WO2019224772A1

WO2019224772A1 - Scouring article with fungicidal texture layer

Info

Publication number: WO2019224772A1
Application number: PCT/IB2019/054283
Authority: WO
Inventors: Stewart H. Corn; Irem Bolukbasi; Sedat GUNES; Windy Ann Santa Cruz; Myhanh T. Truong; Yifan Zhang
Original assignee: 3M Innovative Properties Company
Priority date: 2018-05-24
Filing date: 2019-05-23
Publication date: 2019-11-28
Also published as: TW202005594A

Abstract

The present invention is a scouring article including a substrate having a first surface, a second surface opposite the first surface, and a texture layer formed on at least one of the first and second surfaces of the substrate. The texture layer includes a plurality of discrete segments and includes a fungicide. The fungicide remains active before and after being subjected to AATCC Test Method 130-2000, section 8 with a water temperature of approximately 41°C and using 1993 AATCC Standard Reference Detergent.

Description

SCOURING ARTICLE WITH FUNGICIDAL TEXTURE LAYER

TECHNICAL FIELD

The present invention relates generally to scouring articles. In particular, the present invention is a scouring article having a fungicidal texture layer.

BACKGROUND

A variety of cleaning articles in the form of pads, wipes and cloths have been developed and made commercially available for household and industrial use. Consumers oftentimes desire to use the articles for cleaning or surface treating tasks requiring scrubbing which in turn may include various degrees of wiping, abrading and/or scouring.

Scrub sponges in particular are hospitable environments for microbial growth because they frequently come into contact with water. One method of preventing and limiting microbial growth is by the addition of anti-microbials to the cleaning article. Anti-microbials are known to protect dried coatings from attack from bacteria, fungi (i.e., mildew, mold), and algae. Of these, fungi are perhaps the most destructive to dried coatings. Protection can be demonstrated by long term field studies, or by microbial laboratory tests such as ASTM G21, American Association of Textile Chemists and Colorists (AATCC) TM-30, etc. Protection in microbial laboratory tests is shown by (a) lack of growth on the test coating and/or (b) a zone of inhibition around the test coating.

A zone of inhibition indicates diffusion of the antimicrobial away from the coating, which is typically thought to be important in protecting dried coatings that are exposed to moisture. The diffusion rate must be high enough such that an effective antimicrobial dose is maintained at the surface of the coating despite repeated exposure to moisture.

Too high a diffusion rate may result in premature depletion of the anti-microbial agent.

On the other hand, if no diffusion occurs, it may be that the antimicrobial has become inactivated. Even if the anti-microbial remains active, too slow a diffusion rate may result in the anti-microbial becoming consumed or overwhelmed at the surface of a coating. Thus, a fungicide with a controlled, sustained, observable rate of diffusion in coatings is desirable for certain coatings.

The anti-microbial agent can be added to various materials or locations of the cleaning article. Scrub sponges typically have an abrasive texture layer. Adding an anti- microbial agent to an abrasive scouring pad is generally known in the art. However, current hurdles to an efficient process include that the anti-microbial agent must be cured at lower temperatures, that the anti-microbial agent may not diffuse from the coating, and that multiple treatment steps are required to incorporate the anti-microbial agent throughout the substrate.

SUMMARY

In one embodiment, the present invention is a scouring article including a substrate having a first surface, a second surface opposite the first surface, and a texture layer formed on at least one of the first and second surfaces of the substrate. The texture layer includes a plurality of discrete segments and includes a fungicide. The fungicide remains active before and after being subjected to AATCC Test Method 130-2000, section 8 with a water temperature of approximately 4l°C and using 1993 AATCC Standard Reference Detergent.

In another embodiment, the present invention is a scouring article including a substrate having a first surface, a second surface opposite the first surface, and a discrete segment protruding from at least one of the first and second surfaces of the substrate. The discrete segment includes a fungicide. The fungicide remains active before and after being subjected to AATCC Test Method 130-2000, section 8 with a water temperature of approximately 4l°C and using 1993 AATCC Standard Reference Detergent.

The details of one or more examples of the disclosure are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the disclosure will be apparent from the description and drawings, and from the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. l is a perspective view of a scouring article having a texture layer of the present invention.

FIG. 1 A is an enlarged plan view of a portion of the surface of the texture layer of

FIG. 1.

FIG. 2A is a picture of the zone of inhibition before durability testing of

Formulation FM1 (control), as reported in Table 3. FIG. 2B is a picture of the zone of inhibition after durability testing of Formulation FM2, as reported in Table 3.

FIG. 2C is a picture of the zone of inhibition after durability testing of Formulation FM16, as reported in Table 3.

The illustrated embodiments are not intended to be exhaustive of all embodiments according to the invention. It is to be understood that other embodiments may be utilized and structural or logical changes may be made without departing from the scope of the present invention.

DETAILED DESCRIPTION

FIGS. 1 and 1 A show a perspective view and an enlarged plan view, respectively, of a scouring article 10 of the present invention including a fungicidal texture layer 12 on at least one surface of the scouring article 10. The fungicidal texture layer 12 of the scouring article 10 is both durable and provides controlled release of the fungicide, providing a zone of inhibition from fungal bacteria for an extended amount of time. The fungicidal texture layer 12 of the scouring article 10 is effective even after high curing temperatures. For example, even after curing at l75°C, the fungicidal texture layer retained its properties, demonstrating a zone of inhibition in microbiological tests both before and after durability tests.

The scouring article 10 may be described as a consumer cleaning or scouring article. As used throughout this Specification, the term“consumer” is in reference to any household, cosmetic, industrial, hospital or food industry applications and the like of the scouring article. Certain embodiments can be used as scrub sponges, for example. Further as used throughout this Specification, the term“scouring” is used to describe surface treating and may include cleaning, abrading, including various levels or degrees of abrading action (e.g., heavy duty, non-scratch, etc.).

The scouring article 10 generally includes a substrate 14 and a texture layer 12.

The substrate 14 includes a first surface 16 and a second surface 18 opposite the first surface 16. The texture layer 12 is formed at least partially on the first surface 16 of the substrate 14 to create the scouring article 10, as shown in FIGS. 1 and 1A. The texture layer 12 is formed of a plurality of discrete segments 20 projecting from the surface on which it is formed. In one embodiment, the texture layer 12 covers the entirety of the first surface 16 of the substrate 10. In another embodiment, the texture layer is each individual discrete segment.

The substrate 14 can be composed of any variety of materials having various properties. For example, the substrate 14 may be absorbent, having the ability to absorb a material (e.g., a liquid) reversibly, at least to some degree. Stated otherwise, an absorbent material can be defined as one that a liquid can penetrate into and, rather than trap and irreversibly hold the liquid, the material may release the liquid either by evaporation (drying) or physical force (e.g., hand pressure/wringing).

The materials and forms of the substrate 14 can be selected to provide varying ranges of desired properties, such as extensibility, elasticity, durability, flexibility, etc., that are particularly suited to a given scouring task and/or are particularly suited to depositing or forming of a texture composition thereon. Any substrate material or combination of materials suitable for use as a consumer scouring article can be used including, without limitation, various woven, knitted, and non-woven materials. In one embodiment, the substrate can be a nonwoven web constituted of a network of synthetic fibers of filaments which provide surfaces on which the texture layer is formed. In one embodiment, the substrate 14 may include, but is not limited to, a cellulosic foam or polyurethane. Although the specification describes the substrate 14 primarily as being a nonwoven, the substrate 14 can be any material known in the art, including, but not limited to: a film, a slurry, or a foam. The substrate 14 can also take on any form known in the art, including, but not limited to: a sheet, cloth, or sponge.

The scouring article 10 may be composed of the texture layer 12 disposed on a single substrate 14, or may be composed of the texture layer 12 disposed on a first substrate, which is disposed on a second substrate. This construction allows the scouring article 10 to exhibit a number of properties. For example, the scouring article 10 may have absorbent properties on one surface and scouring/abrasive properties on the opposite surface. In one embodiment, the texture layer is disposed on a nonwoven fabric or sheet. In one embodiment, the texture layer is disposed on a nonwoven web, which is disposed on a sponge to form a scrub sponge article.

In addition to the properties provided by the substrate 14, the scouring article 10 also provides a scouring or abrasive attribute that is given by the texture layer 12. The term“scouring” is in reference to an ability to abrade or remove a relatively small, undesirable item otherwise affixed to a surface as the scouring article is moved back and forth over the item, as described more fully below. The performance of the texture layer 12 is also affected by the extent to which the discrete segments 20 extend from or beyond the substrate surface, in conjunction with side-to-side spacing between discrete segments of the texture layer 12. In one embodiment, the texture layer 12 has a discrete segment density (i.e., percentage of the surface covered by the discrete segments) of between about 2 and about 80%, particularly between about 5 and about 50%, and more particularly between about 10 and about 20%.

As mentioned above, the texture layer 12 is defined by a plurality of discrete segments 20 (e.g., the various dot-like portions shown in FIGS. 1 and 2). The discrete segments 20 may form a randomly textured surface or may form a pattern on the substrate surface 16. Further, the discrete segments 20 may include varying relative sizes or may be substantially uniform in size. Further, the discrete segments 20 may extend or project outwardly from the surface at substantially uniform distances or, alternatively, may extend or project outwardly from the surface at varying distances. In some embodiments, discrete segments 20 may extend to a distance of 500 microns or less outwardly from the substrate surface. In other embodiments, the discrete segments 20 may extend to any distance in a range of about 10 to about 500 microns outwardly from the substrate surface. In still further embodiments, discrete segments 20 may extend to any distance in a range of about 10 to about 20 microns outwardly from the substrate surface.

In practice, during a scouring application, a user may position the scouring article 10 such that one or the other of the first and second surfaces 16, 18 of the substrate 14 is facing the surface to be cleaned. FIG. 1 illustrates the scouring article 10 in a position such that the first surface 16 having the texture layer 12 formed thereon is facing the surface to be scrubbed. In FIG. 1, the scouring article 10 is positioned to clean or otherwise treat the surface. As should be understood, the surface to be cleaned is application specific, and can be relatively hard (e.g., a table top or cooking pan) or relatively soft (e.g., human skin, polymeric baking vessels, etc.). Regardless, in the exemplary embodiment of FIG. 1, the surface to be cleaned may have a mass that is undesirably affixed thereto. Again, the mass will be unique to the particular scrubbing application, but includes matters such as dirt, dried food, dried blood, etc. The scouring article 10 , and in particular the surface having the textured layer thereon, facilitates removal of the mass as a user repeatedly forces the texture layer (or a portion or section thereof) back and forth across the mass. Each section of the texture layer 12 must be sufficiently hard to either abrade or entirely remove the mass during the scrubbing motion. Further, it is desirable that the texture layer 12 has abrasion resistance such that the composition forming the texture layer remains substantially intact on the substrate during and after the scouring article is used to clean a surface.

As discussed above, the texture layer 12 is an abrasive, fungicidal composition.

The exact composition of the texture layer 12 can vary depending upon desired end performance characteristics. To this end, a texture layer composition is initially formulated and then deposited or formed on the substrate. The texture layer generally includes a binder, an abrasive, and a fungicide.

Useful binder resins in accordance with the present disclosure can assume a wide variety of forms and are generally selected to promote robust securement of the texture layer to the particular format of the substrate. The binder resin can include a resin capable of solidifying or hardening by various mechanisms, such as drying/release of water, exposure to external energy (e.g., heat, UV light, electron beam irradiation, etc.), and with or without crosslinking. Some acceptable binder resins include those binder resins selected from the group consisting of polyolefins, styrene-butadiene resin, acrylic resin, phenolic resin, nitrile resin, ethylene vinyl acetate resin, polyurethane resin, styrene-acrylic resin, vinyl acrylic resin and combinations thereof. Other non- limiting examples of binder resins useful with the present disclosure include amino resins, alkylated urea-formaldehyde resins, melamine-formaldehyde resins, modified acrylic resins (including acrylates and methacrylates) such as vinyl acrylates, acrylated epoxies, acrylated urethanes, acry!ated polyesters, acrylated acrylics, acrylated polyethers, vinyl ethers, acrylated oils, and acrylated silicones, alkyd resins such as urethane alkyd resins, polyester resins, reactive urethane resins, phenolic resins such as resole and novolac resins, phenolic/latex resins, epoxy resins, and the like. The resins may be provided as monomers, oligomers, polymers, or combination thereof. Monomers may include multifunctional monomers capable of forming a crosslinked structure, such as epoxy monomers, olefins, styrene, butadiene, acrylic monomers, phenolic monomers, substituted phenolic monomers, nitrile monomers, ethylene vinyl acetate monomer, isocyanates, vinyl acrylic monomer and combinations thereof. Other non-limiting examples of binder resins useful with the present disclosure include amino acids, alkylated urea monomers, melamines, modified acrylic monomers (including acrylates and methacrylates) such as vinyl acrylates, acry!ated epoxies, acrylated urethanes, acrylated polyesters, acry!ated acrylics, acry!ated ethers, vinyl ethers, aerylated oils, and acrylated silicones, alkyd monomers such as urethane alkyd monomers, esters, and the like.

The binder resin is typically applied as a mixture with water, and optionally, a crosslinking agent that, where desired, promotes optional crosslinking of the polymer in the resin. Example of suitable binder resins with optional crosslinking embodiments of the present disclosure includes, for example, latexes such as a carboxylated styrene- butadiene emulsion available under the trade name Rovene 5900 from Mallard Creek Polymers of Charlotte, NC. Other examples include Rhoplex TR-407 available from Dow Company of New Jersey and Aprapoie SAFI 7 available from AP Resinas of Mexico City, Mexico. With embodiments in which crosslinking of the selected binder resin is desired, the texture layer composition can include an appropriate crosslinking agent such as, for example, melamine formaldehyde dispersions. Other optional crosslinking initiator, promoter or retardant agents can alternatively be provided as part of the formulation of the texture layer composition (e.g., that assist with optional UV crosslinking and/or e-beam crosslinking or polymerization).

With embodiments in which crosslinking of the selected binder resin is not necessary or intended, the binder resin can assume a variety of forms, and may or may not be a thermoplastic. The non-crosslinks ng binder resin can be a polyacrylate, modified polyacrylate, polyurethane, polyvinyl acetate, copolyamide, copolyester, or phenolic, as well as other latexes.

The particular binder resin and weight percent relative to the texture layer composition can be fine-tuned to satisfy the desired end application constraints. However, the selected binder resin is characterized as being flowable in matrix form in a manner that will soak only partially, if at all, into the substrate (i.e., will not soak through or wet out the substrate) upon forming thereon, and will harden, cure or coalesce optionally upon exposure to various conditions (e.g., heat, UV, e-beam, etc.). Additionally, the binder resin component of the texture layer is optionally non-ionic in some embodiments. The non ionic nature of the binder resin facilitates use of virtually any form of chemical solution with the scouring article where so desired. In one embodiment, the texture layer includes between about 20 and about 80 wt% binder, particularly between about 40 and about 75 wt% binder, and more particularly between about 60 and about 70 wt% binder.

The abrasive, or filler, is used to provide scouring efficacy to the texture layer 12. A wide variety of minerals or fillers as known in the art can be employed. Useful minerals include, but are not limited to, AI2O3, "Minex" (available from The Cary Co. of Addison, Illinois), S1O2, T1O2, etc. Exemplary fillers include, but are not limited to: CaCCb, talc, etc. Further, the particulate component may consist of inorganic, hard, and small particles. For example, the "Minex" mineral particulate component has a median particle size of 2 microns and a Knoop hardness of about 560. Of course, other particle size and hardness values may also be useful. The inorganic nature of the particulate component, in conjunction with the non-ionic resin component, renders the resulting texture layer amenable for use with any type of chemical solution. In one embodiment, the texture layer includes between about 5 and about 50 wt% abrasive, in particular, between about 15 and about 45 wt% abrasive, and more particularly between about 20 and about 40 wt% abrasive.

Certain fungicides have been found to give durable anti-fungal properties to the texture layer. The fungicide used in the texture layer of the present invention must have durability as well as provide a zone of inhibition. The fungicide is durable if it remains active before and after the scouring article has been subjected to AATCC Test Method 130-2000, section 8 with a water temperature of approximately 4l°C and using 1993 AATCC Standard Reference Detergent. A fungicide is considered“active” if it creates a zone of inhibition around it. In one embodiment, the fungicide provides a zone of inhibition of about 0.1 centimeters or greater, and particularly of about 0.2 centimeters or greater.

In one embodiment, suitable fungicides include zinc pyrithione, benzimidazole, thiabendazole, and benzisothiazolin. Particularly suitable fungicides include zinc pyrithione and benzimidazole. Ineffective fungicides included quaternary compounds, such as n-alkyl dimethyl benzyl ammonium chloride (ADBAC), soyethyl morpholinium ethosulfate, silane quaternary ammonium salt (AEM 5772), and the like. Non-durable agents included sodium pyrithione, propiconazole, chlorophenol, and 3- iodopropynylbutyl carbamate (IPBC). In one embodiment, the fungicide present in the scouring article protects from the fungal species Aspergillus brasiliensis . In one embodiment, the texture layer includes between about 0.05 and about 5 wt% fungicide, in particular between about 0.1 and about 2 wt% fungicide, and more particularly between about 0.3 and about 1 wt% fungicide.

To add the fungicide to the texture layer, a small amount of fungicide is added to the texture layer in the wet state, coated onto the substrate, then cured at high temperature to solidify the composition. In one embodiment, less than about 5% by weight of fungicide is added. In contrast to“loaded'’ articles, the fungicide is not sprayed or deposited onto, or absorbed into a finished texture layer of the present invention. Rather, the fungicide stays largely in place during use, providing a slow controlled release of fungicide to protect the scouring article from fungal attack over an extended period of use. Furthermore, because so little fungicide is used, the size of the texture layer does not visibly diminish as the fungicide is released, as shown during durability testing in which the texture layer does not appreciably abrade. In contrast,“loaded” articles provide release of chemical to clean and/or disinfect a surface being wiped, not protect the scouring article itself. Even if the chemicals used in“loaded” or disinfecting articles were incorporated into the texture layer of the present invention prior to curing, most would likely wash away completely during one wash cycle of the durability test described in the examples due to high water solubility, rendering them incapable of defending the scouring article.

Other materials can be added to the texture layer for special purposes, including, but not limited to: pigments, surfactants, silicone antifoams, thickeners, and water. In one embodiment, when included, the texture layer includes up to about 15 wd% surfactant, particularly between about 1 and about 10 wd% surfactant, and more particularly between about 2 and about 6 wt% surfactant. In one embodiment, when included, the texture layer includes up to about 10 wd% silicone antifoam, particularly between about 0.005 and about 5 wt% silicone antifoam, and more particularly between about 0.5 and about 1 wt% silicone antifoam. In one embodiment, when included, the texture layer includes up to about 10 wd% thickener, particularly between about 0.05 and about 5 wt% thickener, and more particularly between about 0.1 and about 1 wd% thickener. In one embodiment, when included, the texture layer includes up to about 10 wt% pigment, particularly between about 0.05 and about 8 wd% pigment, and more particularly between about 0.1 and about 5 wd% pigment. In one embodiment, when included, the texture layer includes up to about 50 wt% water. The texture layer composition can be formed on the substrate using a variety of known techniques such as printing, (e.g., screen printing, gravure printing, flexographic printing, etc.), coating (e.g., roll, spray, electrostatic), etching, laser etching, injection molding, micro-replication and embossing such as described in U.S. Provisional Patent Applications Serial Nos. 62/121,644 and 62/121,766, each incorporated by reference herein above.

Other known ingredients may be included within the scouring article 10 of the invention, as known to those skilled in the art. Examples include, but are not limited to: lubricants, wetting agents, dyes, coupling agents, plasticizers, suspending agents, antistatic agents, and the like. Detergents or soaps may also be coated over or otherwise applied to the articles of the invention in a known manner.

To make the scouring article 10 of the present invention, a single print/cure step is used. In one embodiment, the scouring article 10 is formed at a cure temperature of up to about 350°F (l75°C) for about 3 minutes and particularly up to about 400°F (204°C). In one embodiment, the texture layer 12 has a coating weight of between about 10 and about 500 g/m2, particularly between about 20 to about 300g/m2, and more particularly between about 40 to about 130 g/m2 when coated onto a substrate, such as a nonwoven fabric, of between about 40 and about 400 g/m2, particularly between about 50 and 240 g/m2, and more particularly between about 80 and about 130 g/m2.

In an embodiment where the scouring article is a scrub sponge, the scrub sponge can be made by disposing the texture layer on a first side of a nonwoven web. In one embodiment, the nonwoven web is abrasive. The second side of the nonwoven web is then sprayed with a spray adhesive to bind the nonwoven web to a layer of cellulose sponge or polyurethane foam. A side of a cellulose sponge or polyurethane foam is then sprayed with spray adhesive. Suitable adhesives can be readily selected by those skilled in the art. Illustrative examples of suitable adhesives include, but are not limited to: water- based adhesives, solvent-based adhesives, hot melt adhesives, moisture-curing adhesives, pressure-sensitive adhesives, contact and thermosetting type adhesives. Suitable chemistries could include acrylates, urethanes, silicones, epoxies, melamines, phenols, isocyanates, isocyanurates, polymer-dispersion, and rubber-based polymer solutions or suspensions. The adhesive can be applied, for example, by coating, spraying, dipping, foaming, screen-printing, adhesive-transfer, etc. The abrasive layer might be substantially continuous or may be patterned. The two adhesive coated sides are then immediately joined together under pressure until bonded. In one embodiment, the sides are joined together under about 3500 Pa pressure. In one embodiment, the sides are bonded after about 10 minutes. Scrub sponges are then cut to a desired size by slitting, die cutting, cross cutting, laser cutting, etc.

Although the article of the present disclosure has been described with reference to specific exemplary embodiments, those of ordinary skill in the art will readily appreciate that changes and modifications may be made thereto without departing from the spirit and scope of the present disclosure.

EXAMPLES

The present invention is more particularly described in the following examples that are intended as illustrations only, since numerous modifications and variations within the scope of the present invention will be apparent to those skilled in the art. ETnless otherwise noted, all parts, percentages, and ratios reported in the following examples are on a weight basis.

MATERIALS

PREPARATION OF SOLUTION

Solutions of the invention were prepared as follows. All ingredients were weighted out to the nearest 0.01 grams in separate plastic containers in desired quantities. A mixture was prepared by sequentially adding all ingredients to a rigid plastic container that was stirred continuously using a high shear mixing blade (commercially available from Premier Mill Corporation, Temple, PA, USA under the trade designation“Dispersator”). Ingredients were added in order as listed in Tables 1 and 2 below. After all the ingredients 5 were added, the mix was stirred for an additional 5-10 minutes. The formulations (FM) are provided in Table 1.

Table 1

10 Table 1 continued

Examples 1-19

Nineteen sample scouring articles were prepared with each of the Formulations 1- 19. A rectangular specimen (non-woven fabric) with approximate dimensions of 30 cm x 5 20 cm was secured on a flat laboratory bench by applying adhesive tape on its edges.

Next, a metal stencil with the desired printing pattern was placed on top of the substrate specimen. Approximately 50 grams of the prepared printing mixture was placed on the stencil with the help of a wooden applicator. The printing mixture was then applied on the printing pattern of the stencil with a shearing motion while applying hand pressure 10 downwards and with the help of a hand-held squeegee. It was observed that the printing mixture filled the holes of the printing pattern and was transferred onto the substrate specimen. The stencil was removed and the printed substrate specimen was placed into a laboratory, hot air circulating oven (Model VRC2-35-1E, commercially available from DESPATCH INDUSTRIES, Minneapolis, MN, USA) for 3 minutes. The temperature of 15 the oven was set to l75°C.

TEST METHODS

Microbial test

The spore solutions were prepared as follows: first a pellet of Aspergillus 20 brasiliensis derived from ATCC® 9642™ LYFO DISK^® (approximate count per pellet was 2.3 * 10⁵) was added into 9 mL of peptone water to obtain a first spore solution. The first spore solution was designated as (-1) dilution spore solution. 1 mL of (-1) dilution spore solution was then added into 9 mL peptone water to obtain a second spore solution which was designated as the (-2) dilution spore solution. Finally, 1 mL of (-2) dilution spore solution was added into 9 mL peptone water to obtain a third spore solution which was designated as (-3) dilution spore solution.

3M™ Petrifilm™ Rapid Yeast and Mold (RYM) Count plates were inoculated as follows: A 3M Petrifilm RYM Plate was placed on a flat, level surface. The top film was lifted and 1 mL of the desired spore suspension was dispensed onto the center of the bottom film with the pipette perpendicular to the plate. The top film was then rolled down onto the spore solution. A 3M™ Petrifilm™ Flat Spreader (6425) was placed on the center of the 3M Petrifilm RYM Plate and the center of the spreader was pressed under gentle hand pressure to evenly distribute the sample. The inoculum was spread over the entire 3M Petrifilm RYM Plate growth area before a gel was formed.

The 3M Petrifilm Flat Spreader was then removed and the 3M Petrifilm RYM Plate was left undisturbed for at least 10 minutes to permit a gel to form. After a gel had formed, the top film was lifted with the gel and a 1.9 cm disk cut from the printed substrate was introduced onto the center of bottom film. The top film was rolled down onto the sample. 3M™ Petrifilm™ Flat Spreader (6425) was placed on the center of the 3M Petrifilm RYM Plate and the center of the spreader was pressed under gentle hand pressure to distribute the gel evenly and to remove any bubbles that might have formed. 3M Petrifilm RYM Plates were incubated at between 25°C +/- l°C and 28°C +/-l°C for 72 hours in a horizontal position with the clear side up, in stacks of no more than 40 plates. Results were visually analyzed after 72 hours. In some samples, no mold growth was observed (neither on the textured substrate, nor in the zones adjacent to the substrate). Such samples were considered to exhibit a zone of inhibition and designated as samples with antimicrobial properties. For these samples, the zone of inhibition was measured using a ruler. In other samples, mold growth was observed either on the textured substrate or in the zones adjacent to the substrate. Such samples were considered not to exhibit a zone of exhibition and were designated as without antimicrobial properties. Durability test

Printed substrate specimens that initially demonstrated antifungal properties were tested for durability by using the washing procedure described in AATCC Test Method 130-2000, section 8, with a water temperature of approximately l05°F (4l°C) and using 1993 AATCC Standard Reference Detergent. The specimens were then re-evaluated using the microbial test described above.

Results are reported in Table 3, at spore dilution levels of -2 (dil -2) and -3 (dil -3). The zone of inhibition was measured in centimeters and was recorded as a range.

Measurements were taken on samples both before and after the durability test, unless the sample did not show an initial zone of inhibition. Pictures of the zone of inhibition after durability testing of FM1, FM6 and FM16 are shown in FIGS. 2A, 2B, and 2C, respectively.

Table 3

As can be seen by the results, none of the examples made with quaternary ammonium compounds demonstrated a zone of inhibition, even at high concentrations. Examples made with most other fungicides demonstrated a zone of inhibition, at least prior to the durability test. After the durability test, however, only examples made with zinc pyrithione, certain fungicides based on azole chemistry, benzisothiazolin, or mixtures thereof remained active, or demonstrated a zone of inhibition around the specimens.

The foregoing Examples have been provided for clarity of understanding only, and no unnecessary limitations are to be understood therefrom. The tests and test results described in the Examples are intended to be illustrative rather than predictive, and variations in the testing procedure can be expected to yield different results. All quantitative values in the Examples are understood to be approximate in view of the commonly known tolerances involved in the procedures used.

It will be apparent to those skilled in the art that the specific exemplary elements, structures, features, details, configurations, etc., that are disclosed herein can be modified and/or combined in numerous embodiments. The present invention may suitably comprise, consist of, or consist essentially of, any of the disclosed or recited elements. As used herein, the term "consisting essentially of' does not exclude the presence of additional materials which do not significantly affect the desired characteristics of a given

composition or product. In particular, any of the elements that are positively recited in this specification as alternatives, may be explicitly included in the claims or excluded from the claims, in any combination as desired. All such variations and combinations are contemplated by the inventor as being within the bounds of the conceived invention, not merely those representative designs that were chosen to serve as exemplary illustrations. Thus, the scope of the present invention should not be limited to the specific illustrative structures described herein, but rather extends at least to the structures described by the language of the claims, and the equivalents of those structures. To the extent that there is a conflict or discrepancy between this specification as written and the disclosure in any document incorporated by reference herein, this specification as written will control.

Claims

WHAT IS CLAIMED IS:

1. A scouring article comprising:

a substrate having a first surface and a second surface opposite the first surface; and a texture layer formed on at least one of the first and second surfaces of the substrate, wherein the texture layer comprises a plurality of discrete segments, and wherein the texture layer includes a fungicide;

wherein the fungicide remains active before and after being subjected to AATCC Test

Method 130-2000, section 8 with a water temperature of approximately 4l°C and using 1993 AATCC Standard Reference Detergent.

2. The scouring article of claim 1, wherein at least one of the discrete segments has a zone of inhibition at an Aspergillus brasiliensis spore count of 10⁴ before and after being subjected to AATCC Test Method 130-2000, section 8 with a water temperature of approximately 4l°C and using 1993 AATCC Standard Reference Detergent.

3. The scouring article of claim 1, wherein the texture layer demonstrates a zone of inhibition at an Aspergillus brasiliensis spore count of 10⁴ before and after being subjected to AATCC Test Method 130-2000, section 8 with a water temperature of approximately 4l°C and using 1993 AATCC Standard Reference Detergent.

4. The scouring article of claim 1, wherein the texture layer demonstrates a zone of inhibition at an Aspergillus brasiliensis spore count of 10⁴ of about 0.1 centimeters or greater before and after being subjected to AATCC Test Method 130-2000, section 8 with a water temperature of approximately 4l°C and using 1993 AATCC Standard Reference Detergent.

5. The scouring article of claim 1, wherein the texture layer demonstrates a zone of inhibition at an Aspergillus brasiliensis spore count of 10⁴ of about 0.2 centimeters or greater before and after being subjected to AATCC Test Method 130-2000, section 8 with a water temperature of approximately 4l°C and using 1993 AATCC Standard Reference Detergent.

6. The scouring article of claim 1, wherein the fungicide comprises one of zinc pyrithione and an azole compound.

7. The scouring article of claim 1, wherein the texture layer further comprises: a binder; and

an abrasive.

8. The scouring article of claim 7, wherein the texture layer comprises:

between about 20 and about 80 weight percent binder; and

between about 5 and about 50 weight percent abrasive.

9. The scouring article of claim 1, wherein the texture layer has a discrete segment density of between about 10 and about 20%.

10. A scouring article comprising:

a substrate having a first surface and a second surface opposite the first surface; and a discrete segment protruding from at least one of the first and second surfaces of the substrate, wherein the discrete segment includes a fungicide;

11. The scouring article of claim 10, wherein the discrete segment demonstrates a zone of inhibition at an Aspergillus brasiliensis spore count of 10⁴ before and after being subjected to AATCC Test Method 130-2000, section 8 with a water temperature of approximately 4l°C and using 1993 AATCC Standard Reference Detergent.

12. The scouring article of claim 10, wherein the discrete segment demonstrates a zone of inhibition at an Aspergillus brasiliensis spore count of 10⁴ of about 0.1 centimeters or greater before and after being subjected to AATCC Test Method 130-2000, section 8 with a water temperature of approximately 4l°C and using 1993 AATCC Standard Reference Detergent.

13. The scouring article of claim 10, wherein the discrete segment demonstrates a zone of inhibition at an Aspergillus brasiliensis spore count of 10⁴ of about 0.2 centimeters or greater before and after being subjected to AATCC Test Method 130-2000, section 8 with a water temperature of approximately 4l°C and using 1993 AATCC Standard Reference Detergent.

14. The scouring article of claim 10, wherein the fungicide comprises one of zinc pyrithione, benzisothiazolin, and an azole compound.