Title of Invention	A NON-WOVEN WEB MATERIAL
Abstract	An article of manufacture comprising a fibrous substrate and alumina containing particles for various functional compounds is disclosed. The Article incorporates a carrier composition containing alumina particles, silica particles or alumina coated particles. Various functional materials containing particular moieties may be absorbed onto the particles and used as desired. The functional compounds can be, for instance, pharmaceuticals, xenobiotics, anti-microbial agents, anti-viral agents, fragrances, and the like.

Title of Invention

A NON-WOVEN WEB MATERIAL

Abstract

An article of manufacture comprising a fibrous substrate and alumina containing particles for various functional compounds is disclosed. The Article incorporates a carrier composition containing alumina particles, silica particles or alumina coated particles. Various functional materials containing particular moieties may be absorbed onto the particles and used as desired. The functional compounds can be, for instance, pharmaceuticals, xenobiotics, anti-microbial agents, anti-viral agents, fragrances, and the like.

Full Text	DELIVERY SYSTEM FOR FUNCTIONAL COMPOUNDS Background Of The Invention A delivery system generally refers to a system that aids or other-vise facilitates the delivery of a functional materia! to a desired location. ~he functional materia! can be any material that acts upon a substrate or otherwise provides a benefit once delivered to the cesirec :ccaticn. Examples of functional materials that may benefit from the use cf a delivery system include pharmaceuticals that are intended to be ingested, topically applied, or subcutanecusly injected into a patient, fragrances, vitamins and nutrients, and various other and numerous additives. in one particular application, ;or instance, the functional material can be a dye that is intended to be printed or otherwise applied to a substrate, in the past various delivery systems for dyes have been proposed that are intended tc facilitate application of the dye to a substrate, such as a textile material. The delivery systems, for instance, are intended to affix the dye to a substrate, prevent the dye from fading when exposed to sunlight, to prevent the dye from degrading when exposed to the environment, to facilitate application of the dye to the substrate, or, for example, to render the dye mere stable. Even in view of recent advances in the art, furthar +wprovements in defrwry systems for functional materials are stii! needed.. For example, a need currently exists for a delivery system that can bind to various functional materials that does not incorporate relatively expensive chemical formulations or that does not require any complex process steps for incorporating a functional material into the delivery system. With respect to dyes, a need also exists in the art for a delivery system for a dye that is capable of affixing the dye to negatively charged surfaces. For example, a need currently exists for a delivery system for dyes that is capable of affixing the dyes to textile materials containing natural or synthetic polymeric fibers that have a negative surface charge. With respect to pharmaceutical and nutritional materials, a need also exists in the art for a delivery system for such materials that is capable of affixing the pharmaceutical or other health -related compounds to the delivery system. A need aisc exists for a delivery system that will readily and /or selectively release such pharmaceutical materials upon the occurence of a selected event or trigger. A nee Summer/ Of The Invention The present invention is generally directed to a deliver/ system for various functional materials. The functional materials can be; for Instance, colorants, UV absorbers, pharmaceuticals, cdcr control agents, fragrances, anti-microbtai agents, anti-viral agents, antibiotics, xenobictics, nutricauticai agents (nutritional-materials), and the like. In accordance with the present invention, the functional materials are adsorbed onto a particle. For nstance the functional materials are absorbed onto silica particles or alumina that is contained ir./cn a particle. The resulting particle can then be used as is or can be combined with a vehicle, such as a liquid vehicle, to deliver the functional material to a desired location. Additionally, the resulting particle, or particle containing vehicle can be incorporated into a drug delivery device, such as a bandage or tampon. For example, when the functional material is a colorant the particles of the present invention can be incorporated into a liquid vehicle and applied to a substrate using any conventional printing means, if the functional material is a health related compound such as a pharmaceutical or nutritional compound, the particles can likewise be incorporated into a vehicle and applied to a substrate such as a bandage or drug delivery device which can be placed immediately adjacent, in contact with or within a patient's body. For the purposes of this application, the term "patients body" shall mean a human or animal body. In this fashion, the functional material can be delivered to a selected location on or within a patient's body. Alternatively, such particles could be taken by a patient internally where appropriate to deliver the functional material to a desired location. In an alternative embodiment, the functional material may be triggerably released from a particle at a selected location or time, following occurrence of a triggering evant, such as exposure to a chemical, body exudates or moisture or environmental stimuli, such as a change in pH. Thus, in one embodiment, the present invention is directed to a particle containing alumina. At least a portion cf the alumina contained within the particle is present on a surface of the particle. A .functional compound is bonded to the alumina en the surface of the particle. The functional compound prior to bending with the alumina contains a moiety comprising one or more of: a tautomer thereof, or a functional equivalent thereof and wherein R and R' comprise independently hydrogen, an alkyi group, or an aryl group. The above moieties can be present as is on a functional compound. Alternatively, however, each of the above moieties can include further R groups attached to the carbon chain shown above. In general, any such R group can appear in association with the above moieties as long as the R group does not interfere with the bonding of the moiety to an alumina. The above moieties have been found to form a bond with alumina in constructing the compositions of the present invention. Of particular significance, it was discovered that the functional compound, in some embodiments, can bond with alumina without significantly changing the positive charge character of alumina. For example, under certain conditions, alumina may have a positive surface charge. It has been discovered that even after the functional material is bonded to the alumina, the resulting structure still maintains a positive charge. Thus, in one embodiment of the present invention, positively charged particles are formed. Due to their positive charge, the particles may be securely affixed to the surface of a substrate that carries with it a negative charge through coulombic attraction. In one embodiment of the ir.venticn, the functional agent such as the pharmaceutical may be selectively released from the carrier particle (such as an alumina, silica, or alumina- coatee silica particle) so as to release the pharmaceutical at a targeted/desirable :cdy location, or a: a desirable moment, in one such embodiment, such selective -eiease can be accomplished by exposure of the particle to a change in environmental.condition, sucn as a pH change. For example, such selective release may be accomplished by exposure to an alkaline environment Alternatively, such selective release my be accomplished by exposure to an acidic environment. Still further, such selective reiease may be the result of exposure of the carrier particle to particular chemical stimuli. In an alternative embodiment of the invention, a method for applying a health related compound utilizes a health-related compound coated particle, and selectively releasing the compound upon exposure cf the particle to either a change in environmental condition, or upon exposure to a chemical stimuli. The functional compounds can in one embodiment, be selectively released in either a basic or acidic environmental condition. For instance, in one specific embodiment of the invention, the functional compounds can be released in the basic/alkaline environment of a vagina experiencing a yeast infection, in a second embodiment, the functional compounds can be released in the basic environment of the small intestine so as to treat an infection, after passing through the acidic environment of the stomach. In still a further alternative embodiment & functional compound may be released as a result cf environmental stimuli as an alert or in conjunction with the completion of the deliver/ of a oharmaceutical material so as (o provide and indication of such delivery or the success of such treatment. Alternatively, such-indicator may be released as a result of appearance of moisture or body fluids. Such indicator cr signal may be in the form of a dye or fragrance. In most of these situations, whiie the functional compound is released, the particle remains behind on a substrate, or alternatively passes through the body of the patient. - !n still a further alternative embodiment, such indicator or signal may be the result of a functional material contained on a first type of particle, and such coated particle may be included with additional particles of a different variety, that contain - health related compounds (pharmaceutical and/or nutritional compounds). In still a further alternative embodiment, the functional material may be released in response to a particular chemical stimuli, which is intentionally applied to the site of the carrier particles. In still a further alternative embodiment, a method of utilizing a triggerabiy releasable delivery system in the treatment of a patient's body includes the steps of providing at least one type of particle selected from alumina particles, alumina covered particles, and silica particles; adsorbing at least one health related functional compound to the surface of the particle or particles to form at least a partially coated particle or particles; exposing the at least partially coated particle or particles to a patient's body such as by ingestion, injection, transdermal transfer or transmucosal transfer, and exposing the particle or particles to an environmental or chemical condition whereby the health related compound is released from the surface of the particle to the patient's body (which could be either an animal or human body), in an alternative embodiment, such health related compound is released from particles contained on a drug delivery device, but because of charge attraction (as previously described) the particles themselves remain affixed to the drug delivery device. In a further alternative embodiment of the invention, a triggerable delivery system includes a particle selected from silica, alumina or alumina coated particles; and a health-related compound adsorbed to the surface of the particle, the health-related compound capable of being released from the particle upon either exposure to a change in pH, moisture, chemical stimuli* or body exudates. In- still a further alternative embodiment, the triggerable delivery system includes a particle containing alumina, at least a oortion of the alumina beina present on a surface of the particle; and a health related compound adsorbed to the alumina surface of the panels, the health related compound, prior to being adsorbed with the alumina or the surface of -he particle containing a moiety including at least one of or a tautomer thereof, or a functional equivalent thereof and wherein-R-and R' comprise independently hydrogen, an alkyl group, or an ar/l group. In still a further alternative embodiment, a drug delivery device such as a~ topical bandage or a tampon, induces a triggerabie -delivery system. The triggerable delivery system includes a particle; and a health-related compound adsorbed to the surface of the particle, with the hearth-related compound capable of being released from the particle upon either exposure to a change in pH, moisture, chemical stimuli, or body exudates. Other features and aspects of the present invention are discussed in greater detail. Detailed Description It is to be understood by one cf crdinan/ skill in the art that the present discussion is a description of exemplany embodiments only, and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied in the exemplary construction. In general, the present invention .is directed to a delivery system for functional compounds. Functional compounds can be any suitable substance that can provide a benefit to a location once delivered. In accordance with the present invention, the delivery system is generally directed to the construction of a particle. For example such particle may be erther silica or desirably containing alumina. The alumina contained within the particle provides a bonding site on the surface of the particle for a functional compound. Specifically, the functional compound becomes adsorbed onto the surface cf the alumina (or silica, if it is an entirely siiica particle). Once the functional compound is boncec ro the alumina, the resulting particle can then be used :c deliver the functional compound to a particular location. The particles car. be used as is, for instance, cr can be combined with a ' iid vehicle whicr may facilitate delivery of the particles depending upon the particular application. The particles or liquid vehicles containing the particles may further be placed within a drug delivery device such as a tampon, bandage or other transdermal delivery device. Functional compounds that are ".veil suited far-use in the present invention include compounds that contain at least me of the following moieties: one or more of: a tautomer thereof, or a functional equivalent thereof and wherein R and R' comprise independently hydrogen, an aikyl group, or an aryl group. As used herein, a functional equivalent to one cf the above moieties refers to functional materials that include similar reactive groups as shown above, but which are not positioned on a molecule as exactly shown above and yet will still bond with alumina in a similar manner. Referring to the moieties shown above, moiety (1) may be considered a carboxy-hydroxy moiety. Moiety (2) may be considered a hyrdoxy-hydroxy moiety, while moiety (3) may be considered a carboxy-carboxy moiety. Moieties (4) and (5), on the other hand, can be considered vinylalogous amide moieties. In moieties (4) and (5) above, the amine grcups can be primary amines, secondary amines, or tertiary amines. Moieties (5; and (7) may be considered hydroxy) carbonyl moieties. Moiety (8) may be considered a carboxy amine. Moieties such as (8) may be found in amino acids/ Moiety (9) may.be considered a hydroxy imine. (n general; any suitable functional compound containing one of the above moieties or a functional equivalent 'ir.erecj may be used in accordance with the present invention. Further, ■'; 5ncu:c ce understood that various additional F groups may be included with the above moieties as long as the R groups do net interfere with the bond that is fcrmsd ,v:ih alumina. The present inventors have discovered tnat the above mcieties may form a relatively strong bond to at least an a.umina surface. The funciicnai compounds may be bended to the alumina surface in order to chance the properties of the resulting particle or to perform a particular function. Without wishing to be bound by theory, it is believed that the above moieties form a bidentate licand bonding system with alumina surfaces. For instance, it is believed that alumina forms a covalent bond and a coordinate bene with the above moieties. Further, it is believed that a surface reaction occurs causing :ne functional compound to remain on the surface of the particle and form a coating thereon. The functional material can cover the entire resulting particle or can be located at particular locations on the particle. Further, it should be -ncerstccc that the particles of the present invention can contain more than cr.e functional compound, or alternatively, numerous different particles can contain.include different functional compounds. Of particular advantage, in many embodiments, it has also been discovered that a functional compound can be bonded to alumina without signifrcantly impacting on the positive surface charge of alumina, which can be measured as zeta potential. The term "zeta potential* is used herein to mean without limitation a potential gradient that arises across an interface. This term especially refers to the potential gradient that arises across the interface between the Stern layer in contact with the particle of the present invention and the diffuse layer surrounding the particle. Zeta potential measurements can be taken using, for instance, a Zetapals instrument which are available from the Brookhaven Instrument Corporation of Holtsville, New York. For example, zeta potential measurements can be conducted by adding one to three drops of a sample into a cuvet containing 1 mM KCI solution, using the instrument's default functions preset for aqueous solutions. in some applications, the alumina and the dye containing a reactive moiety can be combined and reacted in an aqueous solution. In some embodiments, however, the dye may be difficult to dissolve in water. In this embodiment, the dye can first be dissolved in a minimum quantity of a solvent The solvent can be, for instance, acetone, ethanol or a similar liquid that is miscible with water. After the dye is combined with the solvent, if desired, a surfactant can be added in an amount greater than about 0% to about 50% by weight of dye solids added. In general, the amount of surfactant added to the solvent should be minimized. One suitable surfactant that can be used, for instance, is SURFYNOL 440 surfactant sold by Air Products and Chemicals, Inc. located in Ailentown, Pennsylvania. With rapid stirring, the dissolved .dye solution can then be added to a dilute aqueous suspension that contains particles comprising alumina. Although not critical, better results may be achieved if the aqueous suspension is slightly heated. After constant stirring for a sufficient amount of time, the dye disperses by precipitation throughout the mixture and slowly dissolves into the water. Once dissolved into the water, the dye can be adsorbed by the alumina contained in/on the particles. Once the dye is adsorbed onto the alumina, the resulting particles can be used to formulate a suitable colorant composition for use in various processes, such as in a suitable printing process. The colorant composition may comprise an aqueous or non-aqueous medium, although an aqueous medium is useful for applications which employ liquid printing mediums. The colorant compositions of the present invention contain particles, as well as, desirable colorant stabilizers and additives. For example, the colorant composition may contain the above-described particles in combination with any of the following additives; a second colorant; a colorant stabilizer, such as a porphine; a molecular indudant; a pre-polymer; and any additional components as described above/ The present invention encompasses recording mediums such as jnk jet inRs . comprising the nanoparticles disclosed herein. Inks used in ink jet printers are described in U.S. Patent No. 5,681,380, assigned to Kimberly-Clark Worldwide, Inc., which is incorporated herein by reference in its entirety. Ink jet inks will usually contain water as the principal solvent, preferably deionized water in a range of between about 20 to about 95 percent by weight, various co-solvents in an amount of between about 0.5 and about 20 percent by weight, and the particles of the present invention. Various co-solvents may also be included in the ink formulation. Examples of such co-solvents include a lactam such as N-methyl pyrrolidone. However, other examples of optional co-solvents include N-methylacetamide, N-methylmorpholine-N-oxide, N,N-dimethyiacetamide, N-methyl forrnamide, propyleneglycol-monomethylether, tetramethylene suifone, and tripropyleneglycolmonomethylether. Still other solvents which may be used include propylene glycol and triethanolamine (TEA). If an acetamide-based cosolvent is also included in the' formulation it is typically present at about 5 percent by weight, within a range of between about 1.0-12 percent by weight. Optionally, one or more humectants in an amount between about 0.5 and 20 percent by weight may be included in the ink formula. Additional humectants for optional use in the formulation include, but are not limited to, ethylene glycol, diethylene glycol, glycerine, and polyethylene glycol 200, 400, and 600, propane 1,3 diol, other glycols, a propyfeneglycolmonomethyl ether, such as Dowanol PM (Gallade Chemical Inc., Santa Ana, CA), polyhydric alcohols, or combinations thereof. Other additives may"also be included to improve ink performance, such as a chelating agent to sequester metal ions that could become involved in chemical reactions that could spoil the ink over time, for example for use with metal complex dyes, a corrosion inhibitor to help protect metal components of the printer or ink delivery system, a biocide or biostat to control unwanted bacterial, fungal, or yeast growth in the ink, and a surfactant to adjust the ink surface tension. However, the use of a surfactant may be dependent on the type of printhead to be used. If a surfactant is included, it Is typically present in an amount of between about 0.1 to about 1.0 percent by weight. If a corrosion inhibitor is included, it is typically present in an amount between about 0.1 and about 1.0 percent by weight. If a biocide or biostat is included, it is typically present in an amount between about 0.1 and about 0.5 percent by weight. if a biocide or biostat is added to the ink formulation, it may be exemplified by Proxel GXL (Zeneca Corporation, Wilmington, Delaware). Other examples include Bioban DXN (Angus Chemical Company, Buffalo Grove, Illinois). If a corrosion inhibitor is added to the formulation, "rt may be exemplified by Cobratec (PMC Specialty Group Distributing of Cincinnati, Ohio). Alternate corrosion inhibitors include sodium nitrite, triethanolamine phosphate, and n-acyl sarcosine. Still other examples include benzotriazcie (Aldrich Chemical Company, Milwaukee, Wisconsin). If a surfactant is includec in the formulation, it is typicaily a nonionic surfactant exemplified by Surfynci 504 (Air Products and Chemicals, Inc., Allentown, Pennsylvania). Still other examples include Surfynoi 465, and Dynoi 604 also available from Air Products. If a chelating agent is included in the formulation it may be exemplified by an ethylene diaminetetraacetic acid (EDTA). Other additives such as pH stabilizers/buffers, (such as citric acid and acetic acid as well as alkali metal salts derived therefrom), viscosity modifiers, and defoaming agents such as Surfynoi DF-65, may also be included in the formulation, depending on the product application. Depending upon how the colorant composition... is formulated, the composition can be used in various printing processes. For instance, in addition to ink jet printing and other non-impact printers, the colorant composition can beused in screen printing processes, offset lithographic processes, flexographic printing processes, rotogravure printing processes, and the like. In some of the above printing processes, a thickener may need to be added to the colorant-composition. The thickener can be, for instance, an alginate. The recording medium or colorant composition of the present invention may be applied to any substrate to impart a color to the substrate. The substrate to which the composition is applied may include, but is not limited to, paper, wood, a wood product or composite, woven fabrics, non-woven fabrics, textiles, films, plastics, glass, metal, human skin, animal skin, leather and the like. In one aspect, the colorant composition or recording medium may be applied to textile articles such as clothing. In one particular embodiment, a colorant composition containing particles of the present invention may be applied to a substrate having a negative surface charge. As described above, the alumina contained in the particles of the present invention retain a positive charge even after adsorption of a dye; Consequt..^, the particles remain affixed to negatively charged surfaces. In fact, wash durability i of the colorant composition may occur if there is a substantial amount of charge difference between the substrate and the particles of the present invention. (n view of the above, colorant compositions made according to the present invention are particularly well suited to being applied to natural and synthetic^ substrates that have a negative surface charge. For instance, naturally occurring materials that generally contain a negative surface charge include cotton fibers, cellulose fibers, and substrates made therefrcm. Such substrates include all types of fabrics, garments and apparel, paper products, and the like. In addition to the above natural materials, in one particular embodiment, colorant compositions made according to the present invention have been found to be well suited to being applied to substrates made from synthetic polymers, such as thermoplastic polymers. Such substrates can include, for instance, woven and non-woven materials made from a polyolefin polymer such as polypropylene or polyethylene, polyester, and the like. In the past, various problems have been experienced in trying to affix dyes to these types of materials- Consequently, either complicated dye structures have been used or dyes and or pigments have been applied in conjunction with chemical binders. The particles of the present invention, however, can permanently affix to these materials without the use of chemical binders or complex chemical constructions. Although not needed, in some embodiments it may be desirable to pre-treat or post-treat the polymer substrates which may further serve to affix the dyes or other functional compounds described to the materials. For instance, substrates made from synthetic polymers can undergo a pretreatment process for increasing the negative surface charge. For example, such pretreatment processes include subjecting the substrate to a corona treatment or to an electret treatment An electret treatment for instance, is disclosed in U.S. Patent No. 5,964,926 to Cohen, which is incorporated herein by reference in its entirety. Such pretreatments have been found not only to increase the negative surface charge of polymeric materials, but also assist in wetting out the polymer and enhancing surface adhesion between the polymer and the particles of the present invention. In addition to pretreatment processes, substrates contacted with the particles of the-present invention can also undergo various post treatment processes which further serve to affix the particles to the substrate. For example, in one embodiment, the treated substrate can be subjected to radio frequency radiation or to microwave radiation. Alumina is known to adsorb radio frequency radiation and microwave radiation causing the particles to heat. Once heated, it is believed that the particles become further embedded into the polymeric substrate. Further, the particles can be heated without also heating the substrate to higher than desired temperatures. In addition to the foregoing embodiments, functional compounds (health-related compounds) may be adsorbed to the described particles and then either utilized while on the particles to treat a condition or symptoms, or selectivety released from the particles to treat medical conditions or symptoms. Such selective release can be accomplished via an environmental trigger or chemical stimuli. Such coated particles can be applied topically to a patient's body either directly, or with the assistance of a drug delivery device, such as a modified bandage, tampon, or other known transdermal delivery apparatus. Alternatively, such coated particles may be taken internally through various mechanisms. The present invention may be better understood with respect to the following examples. Example 1 Aluminasol 200 (Nissan Chemical America) was diluted with Dl water to give a 2% Aluminasol 200 suspension. Meanwhile, carminic acid (0.02g) was suspended in Dl water (tg). Carminic acid includes hydroxy-carbonyl moieties and can be represented as follows: OH 0 Carminic Arid The zeta potential of alumina particles in the Aluminasol was monitored as carminic acid was dripped into the measurement cell. The zeta potential did not change as more carminic acid was added. A significant color shift was observed as the carminic acid (red / orange) was added to the Aluminasol (bluish magenta). The following zeta potential results were obtained: Zeta Potential 2% Aluminasol 56.70 mV Aluminasol + 2 Drops Carminic 49.27 mV Aluminasol + 5 drops carminic 56.68 mV Aluminasol + 7 drops carminic 58.59 mV As shown above, the positively charged alumina was capable of adsorbing carminic acid without going through a charge reversal step. Example 2 Aluminasol 200 (Nissan Chemical America, 2 g) was diluted with Dl water (98g) with good stirring. Carminic acid (Aidrich, #22,925-3) (0.5011g) was suspended in Dl water (23.7135 g) with good stirring. The carminic acid did not dissolve completely at this concentration, and so whenever portions were taken, they were taken -while stirring vigorously so that suspended solids were also withdrawn. A hypodermic syringe was used to withdraw 1 ml of carminic acid suspension. This was added to the diluted Aluminasol 200 with good stirring. The suspension changed from a white to a bluish red. The Zeta potential was monitored after addition to check for changes as follows: Zeta Potential Initial (2% Aluminasol) +55 JOmV 2 min after carminic acid addition +45.08rnV 5 min after carminic acid addition +45.68mV This mixture was allowed to stir overnight. The next morning, all dye had dissolved, and no dye crystals were observed. Example 3 In this example, in addition :c camiric acid, Ci Acid Blue 25 and C! Acid Blue 45 were bonded to alumina in acccrcance with the present Invention. CI Acid Blue 25 and CI Acid Blue 45 nave the following siructures: Ci Acid Blue 25 0,2008 g CI Acid "Blue 25 (Aidricn) was added to 19.7735 g Dl water and stirred to give a suspension, which was stirred for 30 minutes. 1 ml of this was added to a mixture containing 2g Aluminasci and 98g Dl water. Mixture stirred overnight to ensure that all dye had dissolved. CI Acid Blue 45 0.2507 g of Ci Acid Blue 45 (Aldrich) was suspended in 20.1751 g Di water with stirring for 30 minutes. 1ml (syringe) was added to a mixture of 2g Aluminasoi and 98g of D! water to give a blue complex. Mixture stirred overnight to ensure that all dye dissolved. In the following sample, a high concentration of Aluminasoi 200 was combined with carminic acid. Specifically, 0.111g glacial acetic acid (Fischer, ACS plus reagent grade) was diluted with 29J95g Dl water. This was added to 49.941g of Aluminasoi 200, slowly with good stirring. This mixture was stirred for 20 mins, at which point, 4mi (measured using a syringe) of a suspension of carminic acid in Dl water (0.5011g carminic acid in 23.7135g water) was added at once, with good stirring. -Mixture stirred overnight. A fourth sample was then constructed containing the same ingredients (carminic acid) irvthe same amounts as iistec in Example 2 above. Ai! mixtures appeared to be hcrncger.ecus in that upon standing for three hours, no sludge settled cut, anc no dari\ dye crystal were observed. Zeta cctentiais and particle size analysis were conducive using a Brcckhaven instrument PALS Zeta potential anaiyzer :cr ail :he samples except the sample containing C! Acid Blue 25. The following results were obtained: The above three solutions were then subjectec to a dialysis test to demonstrate that the dye was adsorbed onto the alumina surfaces. Specifically, the three solutions were dialyzed against 3:: glacial acetic acid using Sigma Dialysis Tubing (Cellulose, 12,GCGmw cut off, Sigma D-C655. Tubing was soaked in CM water for two hours prior to use ic remove glycerine, and :o make the tubing flexible.) As a control, a small amount of carminic aclc was added to a dialysis tubing and placed in a bath containing 3% acetic acid. Within 2 hours, carminic acid had traversed the cellulose membrane and had ccicred the 3% acetic acid solution. No color was observed from the aiurr.inasol mixtures, suggesting, along with the color change, that the colorant was strongly sorbed by the particles. The next morning, the 50% aluminasol / carminic acid solution had colored the water bluish red. However, it is believed that the bag had ruptured. Also, a very faint, almost indiscernible blue coloration was noticed in the dialysis solution of the aluminasol acid blue 45 dialysis, suggesting that this colorant did not as strongly adsorb into the alumina. Example 4 The following tests were conducted to'demonstrate the washfastness of the particles of the present invention on cotton. The three compositions prepared in Example 3 aoove containing 2% aluminasol/Acid Blue 45; 2% aiuminescl/carminic acid. and 50% bind to alumina particles. Examples of suc'r, compounds were ascorbic acid (Vitamin C) and- phenylalanine (sweetener found in Eaual®). The structural equations for these materials and their ability to brc :c such particles was demonstrated as can be seer 'n the table -which follows: SAMPLE UV-V1S ABSORPTION fnm) Ascorbic Acid in water • 256 Ascorbic Acid/SN-AK 250 Phenylalanine in water 230 Phenyiaianine/SN-AK 224* w= The structure of the peak changed In addition to the shift. It should be noted here that a shift in the absorption maximum was observed on addition of SNOWTEX-AK to the ascorbic acid solution, however a blue shift was observed (hypsochromatic). This shift was due to binding, as no shift was observed when dilute acid was added to a separate solution of ascorbic acid. In a similar way, a blue shift (hypscchromic shift) was also observed with the phenylalanine binding to SNOWTEX-AK. Examples of Adsorption of Various Pharmaceutical or Nutritional Materials to Carrier Nanoparticles and the Selective Release of Such Materials Upon Occurrence of a Triggering Mechanism: In a further set of e;;arr>oies. charmsceutical materials v/ere adsorbed to carrier alumina particles and then selectively Messed from the carrier particles, in particular, separate 50 mi Soiuticrs cf tetracycline and hydrocortisone agents (G.01 g) in water were prepared tc .vhich the aiumir.a nancoarric;e (SNCW7EX-AK) suspension (5 mi of 20% wt/wi; .vere added. A cathcchromic shift {red shift) in the UV-ViS Lambda maxima was again observed, indicating s:rong binding of these pharmaceuticai agents to the surface of .he alumina particle. The following Tabie shows the shift in the UV-VIS spectra recorced. Once the pharmaceuticai agents had been bound to particles, they were selectively released by a controlled pH trigger mechanism. Thus, by changing the oH cf the modified nanoparticle suspension to high pK values, the pharmaceutical agent was released as observed by a second red shift of the UV-VIS Lambda Maxima. In particular, the alkaline agent, dilute sodium hydroxice (0.1 N).was added in 0.5 mi amounts to the samples; The tetracycline was released from the alumina surface when the suspension of modified nanoparticles was altered to pH 9/10 or greater. The noted shifts correspond to the absorption maximum of the free pharmaceutical agents. Therefore, these two examples cf pharmaceuticai agents demonstrate the w capability of selectively releasing pharmaceuticai agents from the carrier particles. By the use of a npH trigger" the functional compounds can be released in a controlled manner when needed. it should be noted that sucn triggering of the delivery system may be accomplished through environmental Granges such as infection which results in pF changes, taking advantage of irr.ereni differences in p~ depending on body locations, and the intentional act d r.trccucing chemistries such as pH altering materials to the deliver/ systems tc trigger the release ci functional compounds. Chemistries that may be introduced x a -delivery system induce cicarbcnates, carbonates and buffering salts which ,vcuid result in a pH change on becoming wet with water or biological fluid. in still a further alternative emsccimen:. a signal agent, such as a fragrance, may be used by itself or in conjunction with a health related compound on a variety of particle types to both treat a conciticn, ar.c also to provide an indication to the patient of the effectiveness of such treatment cr the occurrence of a particular event. As an example, a fragrance may be adsorbed tc one type of particle and an antibiotic may be adsorbed to a second tyce of particle. The particles can be delivered to an infected site simultaneously, if the infected site is aikaline, it will prompt the release of the antibiotic. Upon removal of the infection, and the return to a more normal acidic environment, the fragrance may be released, thereby providing an indication of the effective treatment of the infection. In a further example, the signal can be used to generate an indication of a particular event, such as the release of body fluids or exudates as in a bandage cr personal care product, such as a feminine care product or child care diaper product. A method used to prepare alumina nanoparticles having functional compounds bonded to the surface included the following steps. The functional compound was dissolved in water with stirring. To this stirred solution was slowly added the alumina nanoparticles and the resulting mixture stirred for about 5 to 10 minutes to allow the functional compound to bond to the surface of the nanoparticle. The UV-VIS. spectrum of the water solution was obtained by taking an aliquot of the stirred mixture and placing it in a quartz cell. The UV-VIS spectra were obtained using a UV-VIS spectrophotometer Model UV- -1601 (Shimadzu Corporation) with water as a reference. Zeta Potential and In additional alternative embodiments, following being affixed to such substrates, upon exposure to a change in condition (such as ?H) the functional compounds would be released from the sucstrate, but the particles would be left behind. in a specific embodiment, carrier panicles (and desirably .rancparticles, that is particles having sizes of less than about 1 micron in size, more desirably between about 5 nm and 500 nm ir size, arc even more desirac-y. between about 10 nm - 200 nm in size) including pharmaceutical compounds, can be applied to a topical bandage by various application methecis. The application methods may include a gel, a water suspension, a dry coating or a pewder placed between the layers of the bandage if the particles are included in a vehicle for ease of application. The bandage can then be driec, if appropriate, whereby the charges of the particles would maintain them in c;cse association with the bandage substrate. It should be recognized that the bound pharmaceutical or nutritional chemistry could be used with or without tricgerable release. Alternatively, some of the bound chemistry in a multiple chemistry carticle system couic be triggerably reieasable, while other bound chemistry could be intentionally retained on the carrier particles. In this fashion, the bound chemistry couid perform its advantageous function while still being attached to the carrier particles, for ease of removal or to lower the potential toxicity of the functional agent/compound. An example of such usage would be using a bound salicylaldoxime to remove heavy metals from the body or waste water without the toss of or exposure to the free complexing agent. In another example, tetracycline could function as an antibiotic while still being bound on a particle. This could allow the antibiotic to function in the stomach and intestines without crossing over into the bloodstream of a patient (because of the size of the particle). This control of the antibiotic release could assist with lowering the risk of sensitization cf patients who are allergic to such medications. These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the an, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims. We Claim, 1. An article of manufacture comprising: a fibrous substrate having a receiving surface containing negative charges; and a plurality of positively charged particles bonded to the receiving surface of the fibrous substrate through coulombic attraction, the particles containing alumina, at least a portion of the alumina being present on a surface of the particles, and wherein a functional compound is bonded to the alumina on the surface of the particle, the functional compound prior to bonding with the alumina containing a moiety comprising: or a tautomer thereof, or a functional equivalent thereof and wherein R and R' comprise independently hydrogen, an alkyl group, or an aryl group. 2. The article as claimed in claim 1, wherein the particle comprises a core material coated with alumina. 3. The article as claimed in claim 1 or 2, wherein the core material comprises silica. 4. The article as claimediany of the foregoing claims, wherein the functional compound comprises a colorant, a UV absorber, a pharmaceutical, an odor control agent, a fragrance, a therapeutic agent, a nutriceutical agent, an antibacterial agent, an anti-microbial agent, an anti-viral agent, a xsnobiotic, or combinations thereof. 5. The article as claimed in any of the foregoing claims, wherein the particle containing alumina bonded to the functional compound has an average dimension of less than about 1 millimeter, and preferably less than about 1,000 nanometers. 6. The article as claimed in any of the foregoing claims, wherein the functional compound comprises hydrocortisone, ascorbic acid, aspartame, or tetracycline. 7. The article as claimed in any of the foregoing claims, wherein the particle containing alumina bonded to the functional compound has a zeta potential of at least 20 mV. 8. The article as claimed in any of the foregoing claims, wherein the plurality of particles are contained within a liquid vehicle when applied to the substrate. 9. The article as claimed in any of the foregoing claims, wherein the substrate is subjected to a corona or electret treatment prior to bonding with the plurality of positively charges particles. 10. The article as claimed in any of the foregoing claims, wherein the article has been exposed to microwave radiation or radio frequency radiation after the substrate and the plurality of charged particles have been bonded together. 11. The article as claimed in any of the foregoing claims, wherein the substrate comprises natural fibers carrying the negative charges. 12. The article as claimed in claim 11, wherein the natural fibers comprise cotton or cellulose fibers. 13. The article as claimed in any of the foregoing claims, wherein the functional compound comprises a dye. 14. The article as claimed in claim 13, wherein the dye contains an anthraquinone chromophore, salicylate, 3-hydroxy-2-naphthoic acid moieties, chromotropic acid, acetoacetanilide, naphthoquinone, or a derivative thereof. 15. The article as claimed in claim 13, wherein the dye contains the moiety: or a tautomer of this moiety . 16. The article as claimed in claim 13, wherein the dye contains the moiety: and wherein Rand R1 are hydrogen. 17. The article as claimed in claim 13, wherein the dye contains the moiety: or a tautomer of this moiety. 18. The article as claimed in any of the foregoing claims, wherein the receiving surface of the substrate and the particles have a surface charge difference of at least 42 mV. 19. The article as claimed in any of the foregoing claims, wherein the fibrous substrate comprises synthetic polymeric fibers. 20. The article as claimed in claim 19, wherein the synthetic polymeric fibers are polyolefin fibers. 21. The article as claimed in claim 19 or 20, wherein the fibrous substrate comprises a non-woven web material. 22. The article as claimed in claim 21, wherein the non-woven material is a spunbond web. 23. A printing process comprising: ejecting a recording medium in the form of droplets from an orifice to form an image on a fibrous substrate, the recording medium comprising a plurality of particles containing alumina, at least a portion of the alumina being present on a surface of the particles; a colorant compound bonded to the alumina on the surface of the particle, the colorant compound prior to bonding with the alumina containing a moiety comprising: or a tautomer thereof, or a functional equivalent thereof and wherein Rand R' comprise independently hydrogen, an alkyl group, or an aryl group; and a liquid vehicle. 24. The process as claimed in claim 23, wherein the particles contain alumina, at least a portion of the alumina being present on a surface of the particles. 25. The process as claimed in claim 23 or 24, wherein the fibrous substrate comprises a woven fabric, a non-woven fabric, paper, or combinations thereof. 26. The process as claimed in claim 23,24 or 25, wherein the process is an ink-jetting process. 27. A triggerable delivery system comprising: a particle; and a health-related compound adsorbed to the surface of the particle, the health-related compound capable of being released from the particle upon either exposure to a change in pH, moisture, chemical stimuli, or body exudates, wherein the health related compound, prior to being adsorbed to the surface of the particle contains a moiety comprising; or a tautomer thereof, or a functional equivalent thereof and wherein Rand R1 comprise independently hydrogen, an alkyl group, or an aryl group. 28. The triggerable delivery system as claimed in claim 27, wherein the particle contains alumina, at least , a portion of the alumina being present on a surface of the particle. 29. A drug delivery device including a triggerable delivery system, the trigrlerable delivery system comprising a particle; and a health-related compound adsorbed to the surface of the particle, the health-related compound capable of being released from the particle upon either exposure to a change in pH, moisture, chemical stimuli, or body exudates, wherein the health-related compound prior to adsorbing with the particle contains a moiety comprising: or a tautomer thereof, or a functional equivalent thereof and wherein R and R' comprise independently hydrogen, an alkyl group, or an aryl group.

Full Text

DELIVERY SYSTEM FOR FUNCTIONAL COMPOUNDS Background Of The Invention
A delivery system generally refers to a system that aids or other-vise facilitates the delivery of a functional materia! to a desired location. ~he functional materia! can be any material that acts upon a substrate or otherwise provides a benefit once delivered to the cesirec :ccaticn. Examples of functional materials that may benefit from the use cf a delivery system include pharmaceuticals that are intended to be ingested, topically applied, or subcutanecusly injected into a patient, fragrances, vitamins and nutrients, and various other and numerous additives.
in one particular application, ;or instance, the functional material can be a dye that is intended to be printed or otherwise applied to a substrate, in the past various delivery systems for dyes have been proposed that are intended tc facilitate application of the dye to a substrate, such as a textile material. The delivery systems, for instance, are intended to affix the dye to a substrate, prevent the dye from fading when exposed to sunlight, to prevent the dye from degrading when exposed to the environment, to facilitate application of the dye to the substrate, or, for example, to render the dye mere stable.
Even in view of recent advances in the art, furthar +wprovements in defrwry systems for functional materials are stii! needed.. For example, a need currently exists for a delivery system that can bind to various functional materials that does not incorporate relatively expensive chemical formulations or that does not require any complex process steps for incorporating a functional material into the delivery system. With respect to dyes, a need also exists in the art for a delivery system for a dye that is capable of affixing the dye to negatively charged surfaces. For example, a need currently exists for a delivery system for dyes that is capable of affixing the dyes to textile materials containing natural or synthetic polymeric fibers that have a negative surface charge. With respect to pharmaceutical and nutritional materials, a need also exists in the art for a delivery system for such

materials that is capable of affixing the pharmaceutical or other health -related compounds to the delivery system. A need aisc exists for a delivery system that will readily and /or selectively release such pharmaceutical materials upon the occurence of a selected event or trigger. A nee Summer/ Of The Invention
The present invention is generally directed to a deliver/ system for various functional materials. The functional materials can be; for Instance, colorants, UV absorbers, pharmaceuticals, cdcr control agents, fragrances, anti-microbtai agents, anti-viral agents, antibiotics, xenobictics, nutricauticai agents (nutritional-materials), and the like. In accordance with the present invention, the functional materials are adsorbed onto a particle. For nstance the functional materials are absorbed onto silica particles or alumina that is contained ir./cn a particle. The resulting particle can then be used as is or can be combined with a vehicle, such as a liquid vehicle, to deliver the functional material to a desired location. Additionally, the resulting particle, or particle containing vehicle can be incorporated into a drug delivery device, such as a bandage or tampon.
For example, when the functional material is a colorant the particles of the present invention can be incorporated into a liquid vehicle and applied to a substrate using any conventional printing means, if the functional material is a health related compound such as a pharmaceutical or nutritional compound, the particles can likewise be incorporated into a vehicle and applied to a substrate such as a bandage or drug delivery device which can be placed immediately adjacent, in contact with or within a patient's body. For the purposes of this application, the term "patients body" shall mean a human or animal body. In this fashion, the functional material can be delivered to a selected location on or within a patient's body. Alternatively, such particles could be taken by a patient internally where appropriate to deliver the functional material to a desired location. In an alternative embodiment, the functional material may be triggerably released from a particle at a selected location or time, following occurrence of a triggering evant,

such as exposure to a chemical, body exudates or moisture or environmental stimuli, such as a change in pH.
Thus, in one embodiment, the present invention is directed to a particle containing alumina. At least a portion cf the alumina contained within the particle is present on a surface of the particle. A .functional compound is bonded to the alumina en the surface of the particle. The functional compound prior to bending with the alumina contains a moiety comprising one or more of:

a tautomer thereof, or a functional equivalent thereof and wherein R and R' comprise independently hydrogen, an alkyi group, or an aryl group.
The above moieties can be present as is on a functional compound. Alternatively, however, each of the above moieties can include further R groups attached to the carbon chain shown above. In general, any such R group can appear in association with the above moieties as long as the R group does not interfere with the bonding of the moiety to an alumina.
The above moieties have been found to form a bond with alumina in constructing the compositions of the present invention. Of particular significance, it was discovered that the functional compound, in some embodiments, can bond with alumina without significantly changing the positive charge character of alumina. For example, under certain conditions, alumina may have a positive surface charge. It has been discovered that even after the functional material is bonded to the alumina, the resulting structure still maintains a positive charge. Thus, in one embodiment of the present invention, positively charged particles are formed. Due to their positive charge, the particles may be securely affixed to the surface of a substrate that carries with it a negative charge through coulombic attraction.

In one embodiment of the ir.venticn, the functional agent such as the pharmaceutical may be selectively released from the carrier particle (such as an alumina, silica, or alumina- coatee silica particle) so as to release the pharmaceutical at a targeted/desirable :cdy location, or a: a desirable moment, in one such embodiment, such selective -eiease can be accomplished by exposure of the particle to a change in environmental.condition, sucn as a pH change. For example, such selective release may be accomplished by exposure to an alkaline environment Alternatively, such selective release my be accomplished by exposure to an acidic environment. Still further, such selective reiease may be the result of exposure of the carrier particle to particular chemical stimuli. In an alternative embodiment of the invention, a method for applying a health related compound utilizes a health-related compound coated particle, and selectively releasing the compound upon exposure cf the particle to either a change in environmental condition, or upon exposure to a chemical stimuli.
The functional compounds can in one embodiment, be selectively released in either a basic or acidic environmental condition. For instance, in one specific embodiment of the invention, the functional compounds can be released in the basic/alkaline environment of a vagina experiencing a yeast infection, in a second embodiment, the functional compounds can be released in the basic environment of the small intestine so as to treat an infection, after passing through the acidic environment of the stomach. In still a further alternative embodiment & functional compound may be released as a result cf environmental stimuli as an alert or in conjunction with the completion of the deliver/ of a oharmaceutical material so as

(o provide and indication of such delivery or the success of such treatment. Alternatively, such-indicator may be released as a result of appearance of moisture or body fluids. Such indicator cr signal may be in the form of a dye or fragrance. In most of these situations, whiie the functional compound is released, the particle remains behind on a substrate, or alternatively passes through the body of the patient.
- !n still a further alternative embodiment, such indicator or signal may be the result of a functional material contained on a first type of particle, and such coated particle may be included with additional particles of a different variety, that contain - health related compounds (pharmaceutical and/or nutritional compounds). In still a further alternative embodiment, the functional material may be released in response to a particular chemical stimuli, which is intentionally applied to the site of the carrier particles. In still a further alternative embodiment, a method of utilizing a triggerabiy releasable delivery system in the treatment of a patient's body includes the steps of providing at least one type of particle selected from alumina particles, alumina covered particles, and silica particles; adsorbing at least one health related functional compound to the surface of the particle or particles to form at least a partially coated particle or particles; exposing the at least partially coated particle or particles to a patient's body such as by ingestion, injection, transdermal transfer or transmucosal transfer, and exposing the particle or particles to an environmental or chemical condition whereby the health related compound is released from the surface of the particle to the patient's body (which could be either an animal or human body), in an alternative embodiment, such health related compound is released from particles contained on a drug delivery device, but because of charge attraction (as previously described) the particles themselves remain affixed to the drug delivery device.
In a further alternative embodiment of the invention, a triggerable delivery system includes a particle selected from silica, alumina or alumina coated particles; and a health-related compound adsorbed to the surface of the particle, the health-related compound capable of being released from the particle upon either exposure to a change in pH, moisture, chemical stimuli* or body exudates.
In- still a further alternative embodiment, the triggerable delivery system includes a particle containing alumina, at least a oortion of the alumina beina

present on a surface of the particle; and a health related compound adsorbed to the alumina surface of the panels, the health related compound, prior to being adsorbed with the alumina or the surface of -he particle containing a moiety including at least one of

or a tautomer thereof, or a functional equivalent thereof and wherein-R-and R' comprise independently hydrogen, an alkyl group, or an ar/l group.
In still a further alternative embodiment, a drug delivery device such as a~ topical bandage or a tampon, induces a triggerabie -delivery system. The triggerable delivery system includes a particle; and a health-related compound adsorbed to the surface of the particle, with the hearth-related compound capable of being released from the particle upon either exposure to a change in pH, moisture, chemical stimuli, or body exudates.
Other features and aspects of the present invention are discussed in greater detail.
Detailed Description
It is to be understood by one cf crdinan/ skill in the art that the present discussion is a description of exemplany embodiments only, and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied in the exemplary construction.
In general, the present invention .is directed to a delivery system for functional compounds. Functional compounds can be any suitable substance that can provide a benefit to a location once delivered. In accordance with the present invention, the delivery system is generally directed to the construction of a particle.

For example such particle may be erther silica or desirably containing alumina. The alumina contained within the particle provides a bonding site on the surface of the particle for a functional compound. Specifically, the functional compound becomes adsorbed onto the surface cf the alumina (or silica, if it is an entirely siiica particle). Once the functional compound is boncec ro the alumina, the resulting particle can then be used :c deliver the functional compound to a particular location. The particles car. be used as is, for instance, cr can be combined with a ' iid vehicle whicr may facilitate delivery of the particles depending upon the particular application. The particles or liquid vehicles containing the particles may further be placed within a drug delivery device such as a tampon, bandage or other transdermal delivery device.
Functional compounds that are ".veil suited far-use in the present invention include compounds that contain at least me of the following moieties: one or more of:

a tautomer thereof, or a functional equivalent thereof and wherein R and R' comprise independently hydrogen, an aikyl group, or an aryl group. As used herein, a functional equivalent to one cf the above moieties refers to functional materials that include similar reactive groups as shown above, but which are not positioned on a molecule as exactly shown above and yet will still bond with alumina in a similar manner.
Referring to the moieties shown above, moiety (1) may be considered a carboxy-hydroxy moiety. Moiety (2) may be considered a hyrdoxy-hydroxy moiety, while moiety (3) may be considered a carboxy-carboxy moiety. Moieties (4) and (5), on the other hand, can be considered vinylalogous amide moieties. In moieties (4) and (5) above, the amine grcups can be primary amines, secondary amines, or tertiary amines. Moieties (5; and (7) may be considered hydroxy)

carbonyl moieties. Moiety (8) may be considered a carboxy amine. Moieties such as (8) may be found in amino acids/ Moiety (9) may.be considered a hydroxy imine. (n general; any suitable functional compound containing one of the above moieties or a functional equivalent 'ir.erecj may be used in accordance with the present invention. Further, ■'; 5ncu:c ce understood that various additional F groups may be included with the above moieties as long as the R groups do net interfere with the bond that is fcrmsd ,v:ih alumina.
The present inventors have discovered tnat the above mcieties may form a relatively strong bond to at least an a.umina surface. The funciicnai compounds may be bended to the alumina surface in order to chance the properties of the resulting particle or to perform a particular function. Without wishing to be bound by theory, it is believed that the above moieties form a bidentate licand bonding system with alumina surfaces. For instance, it is believed that alumina forms a covalent bond and a coordinate bene with the above moieties. Further, it is believed that a surface reaction occurs causing :ne functional compound to remain on the surface of the particle and form a coating thereon. The functional material can cover the entire resulting particle or can be located at particular locations on the particle. Further, it should be -ncerstccc that the particles of the present invention can contain more than cr.e functional compound, or alternatively, numerous different particles can contain.include different functional compounds.
Of particular advantage, in many embodiments, it has also been discovered that a functional compound can be bonded to alumina without signifrcantly impacting on the positive surface charge of alumina, which can be measured as zeta potential. The term "zeta potential* is used herein to mean without limitation a potential gradient that arises across an interface. This term especially refers to the potential gradient that arises across the interface between the Stern layer in contact with the particle of the present invention and the diffuse layer surrounding the particle. Zeta potential measurements can be taken using, for instance, a Zetapals instrument which are available from the Brookhaven Instrument Corporation of Holtsville, New York. For example, zeta potential measurements can be conducted by adding one to three drops of a sample into a cuvet containing 1 mM KCI solution, using the instrument's default functions preset for aqueous solutions.

in some applications, the alumina and the dye containing a reactive moiety can be combined and reacted in an aqueous solution.
In some embodiments, however, the dye may be difficult to dissolve in water. In this embodiment, the dye can first be dissolved in a minimum quantity of a solvent The solvent can be, for instance, acetone, ethanol or a similar liquid that is miscible with water. After the dye is combined with the solvent, if desired, a surfactant can be added in an amount greater than about 0% to about 50% by weight of dye solids added. In general, the amount of surfactant added to the solvent should be minimized. One suitable surfactant that can be used, for instance, is SURFYNOL 440 surfactant sold by Air Products and Chemicals, Inc. located in Ailentown, Pennsylvania.
With rapid stirring, the dissolved .dye solution can then be added to a dilute aqueous suspension that contains particles comprising alumina. Although not critical, better results may be achieved if the aqueous suspension is slightly heated.
After constant stirring for a sufficient amount of time, the dye disperses by precipitation throughout the mixture and slowly dissolves into the water. Once dissolved into the water, the dye can be adsorbed by the alumina contained in/on the particles.
Once the dye is adsorbed onto the alumina, the resulting particles can be used to formulate a suitable colorant composition for use in various processes, such as in a suitable printing process.
The colorant composition may comprise an aqueous or non-aqueous medium, although an aqueous medium is useful for applications which employ liquid printing mediums. The colorant compositions of the present invention contain particles, as well as, desirable colorant stabilizers and additives. For example, the colorant composition may contain the above-described particles in combination with any of the following additives; a second colorant; a colorant stabilizer, such as a porphine; a molecular indudant; a pre-polymer; and any additional components as described above/
The present invention encompasses recording mediums such as jnk jet inRs . comprising the nanoparticles disclosed herein. Inks used in ink jet printers are described in U.S. Patent No. 5,681,380, assigned to Kimberly-Clark Worldwide,

Inc., which is incorporated herein by reference in its entirety. Ink jet inks will usually contain water as the principal solvent, preferably deionized water in a range of between about 20 to about 95 percent by weight, various co-solvents in an amount of between about 0.5 and about 20 percent by weight, and the particles of the present invention.
Various co-solvents may also be included in the ink formulation. Examples of such co-solvents include a lactam such as N-methyl pyrrolidone. However, other examples of optional co-solvents include N-methylacetamide, N-methylmorpholine-N-oxide, N,N-dimethyiacetamide, N-methyl forrnamide, propyleneglycol-monomethylether, tetramethylene suifone, and tripropyleneglycolmonomethylether. Still other solvents which may be used include propylene glycol and triethanolamine (TEA). If an acetamide-based cosolvent is also included in the' formulation it is typically present at about 5 percent by weight, within a range of between about 1.0-12 percent by weight.
Optionally, one or more humectants in an amount between about 0.5 and 20 percent by weight may be included in the ink formula. Additional humectants for optional use in the formulation include, but are not limited to, ethylene glycol, diethylene glycol, glycerine, and polyethylene glycol 200, 400, and 600, propane 1,3 diol, other glycols, a propyfeneglycolmonomethyl ether, such as Dowanol PM (Gallade Chemical Inc., Santa Ana, CA), polyhydric alcohols, or combinations thereof.
Other additives may"also be included to improve ink performance, such as a chelating agent to sequester metal ions that could become involved in chemical reactions that could spoil the ink over time, for example for use with metal complex dyes, a corrosion inhibitor to help protect metal components of the printer or ink delivery system, a biocide or biostat to control unwanted bacterial, fungal, or yeast growth in the ink, and a surfactant to adjust the ink surface tension. However, the use of a surfactant may be dependent on the type of printhead to be used. If a surfactant is included, it Is typically present in an amount of between about 0.1 to about 1.0 percent by weight. If a corrosion inhibitor is included, it is typically present in an amount between about 0.1 and about 1.0 percent by weight. If a biocide or biostat is included, it is typically present in an amount between about 0.1 and about 0.5 percent by weight.

if a biocide or biostat is added to the ink formulation, it may be exemplified by Proxel GXL (Zeneca Corporation, Wilmington, Delaware). Other examples include Bioban DXN (Angus Chemical Company, Buffalo Grove, Illinois). If a corrosion inhibitor is added to the formulation, "rt may be exemplified by Cobratec (PMC Specialty Group Distributing of Cincinnati, Ohio). Alternate corrosion inhibitors include sodium nitrite, triethanolamine phosphate, and n-acyl sarcosine. Still other examples include benzotriazcie (Aldrich Chemical Company, Milwaukee, Wisconsin). If a surfactant is includec in the formulation, it is typicaily a nonionic surfactant exemplified by Surfynci 504 (Air Products and Chemicals, Inc., Allentown, Pennsylvania). Still other examples include Surfynoi 465, and Dynoi 604 also available from Air Products. If a chelating agent is included in the formulation it may be exemplified by an ethylene diaminetetraacetic acid (EDTA). Other additives such as pH stabilizers/buffers, (such as citric acid and acetic acid as well as alkali metal salts derived therefrom), viscosity modifiers, and defoaming agents such as Surfynoi DF-65, may also be included in the formulation, depending on the product application.
Depending upon how the colorant composition... is formulated, the composition can be used in various printing processes. For instance, in addition to ink jet printing and other non-impact printers, the colorant composition can beused in screen printing processes, offset lithographic processes, flexographic printing processes, rotogravure printing processes, and the like. In some of the above printing processes, a thickener may need to be added to the colorant-composition. The thickener can be, for instance, an alginate.
The recording medium or colorant composition of the present invention may be applied to any substrate to impart a color to the substrate. The substrate to which the composition is applied may include, but is not limited to, paper, wood, a wood product or composite, woven fabrics, non-woven fabrics, textiles, films, plastics, glass, metal, human skin, animal skin, leather and the like. In one aspect, the colorant composition or recording medium may be applied to textile articles such as clothing.
In one particular embodiment, a colorant composition containing particles of the present invention may be applied to a substrate having a negative surface charge. As described above, the alumina contained in the particles of the present

invention retain a positive charge even after adsorption of a dye; Consequt..^, the particles remain affixed to negatively charged surfaces. In fact, wash durability i of the colorant composition may occur if there is a substantial amount of charge difference between the substrate and the particles of the present invention.
(n view of the above, colorant compositions made according to the present invention are particularly well suited to being applied to natural and synthetic^ substrates that have a negative surface charge. For instance, naturally occurring materials that generally contain a negative surface charge include cotton fibers, cellulose fibers, and substrates made therefrcm. Such substrates include all types of fabrics, garments and apparel, paper products, and the like.
In addition to the above natural materials, in one particular embodiment, colorant compositions made according to the present invention have been found to be well suited to being applied to substrates made from synthetic polymers, such as thermoplastic polymers. Such substrates can include, for instance, woven and non-woven materials made from a polyolefin polymer such as polypropylene or polyethylene, polyester, and the like. In the past, various problems have been experienced in trying to affix dyes to these types of materials- Consequently, either complicated dye structures have been used or dyes and or pigments have been applied in conjunction with chemical binders. The particles of the present invention, however, can permanently affix to these materials without the use of chemical binders or complex chemical constructions.
Although not needed, in some embodiments it may be desirable to pre-treat or post-treat the polymer substrates which may further serve to affix the dyes or other functional compounds described to the materials. For instance, substrates made from synthetic polymers can undergo a pretreatment process for increasing the negative surface charge. For example, such pretreatment processes include subjecting the substrate to a corona treatment or to an electret treatment An electret treatment for instance, is disclosed in U.S. Patent No. 5,964,926 to Cohen, which is incorporated herein by reference in its entirety. Such pretreatments have been found not only to increase the negative surface charge of polymeric materials, but also assist in wetting out the polymer and enhancing surface adhesion between the polymer and the particles of the present invention.

In addition to pretreatment processes, substrates contacted with the particles of the-present invention can also undergo various post treatment processes which further serve to affix the particles to the substrate. For example, in one embodiment, the treated substrate can be subjected to radio frequency radiation or to microwave radiation. Alumina is known to adsorb radio frequency radiation and microwave radiation causing the particles to heat. Once heated, it is believed that the particles become further embedded into the polymeric substrate. Further, the particles can be heated without also heating the substrate to higher than desired temperatures.
In addition to the foregoing embodiments, functional compounds (health-related compounds) may be adsorbed to the described particles and then either utilized while on the particles to treat a condition or symptoms, or selectivety released from the particles to treat medical conditions or symptoms. Such selective release can be accomplished via an environmental trigger or chemical stimuli. Such coated particles can be applied topically to a patient's body either directly, or with the assistance of a drug delivery device, such as a modified bandage, tampon, or other known transdermal delivery apparatus. Alternatively, such coated particles may be taken internally through various mechanisms.
The present invention may be better understood with respect to the following examples.
Example 1
Aluminasol 200 (Nissan Chemical America) was diluted with Dl water to give a 2% Aluminasol 200 suspension. Meanwhile, carminic acid (0.02g) was suspended in Dl water (tg). Carminic acid includes hydroxy-carbonyl moieties and
can be represented as follows:

OH 0 Carminic Arid

The zeta potential of alumina particles in the Aluminasol was monitored as carminic acid was dripped into the measurement cell. The zeta potential did not change as more carminic acid was added. A significant color shift was observed as the carminic acid (red / orange) was added to the Aluminasol (bluish magenta). The following zeta potential results were obtained:
Zeta Potential
2% Aluminasol 56.70 mV
Aluminasol + 2 Drops Carminic 49.27 mV Aluminasol + 5 drops carminic 56.68 mV Aluminasol + 7 drops carminic 58.59 mV
As shown above, the positively charged alumina was capable of adsorbing
carminic acid without going through a charge reversal step.
Example 2
Aluminasol 200 (Nissan Chemical America, 2 g) was diluted with Dl water (98g) with good stirring. Carminic acid (Aidrich, #22,925-3) (0.5011g) was suspended in Dl water (23.7135 g) with good stirring. The carminic acid did not dissolve completely at this concentration, and so whenever portions were taken, they were taken -while stirring vigorously so that suspended solids were also withdrawn. A hypodermic syringe was used to withdraw 1 ml of carminic acid suspension. This was added to the diluted Aluminasol 200 with good stirring. The suspension changed from a white to a bluish red.
The Zeta potential was monitored after addition to check for changes as follows:
Zeta Potential
Initial (2% Aluminasol) +55 JOmV
2 min after carminic acid addition +45.08rnV
5 min after carminic acid addition +45.68mV
This mixture was allowed to stir overnight. The next morning, all dye had dissolved, and no dye crystals were observed.

Example 3
In this example, in addition :c camiric acid, Ci Acid Blue 25 and C! Acid Blue 45 were bonded to alumina in acccrcance with the present Invention. CI Acid Blue 25 and CI Acid Blue 45 nave the following siructures:
Ci Acid Blue 25 0,2008 g CI Acid "Blue 25 (Aidricn) was added to 19.7735 g Dl water and stirred to give a suspension, which was stirred for 30 minutes. 1 ml of this was added to a mixture containing 2g Aluminasci and 98g Dl water. Mixture stirred overnight to ensure that all dye had dissolved.

CI Acid Blue 45
0.2507 g of Ci Acid Blue 45 (Aldrich) was suspended in 20.1751 g Di water with stirring for 30 minutes. 1ml (syringe) was added to a mixture of 2g Aluminasoi and 98g of D! water to give a blue complex. Mixture stirred overnight to ensure that all dye dissolved.
In the following sample, a high concentration of Aluminasoi 200 was combined with carminic acid. Specifically, 0.111g glacial acetic acid (Fischer, ACS plus reagent grade) was diluted with 29J95g Dl water. This was added to 49.941g of Aluminasoi 200, slowly with good stirring. This mixture was stirred for 20 mins, at which point, 4mi (measured using a syringe) of a suspension of carminic acid in Dl water (0.5011g carminic acid in 23.7135g water) was added at once, with good stirring. -Mixture stirred overnight.

A fourth sample was then constructed containing the same ingredients (carminic acid) irvthe same amounts as iistec in Example 2 above.
Ai! mixtures appeared to be hcrncger.ecus in that upon standing for three hours, no sludge settled cut, anc no dari\ dye crystal were observed. Zeta cctentiais and particle size analysis were conducive using a Brcckhaven instrument PALS Zeta potential anaiyzer :cr ail :he samples except the sample containing C! Acid Blue 25. The following results were obtained:

The above three solutions were then subjectec to a dialysis test to demonstrate that the dye was adsorbed onto the alumina surfaces. Specifically, the three solutions were dialyzed against 3:: glacial acetic acid using Sigma Dialysis Tubing (Cellulose, 12,GCGmw cut off, Sigma D-C655. Tubing was soaked in CM water for two hours prior to use ic remove glycerine, and :o make the tubing flexible.) As a control, a small amount of carminic aclc was added to a dialysis tubing and placed in a bath containing 3% acetic acid. Within 2 hours, carminic acid had traversed the cellulose membrane and had ccicred the 3% acetic acid solution. No color was observed from the aiurr.inasol mixtures, suggesting, along with the color change, that the colorant was strongly sorbed by the particles. The next morning, the 50% aluminasol / carminic acid solution had colored the water bluish red. However, it is believed that the bag had ruptured. Also, a very faint, almost indiscernible blue coloration was noticed in the dialysis solution of the aluminasol acid blue 45 dialysis, suggesting that this colorant did not as strongly adsorb into the alumina.
Example 4
The following tests were conducted to'demonstrate the washfastness of the particles of the present invention on cotton.
The three compositions prepared in Example 3 aoove containing 2% aluminasol/Acid Blue 45; 2% aiuminescl/carminic acid. and 50%

bind to alumina particles. Examples of suc'r, compounds were ascorbic acid (Vitamin C) and- phenylalanine (sweetener found in Eaual®). The structural equations for these materials and their ability to brc :c such particles was demonstrated as can be seer 'n the table -which follows:

SAMPLE UV-V1S ABSORPTION fnm)
Ascorbic Acid in water • 256
Ascorbic Acid/SN-AK 250
Phenylalanine in water 230
Phenyiaianine/SN-AK 224*
w= The structure of the peak changed In addition to the shift.
It should be noted here that a shift in the absorption maximum was observed on addition of SNOWTEX-AK to the ascorbic acid solution, however a blue shift was observed (hypsochromatic). This shift was due to binding, as no shift was observed when dilute acid was added to a separate solution of ascorbic acid. In a similar way, a blue shift (hypscchromic shift) was also observed with the phenylalanine binding to SNOWTEX-AK.

Examples of Adsorption of Various Pharmaceutical or Nutritional Materials to Carrier Nanoparticles and the Selective Release of Such Materials Upon
Occurrence of a Triggering Mechanism:
In a further set of e;;arr>oies. charmsceutical materials v/ere adsorbed to carrier alumina particles and then selectively Messed from the carrier particles, in particular, separate 50 mi Soiuticrs cf tetracycline and hydrocortisone agents (G.01 g) in water were prepared tc .vhich the aiumir.a nancoarric;e (SNCW7EX-AK) suspension (5 mi of 20% wt/wi; .vere added. A cathcchromic shift {red shift) in the UV-ViS Lambda maxima was again observed, indicating s:rong binding of these pharmaceuticai agents to the surface of .he alumina particle. The following Tabie shows the shift in the UV-VIS spectra recorced. Once the pharmaceuticai agents had been bound to particles, they were selectively released by a controlled pH trigger mechanism. Thus, by changing the oH cf the modified nanoparticle suspension to high pK values, the pharmaceutical agent was released as observed by a second red shift of the UV-VIS Lambda Maxima. In particular, the alkaline agent, dilute sodium hydroxice (0.1 N).was added in 0.5 mi amounts to the samples; The tetracycline was released from the alumina surface when the suspension of modified nanoparticles was altered to pH 9/10 or greater. The noted shifts correspond to the absorption maximum of the free pharmaceutical agents.

Therefore, these two examples cf pharmaceuticai agents demonstrate the w capability of selectively releasing pharmaceuticai agents from the carrier particles.

By the use of a npH trigger" the functional compounds can be released in a controlled manner when needed.
it should be noted that sucn triggering of the delivery system may be accomplished through environmental Granges such as infection which results in pF changes, taking advantage of irr.ereni differences in p~ depending on body locations, and the intentional act d r.trccucing chemistries such as pH altering materials to the deliver/ systems tc trigger the release ci functional compounds. Chemistries that may be introduced x a -delivery system induce cicarbcnates, carbonates and buffering salts which ,vcuid result in a pH change on becoming wet with water or biological fluid.
in still a further alternative emsccimen:. a signal agent, such as a fragrance, may be used by itself or in conjunction with a health related compound on a variety of particle types to both treat a conciticn, ar.c also to provide an indication to the patient of the effectiveness of such treatment cr the occurrence of a particular event. As an example, a fragrance may be adsorbed tc one type of particle and an antibiotic may be adsorbed to a second tyce of particle. The particles can be delivered to an infected site simultaneously, if the infected site is aikaline, it will prompt the release of the antibiotic. Upon removal of the infection, and the return to a more normal acidic environment, the fragrance may be released, thereby providing an indication of the effective treatment of the infection. In a further example, the signal can be used to generate an indication of a particular event, such as the release of body fluids or exudates as in a bandage cr personal care product, such as a feminine care product or child care diaper product.
A method used to prepare alumina nanoparticles having functional compounds bonded to the surface included the following steps. The functional compound was dissolved in water with stirring. To this stirred solution was slowly added the alumina nanoparticles and the resulting mixture stirred for about 5 to 10 minutes to allow the functional compound to bond to the surface of the nanoparticle. The UV-VIS. spectrum of the water solution was obtained by taking an aliquot of the stirred mixture and placing it in a quartz cell. The UV-VIS spectra were obtained using a UV-VIS spectrophotometer Model UV- -1601 (Shimadzu Corporation) with water as a reference. Zeta Potential and

In additional alternative embodiments, following being affixed to such substrates, upon exposure to a change in condition (such as ?H) the functional compounds would be released from the sucstrate, but the particles would be left behind.
in a specific embodiment, carrier panicles (and desirably .rancparticles, that is particles having sizes of less than about 1 micron in size, more desirably between about 5 nm and 500 nm ir size, arc even more desirac-y. between about 10 nm - 200 nm in size) including pharmaceutical compounds, can be applied to a topical bandage by various application methecis. The application methods may include a gel, a water suspension, a dry coating or a pewder placed between the layers of the bandage if the particles are included in a vehicle for ease of application. The bandage can then be driec, if appropriate, whereby the charges of the particles would maintain them in c;cse association with the bandage substrate.
It should be recognized that the bound pharmaceutical or nutritional chemistry could be used with or without tricgerable release. Alternatively, some of the bound chemistry in a multiple chemistry carticle system couic be triggerably reieasable, while other bound chemistry could be intentionally retained on the carrier particles. In this fashion, the bound chemistry couid perform its advantageous function while still being attached to the carrier particles, for ease of removal or to lower the potential toxicity of the functional agent/compound. An example of such usage would be using a bound salicylaldoxime to remove heavy metals from the body or waste water without the toss of or exposure to the free complexing agent.
In another example, tetracycline could function as an antibiotic while still being bound on a particle. This could allow the antibiotic to function in the stomach and intestines without crossing over into the bloodstream of a patient (because of the size of the particle). This control of the antibiotic release could assist with lowering the risk of sensitization cf patients who are allergic to such medications.
These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the an, without departing from the spirit and scope of the present invention, which is more particularly set forth in the

appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.

We Claim,
1. An article of manufacture comprising:
a fibrous substrate having a receiving surface containing negative charges; and a plurality of positively charged particles bonded to the receiving surface of the fibrous substrate through coulombic attraction, the particles containing alumina, at least a portion of the alumina being present on a surface of the particles, and wherein a functional compound is bonded to the alumina on the surface of the particle, the functional compound prior to bonding with the alumina containing a moiety comprising:

or a tautomer thereof, or a functional equivalent thereof and wherein R and R' comprise independently hydrogen, an alkyl group, or an aryl group.
2. The article as claimed in claim 1, wherein the particle comprises a core material coated with alumina.
3. The article as claimed in claim 1 or 2, wherein the core material comprises silica.
4. The article as claimediany of the foregoing claims, wherein the functional compound comprises a colorant, a UV absorber, a pharmaceutical, an odor control agent, a fragrance, a therapeutic agent, a nutriceutical agent, an antibacterial agent, an anti-microbial agent, an anti-viral agent, a xsnobiotic, or combinations thereof.
5. The article as claimed in any of the foregoing claims, wherein the particle containing alumina bonded to the functional compound has an average dimension of less than about 1 millimeter, and preferably less than about 1,000 nanometers.
6. The article as claimed in any of the foregoing claims, wherein the functional compound comprises hydrocortisone, ascorbic acid, aspartame, or tetracycline.
7. The article as claimed in any of the foregoing claims, wherein the particle containing alumina bonded to the functional compound has a zeta potential of at least 20 mV.
8. The article as claimed in any of the foregoing claims, wherein the plurality of particles are contained within a liquid vehicle when applied to the substrate.

9. The article as claimed in any of the foregoing claims, wherein the substrate is subjected to a corona or electret treatment prior to bonding with the plurality of positively charges particles.
10. The article as claimed in any of the foregoing claims, wherein the article has been exposed to microwave radiation or radio frequency radiation after the substrate and the plurality of charged particles have been bonded together.
11. The article as claimed in any of the foregoing claims, wherein the substrate comprises natural fibers carrying the negative charges.
12. The article as claimed in claim 11, wherein the natural fibers comprise cotton or cellulose fibers.
13. The article as claimed in any of the foregoing claims, wherein the functional compound comprises a dye.
14. The article as claimed in claim 13, wherein the dye contains an anthraquinone chromophore, salicylate, 3-hydroxy-2-naphthoic acid moieties, chromotropic acid, acetoacetanilide, naphthoquinone, or a derivative thereof.
15. The article as claimed in claim 13, wherein the dye contains the moiety:

or a tautomer of this moiety .
16. The article as claimed in claim 13, wherein the dye contains the moiety:

and wherein Rand R1 are hydrogen.
17. The article as claimed in claim 13, wherein the dye contains the moiety:

or a tautomer of this moiety.
18. The article as claimed in any of the foregoing claims, wherein the receiving
surface of the substrate and the particles have a surface charge difference of
at least 42 mV.

19. The article as claimed in any of the foregoing claims, wherein the fibrous
substrate comprises synthetic polymeric fibers.
20. The article as claimed in claim 19, wherein the synthetic polymeric fibers are
polyolefin fibers.
21. The article as claimed in claim 19 or 20, wherein the fibrous substrate
comprises a non-woven web material.
22. The article as claimed in claim 21, wherein the non-woven material is a
spunbond web.
23. A printing process comprising:
ejecting a recording medium in the form of droplets from an orifice to form an
image on a fibrous substrate, the recording medium comprising a plurality of
particles containing alumina, at least a portion of the alumina being present
on a surface of the particles;
a colorant compound bonded to the alumina on the surface of the particle,
the colorant compound prior to bonding with the alumina containing a moiety
comprising:

or a tautomer thereof, or a functional equivalent thereof and wherein Rand R' comprise independently hydrogen, an alkyl group, or an aryl group; and
a liquid vehicle.
24. The process as claimed in claim 23, wherein the particles contain alumina, at
least a portion of the alumina being present on a surface of the particles.
25. The process as claimed in claim 23 or 24, wherein the fibrous substrate
comprises a woven fabric, a non-woven fabric, paper, or combinations
thereof.
26. The process as claimed in claim 23,24 or 25, wherein the process is an ink-jetting process.
27. A triggerable delivery system comprising:
a particle; and
a health-related compound adsorbed to the surface of the particle, the health-related compound capable of being released from the particle upon either exposure to a change in pH, moisture, chemical stimuli, or body exudates,

wherein the health related compound, prior to being adsorbed to the surface of the particle contains a moiety comprising;

or a tautomer thereof, or a functional equivalent thereof and wherein Rand R1 comprise independently hydrogen, an alkyl group, or an aryl group.
28. The triggerable delivery system as claimed in claim 27, wherein the particle contains alumina, at least , a portion of the alumina being present on a surface of the particle.
29. A drug delivery device including a triggerable delivery system, the trigrlerable delivery system comprising a particle; and a health-related compound adsorbed to the surface of the particle, the health-related compound capable of being released from the particle upon either exposure to a change in pH, moisture, chemical stimuli, or body exudates, wherein the health-related compound prior to adsorbing with the particle contains a moiety comprising:

or a tautomer thereof, or a functional equivalent thereof and wherein R and R' comprise independently hydrogen, an alkyl group, or an aryl group.

Documents:

1127-CHENP-2005 ABSTRACT.pdf

1127-CHENP-2005 CLAIMS.pdf

1127-CHENP-2005 FORM-2.pdf

1127-chenp-2005-abstract.pdf

1127-chenp-2005-assign.pdf

1127-chenp-2005-claims.pdf

1127-chenp-2005-correspondance others.pdf

1127-chenp-2005-corresspondance po.pdf

1127-chenp-2005-description complet.pdf

1127-chenp-2005-form 1.pdf

1127-chenp-2005-form 18.pdf

1127-chenp-2005-form 26.pdf

1127-chenp-2005-form 3.pdf

1127-chenp-2005-form 5.pdf

1127-chenp-2005-pct.pdf

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Patent Number

219104

Indian Patent Application Number

1127/CHENP/2005

PG Journal Number

23/2008

Publication Date

06-Jun-2008

Grant Date

25-Apr-2008

Date of Filing

06-Jun-2005

Name of Patentee

KIMBERLY-CLARK WORLDWIDE, INC

Applicant Address

Inventors:

#	Inventor's Name	Inventor's Address
1	LYE, Jason
2	MACDONALD, John, Gavin

PCT International Classification Number

A23L 1/00

PCT International Application Number

PCT/US2003/39737

PCT International Filing date

2003-12-11

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	10/731,256	2003-12-09	U.S.A.
2	10/325,474	2002-12-20	U.S.A.