MXPA06007293A - Bacteria binding products - Google Patents

Abstract

There is provided products for the removal of negatively charged particles like bacteria from surfaces. The products have a positive charge that may be developed through the use of cationic treatments. The product or substrate from which it is made may be dipped in an aqueous solution of a non-antimicrobial treatmenthaving a positive charge and the excess solution squeezed out. Treatment of the resulting coated substrate with heat at a temperature and for a time sufficient adheres the coating to the substrate. Alternatively, a non-antimicrobial, cationically charged chemical may be imbedded in a substrate web such that it will bloom to the surface when the web is exposed to water. A suitable substrate web may be a pulp and synthetic fiber fabric made by coforming or hydroengling and may be a laminate including other layers. The treated substrate and product remove a substantial amount of the bacteria from a surface yet do not appreciably kill the bacteria. Harsh, oxidizing, chemicals are not used in the preparation of the products and so the products are mild in their effect on the user's skin. The removal of the bacteria, in contrast to killing the bacteria, does not encourage the bacteria to develop immunity to the treatment.

Description

WO 2005/063307 Al m u ?? ?? ?? neither European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, Fl, - before the expiration of the time li IT for amending the FR, GB, GR, HU, DE, IS, IT, LT, LU, MC, NL, PL, PT, RO, claims and to be republished in the event of receipts of SE, SI, SK, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG). For two-letter codes and other abbreviations, refer to the "Guid- Publised: ance Notes on Codes and Abbreviations" appearing at the begin- - wilh inlemalional search repon no ofeach regular issue ofthe PCT Gazelle.

BACTERIAL AGGLUTINANT PRODUCTS This is a continuation in part of a jointly assigned United States of America patent application number 10 / 745,266, filed on December 23, 2003, and the claims that benefit it.

Background of the Invention The invention relates to processes and products for agglutinating and removing negatively charged particles such as bacteria and other microbes without the use of violent chemicals.

A concern grows around allergic reactions to chemicals and around the increased resistance of bacteria to common drug treatments, such as to worry and desire products that avoid violent chemicals yet achieve their purpose. In the case of currently available wet cleaning cloths, for example, the cleaning cloth is impregnated with a solution of chemicals. A typical chemical can be an antimicrobial chemical and the use of the cleaning cloth helps to supply chemicals to contaminated surfaces.

More desirably, however, a cleaning cloth can retain chemicals while removing germs from the surface. A cleaning cloth that removes bacteria but leaves no chemicals on the surface provides the desired effect of decontamination without the unwanted exposure of people to chemicals.

A myriad of different consumer products can benefit from this type of bacteria removal. It is an object of this invention to provide products that remove negatively charged particles without leaving a residue of the chemicals.

Synthesis of the Invention In response to the aforementioned difficulties encountered by those skilled in the art, products have been developed to agglutinate and remove negatively charged particles such as surface bacteria. The products have a positive charge that can be developed through the use of cationic treatments. Chemical treatments can be functionalized polymers, organic or inorganic oligomers, or particles coated with functionalized polymers, organic or inorganic oligomers. After the treatment is applied, the resulting product can be heat treated at a temperature and for a sufficient time to crosslink the coating and couple the coating to the substrate.

The right treatments to use here do not oxidize the surface of the product to which they are applied. This It avoids the need for very harsh conditions during the manufacture of the product. The treatments are, however, cross-linked with the surface of the product.

Brief Description of the Drawings Figure 1 is a drawing of a diaper.

Figure 2 is a drawing of a training underpants.

Figure 3 is a drawing of a pad for female hygiene.

Figure 4 is a drawing of an absorbent underpants.

Detailed description of the invention The present invention involves the agglutination and removal of negatively charged particles such as bacteria, cells, allergens, pathogens, and surface molecules. This has become greatly important for consumers as the number of bacteria resistant to common treatments has increased. This has also had a significant increase for consumers that are not exposed to violent chemicals.

Products that incorporate this chemistry remove negatively charged particles from surfaces. The negatively charged particles are removed without the use of violent chemicals, for example, chemicals that are caustic or that cause irritation to the skin of an average person, so that the consumer is not required to touch an article loaded with chemicals. In the case of bacteria, for example, since the bacteria are not exposed to chemicals that would kill them in substantial numbers, for example, more than 20 percent, the bacteria are not prone to develop immunity to chemical treatment on the substrates of the bacteria. product. The bacteria are simply removed through the application of physical means and of Coulombic attraction. A successful treatment compound does not leach from a substrate in a sufficient amount to substantially kill the bacteria and will therefore have at least 80 percent survival from a control colony, for example, the treatment will kill 20 percent or less of the colonies of bacteria.

Many products are contemplated for the removal of negatively charged particles as taught here. These products include personal care products such as diapers, underpants, cleansing wipes, feminine hygiene products (tampons, feminine pads), absorbent underpants and incontinence garments. The products also include products for the oral care and warehouse items, personal grooming products such as hair and scalp items, nail treatments and skin cleansing products. Products include facial and bath tissue, face masks, surgical gowns, covers and medical devices, and gloves. Products may include household cleaning items such as toilet bowl cleaners, hard surface cleaners, sponges, and other kitchen cleaning materials. Products may include agricultural, animal and pet care items such as brushes, cleaning cloths, cat litter, seed preparations and soil treatments. Products may include air and water filters, and ion removal filters for the removal of dust, allergens, and other contaminants. The products can also include pads for the storage of food such as poultry, and other meat products.

Figures 1-4 are drawings of typical personal care products, such as diapers, training pants, feminine pads and absorbent briefs. Each has a liner 12 and an outer cover or lower sheet 14. The personal care or absorbent products typically have a liner which rests against the wearer, a lower sheet which is the outermost layer, and may also contain other layers such as absorbent cores. The lining is sometimes referred to as a side-to-body lining or top sheet. In the direction of thickness of the article, the material of the lining is the layer against the wearer's skin and thus the first layer in contact with the liquid or other exudates of the wearer. The lining also serves to isolate the user's skin from liquids maintained in an absorbent structure and must be docile, soft to the touch and non-irritating.

Various materials can be used in the formation of the side-to-body liner, including perforated plastic films, weft fabrics, non-woven fabrics, porous foams, cross-linked foams, and the like. Nonwoven materials have been found particularly suitable for use in the formation of the side-to-body liner, including fabrics spun or blown with polyolefin melts, polyesters, polyamide filaments (or other similar fiber-forming polymer), or carded and bonded fabrics of natural polymers (e.g., rayon, or cotton fibers) and / or synthetic polymer fibers (e.g., polypropylene or polyester). For example, the side-to-body liner may be a woven fabric bonded with synthetic polypropylene filament non-woven yarn. The nonwoven fabric may have a basis weight, for example, in the range from about 1 gram per square meter to about 70 grams per square meter.

In addition to the above fabrics, coform fabrics, carded and bonded fabrics and materials placed by air can also be used in care products personnel such as laminates of any of the commonly known nonwovens. Cellulose materials such as paper towels or tissue can also be used. The fabrics can also be made by processes that introduce texture and increased foaming such as by creping, by the bonding of zero tension stretching, not knit bonding, orientation in the Z direction, and other means.

Non-woven fabrics are generally joined in some way as they are produced in order to give them sufficient structural integrity to withstand the rigors of further processing in a finished product. Bonding can be achieved in a number of ways such as hydroentanglement, stitching, ultrasonic bonding, adhesive bonding, stitch bonding, air bonding and thermal bonding, all of which are suitable for the practice of this invention.

The treatment must have a positive charge in order to attract and sustain negatively charged particles. Positive charges can be generated in a number of ways, a cationic charged chemical treatment can be added to the product, for example, and / or an electret treatment can be applied to the product, resulting in a positive charge. Suitable chemicals include functionalized cationic charged polymers, and inorganic or organic oligomers. The nanoparticles coated with functionalized cationic charged polymers or the inorganic or organic oligomers, Examples of suitable inorganic oligomers are aluminum chlorohydrole and aluminum chlorohydrate.

Chemicals useful in generating positive charge on a surface of a product include cationic polymers sold under the brand names of KYMENE®, RETEN®, of Hercules Inc., of Wilmington, Delaware, United States of America, COBOND® of the National Starch and Chemical Company of Bridgewater, New Jersey, United States of America, and Calgon polymers from Galgon, Inc., of Pittsburg, Pennsylvania, United States of America, and others of the polyethyleneimine type, polyelectrolytes of high load of density such as poly (methacryloxyethyl) trimethylammonium bromide, poly (acrylic acid) and functionalized polyamines of epichlorohydrin. Nanoparticles such as SNOWTEX® AK from Nissan Chemicals Inc., of Houston, Texas, United States of America, and aluminum chlorohydrate from Reheis, Inc., of Berkeley Heights, New Jersey, United States of America, may also be used. In addition to having a positive charge, the chemists suitable for the practice of the invention are gentle in their effect on the skin, not appreciably antimicrobial in nature and do not leach substantially once bound to the surface of the substrate.

The amount of chemical that must be added will vary according to the amount of charge of the particular chemical chosen to contribute. Generally, however, the effective amount of the chemical will be between about 0.01 and 10 percent. percent by weight, more desirably between 0.05 and 7 percent by weight, and even more desirably between 0.1 and 5 percent by weight.

The chemical treatment can be applied by methods such as traditional immersion and tightening techniques, where the article is immersed in the chemical treatment and the excess chemical is pressed out of it, or by brush coating, spraying, ink jet printing , and similar. It is also possible to add the chemical treatment as an internal treatment to, for example, a polymer fiber, as described below.

The surface of the chemically treated product can be heat treated at a temperature and for a time sufficient to crosslink the coating and adhere it to the tissue. The cross-linking process for functionalized cationic charged polymers involves the reaction between cross-linked functional groups (e.g., epoxy group) of the coating with any other functional group of the coating (for example, hydroxyl group) or with a functional group of the substrate. For example, the substrate can be cellulose wherein the hydroxyl groups of the fibers can cross-link intramolecularly with epoxy groups of the coating. In the case of alumina oligomers, the cross-linking process involves Al-OH groups of the oligomer and the OH of either the oligomer (cross-linked intramolecularly) or the OH group of the substrate (cross-linked intramolecularly). It is believed that the nanoparticles coated with alumina oligomer can adhere to the OH-containing surfaces by crosslinking the OH group with the Al-OH groups of the oligomer. The combination of time and temperature sufficient to cross-link the polymer will depend on the selected polymer and substrate. In general, however, the time will be between 1 and 60 minutes, more desirably between 5 and 45 minutes, even more desirably between 15 and 35 minutes, with a temperature between 50 and 300 degrees centigrade, more desirably from around 80 and 200 degrees Celsius, still more desirably between about 90 and 125 degrees Celsius. The inventors have found, for example, that a temperature of 100 degrees centigrade for about 20 to 30 minutes cures many polymers of interest.

Depending on the nature of the fibers, functional polymers (such as KYMENE® with epoxy groups) are able to involve both intramolecular cross-linking processes (eg, only within the coating layer) and between molecular (for example, only with the substrate). It is also believed that the cross-linking process will combine with both intramolecular and molecular processes, if the substrates are functional. Alternatively, if the substrate is not able to participate in the chemical cross-linking process, then crosslinking can only occur intramolecularly. In any case, a durable coating is often obtained when the non-functional substrate is made wettable by the previous treatment before coating. The term "adheres to the substrate" therefore includes intramolecular cross-linking instances that create a "sleeve" around the fibrous substrate, as well as cross-linked between molecular where the chemical or a chemical transport (such as a nanoparticle coated with an alumina oligomer) forms a covalent bond on the substrate, and combinations thereof. A cationic charged chemical "adheres to the substrate" if it does not leach from the substrate during use, where the "unleached" of a substrate means that the concentration of the chemical in the liquid left on the surface with which the substrate comes in contact, it is less than the critical concentration for the chemical that has antimicrobial properties.

Alternatively, the cationic charged compound can be embedded in a product made from fibers by extrudate melting of the fiber forming polymer containing a desired amount of the cationic charged compound as an additive in the fibers of the fabric. Such compounds can "bloom" to the surface when the fabric is exposed to hydrophilic solvents such as water. These melt-extruded fibers can contain a polyolefin and a cationic charged compound. The cationic charged compound may also contain a chemical segment (eg, compatibilizer) that is soluble in the polyolefin such that the salt is compatibilized with the polymer. The cationic charged chemistries can be, for example, amphiphilic quaternary ammonium salts which are compatible with hydrophobic fabrics, examples of which are taught by Nohr and Macdonald in U.S. Patent No. 5,853,883, which is incorporated herein by reference. If the hydrophobic segment of the salt that is compatible with the hydrophobic polymer is relatively large (with respect to the ionic segment of the salt) in such a way that the amount of salt that leaches out of the tissue is insufficient to kill bacteria, then the tissue can not have antimicrobial activity. Cationic charged groups generally enter the surface of the polymer fibers predominantly when the fabric is exposed to water. Such flowering gives the tissues properties similar to those of substrates coated with cationic charged compounds.

The inventors tested numerous substrates and chemical treatments for efficient removal and chemical leaching. These materials, treatments, test procedures and results are shown below.

Phosphate buffered salt control (PBS): this refers to saline buffered with sterile phosphate (PBS) and indicates that no cloth, treatment or charged particles They are negatively present in this sample. Phosphate-buffered saline (available from Gibco &Invitrogen at a concentration of .10X) is diluted to IX with distilled water and filtered sterile before use.

Spunbonded Fabric Spunbonded: The spinning linked process is also known as hydroentanglement. The spinning process binds the fiber fabric to fine jets of water at high pressure. When the jets hit the tissue, it replaces and entangles the fibers in a "twisted bound" interwoven fabric. The fabric is then dried in hot ovens. In general, the spunbonded fabrics do not contain chemical binders, and have excellent drapery and softness of the type of a textile, good mechanical and aesthetic properties, and good absorbency and wettability. A wide range of natural and synthetic fibers can be used to make spunbonded weaves, including polypropylene, rayon, polyethylene terephthalate, and nylon. The basic fibers are also used in spun bonded nonwoven products. The spun bonded fabric tested here was made from 65 percent by weight of rayon and 35 percent by weight of polyethylene terephthalate (PET). The fabric was tested in the un-creped state as well as in the creped state where the creping was performed in accordance with the patents of the United States of America numbers 6,197,404 and 6,150,002, which are incorporated herein in their entirety by reference thereto for all purposes These creped materials have bonding regions between filaments which are permanently bent out of plane, alternating with non-inter-filament junction regions. The non-bonded regions include a multiplicity of filament loops that terminate at joining ends in the creped filament-bonded regions.

Curly, polyurethane film: This curly film is made of polyurethane (PU) foam and polyethylene (PE) film through a glutinous spinning process. In glutinous yarn, the polyurethane foam (PU) and the polyethylene (PE) film are laminated together, the polyethylene is partially melted on a hot roll and the surface is fibrillated by pulling the material out of the roll and blowing air at the through to cool it.

Carded and bonded fabric: "Carded and bonded fabric" refers to fabrics that are made of basic fibers that are sent through a combing or carding unit that breaks and aligns the basic fibers in the machine direction. forming a fibrous nonwoven fabric oriented in the direction to the machine, generally. Such fibers are usually purchased in bales that are placed in a separator, which separates the fibers before the carding unit. Once the tissue is formed, it is then joined by one or more of the various known joining methods. One such method of bonding is powder binding, wherein a powder adhesive is distributed through the tissue and then activated, usually by heating the fabric and the adhesive with hot air. Another suitable method of joining is pattern bonding, where heated calendering rolls or ultrasonic bonding equipment are used to join the fibers together, usually in a localized bonding pattern, even when the fabric can be bonded across its entire surface if so desired. Another suitable well-known joining method, particularly when using bicomponent basic fibers, is the bonding through air.

Textured coform laminate (TCL): this material is an elastic laminate that has outer layers on each side of a core. The outer layers have a basis weight of 35 grams per square meter (gsm) each and made in accordance with the coform process, from a mixture of 60 percent by weight of fibrillated southern softwood pulp CF405, from Weyerhaeuser Corp., and 40 percent by weight of blown fibers with polypropylene melting PF105 from Basell Poliolefins Company N.V. of Hoofddorp, The Netherlands. The core has 30 grams per square meter of basis weight and made of filaments and non-woven fabric. The filaments comprise 70 percent by weight of the core and were made of AFFINITY® metallocene-based polyethylene, from the Dow Chemical Company of Midland, Michigan, United States of America. The non-woven fabric was made in accordance with the melt blowing process of 80 percent by weight of AFFINITY® polyethylene, 15 percent by weight of REGALREZ® 1126 hydrocarbon resin from the Eastman Chemical Company of Kingsport, Tennessee, United States. from America, and 5 percent by weight of linear low density polyethylene DNDB 1077, from the Dow Chemical Company.

In the meltblowing process, the fibers are formed by extruding a molten thermoplastic material through a plurality of thin and usually circular capillary matrix vessels with strands or fused filaments into gas jets heated at high speed (for example, air) and converging that attenuate the filaments of molten thermoplastic material to reduce its diameter, which can be to a micro-fiber diameter. After this, the meltblown fibers are carried by the high speed gas jet and are deposited on a collecting surface to form a randomly dispersed meltblown fabric. Such process is described for example, in the patent of the United States of America number 3,849,241 granted to Butin. The melt blown fibers can be continuous or discontinuous, are generally smaller than 10 microns in average diameter and are generally sticky when deposited on a collecting surface.

In the "coform" process, at least one melt blown matrix head is arranged near a hopper through which other materials are added to the fabric while it is in formation. Such other materials can include pulp, super absorbent particles, natural or synthetic basic fibers, for example. The coform processes are shown in the commonly assigned patents of the United States of America numbers 4,100,324 issued to Anderson et al .; 4,818,464 awarded to Lau. The tissues produced by the coform process are generally referred to as coform materials. Natural fibers include wool, cotton, linen, hemp, and wood pulp. Wood pulps include soft standard grade foam wood such as CR-1654 (US Alliance Pulp Mills, Coosa, Alabama). The pulp can be modified in order to improve the inherent characteristics of the fibers and their processing. Curling can be imparted to the fibers by methods that include chemical treatment or mechanical twisting. Curling is typically imparted before cross-linking or kinking. Pulps can be thickened by the use of crosslinking agents such as formaldehyde or its derivatives, glutaraldehyde, epichlorohydrin, methylolated compounds such as urea or urea derivatives, dlaldehydes such as maleic anhydride, non-methylolated urea derivatives, citric acid or other acids polycarboxyliae Some of these agents are less preferable than others due to environmental and health concerns. The pulp can also be stifled by the use of heat or caustic treatments such as mercerizing. Examples of these types of fibers include NHB416 which are southern softwood pulp fibers chemically crosslinked to improve the wet modulus, available from the Weyerheuser Corporation, of Tacoma, Washington. Other useful pulps are debulked pulps (NF405) and pulps without deagglutinating (NB416) also from Weyerhaeuser. The HPZ3 from Buckeye Technologies, Inc., of Memphis, Tennessee, has a chemical treatment that sets a curl and a twist, in addition to imparting added dry and wet stiffness and flexibility to the fiber. Another suitable pulp is the Buckeye HP2 pulp and yet another is the Super Soft IP of the International Paper Corporation. Suitable rayon fibers are 1.5 denier Merge 18453 fibers from Acordis Cellulose Fibers Incorporated, of Axis, Alabama.

HIDROKNIT® material: the HIDROKNIT® material is available from Kimberly-Clark Corporation of Dallas, Texas, United States of America, and is a hydroentangled fabric of soft absorbent cellulose fibers and synthetic fibers joined with yarn. Synthetic fibers are commonly made of polypropylene. The materials tested here have a basis weight of 64 g per square meter and consist of only one pulp in a 75 percent by weight stratum and fibers bound with 25 percent by weight polypropylene yarn. How it is used here, the term "HIDROKNIT® with polypropylene fibers" refers to the fabric described above of HIDROKNIT® having an additional layer of polypropylene fibers bonded with yarn deposited on its surface. This results in a rough texture of the polypropylene fiber layer on the HIDROKNIT® substrate to increase the abrasion properties.

The term "spunbonded fibers" refers to the small diameter fibers that are formed by the extrusion of a molten thermoplastic material as filaments through a plurality of fine spinner capillary vessels having a circular or otherwise shaped configuration, with the diameter of the extruded filaments being rapidly reduced as, for example, in the patent of the United States of America number 4,340,563 granted to Appel and others; U.S. Patent No. 3,692,618 issued to Dorschner et al .; US Pat. Nos. 3,338,992 and 3,341,394 issued to Kinney; U.S. Patent No. 3,802,817 issued to Matsuki et al .; 3,341,394 granted to Le and; U.S. Patent No. 3,502,763 issued to Hartman; U.S. Patent No. 3,542,615 issued to Dobo et al. Spunbonded fibers are generally continuous and have average diameters (of a sample of at least 10) greater than 7 microns, more particularly, between about 10 and 20 microns.

VIVA® Scrub Fabric: This material is a cellulose paper towel and is available from Kimberly-Clark Corporation. It has a polyethylene acetate binder printed on both sides of the base sheet that is composed of 72 percent by weight of bleached soft kraft wood, 13 percent by weight of polyethylene vinyl acetate binder, 11 percent by weight of fiber synthetic (polyester), 3 percent by weight of kraft hardwood, 1 percent by weight of total nitrogen.

Material WYPALL® X80: WYPALL® materials are also available from Kimberly-Clark Corporation. The WYPALL® X80 material is a bulky, highly absorbent HYDROKNIT® material that has high wet strength and capacity. The materials tested here have a basis weight of 125 grams per square meter and were made from 75 percent by weight of pulp and 25 percent by weight of fibers bonded with polypropylene yarn.

Air-laid fabric: "Air-laid" is a well-known air-forming process by which a fibrous non-woven layer can be formed. In the process of placing by air, bales of small fibers that have typical lengths in the range from about 3 to about 52 millimeters are separated and dragged into an air supply and then deposited on a training grid, usually with assistance of a vacuum supply. The randomly deposited fibers are then bonded to one another using, for example, hot air or an adhesive spray. The production of nonwoven composites placed by air is well defined in the literature and documented in the art. Examples include, the DanWeb process as described in U.S. Patent No. 4,640,810 issued to Laureen et al., And assigned to Sean Web of North America, Inc., the Kroyer process as described in the United States patent. United States number 4,494,278 granted to Kroyer and others, and U.S. Patent No. 5,527,171 issued to Soerensen assigned to Niro Separation a / s, U.S. Patent No. 4,375,448 granted to Appel et al., assigned to Kimberly-Clark Corporation, or other similar methods The tested materials were made from 83 percent by weight of Weyerhaeuser CF405 pulp, and 17 percent by weight of latex binder (National Starch Dur-0-Set elite PE) and has a basis weight of 68 grams per square meter.

A number of other processes and materials may be used in the practice of the invention but not all were tested here. Some of these other materials and processes are described below.

Not bound with Pattern or "PUB" means a fabric pattern having continuous bonded areas defining a plurality of discrete unbonded areas as illustrated in U.S. Patent No. 5, 858,515 issued to Stokes and others. The fibers or filaments within the discrete unbonded areas are stabilized in dimension by the continuous bonded areas that surround or encircle each unbonded area, so that a backing or backing layer of film or adhesive is not required. Unbonded areas are specifically designed to afford spaces between the fibers or filaments within the unbonded areas. An adequate process to form a non-woven material not bonded with pattern includes providing a nonwoven fabric or fabric, providing a first and second calender rolls placed and defining a pressure point in the middle, with at least one of the rolls being heated and having a pattern of joining on its outermost surface comprising a continuous pattern of laying areas defining a plurality of discrete openings, apertures, or holes, and passing the nonwoven fabric or fabric within the pressure point formed by the rolls. Each of the openings in the roller or rollers defined by the continuous laying areas forms discrete unbonded areas in at least one surface of the nonwoven fabric or fabric in which the fibers or filaments of the fabric are substantially or completely unbonded. Alternatively noted, the continuous pattern of the placement areas on the roller or rollers forms a continuous pattern of joined areas defining a plurality of discrete unbonded areas on at least one surface of the nonwoven fabric or fabric. Alternative embodiments of the aforementioned process include prebonded fabric or non-woven fabric prior to passing the fabric or fabric into the pressure point formed by the calendering rolls, or providing multiple non-woven fabrics to form an unpatterned laminate. of united.

The zero-tension stretching process generally refers to a process in which at least two layers are joined to one another while in a condition without tension (hence zero tension) and where one of the layers is capable of stretching and elastomeric and the second is capable of stretching but not necessarily elastomeric. Such a laminate is stretched incrementally through the use of one or more pairs of corrugated mixing rolls that reduce the stress rate experienced by the fabric. This results in a volume in the Z direction of the laminate and subsequently elastic extensibility in the direction of the initial stretch at least up to the initial stretch point. Examples of such laminates and their production processes can be found in U.S. Patent Nos. 5,143,679; 5,151,092; 5,167,897; and 5,196,000.

Fiber fabrics oriented in the Z direction can also be used in the practice of this invention. A discussion of this process can be found in the issue of the October 1997 non-woven industry magazine on page 74 in an article by Krema, Jirsak, Hanus and Saunders, entitled "What's new in High-Fiber Production? As well as in the Czech patents 235494 entitled "Fiber Layer, Method of Production and Equipment for the Application of a Fiber Layer Production Method" granted on May 15, 1995 and 263075 entitled "Method for Production of bulky United Textiles ", granted on April 14, 1989.

Other suitable material includes those made in accordance with the patent of the United States of America No. 4,741,941, which teaches a non-woven fabric with projections. The fabric from which the product can be made is formed on the surface having projections with or without openings and which has a vacuum assist. The fabric has fibers with a formation of hollow projections extending out of the fabric and separated by areas of planar placement. The fabric of this type can be made in accordance with any of the non-woven production techniques such as meltblowing, spinning, air-laying and the like.

Suitable products also include those taught in U.S. Patent Nos. 4,775,582; 4,853,281; and 4,833,003. The patents x582 and? 281 teach about uniform wet cleaning cloths made of blown fibers with polyolefin melting. The '003 patent teaches on uniformly wet cleaning cloths having an abrasive surface bonded to the meltblown support layer.

A number of different treatments were used in the Experiments described below. The treatment of the weaves was done as follows: KYMENE® 2064: A 0.1 percent solution to KYMENE® 2064 was prepared by diluting a batch of KYMENE® 2064 solution (from Hercules, Inc., of Wilmington, Delaware, United States of America) (20 percent by weight of solution in 5 milliliters of water) with de-ionized water (995 milliliters). The KYMENE® 2064 was "activated" by adjusting the pH of the solution with NaOH (0.4 M) which was measured at 8.8. The treatment of the substrate involves a "dip and twist" protocol. Each substrate was immersed in a 0.1 percent by weight solution of KYMENE® 2064 and stirred for approximately 1 minute to ensure saturation. The treated material was then twisted to remove the excess treatment solution using an Atlas laboratory drainer of type LW-1 (from Atlas Electrical Devices, Co., Chicago, Illinois, United States of America) equipped with a weight of 5. pounds for twisting pressure. The material was cured at 100 degrees centigrade for 20 minutes, allowing it to cool to room temperature, and washed twice with de-ionized water. The excess water was removed using the same "dip and twist" protocol above. The washed material was allowed to dry at 100 degrees centigrade for 30 minutes.

KYMENE® 450: A 0.1 percent by weight solution of KYMENE® 450 was prepared by diluting a batch of KYMENE® 450 solution (Hercules, Inc.) (20 percent by weight solution in 5 milliliters of water) with water -ionized (995 milliliters). The KYMENE® 450 was "activated" by adjusting the pH of the solution with NaOH (0.4M), which was measured at 9.2. The treatment of the substrates was carried out in the same way as with the previous KYMENE® 2064.

KYMENE® 557: A 0.1 percent by weight solution of KYMENE® 557 LX was prepared by diluting a batch of KYMENE® 557 LX solution (Hercules, Inc.) (12.5 percent by weight solution in 8 milliliters of water) with de-ionized water (992 milliliters). The KYMENE® 450 was "activated" by adjusting the pH of the solution with NaOH (0.4M), which was measured at 8.0. The treatment of the substrates was carried out in the same way as with the previous KYMENE® 2064.

KYMENE® 736: A 0.1 percent by weight solution of KYMENE® 736 was prepared by diluting a batch of KYMENE® 736 solution (Hercules, Inc.) (38 percent by weight solution in 2.6 milliliters of water) with water -ionized (997.4 milliliters). The pH solution was adjusted with NaOH (0.4M), which was measured at 8.0. The treatment of the substrates was carried out in the same way as with the previous KYMENE® 2064.

Oligomer of alumina (aluminum chlorohydrol, aluminum chlorohydrate): A 1 percent solution of alumina oligomer was prepared by diluting a batch of alumina oligomer solution (from GEO Specialty Chemicals,, of Little Rock, Arkansas, United States) of America) (50 percent by weight of solution in 20 milliliters of water) with de-ionized water (980 milliliters). The measured pH of the solution was 4.6. The treatment of the substrate involves a protocol "submerge and twist". Each substrate was immersed in a 1 percent by weight solution of the alumina oligomer solution and stirred for approximately 1 minute to ensure saturation. The treated material was then twisted to remove the excess treatment solution using an Atlas laboratory drainer of type LW-1 (from Atlas Electrical Devices, Co., of Chicago, Illinois, United States of America) equipped with a weight of 5. pounds for twisting pressure. The material was cured at 100 degrees centigrade for 20 minutes, allowing it to cool to room temperature, and washed twice with de-ionized water. The excess water was removed using the same "dip and twist" protocol above. The washed material was allowed to dry at 100 degrees centigrade for 30 minutes.

SNOWTEX® AK Nanoparticle (alumina-coated silicon nanoparticles): A 1 percent nanoparticle solution of SNOWTEX® AK was prepared by diluting a batch of SNOWTEX® AK nanoparticles (from Nissan Chemicals, Ltd., of Houston, Texas, USA). United States) (20 percent by weight of solution in 75 milliliters of water) with deionized water (1425 milliliters). The pH of the solution was measured at 4.0. The treatment of the substrate involves a "dip and twist" protocol. Each substrate was immersed in a 1 percent solution by weight of the SNOWTEX® AK nanoparticle solution and stirred for approximately 1 minute to ensure saturation. The treatment solution for each substrate it was not recycled for subsequent treatments. The treated material was then twisted to remove the excess treatment solution using an Atlas laboratory drainer of type LW-1 (from Atlas Electrical Devices, Co., Chicago, Illinois, United States of America) equipped with a weight of 5. pounds for twisting pressure. The material was cured at 100 degrees centigrade by minutes, allowing it to cool to room temperature, and washing twice with de-ionized water. The excess water was removed using the same "dip and twist" protocol above. The washed material was allowed to dry at 100 degrees centigrade minutes.

Experiment 1- Inhibition test of bacteria growth The KYMENE® chemical classes are generally mild and non-caustic to the skin. Certain KYMENE® chemicals, however, are known to kill bacteria at some level. In order to • determine if KYMENE® treatment chemicals will escape from the substrate and possibly kill the remaining bacteria on a surface, an assay was designed to measure the growth inhibition of the bacterial cells of the leached chemical from the treated materials. This test procedure follows: The treated and untreated materials of two by two inches (5 by 5 centimeters) are placed in 15 milliliter tubes containing 5 milliliters of sterile phosphate buffered saline (PBS). The tubes are placed in a shaking incubator at 37 degrees centigrade for 2-3 hours. One millimeter of each solution was then transferred into a clean culture tube. Ampicillin-resistant E. coli (10 micro-liters ~ 1000 cells) was added to each tube. The sterile phosphate buffered saline (PBS) solution was added to the clean culture tubes as controls. The tubes were returned to the shaking incubator for 30 more minutes. One hundred microliters were removed from each tube and placed on LB agar plates containing ampicillin. Plates were incubated at 37 degrees Celsius, and bacterial colonies were counted the next day to determine if KYMENE® was present in the solution that inhibits colony formation.

LB agar means Luria-Bertani broth (available from Difco and Becton Dickinson) in the amount of 25 grams mixed with agar (also from Difco and Becton Dickinson) in the amount of 15 grams and dissolved in 1 liter of distilled water and autoclaved. The circular plates (100 millimeters by 15 millimeters) are poured after adding ampicillin (100 micrograms / mL) to the LB agar.

The data are listed in terms of the percent of colonies found on the plate compared to the PBS control.

As can be seen from the results, none of the materials not treated except for HIDROKNIT® with polypropylene (PP) fibers appeared to have had a dramatic effect on the growth of the colony. KYMENE® 2064 materials show no appreciable inhibition of growth except for HYDROKNIT® with PP fibers. Materials treated with KYMENE® 736 leached KYMENE® into the solution, which killed most E. coli in the solution. The results are not surprising since it is known that the KYMENE® 2064 will cross-link with the materials listed above while the KYMENE® 736 will generally not. Treatments that are cross-linked to the substrate are more stable and less susceptible to leaching than non-cross treatments and are therefore desirable. A successful treatment will have at least 80% of a control cell sample colony growth, for example, it will inhibit the growth of 20% or less of the bacterial colonies.

Experiment 2-Bacterial growth inhibition test The SNOWTEX® nanoparticles and the aluminum oligomer were tested directly on E. Coli. The serial dilutions of both SNOWTEX® nanoparticles as well as the aluminum oligomer used to coat the nanoparticles were made in sterile PBS. One milliliter of each solution was added to clean the culture tube in duplicate. The sterile PBS was added to the culture tubes as a control. The E. coli resistant to Ampicillin was added (10 microL, -1000 cells) to each solution. The culture tubes were placed in the shaker incubator at 37 ° C for 30 minutes. After incubation about 100 microliters were removed from each tube and placed on the LB agar plates containing ampicillin. Plates were incubated at 37 ° C and bacterial colonies were counted the next day to determine whether the SNOWTEX® nanoparticles or the aluminum oligomer inhibited colony formation. The data are listed in the terms of percent of colonies found on the plate compared to the PBS control.

The results show that the nanoparticle SNOWTEX® did not have an effect on the formation of colony E.

Coli, even at high concentrations (10 mg / mL). The aluminum oligomer decreased the number of E.coli colonies when it was at a concentration of 0.5% and above. The concentration of the aluminum oligomer used to treat the nanoparticles is 1%. These results indicate that bacterial cell death will be observed only if all the oligomer is used to treat the materials that have leached into the solution. As mentioned above, a successful treatment will have at least a 80% survival of the control sample colonies, for example it will kill 20% or less of the bacterial colonies.

Experiment 3-Method to test the effectiveness of the binder bacterium.

Successful treatment should not only kill substantial numbers of bacteria, it should also bind a large proportion of bacteria. In order to determine how efficient the substrate and treatment is in retaining the bacteria cleaned from the surface, the following test procedure was carried out.

The squares of material of 5 cm. by 5 cm. They were cut and weighed in duplicate. The dilutions in A series of ampicillin-resistant E. Coli solution were made to achieve a final concentration of ~105 cells per mL. One hundred microliters of sterile PBS was added to each material. After 5 minutes, 100 microliters of the bacteria solution were added onto each material. The materials were removed and placed in 10 mL of sterile PBS in 50 mL tubes. The tubes were sonicated (5 cycles of 30 seconds activated, 30 seconds deactivated) in a water bath to dislodge any bacteria that were not tightly bound to the material. One hundred microliters of the PBS solution of the tubes containing the material were coated in duplicate on the LB agar plates containing ampicillin. Plates were incubated at 37 ° C and bacterial colonies were counted the next day. The data is shown as the percentage of bacteria reduction is solved in comparison to the PBS control.

* Materials tested multiple times All treated and untreated materials showed a reduction in bacteria in the PBS solution after sonication. The most dramatic results were found in the materials treated with KIMENE® 2064, KYMENE® 450, the aluminum oligomer and in some cases, the nanoparticles of SNOWTEX® AK nanoparticle. In all cases except for the WYPALL® material, the treated materials showed a larger reduction in bacteria and in solution than the untreated materials. It is desirable that the treated materials reduce bacterial growth according to this method of agglutination of bacteria by at least one percent of 50%; more desirably at least 75% and even more desirably at least 90%.

Experiment 4- Zeta potential analysis to measure the surface charge of treated substrates.

When an electrolyte solution is forced through a plug of porous material, a running potential develops due to the movement of the ions in the diffusion layer which can be measured by an electrostype analyzer (from Brookhaven Instruments Corporation, of Holtsville , NY, USA). This value is then used to calculate the Zeta potential according to the formula published by D. Fairhurst and V. Ribitsch (Distribution of particle size II, evaluation and characterization, chapter 22, ACS Symposium Series 472, Edited by Proveer, Theodore, ISBN 0841221170).

During the sample preparation, the treated and untreated substrates were cut into two identical pieces (120 millimeters by 50 millimeters) and then placed in the sample cell with TEFLON® spacers between them. After the sample cell was mounted on the instrument, all air bubbles were removed by purging. Then the KCl solution (1 mM, pH = 5.9, temperature = 22 ° C) were forced through the two media layers and the Ag / AgCl electrodes were used to measure the runoff potential. All samples were tested under a similar pH, solution conductivity and using the same number of spacers.

Each test was repeated four times, and the results are summarized in the table given below.

As can be seen from the data, the Zeta potential for untreated substrates was negative, varying from -11 mV to -1 mV at a pH of ~ 5.9. Negative values for untreated surfaces indicated that there was repulsion between most bacteria and untreated substrates. After treatment, the Zeta potential for all substrates became positive. The most cationically charged substrates were found to be materials treated with KYMENE® 2064 and KYMENE® 450, the aluminum oligomer and nanoparticles of SNOWTEX® AK.

Experiment 5- Removal of bacteria through cleaning.

TCL materials treated (1% by weight) and not treated with aluminum chlorohydrate were cut into samples of 5 cm by 15 cm. The materials were soaked in filtered and sterile PBS (3 mL per sample) for two hours before beginning the cleaning experiments. Serial dilutions of an E. coli solution resistant to ampicillin were made to achieve a final concentration of ~106 cells per mL. Five hundred microliters of 106 cells per mL of E.coli cell solution were stained on a piece of ceramic tile. The sample of the material was placed on top of E. Coli and a number of cleanings (1-5) were carried out. After cleaning, the complete run of the tile surface was treated with a swab with respect to the bacteria. The swabs were placed in 1 mL of sterile PBS. One hundred microliters of the PBS solution were placed in duplicates on LB agar plates containing ampicillin. The data are described as the percent residual bacteria found in the tile after cleaning and are presented in the table given below.

Experiment 6-Transfer of bacteria through cleaning.

Cleaning was carried out using treated and untreated TCL materials as described in example 5 given above. After 4 cleaning, a sterile tile surface was cleaned four times with the material containing the bacteria. The tile surface was rubbed with a swab as described above to capture any bacteria that were transferred onto the surface. The swabs were placed in 1 mL of sterile PBS. 100 microliters of the PBS solution were coated in duplicates on LB agar plates containing ampicillin. The data are presented in the table given below (the data are numbers of colonies found on the LB / ampicillin plates).

Bacterial entry = 7.1 x 105 cells, Bacteria entry = 7.0 x 105 cells.

Experiment 7-Transfer of bacteria through direct contact.

Another experiment set was carried out in which the bacteria were added directly to the test material that remained on the ceramic tile. The paper towels Scott® TCL treated with aluminum chlorhydrate (1% by weight) and the sponges (ScotchBrite® of 3M) were placed on a ceramic tile. Five hundred microliters of a solution containing bacteria (~5 x 105 cells) were added directly to each material. The material was lifted out of the tile, and any bacteria that had leaked through the material was removed with a swab that was placed in 1 mL of PBS. The material was then placed with the bacteria down on a clean and sterile tile. A weight of 1.2 kg was then placed on top of the material for a few minutes. The weight and material were removed, and any bacteria that were transferred on the clean surface were removed with a swab that was placed in 1 mL of PBS. One hundred microliters of the PBS / hyssop solutions were coated in duplicate. The data are presented in the table given below (the data or numbers of colonies found on the LB / ampicillin plates) Input bacteria = 5.8 x 10 cells Experiment 8-Visual capture indicator; Another set of experiments was carried out in which the negatively charged microspheres of blue color similar in size to bacteria (around 1 μm) were used to provide visual evidence of the capture. The microspheres were diluted 1: 3 in PBS. One hundred microliters of the micro beads solution were added to an untreated TCL baby wipe and TCL treated as described above with aluminum chlorohydrate. The substrates were then vigorously washed in deionized water. After washing, the untreated substrates were essentially free of blue coloring, showing that the microbeads had washed out. The TCL clearly treated retained the blue color, showing the retention of the micro accounts.

As will be appreciated by those skilled in the art, changes and variations to the invention are considered to be within the ability of those skilled in the art. Examples of such changes are contained in the patents identified above each of which is incorporated herein by reference in its entirety to the extent that it is consistent with this disclosure. Such changes and variations are attempted by the inventors to be within the scope of the invention. It is understood that the scope of the present invention should not be construed as limiting the specific embodiments described herein but only in accordance with the appended claims when read in the light of the following description.

Claims (19)

R E I V I N D I C A C I O N S

1. A product for the removal of negatively charged particles comprising a substrate having on it a positively charged chemical compound wherein said chemical compound allows a survival of at least 80% of a bacterial colony.

2. The product as claimed in clause 1 characterized in that the positively charged chemical compound is embedded in the melted extruded polymer fibers.

3. The product as claimed in clause 1 characterized in that the positively charged chemical compound is applied to a surface of said substrate.

4. The product as claimed in clause 1 characterized in that said chemical compound is a cationic polymer.

5. The product as claimed in clause 1 characterized in that said chemical compound is an epichlorohydrin-functionalized polyamine.

6. The product as claimed in clause 1 characterized in that the chemical compound is positively charged nanoparticles.

7. The product as claimed in clause 1 characterized in that the chemical compound is an alumina oligomer.

8. The product as claimed in clause 3, characterized in that the substrate is heat treated at a temperature and for a sufficient time to adhere said compound to said substrate.

9. The product as claimed in clause 1 characterized in that the substrate is made of a non-woven fabric made according to a method selected from the group consisting of meltblowing, coformming, spunbonding, air-laying, bonded and carding, zero tension stretching and orientation in the Z direction.

10. The product as claimed in clause 3 characterized in that said chemical compound is applied to said substrate in an amount of between 0.01 and 10% by weight on an aqueous base.

11. The product as claimed in clause 3 characterized in that said chemical compound is applied to said substrate in an amount of between 0.05 and 7% by weight on an aqueous basis.

12. The product as claimed in clause 3 characterized in that said chemical compound is applied to said substrate in an amount of between 0.1 and 5% by weight on an aqueous base.

13. The product as claimed in clause 1 characterized in that the substrate reduces the bacterial growth according to the method of agglutination of bacteria by at least 50%.

14. The product as claimed in clause 1 characterized in that the substrate reduces bacterial growth according to the method of agglutination of bacteria by at least 75%.

15. The product as claimed in clause 1 characterized in that the substrate reduces bacterial growth according to the method of agglutination of bacteria by at least 90%.

16. The product as claimed in clause 1 characterized in that the substrate is selected from the group consisting of personal care products such as oral care products, storage articles, personal care products, facial tissue, toilet tissue, face masks, surgical suits, covers, medical devices, gloves, toilet bowl cleaners, hard surface cleaners, sponges, kitchen cleaning materials, agricultural products, for the care of animals and pets, cat litter, seed preparations, soil treatments, air filters, water filters, ion removal filters and food storage pads.

17. A product for the removal of bacteria from surfaces comprising a cationic chemical compound coated on a substrate at a temperature and for a time sufficient to adhere said chemical compound to said substrate, wherein said chemical compound allows a survival of at least 80 % of a bacterial colony.

18. The product as claimed in clause 17, characterized in that it comprises hydroentangled pulp and synthetic fibers.

19. A product for the removal of bacteria from surfaces comprising a pulp fabric and synthetic fibers having a non-cationic nanoparticle treatment thereon. E S U M E Products are provided for the removal of negatively charged particles such as surface bacteria. The products have a positive charge that can be developed through the use of cationic treatments. The product or substrate from which it is made can be immersed in an aqueous solution of a non-microbial treatment that has a positive charge and the excess solution squeezed out. The treatment of the resulting coated substrate with heat at a temperature and for a sufficient time adheres the coating of the substrate. Alternatively, a non-antimicrobial, cationically charged chemical can be embedded in a substrate fabric so that it will bloom to the surface when the tissue is exposed to water. A suitable substrate fabric can be a synthetic fiber and pulp fabric made by coforming or hydroentanglement and can be a laminate including other layers. The treated substrate and the product remove a substantial amount of the bacteria from a surface but do not kill the bacteria appreciably. Oxidizing and harsh chemicals are not used in the preparation of the products and in this way the products are gentle in their effect on the user's skin. Removal of bacteria, in contrast to killing bacteria, does not encourage bacteria to develop immunity to treatment.