Patent Application
20110245136
The present application relates to encapsulated, solid, water soluble benefit agents and products comprising such encapsulates, as well as processes for making and using such encapsulates and products comprising such encapsulates.
Products (e.g., consumer products) may comprise one or more solid, water soluble benefit agent that can provide a desired benefit to such product and/or a situs that is contacted with such a product (e.g., stain removal and/or bleaching). Unfortunately such benefit agents may be degraded by or degrade components of a product before such product is used. Thus, a protection system that protects the components of a product is desired. Protection systems include coating processes such as starch encapsulation and agglomeration. While such processes offer certain benefits, new protection processes that allow for triggered benefit agent release are desired. While melamine formaldehyde encapsulating technologies exist, Applicants recognized that such technologies do not allow the effective encapsulation of solid, water soluble benefit agents as such solid, water soluble benefit agents dissolve during the emulsification step of the encapsulation process. Furthermore, Applicants recognized that negative interactions between the benefit agent and shell materials that occur during particle making and processing can be eliminated or minimized by employing a protective suspension agent. In short, Applicants recognized the source of the problem and in the present specification disclose a solution to such problems as well as an effective encapsulation process that employs such solution. In addition, encapsulates made by such process and products comprising such encapsulates are disclosed.
The present application relates to encapsulated, solid, water soluble benefit agents and products comprising such encapsulates, as well as processes for making and using such encapsulates and products comprising such encapsulates. The encapsulation processes disclosed herein offer solutions to emulsification problems and minimize negative interactions between the benefit agent and shell materials that occur during particle making and processing, by employing a protective suspension agent.
As used herein “consumer product” means baby care, beauty care, fabric & home care, family care, feminine care, health care, snack and/or beverage products or devices generally intended to be used or consumed in the form in which it is sold. Such products include but are not limited to diapers, bibs, wipes; products for and/or methods relating to treating hair (human, dog, and/or cat), including, bleaching, coloring, dyeing, conditioning, shampooing, styling; deodorants and antiperspirants; personal cleansing; cosmetics; skin care including application of creams, lotions, and other topically applied products for consumer use including fine fragrances; and shaving products, products for and/or methods relating to treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, including: air care including air fresheners and scent delivery systems, car care, dishwashing, fabric conditioning (including softening and/or freshening), laundry detergency, laundry and rinse additive and/or care, hard surface cleaning and/or treatment including floor and toilet bowl cleaners, and other cleaning for consumer or institutional use; products and/or methods relating to bath tissue, facial tissue, paper handkerchiefs, and/or paper towels; tampons, feminine napkins; products and/or methods relating to oral care including toothpastes, tooth gels, tooth rinses, denture adhesives, tooth whitening; and over-the-counter health care.
As used herein, the term “cleaning and/or treatment composition” is a subset of consumer products that includes, unless otherwise indicated, beauty care, fabric & home care products. Such products include, but are not limited to, products for treating hair (human, dog, and/or cat), including, bleaching, coloring, dyeing, conditioning, shampooing, styling; deodorants and antiperspirants; personal cleansing; cosmetics; skin care including application of creams, lotions, and other topically applied products for consumer use including fine fragrances; and shaving products, products for treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, including: air care including air fresheners and scent delivery systems, car care, dishwashing, fabric conditioning (including softening and/or freshening), laundry detergency, laundry and rinse additive and/or care, hard surface cleaning and/or treatment including floor and toilet bowl cleaners, granular or powder-form all-purpose or “heavy-duty” washing agents, especially cleaning detergents; liquid, gel or paste-form all-purpose washing agents, especially the so-called heavy-duty liquid types; liquid fine-fabric detergents; hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents, including the various tablet, granular, liquid and rinse-aid types for household and institutional use; liquid cleaning and disinfecting agents, including antibacterial hand-wash types, cleaning bars, mouthwashes, denture cleaners, dentifrice, car or carpet shampoos, bathroom cleaners including toilet bowl cleaners; hair shampoos and hair-rinses; shower gels, fine fragrances and foam baths and metal cleaners; as well as cleaning auxiliaries such as bleach additives and “stain-stick” or pre-treat types, substrate-laden products such as dryer added sheets, dry and wetted wipes and pads, nonwoven substrates, and sponges; as well as sprays and mists all for consumer or/and institutional use; and/or methods relating to oral care including toothpastes, tooth gels, tooth rinses, denture adhesives, tooth whitening.
As used herein, the term “fabric and/or hard surface cleaning and/or treatment composition” is a subset of cleaning and treatment compositions that includes, unless otherwise indicated, granular or powder-form all-purpose or “heavy-duty” washing agents, especially cleaning detergents; liquid, gel or paste-form all-purpose washing agents, especially the so-called heavy-duty liquid types; liquid fine-fabric detergents; hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents, including the various tablet, granular, liquid and rinse-aid types for household and institutional use; liquid cleaning and disinfecting agents, including antibacterial hand-wash types, cleaning bars, car or carpet shampoos, bathroom cleaners including toilet bowl cleaners; and metal cleaners, fabric conditioning products including softening and/or freshening that may be in liquid, solid and/or dryer sheet form; as well as cleaning auxiliaries such as bleach additives and “stain-stick” or pre-treat types, substrate-laden products such as dryer added sheets, dry and wetted wipes and pads, nonwoven substrates, and sponges; as well as sprays and mists. All of such products which are applicable may be in standard, concentrated or even highly concentrated form even to the extent that such products may in certain aspect be non-aqueous.
As used herein, the terms “particle” and “encapsulate” are synonymous.
As used herein, articles such as “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.
As used herein, the terms “include”, “includes” and “including” are meant to be non-limiting.
As used herein, the term “solid” includes granular, powder, bar and tablet product forms.
As used herein, the term “fluid” includes liquid, gel, paste and gas product forms.
As used herein, the term “situs” includes paper products, fabrics, garments, hard surfaces, hair and skin.
Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated.
It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
In one aspect, a particle comprising:
said shell material encapsulating said core material, is disclosed.
In one aspect, a particle comprising:
In one aspect, a particle comprising:
In one aspect of said particle, said water soluble benefit agent may have a water solubility of at least 10 g/liter, from about 1 mg/liter to about 800 g/liter, from about 1 g/liter to about 600 g/liter, from about 100 g/liter to about 500 g/liter or even from about 150 g/liter to about 400 g/liter.
In one aspect, the particle's shell may comprise bleach reactive monomers in addition the specific bleach reactive monomers that were previously disclosed.
In one aspect, said shell may comprise one or more layers for example, 2, 3, 4, 5, or 6, layers.
In one aspect, a consumer product comprising a particle, said particle comprising:
In one aspect, a consumer product that may comprise one or more species of particle disclosed above is disclosed. In one aspect, said particles' core material may comprise, based total core weight, from about 0.01% to about 80%, from about 0.1% to about 50%, from about 1% to about 25% or from about 1% to about 10% of said solid, water soluble benefit agent.
In one aspect of said consumer product, said water soluble benefit agent may have a water solubility of at least 10 g/liter, from about 1 mg/liter to about 800 g/liter, from about 1 g/liter to about 600 g/liter, from about 100 g/liter to about 500 g/liter or even from about 150 g/liter to about 400 g/liter.
In one aspect of said particle, said solid, water soluble benefit agent needs to be micronized at a particle size below the particle size of the capsule. In one embodiment, 50%, 75%, 90% or even 99% of said micronized solid, water soluble benefit agent has a particle size below 80 microns, below 50 microns, below 20 microns, below 8 microns or even below 5 microns. In one embodiment, the solid, water soluble benefit agent, is micronized by a grinding process.
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise, based total core weight, from about 0.1% to about 99%, from about 1% to about 95%, from about 1% to about 80% or from about 5% to about 50% of said protective suspension agent, is disclosed.
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise, based total core weight, from about 0.1% to about 99%, from about 1% to about 95%, from about 1% to about 80% or from about 5% to about 80% of said hydrophobic organic material, is disclosed.
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise, based total particle weight, from about 1% to about 95%, from about 1% to about 95%, from about 5% to about 80% or from about 5% to about 50% of said core material, is disclosed.
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise, based total consumer product weight, from about 0.01% to about 80%, from about 0.1% to about 50%, from about 1% to about 25% or from about 1% to about 10% of said particle, is disclosed.
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise a solid, water soluble benefit agent that may comprise a material selected from the group consisting of a metal catalyst, a non-metal catalyst, an activator, a pre-formed peroxy carboxylic acid, a diacyl peroxide, a hydrogen peroxide source, an enzyme and mixtures thereof, is disclosed.
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise a solid, water soluble benefit agent that may comprise:
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise a protective suspension agent that may comprise an organosilicone said organosilicone being linear, branched and/or crosslinked and having a viscosity at 25° C. of from about 500 centistokes to about 2,000,000 centistokes, from about 1000 centistokes to about 800,000 centistokes or even from about 1000 centistokes to about 300,000 centistokes, is disclosed.
In one aspect, the protective suspension agent may comprise:
Other silicones that are useful as hydrophobic organic materials and that are available from Dow Corning, Midland, Mich., include silicone DC 245 Fluid and silicone DC 246 Fluid.
In one aspect, the protective suspension agent may have a viscosity of at least 500 centistokes. For purposes of the invention, the protective suspension agent could be blended with differing viscosity materials such as silicone 60,000 centistokes (cSt) and silicone 100 cSt to achieve a resultant viscosity of at least 500 centistokes. Such blends with resultant viscosities of at least 500 cSt are intended as encompassed by the phrase “the protective agent has a viscosity of at least 500 cSt”.
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material comprises, an organosilicone that may comprise a material selected from the group consisting of non-functionalized siloxane polymers, functionalized siloxane polymers and mixtures thereof, is disclosed.
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise a functionalized siloxane polymer that may comprise an aminosilicone, is disclosed.
Organosilicones that may be suitable for use in the disclosed consumer product include organosilicones that may comprise Si—O moieties. Such organosilicones may be selected from (a) non-functionalized siloxane polymers, (b) functionalized siloxane polymers, and combinations thereof. The molecular weight of the organosilicone is usually indicated by the reference to the viscosity of the material. In one aspect, the organosilicones may comprise a viscosity of from about 10 to about 2,000,000 centistokes at 25° C. In one aspect, suitable organosilicones may have a viscosity of from about 10 to about 800,000 centistokes at 25° C.
Suitable organosilicones may be linear, branched or cross-linked. In one aspect, the organosilicones may be linear.
In one aspect, the organosilicone may comprise a non-functionalized siloxane polymer that may have Formula I below, and may comprise polyalkyl and/or phenyl silicone fluids, resins and/or gums.
[R1R2R3SiO1/2]n[R4R4SiO2/2]m[R4SiO3/2]j (Formula I)
wherein:
i) each R1, R2, R3 and R4 may be independently selected from the group consisting of H, —OH, C1-C20 alkyl, C1-C20 substituted alkyl, C6-C20 aryl, C6-C20 substituted aryl, alkylaryl, and/or C1-C20 alkoxy, moieties;
ii) n may be an integer from about 2 to about 10, or from about 2 to about 6; or 2; such that n=j+2;
iii) m may be an integer from about 5 to about 8,000, from about 7 to about 8,000 or from about 15 to about 4,000;
iv) j may be an integer from about 0 to about 10, or from about 0 to about 4, or 0;
In one aspect, R2, R3 and R4 may comprise methyl, ethyl, propyl, C4-C20 alkyl, and/or C6-C20 aryl moieties. In one aspect, each of R2, R3 and R4 may be methyl. Each R1 moiety blocking the ends of the silicone chain may comprise a moiety selected from the group consisting of hydrogen, methyl, methoxy, ethoxy, hydroxy, propoxy, and/or aryloxy.
As used herein, the nomenclature SiO“n”/2 represents the ratio of oxygen and silicon atoms. For example, SiO1/2 means that one oxygen is shared between two Si atoms. Likewise SiO2/2 means that two oxygen atoms are shared between two Si atoms and SiO3/2 means that three oxygen atoms are shared are shared between two Si atoms.
In one aspect, the organosilicone may be polydimethylsiloxane, dimethicone, dimethiconol, dimethicone crosspolymer, phenyl trimethicone, alkyl dimethicone, lauryl dimethicone, stearyl dimethicone and phenyl dimethicone. Examples include those available under the trade names DC 200 Fluid, DC 1664, DC 349, DC 346G available from offered by Dow Corning Corporation, Midland, Mich., and those available under the trade names SF1202, SF1204, SF96, and Viscasil® available from Momentive Silicones, Waterford, N.Y.
In one aspect, the organo silicone may comprise a cyclic silicone. The cyclic silicone may comprise a cyclomethicone of the formula [(CH3)2SiO]n where n is an integer that may range from about 3 to about 7, or from about 5 to about 6.
In one aspect, the organosilicone may comprise a functionalized siloxane polymer. Functionalized siloxane polymers may comprise one or more functional moieties selected from the group consisting of amino, amido, alkoxy, hydroxy, polyether, carboxy, hydride, mercapto, sulfate phosphate, and/or quaternary ammonium moieties. These moieties may be attached directly to the siloxane backbone through a bivalent alkylene radical, (i.e., “pendant”) or may be part of the backbone. Suitable functionalized siloxane polymers include materials selected from the group consisting of aminosilicones, amidosilicones, silicone polyethers, silicone-urethane polymers, quaternary ABn silicones, amino ABn silicones, and combinations thereof.
In one aspect, the functionalized siloxane polymer may comprise a silicone polyether, also referred to as “dimethicone copolyol.” In general, silicone polyethers comprise a polydimethylsiloxane backbone with one or more polyoxyalkylene chains. The polyoxyalkylene moieties may be incorporated in the polymer as pendent chains or as terminal blocks. Such silicones are described in USPA 2005/0098759 A1, and U.S. Pat. Nos. 4,818,421 and 3,299,112. Exemplary commercially available silicone polyethers include DC 190, DC 193, FF400, all available from Dow Corning Corporation, and various Silwet surfactants available from Momentive Silicones.
In one aspect, the functionalized siloxane polymer may comprise an aminosilicone. Suitable aminosilicones are described in U.S. Pat. Nos. 7,335,630 B2, 4,911,852, and USPA 2005/0170994 A1. In one aspect, the aminosilicone may comprise the structure of Formula II:
[R1R2R3SiO1/2]n[(R4Si(X—Z)O2/2]k[R4R4SiO2/2]m[R4SiO3/2]j (Formula II)
wherein
In one aspect, R1 may comprise —OH. In this aspect, the organosilicone may be amodimethicone.
Exemplary commercially available aminosilicones include DC 8822, 2-8177, and DC-949, available from Dow Corning Corporation, and KF-873, available from Shin-Etsu Silicones, Akron, Ohio.
In one aspect, the organosilicone may comprise amine ABn silicones and quat ABn silicones. Such organosilicones are generally produced by reacting a diamine with an epoxide. These are described, for example, in U.S. Pat. Nos. 6,903,061 B2, 5,981,681, 5,807,956, 6,903,061 B2 and 7,273,837 B2. These are commercially available under the trade names Magnasoft® Prime, Magnasoft® JSS, Silsoft® A-858 (all from Momentive Silicones).
In one aspect, the functionalized siloxane polymer may comprise silicone-urethanes, such as those described in U.S. PA Ser. No. 61/170,150. These are commercially available from Wacker Silicones under the trade name SLM-21200.
When a sample of organosilicone is analyzed, it is recognized by the skilled artisan that such sample may have, on average, non-integer indices for Formula I and II above, but that such average indice values will be within the ranges of the indices for Formula I and II above.
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise a hydrophobic organic material that may comprise a material having a ClogP from about 1.5 to about 10, from about 1.5 to about 6, from about 2 to about 5 or even from about 2.2 to about 4.5, is disclosed.
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise a hydrophobic organic material that may comprise a material selected from the group consisting of an aliphatic hydrophobic organic material; an aromatic hydrophobic organic material and mixtures thereof, is disclosed.
In one aspect, a consumer product, that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise a hydrophobic organic material that may comprise a material selected from the group consisting of a carboxylic acid, an ester, an alcohol, a fatty acid, a natural oil, a synthetic oil, an aldehyde, a ketone, a nitrile, a hydrocarbon, an ether, an acetal, a Schiff Base, a wax and mixtures thereof, is disclosed.
In one aspect, a consumer product that may comprise one or more species of particle disclosed above, wherein said particles' core material may comprise:
In one aspect of said consumer product, said particle may have a benefit agent release of at least 10%, at least 25%, at least 35%, from 50% to about 100%, from 65% to about 95%, or even from 85% to about 95% of said benefit agent after 10 minutes, 8 minutes or even 5 minutes of use of such consumer product containing said particles.
In one aspect, a consumer product, wherein at least 75%, 85% or even 90% of said particles may have a particle size of from about 1 micron to about 120 microns, or from about 1 micron to about 20 microns, is disclosed. In another aspect, said particles may have a particle size from about 15 microns to about 80 microns or even form about 25 microns to about 45 microns.
In one aspect, a consumer product, wherein, at least 75%, 85% or even 90% of said particles may have a particle wall thickness of from about 30 nm to about 500 nm, from about 40 nm to about 250 nm, or even from about 50 nm to about 150 nm, is disclosed.
In one aspect, a consumer product, that may comprise a material selected from the group consisting of a scavenger, a structurant, an anti-agglomeration agent and mixtures thereof, is disclosed.
In one aspect, the core of said consumer product's particle comprises at least a portion of said structurant.
In one aspect, a consumer product, that may comprise, based total consumer product weight, less than 85%, less than 60, less than 40%, less than 20% total water, is disclosed.
In one aspect, a consumer product that may comprise, based total consumer product weight, from about 1% to about 85%, from about 3% to about 60%, from about 5% to about 40%, from about 5% to about 20% total water, is disclosed.
In one aspect of said consumer product, said consumer product may comprise a perfume delivery or any combination of perfume delivery systems described, for example, in USPA 2007/0275866 A1: Molecule-Assisted Delivery (MAD) systems; Fiber-Assisted Delivery (FAD) systems; Amine Assisted Delivery (AAD; Cyclodextrin Delivery System (CD); Starch Encapsulated Accord (SEA); Inorganic Carrier Delivery System (ZIC); Pro-Perfume (PP) including Amine Reaction Products (ARPs); and other Polymer Assisted Delivery (PAD) systems.
In addition to the foregoing aspects of said consumer product, aspects of Applicants consumer products may comprise/have any combination of characteristics and/or parameters disclosed in the present specification. Thus, by way of example, a consumer product may comprise any combination of characteristics and/or combination of particles disclosed in this specification.
The suitable materials and equipment for practicing the present invention may be obtained from: United Initiators, GmbH & Co. KG, Dr.-Gustav-Adolph-Str.3, 82049 Pullach, Germany; Emerson Resources INC, Suite 1, 600 Markley Street, Norristown, Pa. 19401, United States; Appleton, 825 E Wisconsin Avenue, P.O. Box 359, WI 54912-0359, United States; Sigma Aldrich NV/SA, Kardinaal Cardijnplein 8, 2880 Bornem, Belgium; ProCepT nv, Rosteyne 4, 9060 Zelzate, Belgium; Ingeniatrics, Avd. Américo Vespucio 5-4, 1a p., mód. 12, Sevilla, Spain; GEA Process Engineering Inc. 9165 Rumsey Road Columbia, Md. 21045, United States; Mettler-Toledo, Inc., 1900 Polaris Parkway, Columbus, Ohio, 43240, United States; IKA-Werke GmbH & Co. KG, Janke & Kunkel Str. 10, 79219 Staufen, Germany; Alfa Aesar GmbH & Co KG, Zeppelinstrasse 7, 76185 Karlsruhe, Germany; Netzsch-Condux Mahltechnik GmbH, Rodenbacher Chaussee 1, 63457 Hanau, Germany; International Flavors & Fragrances, Global Headquarters, 521 West 57th Street, 10019 New York, United States; Firmenich SA—Corporate Headquarters, Rue de la Bergére 7, P.O. Box 148, Meyrin 2 CH-1217, Switzerland; Corporate Headquarters Givaudan SA, 5, chemin de la parfumerie, 1214 Vernier, Switzerland.
In one aspect, a process of making a consumer product, that may comprise a consumer product adjunct material and a particle is disclosed, said process may comprise:
In one aspect, a process of making a consumer product, comprising a consumer product adjunct material and a particle is disclosed, said process may comprise:
f) forming a first composition at temperature of from about 0° C. to about 25° C., by either combining said core material and said first solution and emulsifying said first composition; or emulsifying said core material in said first solution via a micro-device, for example a micro-device selected from the group consisting of a cross flow membrane, and/or a flow focusing technology;
In one aspect, a process of making a consumer product comprising a consumer product adjunct material and a particle, said process may comprise:
In one aspect, a process of making a consumer product, comprising a consumer product adjunct material and a particle is disclosed, said process may comprise:
The aforementioned shell materials may be obtained from CP Kelco Corp. of San Diego, Calif., USA; Degussa AG or Dusseldorf, Germany; BASF AG of Ludwigshafen, Germany; Rhodia Corp. of Cranbury, N.J., USA; Baker Hughes Corp. of Houston, Tex., USA; Hercules Corp. of Wilmington, Del., USA; Agrium Inc. of Calgary, Alberta, Canada G.M. Chemie Pvt Ltd, Mumbai, 400705, India, Eastman Chemical Company, Kingsport, USA and International Specialty Products of Wayne, N.J. USA.
Suitable hydrophobic organic materials are listed in Tables 1-10 below.
Such materials may be used alone or in any combination. Thus, it is understood that, mixtures thereof are disclosed.
For the purposes of the present invention, the non-limiting list of adjuncts illustrated hereinafter are suitable for use in the instant compositions and may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with perfumes, colorants, dyes or the like. It is understood that such adjuncts are in addition to the components supplied by the recited particle and other recited materials such as perfume delivery systems. The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used. Suitable adjunct materials include, but are not limited to, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.
Each adjunct ingredients is not essential to Applicants' compositions. Thus, certain embodiments of Applicants' compositions do not contain one or more of the following adjuncts materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. It is understood that such adjuncts may form a product matrix that is combined with the encapsulates disclosed herein to form a finished consumer product. Generally, when one or more adjuncts are present, such one or more adjuncts may be present as detailed below:
Surfactants—The compositions according to the present invention can comprise a surfactant or surfactant system wherein the surfactant can be selected from nonionic and/or anionic and/or cationic surfactants and/or ampholytic and/or zwitterionic and/or semi-polar nonionic surfactants. The surfactant is typically present at a level of from about 0.1%, from about 1%, or even from about 5% by weight of the cleaning compositions to about 99.9%, to about 80%, to about 35%, or even to about 30% by weight of the cleaning compositions.
Builders—The compositions of the present invention can comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1% builder, or from about 5% or 10% to about 80%, 50%, or even 30% by weight, of said builder. Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders polycarboxylate compounds. ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyl-oxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Chelating Agents—The compositions herein may also optionally contain one or more copper, iron and/or manganese chelating agents. If utilized, chelating agents will generally comprise from about 0.1% by weight of the compositions herein to about 15%, or even from about 3.0% to about 15% by weight of the compositions herein.
Dye Transfer Inhibiting Agents—The compositions of the present invention may also include one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. When present in the compositions herein, the dye transfer inhibiting agents are present at levels from about 0.0001%, from about 0.01%, from about 0.05% by weight of the cleaning compositions to about 10%, about 2%, or even about 1% by weight of the cleaning compositions.
Dispersants—The compositions of the present invention can also contain dispersants. Suitable water-soluble organic materials are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid may comprise at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Enzymes—The compositions can comprise one or more detergent enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, B-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is a cocktail of conventional applicable enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase.
Enzyme Stabilizers—Enzymes for use in compositions, for example, detergents can be stabilized by various techniques. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions that provide such ions to the enzymes.
Catalytic Metal Complexes—Applicants' compositions may include catalytic metal complexes. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methyl-enephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.
If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. No. 5,576,282.
Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Pat. Nos. 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. Pat. Nos. 5,597,936, and 5,595,967.
Compositions herein may also suitably include a transition metal complex of a macropolycyclic rigid ligand—abbreviated as “MRL”. As a practical matter, and not by way of limitation, the compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the benefit agent MRL species in the aqueous washing medium, and may provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the wash liquor.
Suitable transition-metals in the instant transition-metal bleach catalyst include manganese, iron and chromium. Suitable MRL's herein are a special type of ultra-rigid ligand that is cross-bridged such as 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa-decane.
Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in U.S. Pat. No. 6,225,464.
The composition of the present invention may comprise from 0.01% to 5%, or even from 0.1% to 1% by weight of an external structuring system. The external structuring system may be selected from the group consisting of:
(i) non-polymeric crystalline, hydroxy-functional structurants and/or
(ii) polymeric structurants
Such external structuring systems may be those which impart a sufficient yield stress or low shear viscosity to stabilize a fluid laundry detergent composition independently from, or extrinsic from, any structuring effect of the detersive surfactants of the composition. They may impart to a fluid laundry detergent composition a high shear viscosity at 20 s-1 at 21° C. of from 1 to 1500 cps and a viscosity at low shear (0.05 s-1 at 21° C.) of greater than 5000 cps. The viscosity is measured using an AR 550 rheometer from TA instruments using a plate steel spindle at 40 mm diameter and a gap size of 500 μm. The high shear viscosity at 20 s-1 and low shear viscosity at 0.5 s-1 can be obtained from a logarithmic shear rate sweep from 0.1 s-1 to 25 s-1 in 3 minutes time at 21° C. In one embodiment, the compositions may comprise from 0.01 to 1% by weight of a non-polymeric crystalline, hydroxyl functional structurant. Such non-polymeric crystalline, hydroxyl functional structurants may comprise a crystallizable glyceride which can be pre-emulsified to aid dispersion into the final unit dose laundry detergent composition. Suitable crystallizable glycerides include hydrogenated castor oil or “HCO” or derivatives thereof, provided that it is capable of crystallizing in the liquid detergent composition.
Unit dose laundry detergent compositions may comprise from 0.01 to 5% by weight of a naturally derived and/or synthetic polymeric structurant. Suitable naturally derived polymeric structurants include: hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives and mixtures thereof. Suitable polysaccharide derivatives include: pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum, guar gum and mixtures thereof. Suitable synthetic polymeric structurants include: polycarboxylates, polyacrylates, hydrophobically modified ethoxylated urethanes, hydrophobically modified non-ionic polyols and mixtures thereof. In one aspect, the polycarboxylate polymer may be a polyacrylate, polymethacrylate or mixtures thereof. In another aspect, the polyacrylate may be a copolymer of unsaturated mono- or di-carbonic acid and C1-C30 alkyl ester of the (meth)acrylic acid. Such copolymers are available from Noveon inc under the tradename Carbopol® Aqua 30.
Certain of the consumer products disclosed herein can be used to clean or treat a situs inter alia a surface or fabric. Typically at least a portion of the situs is contacted with an embodiment of Applicants' consumer product, in neat form or diluted in a liquor, for example, a wash liquor and then the situs may be optionally washed and/or rinsed. In one aspect, a situs is optionally washed and/or rinsed, contacted with an aspect of the consumer product and then optionally washed and/or rinsed. For purposes of the present invention, washing includes but is not limited to, scrubbing, and mechanical agitation. The fabric may comprise most any fabric capable of being laundered or treated in normal consumer use conditions. Liquors that may comprise the disclosed compositions may have a pH of from about 3 to about 11.5. Such compositions are typically employed at concentrations of from about 500 ppm to about 15,000 ppm in solution. When the wash solvent is water, the water temperature typically ranges from about 5° C. to about 90° C. and, when the situs comprises a fabric, the water to fabric ratio is typically from about 1:1 to about 30:1.
Employing one or more of the aforementioned methods results in a treated situs.
It is understood that the test methods that are disclosed in the Test Methods Section of the present application should be used to determine the respective values of the parameters of Applicants' invention as such invention is described and claimed herein.
(1) Fracture Strength
(2) ClogP
(3) Particle Size
(4) Particle Wall Thickness
Instruments:
Test Procedure
Calculations
(5) Solid, Water Soluble Benefit Agent Release Test
Material and Instruments Needed:
Procedure:
A. Analytical Test for Preformed Peracids, Bleach Activators and Hydrogen Peroxide Sources:
Bleach component+2I−+2H+→I2+2H2O [1]
I2+I−I3− [2]
I3−+2S2O32−→3I−+S4O6 [3]
Equipment:
Chemicals:
Procedure:
B. Analytical Test for Metal Catalysts: Photometric Method
C. Analytical Test for Non-Metal Catalysts:
Isoquinolinium class materials and the activated intermediate can be measured by mass spectrometry. Depending upon the response of the individual molecule, electrospray mass spectrometry operated in positive or negative ion is used to measure the isoquinolinium and the oxized intermediate. MS analysis is done either by direct infusion or by injecting discrete amounts of diluted sample (flow injection analysis). No HPLC separation is needed.
D. Analytical Test for Diacyl Peroxides:
E. Enzyme Release May be Measured Using ASTM Method D0348-89 (2003).
(6) Water Solubility Test
Water solubility may be measured using ASTM method E1148-02(2008)
(7) Solid Particle Size Test
Solid, water soluble benefit agent particle size may be measured using ASTM method E2651-10
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Preparation core: 40 grams of a suspension formed by a solid, water soluble manganese complex, such as of meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane and racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ligands (with 99% of the particles having a particle size of 3.65 microns), a polysiloxane (60,000 centistokes) and a hydrophobic organic composition formulated with materials listed in Tables 1 to 10 is cooled to 25° C. and mixed with 4.482 grams Trimesoyl Chloride (Sigma Aldrich. This mixture is kept at 25° C.
Preparation solution 1: 2 grams of polyvinyl alcohol 87-89% hydrolyzed Mw 13000 (Sigma-Aldrich) are dissolved and mixed in 198 grams deionized water. This solution is cooled to 25° C.
Preparation solution 2: 8.598 grams Diethylenetriamine (Sigma-Aldrich) are mixed with 10 grams deionized water. This solution is cooled to 25° C.
Process: the core is added to the solution 1 at a rate of 5 grams per minute under mechanical agitation in a thermostatic reactor with temperature control—temperature set point 25° C. during all the process—. After mixing under a stable emulsion is obtained (10 min at 1400 rpm), we add solution 2 to the emulsion at a rate of 1 gram per minute under continuous stifling at 500 rpm for 15 minutes. After addition is completed, we stir the mixture at 300 rpm for 3 hours till complete encapsulation.
In order to eliminate the excess of amine, capsules are centrifuged and aqueous phase is removed and substituted by deionized water.
Preparation core: 70 grams of a suspension formed by a solid, water soluble manganese complex, such as of meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane and racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ligands (with 99% of the particles having a particle size of 3.65 microns), a polysiloxane (60,000 centistokes) and a hydrophobic organic composition formulated with materials listed in Tables 1 to 10 is mixed with 0.66 grams PEG 300 (Sigma Aldrich) and 2 grams Ethyl lactate (Sigma-Aldrich). This mixture is kept at 5° C.
Preparation solution 1: 1.8 grams of polyvinyl alcohol Elvanol® 70-75 (DuPont) are dissolved in 148.2 grams deionized water at 60° C. This solution is cooled to 5° C.
Preparation solution 2: 1.87 grams Hydroxypropyl methyl cellulose (Sigma-Aldrich) are dissolved in 60 grams deionized water. This solution is kept at 5° C. till hydroxypropyl methyl cellulose is completely dissolved.
Process: we mix solution 1 and solution 2 at 5° C. and add the core to this mixture under mechanical agitation in a thermostatic reactor with temperature control—temperature set point 5° C. during emulsification step—. After mixing under a stable emulsion is obtained (10 min at 1400 rpm), we increase the temperature to 55° C. at a rate of 0.4 C per minute and maintain this temperature for 3 hours. Then, we stop the stirring and maintain the encapsulate at 55° C. for 12 h. Encapsulate is separated by filtration.
A 10% solution of HPMCP, grade 50 (“HP 50”) (available from SEPPIC SA, 7 Boulevard Franck Kupka, 92039 Paris La Defense, Cedex, France) in a 5% sodium bicarbonate aqueous solution is prepared at 50° C. and filtered with a 1.2 micron filter (Albet, Dassel, Germany). The solution is cooled to room temperature. 10 grams of SPAN 80 (Sigma-aldrich) is added to the solution. 100 grams of a suspension formed by a solid, water soluble manganese complex, such as of meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane and racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ligands, a polysiloxane (30,000 centistokes) and a hydrophobic organic composition formulated with materials listed in Tables 1 to 10, is added to the previous mixture under mechanical agitation. After mixing until a stable emulsion is obtained a spray-dryer is then used to collect the particles (4M8 Spray-Dryer from ProCepT, Belgium). Parameters used in the spray-drying process are as follows: nozzle 0.4 mm; schuin 60 cyclone; temperature inlet air 140° C.; air flow 0.4 m3/min; feeding speed 2 mL/min with syringe. An average capsule size of 20 um is obtained as analyzed by a Model 780 Accusizer.
100 grams of a suspension formed by a solid, water soluble manganese complex, such as of meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane and racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ligands, a polysiloxane (15,000 centistokes) and a hydrophobic volatile organic solvent -methylene chloride- is mixed with 10 g poly(styrene-co-methyl methacrylate). This mixture is added to an aqueous solution with 5% polyvinyl alcohol as surfactant under mechanical agitation. We close the reactor and apply vacuum while stifling till solvent has been evaporated and particles are formed. An average capsule size of 75 um is obtained as analyzed by a Model 780 Accusizer.
Non-limiting examples of product formulations containing an encapsulated solid water soluble benefit agent summarized in the following table
aslurry of encapsulated water soluble manganese complex, such as of meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane and racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ligands
bencapsulate water soluble manganese complex, such as of meso-5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetraazacyclotetradecane and racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ligands as solid, like collected from spray-drying.
Non-limiting examples of product formulations containing particles of the aforementioned examples are summarized in the following table.
The following are examples of unit dose executions wherein the liquid composition is enclosed within a PVA film. The preferred film used in the present examples is Monosol M8630 76 μm thickness.
1Polyethylenimine (MW = 600) with 20 ethoxylate groups per-NH.
3RA = Reserve Alkalinity (g NaOH/dose)
A 15.5% polyvinyl alcohol solution is prepared by adding 593.02 grams of deionized water to a water jacketed vessel set to 80° C. The water is stirred with a paddle mixer while 108.4 grams of granular Acetic Acid Ethenyl Ester, polymer with Ethenol (Celvol 523, Partially Hydrolyzed, (Celanese Ltd. Dallas, Tex. U.S.A.)) is added slowly over one minute. The granules are allowed to mix and cook at this temperature for 30 minutes before being removed and cooled to room temperature.
47.85 grams of the cooked 15.5% 523 polyvinyl alcohol solution is added to a 1 kg reactor to which is previously added 210.58 grams distilled water. The mixture is stirred with a 2 inch diameter, 4 point star blade mixer for a period of 5 minutes at 425 RPM. 200.18 grams of a suspension formed by a solid, water soluble manganese complex, such as of meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane and racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ligands, a polysiloxane (60,000 centistokes) and a hydrophobic organic composition formulated with materials listed in Tables 1 to 10, is added to the previous mixture under mechanical agitation. The mixture is milled with the same flat 4 point star blade, 2 inches in diameter at 1500 rpm for a period of 4 minutes to achieve a stable emulsion with a desired particle size.
After milling, the star mixer is changed to a paddle mixer and the slurry is allowed to mix at 700 RPM while, 3.87 grams of Potassium Persulfate (CAS 7727-21-1) is added slowly over a period of 30 seconds and allowed to finish mixing for another 40 minutes at 700 RPM. An average capsule size of 14.2 microns is obtained and analyzed by the method described above.
The total time for the preparation of the Celvol 523 solution is approximately 40 minutes. The microencapsulation procedure can occur at room temperature or elevated temperatures up to 85° C. in about 20 minutes.
A 12.5% polyvinyl alcohol solution is prepared by adding 612.89 grams of deionized water to a water jacketed vessel set to 80° C. The water is stirred with a paddle mixer while 87.52 grams of granular Acetic Acid Ethenyl Ester, polymer with Ethenol (Celvol 523, Partially Hydrolyzed, (Celanese Ltd. Dallas, Tex. U.S.A.)) is added slowly over one minute. The granules are allowed to mix and cook at this temperature for 30 minutes before being removed and cooled to room temperature.
An amine solution is prepared by adding 3.66 grams of tetraethylenepentamine (TEPA, (The Dow Chemical Company Midland, Mich. U.S.A.)) and 25.65 grams of deionized water to a beaker with magnetic stir bar. The solution is allowed to stir under mild mixing for 15 minutes and set aside until needed.
47.51 grams of the cooked 12.5% 523 polyvinyl alcohol solution are added to a 38° C. 1 kg reactor to which is previously added 166.25 grams distilled water. The mixture is stirred with a 2 inch diameter, 4 point star blade mixer for a period of 5 minutes at 600 RPM. 185.01 grams of a suspension formed by 28.5 grams of Hexamethylene-1,6-Diisocyanate (N3400, 21.9% NCO, (Bayer MaterialScience Pittsburgh, Pa. U.S.A.)) and 156.51 grams of a solid, water soluble manganese complex, such as of meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane and racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ligands, a polysiloxane (60,000 centistokes) and a hydrophobic organic composition formulated with materials listed in Tables 1 to 10, is added to the previous mixture under mechanical agitation. The mixture is milled with the same flat 4 point star blade, 2 inches in diameter at 38° C. 2000 rpm for 10 minutes forming a stable emulsion with desired particle size.
The flat 4-point star mixer is changed to a paddle mixer and the RPM set to 450. The TEPA solution is added drop-wise over 8 minutes at 38° C. The mixture is then heated to 52° C. and kept here for at least 5 minutes, preferable, 2, 4, 6, or even 24 hours with stirring to complete the encapsulation. The average particle size is 30 microns as analyzed by the method described in the test method section of this specification.
A 12.5% polyvinyl alcohol solution is prepared by adding 612.89 grams of deionized water to a water jacketed vessel set to 80° C. The water is stirred with a paddle mixer while 87.52 grams of granular Acetic Acid Ethenyl Ester, polymer with Ethenol (Celvol 523, Partially Hydrolyzed, (Celanese Ltd. Dallas, Tex. U.S.A.)) is added slowly over one minute. The granules are allowed to mix and cook at this temperature for 30 minutes before being removed and cooled to room temperature.
An amine solution is prepared by adding 5.24 grams of tetraethylenepentamine (TEPA, (The Dow Chemical Company Midland, Mich. U.S.A.)) and 25.65 grams of deionized water to a beaker with magnetic stir bar. The solution is allowed to stir under mild mixing for 15 minutes and set aside until needed.
60.3 grams of the cooked 12.5% 523 polyvinyl alcohol solution are added to a 45° C. 1 kg reactor to which is previously added 190.15 grams distilled water. The mixture is stirred with a 2 inch diameter, 4 point star blade mixer for a period of 5 minutes at 600 RPM. 221.35 grams of a suspension formed by 30.21 grams of Diphenylmethane Diisocyanate, isomers and homologues 4,4′-Methylenediphenyl diisocyanate (PAPI27, 31.4% NCO, (The Dow Chemical Company Midland, Mich. U.S.A.) and 191.14 grams of a solid, water soluble manganese complex, such as of meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane and racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ligands, a polysiloxane (60,000 centistokes) and a hydrophobic organic composition formulated with materials listed in Tables 1 to 10, is added to the previous mixture under mechanical agitation. The mixture is milled with the same flat 4 point star blade, 2 inches in diameter at 45° C. 2500 rpm for 15 minutes to form a stable emulsion with desired particle size.
The flat 4-point star mixer is changed to a paddle mixer and the RPM set to 450. The TEPA solution is added drop-wise over 5 minutes at 45° C. The mixture is then heated to 65° C. and kept here for at least 2 minutes, preferable, 2, 4, 6, or even 24 hours with stirring to complete the encapsulation. The average particle size is 10 microns as analyzed by the method described in the test method section of this specification.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”
All documents cited in the Detailed Description of the Invention are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention. To the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application Ser. No. 61/321,323 filed Apr. 6, 2010, U.S. Provisional Application Ser. No. 61/348,450 filed May 26, 2010, U.S. Provisional Application Ser. No. 61/353,393 filed Jun. 10, 2010 and U.S. Provisional Application Ser. No. 61/367,098 filed Jul. 23, 2010.
| Number | Date | Country | |
|---|---|---|---|
| 61321323 | Apr 2010 | US | |
| 61348450 | May 2010 | US | |
| 61353393 | Jun 2010 | US | |
| 61367098 | Jul 2010 | US |
