
R
3 N-+O, wherein R 1 contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about I glyceryl moiety, and R 2 and R 3 contain from about 1 to about 3 carbon atoms and from 0 to about 1 25 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals. The arrow in the formula is a conventional representation of a semipolar bond. Examples of amine oxides suitable for use in this invention include dimethyl-dodecylamine oxide, oleyldi(2-hydroxyethyl) amine oxide, dimethyloctylamine oxide, dimethyl-decylamine oxide, dimethyl-tetradecylamine oxide, 3,6,9 trioxaheptadecyldiethylamine oxide, di(2-hydroxyethyl)-tetradecylamine oxide, 2 30 dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl)amine oxide, dimethylhexadecylamine oxide. 36 WO 01/35905 PCT/USOO/31679 Nonlimiting examples of preferred nonionic surfactants for use herein are those selected form the group consisting of C8-C14 glucose amides, C8-Cl4 alkyl polyglucosides, sucrose cocoate, sucrose laurate, lauramine oxide, cocoamine oxide, and mixtures thereof. Cationic Lathering Surfactants 5 Cationic lathering surfactants are also useful in the articles of the present invention. Suitable cationic lathering surfactants include, but are not limited to, fatty amines, di-fatty quaternary amines, tri fatty quaternary amines, imidazolinium quaternary amines, and combinations thereof. Suitable fatty amines include monalkyl quaternary amines such as cetyltrimethylammonium bromide. A suitable quaternary amine is dialklamidoethyl hydroxyethylmonium methosulfate. The fatty amines, however, are 10 preferred. It is preferred that a lather booster is used when the cationic lathering surfactant is the primary lathering surfactant of the cleansing component. Additionally, nonionic surfactants have been found to be particularly useful in combination with such cationic lathering surfactants. Amphoteric Lathering Surfactants The term "amphoteric lathering surfactant," as used herein, is also intended to encompass 15 zwitterionic surfactants, which are well known to formulators skilled in the art as a subset of amphoteric surfactants. A wide variety of amphoteric lathering surfactants can be used in the compositions of the present invention. Particularly useful are those which are broadly described as derivatives of aliphatic secondary and tertiary amines, preferably wherein the nitrogen is in a cationic state, in which the aliphatic radicals can 20 be straight or branched chain and wherein one of the radicals contains an ionizable water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Nonlimiting examples of amphoteric surfactants useful in the compositions of the present invention are disclosed in McCutcheon's, Detergents and Emulsifiers, North American edition (1986), published by allured Publishing Corporation; and McCutcheon's, Functional Materials, North American 25 Edition (1992); both of which are incorporated by reference herein in their entirety. Nonlimiting examples of amphoteric or zwitterionic surfactants are those selected from the group consisting of betaines, sultaines, hydroxysultaines, alkyliminoacetates, iminodialkanoates, aminoalkanoates, and mixtures thereof. Examples of betaines include the higher alkyl betaines, such as coco dimethyl carboxymethyl 30 betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, cetyl dimethyl betaine (available as Lonzaine 16SP from Lonza Corp.), lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethy betaine, coco dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine, amidobetaines and amidosulfobetaines 35 (wherein the RCONH(CH 2
)
3 radical is attached to the nitrogen atom of the betaine), oleyl betaine 37 WO 01/35905 PCT/USOO/31679 (available as amphoteric Velvetex OLB-50 from Henkel), and cocamidopropyl betaine (available as Velvetex BK-35 and BA-35 from Henkel). Examples of sultaines and hydroxysultaines include materials such as cocamidopropyl hydroxysultaine (available as Mirataine CBS from Rhone-Poulenc). 5 Preferred for use herein are amphoteric surfactants having the following structure: O R2 I +1 . R (C-N H-(CH2)m)-NR 4 -X
R
3 wherein RI is unsubstituted, saturated or unsaturated, straight or branched chain alkyl having from about 9 to about 22 carbon atoms. Preferred R I has from about 11 to about 18 carbon atoms; more preferably from about 12 to about 18 carbon atoms; more preferably still from about 14 to about 18 carbon atoms; m is an 10 integer from 1 to about 3, more preferably from about 2 to about 3, and more preferably about 3; n is either 0 or 1, preferably 1; R 2 and R 3 are independently selected from the group consisting of alkyl having from 1 to about 3 carbon atoms, unsubstituted or mono-substituted with hydroxy, preferred R 2 and R 3 are CH 3 ; X is selected from the group consisting of C0 2 , SO 3 and SO 4 ; R 4 is selected from the group consisting of saturated or unsaturated, straight or branched chain alkyl, unsubstituted or monosubstituted with hydroxy, 15 having from 1 to about 5 carbon atoms. When X is CO 2 , R 4 preferably has 1 or 3 carbon atoms, more preferably 1 carbon atom. When X is SO 3 or S04, R 4 preferably has from about 2 to about 4 carbon atoms, more preferably 3 carbon atoms. Examples of amphoteric surfactants of the present invention include the following compounds: Cetyl dimethyl betaine (this material also has the CTFA designation cetyl betaine)
CH
3 + | C1 6
H
33
~-N-CH
2 -C0 2 O
H
3 20 Cocamidopropylbetaine + H3 R-C-NH-(C H 2
)
3 -N-C H 2 -C0 2
CH
3 wherein R has from about 9 to about 13 carbon atoms Cocamidopropyl hydroxy sultaine 38 WO 01/35905 PCTIUSOO/31679 H3 H
R-C-NH-(CH
2 )3 N-CH 2 -CH-CH2-S03
COH
3 wherein R has from about 9 to about 13 carbon atoms, Examples of other useful amphoteric surfactants are alkyliminoacetates, and iminodialkanoates and aminoalkanoates of the formulas RN[CH2imCO2M]2 and RNH(CH2 mCO 2M wherein m is from 1 to 5 4, R is a C 8
-C
2 2 alkyl or alkenyl, and M is H, alkali metal, alkaline earth metal ammonium, or alkanolammonium. Also included are imidazolinium and ammonium derivatives. Specific examples of suitable amphoteric surfactants include sodium 3-dodecyl-aminopropionate, sodium 3-dodecylamino propane sulfonate, N-higher alkyl aspartic acids such as those produced according to the teaching of U. S. Patent 2,438,091 which is incorporated herein by reference in its entirety; and the products sold under the 10 trade name "Miranol" and described in U. S. Patent 2,528,378, which is incorporated herein by reference in its entirety. Other examples of useful amphoterics include amphoteric phosphates, such as coamidopropyl PG-dimonium chloride phosphate (commercially available as Monaquat PTC, from Mona Corp.). Also useful are amphoacetates such as disodium lauroamphodiacetate, sodium lauroamphoacetate, and mixtures thereof. 15 Preferred lathering surfactants are selected from the group consisting of anionic lathering surfactants selected from the group consisting of ammonium lauroyl sarcosinate, sodium trideceth sulfate, sodium lauroyl sarcosinate, ammonium laureth sulfate, sodium laureth sulfate, ammonium lauryl sulfate, sodium lauryl sulfate, ammonium cocoyl isethionate, sodium cocoyl isethionate, sodium lauroyl isethionate, sodium cetyl sulfate, sodium monolauryl phospate, sodium cocoglyceryl ether sulfonate, 20 sodium C 9 -C22 soap, and combinations thereof; nonionic lathering surfactants selected from the group consisting of lauramine oxide, cocoamine oxide, decyl polyglucose, lauryl polyglucose, sucrose cocoate, C12-14 glucosamides, sucrose laurate, and combinations thereof; cationic lathering surfactants selected from the group consisting of fatty amines, di-fatty quaternary amines, tri-fatty quaternary amines, imidazolinium quaternary amines, and combinations thereof; amphoteric lathering surfactants selected 25 from the group consisting of disodium lauroamphodiacetate, sodium lauroamphoacetate, cetyl dimethyl betaine, cocoamidopropyl betaine, cocoamidopropyl hydroxy sultaine, and combinations thereof. Cationic Surfactants Cationic surfactants are typically categorized as non-lathering surfactants but may be used in the articles of the present invention provided they do not negatively impact the desired benefits of the articles. 30 Nonlimiting examples of cationic surfactants useful herein are disclosed in McCutcheon's, Detergents and Emulsifiers, North American edition (1986), published by allured Publishing Corporation; and McCutcheon's, Functional Materials, North American Edition (1992); both of which are incorporated by reference herein in their entirety. 39 WO 01/35905 PCTIUSOO/31679 Nonlimiting examples of cationic surfactants useful herein include cationic alkyl ammonium salts such as those having the formula:
R
1
R
2
R
3
R
4 N+ X wherein R , is selected from an alkyl group having from about 12 to about 18 carbon atoms, or aromatic, 5 aryl or alkaryl groups having from about 12 to about 18 carbon atoms; R , R , and R are independently 2 3 4 selected from hydrogen, an alkyl group having from about I to about 18 carbon atoms, or aromatic, aryl or alkaryl groups having from about 12 to about 18 carbon atoms; and X is an anion selected from chloride, bromide, iodide, acetate, phosphate, nitrate, sulfate, methyl sulfate, ethyl sulfate, tosylate, lactate, citrate, glycolate, and mixtures thereof. Additionally, the alkyl groups can also contain ether linkages, or hydroxy 10 or amino group substituents (e.g., the alkyl groups can contain polyethylene glycol and polypropylene glycol moieties). More preferably, R 1 is an alkyl group having from about 12 to about 18 carbon atoms; R 2 is selected from H or an alkyl group having from about I to about 18 carbon atoms; R 3 and R 4 are independently selected from H or an alkyl group having from about I to about 3 carbon atoms; and X is as 15 described in the previous paragraph. Most preferably, RI is an alkyl group having from about 12 to about 18 carbon atoms; R 2 , R 3 , and R 4 are selected from H or an alkyl group having from about 1 to about 3 carbon atoms; and X is as described previously. Alternatively, other useful cationic surfactants include amino-amides, wherein in the above 20 structure R 1 is alternatively R5CO-(CH 2 )n -, wherein R 5 is an alkyl group having from about 12 to about 22 carbon atoms, and n is an integer from about 2 to about 6, more preferably from about 2 to about 4, and most preferably from about 2 to about 3. Nonlimiting examples of these cationic emulsifiers include stearamidopropyl PG-dimonium chloride phosphate, stearamidopropyl ethyldimonium ethosulfate, stearamidopropyl dimethyl (myristyl acetate) ammonium chloride, stearamidopropyl dimethyl cetearyl 25 ammonium tosylate, stearamidopropyl dimethyl ammonium chloride, stearamidopropyl dimethyl ammonium lactate, and mixtures thereof. Nonlimiting examples of quaternary ammonium salt cationic surfactants include those selected from the group consisting of cetyl ammonium chloride, cetyl ammonium bromide, lauryl ammonium chloride, lauryl ammonium bromide, stearyl ammonium chloride, stearyl ammonium bromide, cetyl 30 dimethyl ammonium chloride, cetyl dimethyl ammonium bromide, lauryl dimethyl ammonium chloride, lauryl dimethyl ammonium bromide, stearyl dimethyl ammonium chloride, stearyl dimethyl ammonium bromide, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, lauryl trimethyl ammonium chloride, lauryl trimethyl ammonium bromide, stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, lauryl dimethyl ammonium chloride, stearyl dimethyl cetyl ditallow 40 WO 01/35905 PCT/USOO/31679 dimethyl ammonium chloride, dicetyl ammonium chloride, dicetyl ammonium bromide, dilauryl ammonium chloride, dilauryl ammonium bromide, distearyl ammonium chloride, distearyl ammonium bromide, dicetyl methyl ammonium chloride, dicetyl methyl ammonium bromide, dilauryl methyl ammonium chloride, dilauryl methyl ammonium bromide, distearyl methyl ammonium chloride, distearyl 5 dimethyl ammonium chloride, distearyl methyl ammonium bromide, and mixtures thereof. Additional quaternary ammonium salts include those wherein the C12 to C22 alkyl carbon chain is derived from a tallow fatty acid or from a coconut fatty acid. The term "tallow" refers to an alkyl group derived from tallow fatty acids (usually hydrogenated tallow fatty acids), which generally have mixtures of alkyl chains in the C16 to C18 range. The term "coconut" refers to an alkyl group derived from a coconut fatty acid, 10 which generally have mixtures of alkyl chains in the C12 to C14 range. Examples of quaternary ammonium salts derived from these tallow and coconut sources include ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di(hydrogenated tallow) dimethyl ammonium chloride, di(hydrogenated tallow) dimethyl ammonium acetate, ditallow dipropyl ammonium phosphate, ditallow dimethyl ammonium nitrate, di(coconutalkyl)dimethyl ammonium chloride, 15 di(coconutalkyl)dimethyl ammonium bromide, tallow ammonium chloride, coconut ammonium chloride, stearamidopropyl PG-dimonium chloride phosphate, stearamidopropyl ethyldimonium ethosulfate, stearamidopropyl dimethyl (myristyl acetate) ammonium chloride, stearamidopropyl dimethyl cetearyl ammonium tosylate, stearamidopropyl dimethyl ammonium chloride, stearamidopropyl dimethyl ammonium lactate, and mixtures thereof. 20 Preferred cationic surfactants useful herein include those selected from the group consisting of dilauryl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dimyristyl dimethyl ammonium chloride, dipalmityl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and mixtures thereof. Chelators 25 The articles of the present invention may also comprise a safe and effective amount of a chelator or chelating agent. As used herein, "chelator" or "chelating agent" means an active agent capable of removing a metal ion from a system by forming a complex so that the metal ion cannot readily participate in or catalyze chemical reactions. The inclusion of a chelating agent is especially useful for providing protection against UV radiation that can contribute to excessive scaling or skin texture changes and against 30 other environmental agents, which can cause skin damage. A safe and effective amount of a chelating agent may be added to the compositions of the subject invention, preferably from about 0.1% to about 10%, more preferably from about 1% to about 5%, of the composition. Exemplary chelators that are useful herein are disclosed in U.S. Patent No. 5,487,884, issued 1/30/96 to Bissett et al.; International Publication No. 91/16035, Bush et al., published 10/31/95; and 35 International Publication No. 91/16034, Bush et al., published 10/31/95. Preferred chelators useful in compositions of the subject invention are furildioxime and derivatives thereof. Flavonoids 41 WO 01/35905 PCT/USOO/31679 The articles of the present invention may optionally comprise a flavonoid compound. Flavonoids are broadly disclosed in U.S. Patents 5,686,082 and 5,686,367, both of which are herein incorporated by reference. Flavonoids suitable for use in the present invention are flavanones selected from the group consisting of unsubstituted flavanones, mono-substituted flavanones, and mixtures thereof; chalcones 5 selected from the group consisting of unsubstituted chalcones, mono-substituted chalcones, di-substituted chalcones, tri-substituted chalcones, and mixtures thereof; flavones selected from the group consisting of unsubstituted flavones, mono-substituted flavones, di-substituted flavones, and mixtures thereof; one or more isoflavones; coumarins selected from the group consisting of unsubstituted coumarins, mono substituted coumarins, di-substituted coumarins, and mixtures thereof; chromones selected from the group 10 consisting of unsubstituted chromones, mono-substituted chromones, di-substituted chromones, and mixtures thereof; one or more dicoumarols; one or more chromanones; one or more chromanols; isomers (e.g., cis/trans isomers) thereof; and mixtures thereof. By the term "substituted" as used herein means flavonoids wherein one or more hydrogen atom of the flavonoid has been independently replaced with hydroxyl, CI-C8 alkyl, Cl-C4 alkoxyl, 0-glycoside, and the like or a mixture of these substituents. 15 Examples of suitable flavonoids include, but are not limited to, unsubstituted flavanone, mono hydroxy flavanones (e.g., 2'-hydroxy flavanone, 6-hydroxy flavanone, 7-hydroxy flavanone, etc.), mono alkoxy flavanones (e.g., 5-methoxy flavanone, 6-methoxy flavanone, 7-methoxy flavanone, 4'-methoxy flavanone, etc.), unsubstituted chalcone (especially unsubstituted trans-chalcone), mono-hydroxy chalcones (e.g., 2'-hydroxy chalcone, 4'-hydroxy chalcone, etc.), di-hydroxy chalcones (e.g., 2', 4-dihydroxy 20 chalcone, 2',4'-dihydroxy chalcone, 2,2'-dihydroxy chalcone, 2',3-dihydroxy chalcone, 2',5'-dihydroxy chalcone, etc.), and tri-hydroxy chalcones (e.g., 2',3',4'-trihydroxy chalcone, 4,2',4'-trihydroxy chalcone, 2,2',4'-trihydroxy chalcone, etc.), unsubstituted flavone, 7,2'-dihydroxy flavone, 3',4'-dihydroxy naphthoflavone, 4'-hydroxy flavone, 5,6-benzoflavone, and 7,8-benzoflavone, unsubstituted isoflavone, daidzein (7,4'-dihydroxy isoflavone), 5,7-dihydroxy-4'-methoxy isoflavone, soy isoflavones (a mixture 25 extracted from soy), unsubstituted coumarin, 4-hydroxy coumarin, 7-hydroxy coumarin, 6-hydroxy-4 methyl coumarin, unsubstituted chromone, 3-formyl chromone, 3-formyl-6-isopropyl chromone, unsubstituted dicoumarol, unsubstituted chromanone, unsubstituted chromanol, and mixtures thereof. Preferred for use herein are unsubstituted flavanone, methoxy flavanones, unsubstituted chalcone, 2', 4-dihydroxy chalcone, and mixtures thereof. Most preferred are unsubstituted flavanone, unsubstituted 30 chalcone (especially the trans isomer), and mixtures thereof. They can be synthetic materials or obtained as extracts from natural sources (e.g., plants). The naturally sourced material can also further be derivatized (e.g., a glycoside, an ester or an ether derivative prepared following extraction from a natural source). Flavonoid compounds useful herein are commercially available from a number of sources, e.g., Indofine Chemical Company, Inc. (Somerville, 35 New Jersey), Steraloids, Inc. (Wilton, New Hampshire), and Aldrich Chemical Company, Inc. (Milwaukee, Wisconsin). Mixtures of the above flavonoid compounds may also be used. 42 WO 01/35905 PCT/USOO/31679 The herein described flavonoid compounds are preferably present in the instant invention at concentrations of from about 0.01% to about 20%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%. Sterols 5 The articles of the present invention may comprise a safe and effective amount of one or more sterol compounds. Examples of useful sterol compounds include sitosterol, stigmasterol, campesterol, brassicasterol, lanosterol, 7-dehydrocholesterol, and mixtures thereof. These can be synthetic in origin or from natural sources, e.g., blends extracted from plant sources (e.g., phytosterols). Anti-Cellulite Agents 10 The articles of the present invention may also comprise a safe and effective amount of an anti cellulite agent. Suitable agents may include, but are not limited to, xanthine compounds (e.g., caffeine, theophylline, theobromine, and aminophylline). Skin Lightening Agents The articles of the present invention may comprise a skin lightening agent. When used, the 15 compositions preferably comprise from about 0.1% to about 10%, more preferably from about 0.2% to about 5%, also preferably from about 0.5% to about 2%, by weight of the composition, of a skin lightening agent. Suitable skin lightening agents include those known in the art, including kojic acid, arbutin, ascorbic acid and derivatives thereof, e.g., magnesium ascorbyl phosphate or sodium ascorbyl phosphate or other salts of ascorbyl phosphate. Skin lightening agents suitable for use herein also include those described in 20 copending patent application Serial No. 08/479,935, filed on June 7, 1995 in the name of Hillebrand, corresponding to PCT Application No. U.S. 95/07432, filed 6/12/95; and copending patent application Serial No. 08/390,152, filed on February 24, 1995 in the names of Kalla L. Kvalnes, Mitchell A. DeLong, Barton J. Bradbury, Curtis B. Motley, and John D. Carter, corresponding to PCT Application No. U.S. 95/02809, filed 3/1/95, published 9/8/95. 25 Binders The articles of the present invention may optionally comprise binders. Binders or binding materials are useful for sealing the various layers of the present articles to one another thereby maintaining the integrity of the article. The binders may be in a variety of forms including, but not limited to, spray on, webs, separate layers, binding fibers, etc. Suitable binders may comprise latexes, polyamides, polyesters, 30 polyolefins and combinations thereof. Additional Layers In another embodiment, the article of the present invention may comprise one or more additional layers which one having ordinary skill in the art would recognize as separate and distinct from nonwoven layer yet which are attached to the nonwoven layer at some point. The additional layers are suitable for 35 enhancing the overall grippability of the side of the article closest to the hand or other means for exerting mechanical action on the surface to be cleansed. Also, the additional layers are suitable for enhancing the soft feel of the side of the article which contacts the area to be cleansed. In any instance, these additional 43 WO 01/35905 PCTIUSOO/31679 layers may also be referred to as consecutively numbered layers in addition to the two essential layers of the articles of the present invention, e.g., third layer, fourth layer, etc.. Suitable additional layers may be macroscopically expanded. As used herein, "macroscopically expanded, refers to webs, ribbons, and films which have been caused to conform to the surface of a three 5 dimensional forming structure so that both surfaces thereof exhibit a three-dimensional forming pattern of surface aberrations corresponding to the macroscopic cross-section of the forming structure, wherein the surface aberrations comprising the pattern are individually discernible to the normal naked eye (i.e., normal naked eye having 20/20 vision) when the perpendicular distance between the viewer's eye and the plane of the web is about 12 inches. 10 As used herein, "embossed" it is meant that the forming structure of the material exhibits a pattern comprised primarily of male projections. On the other hand, "debossed" refers to when the forming structure of the material exhibits a pattern comprised primarily of female capillary networks. Preferred macroscopically expanded films comprise formed films which are structural elastic-like films. These films are described in U. S. Patent No. 5,554,145, issued September 10, 1996, to Roe et al., 15 which is incorporated by reference herein in its entirety. Materials suitable for use in the additional layer having a thickness of at least one millimeter include, but are not limited to, those web materials disclosed in U. S. Patent No. 5,518,801, issued to Chappell et al. on May 21, 1996, which is incorporated by reference herein in its entirety. METHODS OF MANUFACTURE 20 The personal care articles of the present invention are manufactured by adding the therapeutic benefit component to the appropriate sheet of the nonwoven layer via a conventional method which may include, but is not limited to, sprinkling, dip coating, spraying, slot coating, and roll transfer (e.g., pressure roll or kiss roll). The sheet of the remaining layer is then placed on the sheet of the first layer, preferably, but not always, over the therapeutic benefit component. The sheets are sealed together by a conventional 25 sealing method which may include, but is not limited to, heat, pressure, glue, ultrasound, etc. Heat sealing devices vary in design, and where a seal may not be able to be effected an interposing layer of a low melting heat-sealable fibrous web such as the polyamide fibrous web known as Wonder Under (manufactured by Pellon, available from H. Levinson & Co., Chicago, IL) may be used between layers for this and other examples without changing the effect or utility of the articles. The sealed sheets are then 30 partitioned into units for the consumer's use. Optional manufacturing steps may include calendaring to flatten the article, drying, creping, shrinking, stretching, or otherwise mechanically deforming. METHODS OF CLEANSING AND DELIVERING A THERAPEUTIC OR AESTHETIC BENEFIT AGENT TO THE SKIN OR HAIR The present invention also relates to a method of cleansing the skin and/or hair with a personal 35 care article of the present invention. These methods comprise the steps of: a) wetting with a substantially dry, disposable personal care article, said article comprising a water insoluble substrate comprising a 44 WO 01/35905 PCTIUSOO/31679 nonwoven layer; and a therapeutic benefit component, disposed adjacent to said water insoluble substrate, wherein said component comprises from about 10% to about 1000%, by weight of the water insoluble substrate, of a therapeutic benefit composition comprising a safe and effective amount of a cationic polymer and a safe and effective amount of an anionic surfactant, wherein said composition forms a 5 coacervate when the article is exposed to water and b) contacting the skin or hair with the wetted article. The articles of the present invention are water-activated and are therefore intended to be wetted with water prior to use. As used herein, "water-activated" means that the present invention is presented to the consumer in dry form to be used after wetting with water. It is found that when the articles of the present invention include a lathering surfactant they produce a lather or are "activated" upon contact with 10 water and further agitation. Accordingly, the article is wetted by immersion in water or by placing it under a stream of water. When the articles of the present invention comprise a lathering surfactant, lather may be generated from the article by mechanically agitating and/or deforming the article either prior to or during contact of the article with the skin or hair. The resulting lather is useful for cleansing the skin or hair. During the cleansing process and subsequent rinsing with water, any therapeutic or aesthetic benefit agents 15 are deposited onto the skin or hair. Deposition of the therapeutic or aesthetic benefit agents are enhanced by the physical contact of the substrate with the skin or hair as well by the inclusion of one or more deposition aids. EXAMPLES The following examples further describe and demonstrate embodiments within the scope of the 20 present invention. In the following examples, all ingredients are listed at an active level. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention. Ingredients are identified by chemical or CTFA name. 25 I. Cleansing Components Example 1 A representative powdery cleansing component for the articles of the present invention is prepared in the following manner. Shave 40.0 gms of a bar soap which includes the following components: Component Wt % Soap (Magnesium and Sodium) 80.16 Water 11.50 Stearic Acid 5.70 NaCl 1.10 EDTA 0.25 Perfume 1.15 45 WO 01/35905 PCT/USOO/31679 Miscellaneous (including pigments) 0.14 Total 100 Blend the bar soap flakes with sodium bicarbonate in a 90:10 weight ratio. Mill the mixture twice in a standard 3-roll mill. Collect the flakes and store in a suitable sealed container. Example 2 Prepare a representative cleansing component which includes the following components. Component Wt% Decylpolyglucose 12.0 Cocamidopropyl betaine 12.0 Sodium lauroyl sarcosinate 12.0 Butylene glycol 3.6 PEG 14M 1.8 Polyquaternium- 10 0.9 Dex panthenol 0.7 Phenoxyethanol 0.5 Benzyl alcohol 0.5 Methylparaben 0.45 Propylparaben 0.25 Disodium EDTA 0.2 Water 55.1 5 Example 3 Prepare a representative cleansing component which includes the following components. Component Wt% Monosodium lauroyl glutamate 22.0 Cocamidopropyl betaine 2.0 Sodium chloride 1.0 Glycerin 2.5 Water 72.5 Heat the components together with gentle stirring until homogeneous. II. Therapeutic Benefit Components Example 4 10 Prepare a representative skin conditioning component by mixing the following components. Component Example 4 SEFA* Cottonate 48.0 46 WO 01/35905 PCT/USOO/31679 SEFA* Behenate 12.0 Petrolatum 10.0 Cholesterol Ester 25.0 *SEFA is an acronym for sucrose esters of fatty acids 'Hamplex TNP, Hampshire Chemical Co. Example 5 Prepare a representative conditioning component for the articles of the present invention in the following 5 manner. Component Example 5 Hydrophobic Phase: SEFA* cottonate 15.5 SEFA* behenate 8.0 Tribehenin 6.0 Petrolatum 4.0 CIO-C30 13.0 Cholesterol/Lanosterol esters PEG 30 3.0 dipolyhydroxystearate 3 Hydrophilic Phase: Glycerin 42.30 PVM/MA decadiene 0.25 crosspolymer 4 Sodium hydroxide 0.25 (10% solution) Active skin care ingredients: Panthenol 2.50 Nicotinamide 2.50 Urea 2.50 Allantoin 0.20 * SEFA is an acronym for sucrose esters of fatty acids 'Available as AMS-C30 from Dow Coming 2 Available as Abil WE-09 from Goldschmidt 47 WO 01/35905 PCT/USOO/31679 Available as Arlacel P135 from ICI 'Available as Stabileze 06 from ISP Process for all emulsions: Heat the hydrophobic phase to 70*C, add the hydrophobic active skin care ingredients, and stir 5 until homogenous. Premix the hydrophilic phase ingredients with the hydrophilic active skin care ingredients, heating gently if necessary to dissolve or disperse them. Add these slowly to the hydrophobic phase, continuing to stir. Homogenize (high shear mixer; ultrasonic homogenizer; or high pressure homogenizer such as Microfluidizer from Microfluidics Corp.). Apply immediately to substrate surface or cool rapidly to below room temperature in ice or ice water. Store in controlled environment, under nitrogen 10 if needed for chemical stability. Examples 6-11 Prepare a representative conditioning component for the articles of the present invention in the following manner. Part A Example 6 Example 7 Example 8 Example Example Example 9 10 11 Sodium 15.0 6.51 6.20 5.9 lauroyl ether sulfate (SLES, add as 27% active) Cocamido- 13.5 5.85 5.57 5.82 5.19 5.3 propyl betainel Sodium 1.35 0.60 0.57 6.01 5.36 0.54 lauroyl sarcosinate2 Decylpoly- 5.80 5.18 glucose Lauryl alcohol 1.31 0.56 0.54 0.54 Polyethylene- 7.87 3.38 3.22 2.64 2.36 3.2 imine 4 Citric acid 0.32 0.11 0.11 0.09 (add as 50% aqueous solution) Tetrasodium 0.28 EDTA 48 WO 01/35905 PCT/USO0/31679 Sulfuric acid 5.4 2.37 2.25 2.2 Preservative, 0.62 0.45 0.43 2.86 2.55 0.3 fragrance Sodium sulfate 7.9 3.47 3.21 3.0 Glycerin 26.45 56.7 46.4 44.1 39.36 44.8 Sorbitol 5.0 SEFA* 12.8 cottonate SEFA* 8.0 behenate Part B - Polymer gelling agents Gelatin 4.2 Polyacryl- 7.5 amide and isoparaffin 5 Polyurethane 34.1 latex in 50% isopropanol 6 Polyacrylate 7.5 copolymer 7 Polystyrene 1.1 sulfonates copolymer Chitosan 5.4 lactate Part C - Physical gelling agents 12-Hydroxy- 10.0 10.66 stearic acid Stearyl alcohol 10.0 20.0 20.0 7.11 15.0 * SEFA is an acronym for sucrose esters of fatty acids Available as Tegobetaine F from Goldschmidt 5 2 Available as Hamposyl L-30 (type 721) from Hampshire Chemical, 31% active 3 Available as Plantaren 2000NP from Henkel 4 Available as Epomin SP-0 18, molecular weight about 1800, from Nippon Shokubai Co. 5 Available as Carbopol Ultrez from B.F. Goodrich 49 WO 01/35905 PCTUSOO/31679 6 Available as Sancure 2710 from B.F. Goodrich, prepared as premix comprising about 20% polymer, 30% water, 50% IPA 6 Available as Sepigel 305 from Seppic Corp. 7 Available as AQ38S from Eastman Chemical 5 Blend the surfactants and fatty alcohol while heating to 65*C with a low speed impeller mixer. Remove from heat, allow to cool to 65*C while continuing to mix. Add the cationic polymer and stir until homogeneous. Slowly add remaining Part A ingredients while stirring. Homogenize to disperse the SEFA as an emulsion. Titrate with concentrated sulfuric acid until a pH of about 6.5 is reached. Prepare a dried mixture by spreading the Part A composition in trays and drying in a suitable (vacuum or convection) oven 10 at a temperature not exceeding 65*C until essentially no water remains. Blend the dried Part A ingredients with the polymeric gelling agents from Part B, heat to dissolve or disperse. Blend the resulting composition with the physical gelling agents. Heat to melt and dissolve gelling agents into the composition. Apply to substrate surface(s) or cool to room temperature and store. Examples 12-17 15 Prepare a representative conditioning component for the articles of the present invention as described in Examples 6-11 using the following ingredients. Part A Example Example Example Example Example Example 12 13 14 15 16 17 Sodium lauroyl 8.87 11.4 10.8 10.8 sarcosinate' Polyethylene- 7.39 7.50 7.50 9.5 9.0 9.0 imine 2 Water 4.43 3.00 3.00 5.7 5.4 5.4 Sulfuric acid 6.36 QS QS 8.1 7.7 7.7 Fragrance, misc. Glycerin 34.45 52.5 45.0 41.3 39.25 34.25 Propylene 2.50 glycol Urea 2.50 2.50 2.0 1.9 1.9 Panthenol 2.0 1.9 1.9 Nicotinamide 2.50 2.50 2.0 1.9 1.9 Salicylic acid Polymethyl- 4.20 4.20 silsesquioxane 3 Mica, 3.85 3.85 50 WO 01/35905 PCT/USOO/31679 pearlescent Stearylmethi- 5.0 cone wax SEFA cottonate 5.0 Petrolatum 5.0 Part B - Polymer gelling agents Gelatin 0.1 Polyacrylamide 16.0 12.0 12.0 and isoparaffin 4 Part C - Physical gelling agents 12- 12.0 12.0 10.5 Hydroxystearic acid Carnauba wax 18.0 14.1 14.1 Stearyl alcohol 8.0 8.0 7.0 Available as Hamposyl L-95 from Hampshire Chemical, dry 2 Available as Epomin SP-018, molecular weight about 1800, from Nippon Shokubai Co. 5 3 Available as Tospearl 145A from Kobo, Inc. 4 Available as Sepigel 305 from Seppic Corp. III. Intermediate Personal Care Articles Example 18 Prepare a representative skin cleansing article in the following manner. 10 Four grams of the cleansing component of Example 2 is applied to one side of a permeable, fusible web comprised of low-melting heat-sealable polyamide fibers. The permeable web is Wonder Under manufactured by Pellon, available from H. Levinson & Co., Chicago, IL. The cleansing component is applied to an oval area approximately 13 cm by 18 cm. The cleansing component is air dried. A layer of 2 oz/sq yd polyester batting cut to the same size as the web is placed over the fusible web. The polyester 15 batting has a basis weight of 2 oz/yd 2 and is comprised of a blend of fibers of about 23 microns and 40 microns average diameter, at least some of which are crimped. The thickness of the batting is about 0.23 in. measured at 5 gsi. The batting is believed to be heat-bonded, utilizing no adhesive. A layer of a nonwoven is placed under the fusible web to form the second side of the article. The nonwoven is a spunlace blend of 70% rayon and 30% PET fibers, bonded with a styrene-butadiene adhesive, which is 20 hydroapertured to form holes about 2 mm in diameter and having a basis weight of about 70 gsm. The shape of the article is about 122 mm x 160 mm oval. The layers are sealed together using point bonds in a grid pattern with a heat sealing die utilizing a pressure-platen heat sealing device such as a Sentinel Model 51 WO 01/35905 PCT/USOO/31679 808 heat sealer available from Sencorp, Hyannis, MA. The point bonds measure about 4 mm diameter each and there are about 51 individual sealing points evenly spaced. The article is trimmed and ready for use. Example 19 Prepare a representative skin cleansing article in the following manner. 5 The cleansing component of Example 2 is applied to one side of a first substrate by extruding it through a coating head continuously in four lines separated by a distance of 20 mm, 40 mm, and 20 mm respectively, measuring widthwise across the web, making a pair of parallel lines on each side of the web. The cleansing component is extruded at a rate to yield 4.4 grams of cleansing component per finished article. The substrate is a spunlace blend of 70% rayon and 30% PET fibers, bonded with a styrene 10 butadiene adhesive, which is hydroapertured to form holes about 2 mm in diameter and having a basis weight of about 70 gsm. A second web which is an airlaid, lofty, low density batting is continuously fed over the first substrate placing it in contact with the surfactant-containing layer. The batting comprises a blend of 30% 15 denier PET fibers, 35% 3 denier bicomponent fibers with PET core and PE sheath, and 35% 10 denier bicomponent fibers of the same core-sheath composition, and has a basis weight of about 15 100 grams per square meter (gsm). The webs are continuously fed to an ultrasonic sealer which seals a dot pattern comprising a grid of 4 mm diameter sealing points spaced evenly across the web. The web is cut into individual articles measuring about 120 mm x 160 mm rectangles with rounded comers, which has a total of about 51 sealing points per article. IV. Personal Care Articles of the Present Invention 20 Example 20 Prepare a representative skin cleansing and conditioning article in the following manner. Three grams of the skin conditioning composition of Example 12 is applied, half to each side, of the finished article of Example 18. The composition is applied by slot coating the composition as a hot liquid (60-70*C) to the article surfaces evenly, half of the composition on each side of the article. 25 Example 21 Prepare a representative skin cleansing and conditioning article in the following manner. Three grams of the skin conditioning composition of Example 5 is applied, half to each side, of the finished article of Example 19. The composition is applied by slot coating the composition as a hot liquid (60-70'C) to the article surfaces evenly, half of the composition on each side of the article. 30 Example 22 Prepare a representative skin cleansing and conditioning article in the following manner. Three grams of the skin conditioning composition of Example 4 is applied, half to each side, of the finished article of Example 19. The composition is applied by slot coating the composition as a hot liquid (60-70'C) to the article surfaces evenly, half of the composition on each side of the article. 35 Example 23 Prepare a representative skin cleansing and conditioning article in the following manner. 52 WO 01/35905 PCT/USOO/31679 Three grams of the skin conditioning composition of Example 12 is applied, half to each side, of the finished article of Example 19. The composition is applied by slot coating the composition as a hot liquid (60-70*C) to the article surfaces evenly, half of the composition on each side of the article. Examples 24-31 5 Prepare representative skin cleansing and conditioning articles in the following manner, utilizing the skin conditioning compositions of Examples 6-10, and 15-17. Four grams of the cleansing component of Example 2 is spread evenly by hand across a lofty batting. The batting i an airlaid, lofty, low density batting comprising a blend of 30% 15 denier PET fibers, 35% 3 denier bicomponent fibers with PET core and PE sheath, and 35% 10 denier bicomponent 10 fibers of the same core-sheath composition, and has a basis weight of about 100 grams per square meter (gsm). A layer of fibrous nonwoven which is a hydroentangled blend of 55% cellulose and 45% polyester having a basis weight of about 65 gsm (available as Technicloth II from The Texwipe Company, Saddle River, NJ) is placed over the cleansing component coated side of the batting. The layers are sealed together using interlocking sealing plates using an unheated plate having inverted thimble-shaped reservoirs spaced 15 evenly in a hexagonal grid pattern. The thimble shaped reservoirs are about 1.2 cm diameter at the base and are spaced about 2 cm apart, center-to-center. The land area between the dimples on the unheated plate is concave inwards by several mm, forming an interconnected trough. The heated plate has an external ridge which fit precisely into the trough on the land area of the unheated plate. The heated plate contacts the cellulose/polyester substrate and a heat seal is effected using pressure-platen heat sealing device such as 20 a Sentinel Model 808 heat sealer available from Sencorp, Hyannis, MA. The resulting unfinished article has pronounced thimble shapes rising up on the batting side, and shorter dimples or 'buttons' rising up on the cellulose/polyester substrate side of the article, making both sides easy to grip. The article is cut into a rectangle about 120 mm by 160 mm. Three grams of skin conditioning composition per article is pipetted into the trough area while the composition is hot, and allowed to cool and solidify. The article is packaged 25 until ready for use. Example 32-33 Prepare representative skin cleansing and conditioning articles utilizing the skin conditioning compositions of Examples 13 and 14 in the following manner. The liquid cleansing component of Example 3 is applied to a first substrate by dipping a 120 mm 30 by 160 mm section of the substrate in a bath of the composition until it has increased its weight by about 8 grams. The substrate is a batting comprising a blend of 30% 15 denier PET fibers, 35% 3 denier bicomponent fibers with PET core and PE sheath, and 35% 10 denier bicomponent fibers of the same core sheath composition, and has a basis weight of about 100 grams per square meter (gsm). The substrate is dried. A piece of a second substrate which is a spunlace blend of 70% rayon and 30% PET fibers, bonded 35 with a styrene-butadiene adhesive and hydroapertured to form holes about 2 mm in diameter, having a basis weight of about 70 gsm is placed over the first substrate. The substrates are sealed together using an ultrasonic sealer which seals a dot pattern comprising a grid of 4 mm diameter sealing points spaced evenly 53 WO 01/35905 PCT/USOO/31679 across the article. Four grams of skin conditioning composition is applied evenly over both sides of the article by feeding the composition through a slotted rolling device with a machined 1.5 mm gap and a feed reservoir held at about 60'C. The composition quickly cools on the article surface and is stored in a sealed, metallized film package until ready for use. 5 Example 34 Prepare a representative skin cleansing and conditioning article in the following manner. Four grams of the cleansing component of Example 2 is spread evenly by hand across a lofty batting. The batting is a 4 oz/sq yd polyester batting cut to a size of 130 mm by 175 mm, comprising polyester fibers of about 30 microns average diameter and is adhesive bonded, available for example as 10 Mountain Mist Extra Heavy Batting #205 from Steams Textiles, Cincinnati, OH. A layer of fibrous nonwoven which is a hydroentangled blend of 55% cellulose and 45% polyester having a basis weight of about 65 gsm (available as Technicloth II from The Texwipe Company, Saddle River, NJ) is placed over the surfactant coated side of the batting. The layers are sealed together using interlocking sealing plates using an unheated plate having inverted thimble-shaped reservoirs spaced evenly in a hexagonal grid 15 pattern. The thimble shaped reservoirs are about 1.2 cm diameter at the base and are spaced about 1.5 cm apart, center-to-center. The land area between the dimples on the unheated plate is convex upwards by several mm, forming an interconnected ridge. The heated plate has an external trough which fits precisely onto the ridge of the unheated plate. The heated plate contacts the cellulose/polyester substrate and a heat seal is effected using a pressure-platen heat sealing device such as a Sentinel Model 808 heat sealer 20 available from Sencorp, Hyannis, MA. The resulting unfinished article has topographical features on both sides, assisting lather generation and also making it easy to grip and slide across the skin surface during use. The article is cut into a rectangle about 120 mm by 160 mm. A skin conditioning inverse emulsion paste is prepared for use with the article, as follows: Component Per cent PEG 30-dipolyhydroxystearate 3.0 SEFA cottonate 20.0 Petrolatum 4.0 Tribehenin 5.0 C1O-C30 Cholesterol/Lanosterol Esters 13.0 SEFA behenate 5.0 Glycerin 50.0 The lipid soluble ingredients are heated to 70'C while stirring. Glycerin is slowly added with vigorous 25 stirring. The composition is homogenized. Three grams of the skin conditioning inverse emulsion paste is pipetted hot into the depressed zones on the cellulose/polyester side of the article. The composition quickly cools to a semi-solid paste. The article is packaged until ready for use. 54 WO 01/35905 PCT/US00/31679 Example 35 Prepare a representative skin conditioning article in the following manner using the skin conditioning composition of Example 7. The conditioning composition is applied to one side of a first substrate by extruding it through a 5 coating head continuously in four strips, each 5 mm wide, separated by a distance of 20 mm, 40 mm, and 20 mm respectively, measuring widthwise across the web, making a pair of parallel lines on each side of the web. The composition is extruded at a rate to yield 3 grams of composition per finished article. The substrate is a spunlace blend of 70% rayon and 30% PET fibers, bonded with a styrene-butadiene adhesive, which is hydroapertured to form holes about 2 mm in diameter and having a basis weight of about 70 gsm. 10 A second web which is an airlaid, lofty, low density batting is continuously fed over the first substrate placing it in contact with the first substrate on the side containing no skin conditioning composition. The batting comprises a blend of 30% 15 denier PET fibers, 35% 3 denier bicomponent fibers with PET core and PE sheath, and 35% 10 denier bicomponent fibers of the same core-sheath composition, and has a basis weight of about 100 grams per square meter (gsm). The webs are continuously fed to an ultrasonic sealer 15 which seals a dot pattern comprising a grid of 4 mm diameter sealing points spaced evenly across the web. The web is cut into individual articles measuring about 120 mm x 160 mm rectangles with rounded corners, which has a total of about 51 sealing points per article. Example 36 Prepare a representative skin conditioning article in the following manner using the skin conditioning 20 composition of Example 16. The conditioning composition is applied to one side of a first substrate by extruding it through a coating head continuously in four strips, each 5 mm wide, separated by a distance of 20 mm, 40 mm, and 20 mm respectively, measuring widthwise across the web, making a pair of parallel lines on each side of the web. The composition is extruded at a rate to yield 1.1 grams of composition per finished article. The 25 substrate is a spunlace blend of 70% rayon and 30% PET fibers, bonded with a styrene-butadiene adhesive, which is hydroapertured to form holes about 2 mm in diameter and having a basis weight of about 70 gsm. A second web which is an airlaid, lofty, low density batting is continuously fed over the first substrate placing it in contact with the first substrate on the side containing no skin conditioning composition. The batting comprises a blend of 10% 15 denier PET fibers, 50% 3 denier bicomponent fibers with PET core 30 and PE sheath, and 40% 10 denier bicomponent fibers of the same core-sheath composition, and has a basis weight of about 80 grams per square meter (gsm). The webs are continuously fed to an ultrasonic sealer which seals a dot pattern comprising a grid of 4 mm diameter sealing points spaced evenly across the web. The web is cut into individual articles measuring about 120 mm x 90 mm rectangles with rounded corners, which has a total of about 51 sealing points per article. The article is convenient for application to smaller 35 areas of skin, for example the face, elbows, neck and/or feet. 55 WO 01/35905 PCT/USOO/31679 Example 37 Prepare a representative skin cleansing and conditioning article utilizing the skin conditioning composition of Example 16. The cleansing component of Example 2 is applied to one side of a first substrate by extruding it 5 through a coating head continuously in four lines separated by a distance of 20 mm, 40 mm, and 20 mm respectively, measuring widthwise across the web, making a pair of parallel lines on each side of the web. The cleansing component is extruded at a rate to yield 0.52 grams of cleansing component per finished article. The substrate is a spunlace blend of 70% rayon and 30% PET fibers, bonded with a styrene butadiene adhesive, which is hydroapertured to form holes about 2 mm in diameter and having a basis 10 weight of about 70 gsm. A second substrate web which is an airlaid, lofty, low density batting is continuously fed over the first substrate placing it in contact with the surfactant layer. The batting comprises a blend of 10% 15 denier PET fibers, 50% 3 denier bicomponent fibers with PET core and PE sheath, and 40% 10 denier bicomponent fibers of the same core-sheath composition, and has a basis weight of about 80 grams per square meter (gsm). A third substrate web which is the same as the second substrate 15 web is continuously fed over the second substrate web placing it in contact with the second substrate. The webs are continuously fed to an ultrasonic sealer which seals a dot pattern comprising a grid of 4 mm diameter sealing points spaced evenly across the web. Skin conditioning composition is slot coated from a hot reservoir pumped through a slot dye onto both sides of the substrate web at a rate equal to 1.25 grams of skin conditioning composition per finished article (about 55 gsm add-on per side), and passed across a 20 cooling fan so the composition cools quickly on the article outer surfaces. The web is cut into individual articles measuring about 120 mm x 90 mm rectangles with rounded corners. Example 38 Prepare a representative skin cleansing and conditioning article in the following manner. A substrate is prepared on an airlaying process. A thin first web of 20 gsm continuous 25 polypropylene filamented fiber is fed to a continuous forming screen. Cellulose (Kraft fiber) comprising a second web is airlaid onto the first web at a rate of 100 gsm. The surfactant composition of Example 1 is co-metered with the cellulose fibers at a rate of about 80 gsm. A third web which is the same as the first web is fed onto the airlaid cellulose. A substrate is prepared by heat bonding the edges and dot sealing about 51, 3 mm points of a 10 inch by 8.5 inch rectangular section of the composite web. The skin 30 conditioning composition of Example 15 is melted and slot coated evenly onto both sides of the article at a rate of 3 grams of composition per article, or 1.5 grams per side, followed by rapid cooling. The article is packaged until ready for use. Example 39 Prepare a representative skin cleansing and conditioning article in the following manner. 35 The article of Example 38 is prepared with the exception that a biodegradable polylactic acid polymer is substituted for the polypropylene to make a biodegradable article. 56
Claims (10)
1. A substantially dry, disposable personal care article characterized in that said article comprises: a) a water insoluble substrate; and b) a therapeutic benefit component, disposed adjacent to said water insoluble substrate, wherein said component comprises from 10% to 1000%, by weight of the water insoluble substrate, of a therapeutic benefit composition comprising: 1) a safe and effective amount of a cationic polymer; 2) a safe and effective amount of an anionic surfactant; wherein said composition forms a coacervate when said article is exposed to water.
2. The article of Claim I wherein said nonwoven layer comprises fibers selected from the group consisting of natural fibers, synthetic fibers, and combinations thereof
3. The article of any one of the preceding claims wherein said fibers are synthetic fibers selected from the group consisting of nylon fibers, rayon fibers, polyolefin fibers, polyester fibers, and combinations thereof.
4. The article of any one of the preceding claims wherein said nonwoven layer comprises materials selected from the group consisting of cellulosic nonwovens, sponges (i.e., both natural and synthetic), formed films, battings, and combinations thereof
5. The article of any one of the preceding claims wherein said cationic polymer is selected from the group consisting of natural backbone quaternary ammonium polymers, synthetic backbone quaternary ammonium polymers, natural backbone amphoteric type polymers, synthetic backbone amphoteric type polymers, and combinations thereof.
6. The article of any one of the preceding claims wherein said anionic surfactant is selected from the group consisting of sarcosinates, glutamates, sodium alkyl sulfates, ammonium alkyl sulfates, sodium alkyleth sulfates, ammonium alkyleth sulfates, ammonium laureth-n-sulfates, sodium laureth-n sulfates, isethionates, glycerylether sulfonates, sulfosuccinates and combinations thereof
7. The article of any one of the preceding claims wherein said therapeutic benefit component further comprises a therapeutic benefit agent selected from the group consisting of vitamin compounds, skin treating agents, anti-acne actives, anti-wrinkle actives, anti-skin atrophy actives, anti-inflammatory actives, topical anesthetics, artificial tanning actives and accelerators, anti-microbial actives, anti 57 WO 01/35905 PCTUSOO/31679 fungal actives, anti-viral agents, enzymes, sunscreen actives, anti-oxidants, skin exfoliating agents, hydrophobic conditioning agents, hydrophilic conditioning agents, and combinations thereof.
8. A method of conditioning the skin and/or hair, said method comprising the steps of: a) wetting the article of Claim 1; and b) contacting the skin and/or hair with the wetted article.
9. The article of any one of the preceding claims wherein said article further comprises a lathering surfactant.
10. A method of cleansing the skin and/or hair, said method comprising the steps of: a) wetting the article of Claim 9; and b) contacting the skin and/or hair with the wetted article. 58
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US44228699A | 1999-11-19 | 1999-11-19 | |
US09442286 | 1999-11-19 | ||
PCT/US2000/031679 WO2001035905A2 (en) | 1999-11-19 | 2000-11-17 | Personal care articles comprising cationic polymer coacervate compositions |
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AU1775501A true AU1775501A (en) | 2001-05-30 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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AU17755/01A Abandoned AU1775501A (en) | 1999-11-19 | 2000-11-17 | Personal care articles comprising cationic polymer coacervate compositions |
Country Status (10)
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EP (1) | EP1229897A2 (en) |
JP (1) | JP2003513996A (en) |
KR (1) | KR20020063895A (en) |
CN (1) | CN1424903A (en) |
AU (1) | AU1775501A (en) |
BR (1) | BR0015654A (en) |
CA (1) | CA2391032A1 (en) |
CZ (1) | CZ20021636A3 (en) |
MX (1) | MXPA02005060A (en) |
WO (1) | WO2001035905A2 (en) |
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---|---|---|---|---|
US6634037B2 (en) * | 2001-12-17 | 2003-10-21 | Unilever Home And Personal Care, Usa Division Of Conopco, Inc. | Personal cleansing system |
DE10162811A1 (en) * | 2001-12-20 | 2003-07-10 | Henkel Kgaa | Oil absorbing cleaning cloth |
JP3843020B2 (en) | 2002-01-21 | 2006-11-08 | 花王株式会社 | Hair cleanser |
US20040009210A1 (en) * | 2002-07-09 | 2004-01-15 | Kimberly-Clark Worldwide, Inc. | Wound management products incorporating cationic compounds |
US20040009141A1 (en) * | 2002-07-09 | 2004-01-15 | Kimberly-Clark Worldwide, Inc. | Skin cleansing products incorporating cationic compounds |
ITTO20110690A1 (en) * | 2011-07-28 | 2013-01-29 | Turati Idrofilo Spa | WIPES FOR THE APPLICATION OF AN ACTIVE PRINCIPLE ON THE SKIN |
WO2019236788A1 (en) | 2018-06-07 | 2019-12-12 | Ecolab Usa Inc. | Enzymatic pot and pan detergent |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US6132746A (en) * | 1997-05-22 | 2000-10-17 | The Procter & Gamble Company | Cleansing products with improved moisturization |
DE69808790T3 (en) * | 1997-09-12 | 2009-07-16 | The Procter & Gamble Co., Cincinnati | SKIN CLEANSING AND CONDITIONING ITEMS FOR SKIN AND HAIR |
EP1024785B1 (en) * | 1997-10-24 | 2003-01-15 | The Procter & Gamble Company | Cleansing and conditioning article for skin or hair having improved fragrance delivery |
CA2332948A1 (en) * | 1998-04-24 | 1999-11-04 | The Procter & Gamble Company | Cleansing articles for skin and/or hair which also deposits skin care actives |
US6428799B1 (en) * | 1999-08-02 | 2002-08-06 | The Procter & Gamble Company | Personal care articles |
-
2000
- 2000-11-17 EP EP00980502A patent/EP1229897A2/en not_active Withdrawn
- 2000-11-17 CZ CZ20021636A patent/CZ20021636A3/en unknown
- 2000-11-17 WO PCT/US2000/031679 patent/WO2001035905A2/en not_active Application Discontinuation
- 2000-11-17 KR KR1020027006367A patent/KR20020063895A/en not_active Application Discontinuation
- 2000-11-17 AU AU17755/01A patent/AU1775501A/en not_active Abandoned
- 2000-11-17 CA CA002391032A patent/CA2391032A1/en not_active Abandoned
- 2000-11-17 JP JP2001537700A patent/JP2003513996A/en active Pending
- 2000-11-17 MX MXPA02005060A patent/MXPA02005060A/en unknown
- 2000-11-17 BR BR0015654-0A patent/BR0015654A/en not_active Application Discontinuation
- 2000-11-17 CN CN00818468A patent/CN1424903A/en active Pending
Also Published As
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CA2391032A1 (en) | 2001-05-25 |
WO2001035905A2 (en) | 2001-05-25 |
BR0015654A (en) | 2002-07-23 |
EP1229897A2 (en) | 2002-08-14 |
CN1424903A (en) | 2003-06-18 |
KR20020063895A (en) | 2002-08-05 |
WO2001035905A3 (en) | 2002-01-17 |
MXPA02005060A (en) | 2002-11-07 |
JP2003513996A (en) | 2003-04-15 |
CZ20021636A3 (en) | 2002-11-13 |
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