Cleaning supplies

Abstract

A cleaning article is provided, the cleaning article comprising a nonwoven fibrous web, which may be a vertically wrapped nonwoven web or a nonwoven web having fibers substantially oriented at an angle of 45 degrees to 90 degrees relative to a major surface along an interior portion of the nonwoven fibrous web. The outer surface of the nonwoven fibrous web comprises a densified layer extending throughout the nonwoven fibrous web, the densified layer comprising a coating received within voids in the nonwoven fibrous web, regions of heat-induced compression, or a combination thereof.

Description

[Technical Field]

[0001] Cleaning articles, particularly those useful for household scrubbing applications, and methods and assembly thereof are provided. [Background technology]

[0002] Scrubbing pads are widely used to clean surfaces in the home, including surfaces in homes, and surfaces in vehicles. Scrubbing pads are typically used with water and soap or detergent, and the scrubbing surface of the scrubbing pad is used to clean surfaces. Such surfaces include dishes, utensils, glasses, pots, pans, grills, walls, floors, countertops, and vehicle surfaces and windows.

[0003] Scrubbing materials are manufactured in a variety of forms, including nonwoven webs (e.g., the low-density nonwoven abrasive web described in U.S. Pat. No. 2,958,593 (Hoover et al.)). After manufacture, the web of scrubbing material may be cut into individual pieces sized for manual use (e.g., rectangular pads described in U.S. Pat. No. 2,958,593 (Hoover et al.)), or the web may be separated into convenient sizes by the end user as needed (e.g., as described in WO 00 / 006341 (Mateos et al.) and U.S. Pat. No. 5,712,210 (Windisch et al.)). An example of a non-scratch scrubbing pad is sold under the trade name "SCOTCH-BRITE" by 3M Company, St. Paul, Minnesota. A specific example of a non-scratch scrubbing pad is the "SCOTCH-BRITE Dobie Cleaning Pad" sold by 3M Company, St. Paul, Minnesota, which is composed of a polyurethane foam pad enclosed in a net or mesh. Summary of the Invention

[0004] The present disclosure describes the use of nonwoven fibers in structures that resemble conventional foam (i.e., polyurethane) sponges in physical properties and appearance, but with significant sustainability advantages. Nonwoven fibrous webs are provided that are at least partially densified to provide cleaning articles suitable for scrubbing applications without the need for encapsulation in a separate net or mesh. Such densified nonwoven fibrous webs can be manufactured from sustainable or recycled polymers and can overcome the technical shortcomings of conventional cleaning articles related to durability, scrubbing performance, and compression resistance, while maintaining adequate softness and hydrophilicity.

[0005] In a first aspect, a cleaning article is provided, the cleaning article comprising a nonwoven fibrous web having fibers oriented along an interior portion thereof substantially at an angle between 45 degrees and 90 degrees relative to a major surface thereof, the outer surface of the nonwoven fibrous web comprising a densified layer extending throughout the nonwoven fibrous web, the densified layer comprising a coating received within voids in the nonwoven fibrous web, regions of heat-induced compression, or a combination thereof.

[0006] In a second aspect, a cleaning article is provided, the cleaning article comprising a nonwoven fibrous web, including a vertically wrapped nonwoven web, an outer surface of the cleaning article comprising a densified layer extending across the nonwoven fibrous web, the densified layer comprising either a coating received within voids of the nonwoven fibrous web, regions of heat-induced compression, or a combination thereof, and further wherein the densified layer has a solidity of 0.2% to 10%.

[0007] In a third aspect, there is provided a method for manufacturing a cleaning article, the method comprising: providing a nonwoven fibrous web having fibers substantially oriented at angles between 45 degrees and 90 degrees along an interior portion thereof; and densifying the nonwoven fibrous web to obtain a densified layer, the densified layer characterized by a density between 10% and 1000% of the solidity of the original undensified state, wherein an outer surface of the nonwoven fibrous web comprises the densified layer.

[0008] In a fourth aspect, a cleaning assembly is provided, the cleaning assembly including a cleaning article and a substrate having a mounting surface removably associated with the cleaning article. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a cross-sectional view of a precursor material useful for making the cleaning articles described herein. [Figure 2] 1 is a cross-sectional view of a precursor material useful for making the cleaning articles described herein. [Figure 3] FIG. 1 is a side view of a cleaning article according to various embodiments. [Figure 4] FIG. 1 is a side view of a cleaning article according to various embodiments. [Figure 5] FIG. 1 is a side view of a cleaning article according to various embodiments. [Figure 6] FIG. 1 is a schematic diagram illustrating an example of a method for manufacturing a cleaning article. [Figure 7] 1 is a cross-sectional optical micrograph showing a densified nonwoven fibrous web useful for making cleaning articles. [Figure 8] 8A to 8D are photographs showing plan views of cleaning articles according to four different embodiments. [Figure 9] 9A to 9D are photographs showing the results of durability tests of cleaning articles reported in the examples. [Figure 10] FIG. 1 is a perspective view of a cleaning assembly in which a cleaning article is removably combined with a functional substrate. [Figure 11]FIG. 1 is a perspective view of a cleaning assembly in which a cleaning article is removably combined with a functional substrate.

[0010] Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present disclosure. It is to be understood that numerous other modifications and embodiments may be devised by those skilled in the art within the scope and spirit of the principles of the present disclosure. The drawings may not necessarily be drawn to scale. DETAILED DESCRIPTION OF THE INVENTION

[0011] [Definition] As used herein: "Room temperature" means 21°C. "Density," as applied to nonwoven webs, refers to sponge density as measured according to the test method in the Examples. "Substantially" means at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97%, or 100%.

[0012] [Detailed explanation] As used herein, the terms "preferred" and "preferably" refer to embodiments described herein that may offer certain advantages, under particular circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

[0013] In this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a component preceded by "a" or "the" can include one or more of that component, and equivalents thereof known to those of ordinary skill in the art. Furthermore, the term "and / or" means any one, all, or any combination of two or more of the listed elements. The terms "comprise" and variations thereof do not have a limiting meaning when these terms appear in the description. Additionally, the terms "a," "an," "the," "at least one," and "one or more" are used interchangeably herein. Relative terms such as left, right, front, rear, top, bottom, lateral, upper, lower, horizontal, vertical, etc., may be used herein, and when so used, are from the perspective observed in a particular drawing. These terms are intended to simplify the description and are not intended to limit the scope of the invention in any way.

[0014] Throughout this specification, the references to "one embodiment," "a particular embodiment," "one or more embodiments," or "an embodiment" mean that the particular feature, structure, material, or characteristic described in connection with that embodiment is included in at least one embodiment of the invention. Thus, the appearances of phrases such as "in one or more embodiments," "a particular embodiment," "in one embodiment," or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment.

[0015] 1 and 2 show cross-sectional views of nonwoven webs used as precursor materials in the manufacture of cleaning articles, where the nonwoven webs are designated by the numerals 50 and 60, respectively. These figures are illustrative and illustrate the differences in the internal fiber structures of these webs: nonwoven web 50 was produced using an airlaid process, and nonwoven web 60 was produced using a vertical lapping process.

[0016] Each of the nonwoven fibrous webs 50, 60 can be made from a blend of structural and adhesive fibers, either of which may be staple fibers. Structural staple fibers are typically monocomponent. Materials useful in the provided articles include, but are not limited to, polyethylene terephthalate (PET), polyamide, wool, polyvinyl chloride, and polyolefins (e.g., polypropylene).

[0017] Structural fibers can be made from virgin sources or sustainable sources, such as biodegradable, bio-based, reusable, or compostable, or can be made from recycled materials. Examples of sustainable materials include natural fibers, naturally derived fibers, recycled synthetic fibers, or biodegradable synthetic fibers. Examples of natural fibers include bamboo, sisal, agave, coconut, flax, hemp, and cotton. Examples of naturally derived fibers include rayon, bamboo-derived rayon, and polylactic acid (PLA). Examples of recycled synthetic fibers include recycled PET, recycled nylon, and recycled polyolefin. Examples of biodegradable synthetic fibers include viscose, as well as melt-processable fibers such as polylactic acid (PLA), polybutylene succinate (PBS), polyglycolic acid, polyesteramides, dimer acid polyamides, polyhydroxyalkanoates (PHAs), polyhydroxybutyrates (PHBs), blends of PLA / PBS, blends of PLA / dimer acid polyamides, blends of PBS / dimer acid polyamides, blends of PHA / PHB, blends of PHA / PLA, and blends of PHA / PBS.

[0018] Both crimped and uncrimped structural fibers can be used to prepare the nonwoven web of the provided articles. In some embodiments, the structural fibers are crimped fibers, preferably having 1 to 10 crimps / cm, more preferably 1 to 5 crimps / cm. In some embodiments, the structural fibers may have at least 1, 1.5, or 2 crimps / cm. In some embodiments, the structural fibers may have up to 10, 5, or 2 crimps / cm.

[0019] The length of structural fibers suitable for use in the nonwoven web of the provided articles is not particularly limited and may be from 15 mm to 150 mm, from 20 mm to 75 mm, from 25 mm to 50 mm, and in some embodiments, less than, equal to, or greater than: 15, 20, 25, 30, 35, 40, 45, 50, 60, 75, 80, 100, 125, or 150 mm.

[0020] The diameter of structural fibers can vary widely, and such variations can significantly alter the physical properties of the stabilized nonwoven web. Generally, finer denier fibers decrease the compressive strength of the nonwoven web, while larger denier fibers increase it. Useful fiber denier values ​​for structural fibers can range from 1 to 100 denier, 1 to 50 denier, or 1 to 15 denier, and blends or mixtures of fiber denier values ​​are often used to impart desired mechanical properties to the nonwoven web. In some embodiments, structural fibers may have a denier of at least 1, 3, 6, 15, 50, 60, or 100. In some embodiments, structural fibers may have a denier of up to 100, 60, 50, 15, 6, 3, or 1. A small amount (e.g., less than 20% by weight) of microfibers, preferably meltblown microfibers in the range of 2 to 10 μm, can also be incorporated into the nonwoven web of the provided article.

[0021] Various bonding fibers are suitable for use in stabilizing the nonwoven web of the provided article, including amorphous meltable fibers, adhesive-coated fibers that may be discontinuously coated, and bicomponent bonding fibers, which have an adhesive component and a support component arranged along the length of the fiber in a side-by-side, concentric sheath-core, or elliptical sheath-core configuration, with the adhesive component forming at least a portion of the outer surface of the bicomponent fiber. The adhesive component of the bondable fiber can be bonded by, for example, heat, solvent bonding, solvent vapor bonding, and salt bonding. The adhesive component of the thermal bonding fiber must be heat-activatable (i.e., meltable) at a temperature below the melting point of the structural staple fiber of the nonwoven web.

[0022] Depending on the desired durability and handling characteristics of the resulting article, a range of adhesive fiber sizes, such as 1 to 15 denier, can be useful. In some embodiments, the adhesive fibers may have a denier of at least 1, 4, or 15. In some embodiments, the adhesive fibers may have a denier of up to 15, 4, or 1. As with structural fibers, smaller denier adhesive fibers reduce the compressive strength of the nonwoven web, while larger denier adhesive fibers improve the compressive strength of the nonwoven web. The adhesive fiber length can be 15 to 100 mm, 25 to 100 mm, or 25 to 75 mm, with fibers up to 150 mm in length also being useful. Preferably, the adhesive fibers are crimped, having 1 to 10 crimps / cm, more preferably 2 to 5 crimps / cm. Adhesive powders and sprays can also be used to bond the structural fibers.

[0023] Particularly useful adhesive fibers for stabilizing the nonwoven web of the provided article are crimped sheath-core adhesive fibers having a crystalline polyethylene terephthalate core surrounded by a sheath of an adhesive polymer formed from isophthalate and terephthalate ester. The sheath is heat-softenable at a lower temperature than the core material. Certain fibers, such as those available under the trade name MELTY from Unitika Co., Ltd. (Osaka, Japan), are particularly useful in preparing the nonwoven web of the provided article. Other sheath / core adhesive fibers can also be used to improve the properties of the nonwoven web of the provided article. Representative examples include fibers with a high modulus core to improve the resilience of the nonwoven web and fibers with a sheath that has better solvent resistance to improve the dry-cleanability of the nonwoven web.

[0024] The amount of structural staple fibers and adhesive staple fibers in the nonwoven web of the provided articles can vary over a wide range. Generally, the nonwoven web preferably comprises 0-90 weight percent structural fibers and 10-100 weight percent adhesive fibers, and more preferably 60-90 weight percent structural fibers and 10-40 weight percent adhesive fibers. In some embodiments, the nonwoven web may comprise at least 0, 20, 40, 50, 60, 70, 80, or 90 weight percent structural fibers. In some embodiments, the nonwoven web may comprise up to 90, 80, 70, 60, 50, 40, 20, or 0 weight percent structural fibers. In some embodiments, the nonwoven web may comprise at least 10, 20, 40, 50, 60, 70, 80, 90, or 100 weight percent adhesive fibers. In some embodiments, the nonwoven web may include up to 100, 90, 80, 70, 60, 50, 40, 20, or 10 weight percent bonding fibers.

[0025] The nonwoven web of the provided article can be formed from an airlaid web formed from a blend of structural staple fibers and bonding staple fibers. These webs can be produced on equipment such as airlaid machines available from Rando Machine Corp. of Macedon, New York, USA, and have a shingled structure unique to the process. Figure 1 shows a representative cross-section of an airlaid web formed on a RANDO WEBBER airlaid machine. The fibers are laid down in shingles, with the shingles typically inclined at an angle of 10 to 40 degrees relative to the major surface of the web. The most important factors affecting the shingle angle include the length of the fibers used to form the web, the type of collector used on the machine, and the basis weight of the web.

[0026] Longer fibers generally produce webs with higher shingle angles than shorter fibers. Webs with lower basis weights generally have lower shingle angles than similar webs with higher basis weights. The collector is typically an angled wire or perforated metal cylinder, with cylinders being preferred. Smaller diameter cylinders produce webs with higher shingle angles than larger diameter cylinders. The length of the web contact zone on the collector, i.e., the distance the web contacts the collector cylinder, also affects the shingle angle; the longer the contact distance, the lower the shingle angle.

[0027] The web shingle structure can be advantageously utilized to create a web structure with superior thermogravimetric efficiency compared to down and the resilience of down. By reconfiguring the fiber orientation within the shingle structure from its original shallow angle of 10 to 40 degrees to an angle of at least 50 degrees or greater, preferably at least 60 degrees, and most preferably approaching 90 degrees at the center along the web's thickness, as shown in Figure 1, the web can adopt a substantially columnar structure that can withstand compressive loads and provide a lower bulk density than that associated with the starting web. The reconfigured web structure takes advantage of the natural resilience of the fibers by orienting them substantially longitudinally with respect to compressive forces applied to the web.

[0028] The nonwoven web of the provided article can also be formed from a vertically wrapped web formed from a blend of structural staple fibers and adhesive staple fibers. In the vertical wrapping process, the blend of structural and adhesive fibers is first converted into a nonwoven web using standard fiber mixing and carding equipment known to those skilled in the art. The vertical wrapping machine converts a preformed nonwoven web into a nonwoven mat by folding the input web back and forth vertically onto itself, resulting in a nonwoven mat having a highly oriented vertical wrapping structure in the Z direction. Figure 2 shows a representative cross-section of a vertically wrapped web formed by a vertical wrapping machine. Such vertical wrapping nonwoven mats can be constructed using the apparatus described in International Publication No. WO 99 / 61693, "A DEVICE FOR PERPENDICULAR STRATIFICATION OF PLANARY FIBROUS SHAPES," incorporated herein by reference, or using the V-Lap Vertical Lapping System manufactured by V-Lap PTY Ltd, Australia (e.g., as described in International Publication No. WO 2006 / 092029, incorporated herein by reference), or using STRUTO material manufactured using a Struto system (Struto International Inc.) (described in Russell SJ, Handbook of Nonwovens, Chapter 2.12, Woodhead Publishing Limited, Cambridge, England, 2007, incorporated herein by reference). The fiber orientation angle in the vertical wrapping nonwoven mat is at least greater than 60 degrees, preferably at least 75 degrees, and most preferably approaches 90 degrees relative to the major surface of the web, as shown in FIG. 2.

[0029] In preferred embodiments, the nonwoven fibrous web has fibers along its interior portion that are substantially oriented at angles between 45° and 90°, 60° and 90°, or 80° and 90° relative to the major surface. As used herein, "substantially oriented" means that when the nonwoven web is viewed in cross section, a substantial proportion (or percentage) of the visible fibers have the specified orientation angle or range. The "interior portion" of the nonwoven web can be defined along the thickness of the nonwoven web, and can be, for example, an interior layer representing the central 25%, central 50%, or central 75%. In this disclosure, the substantial orientation of a nonwoven web is evaluated using the Fiber Perpendicularity Test described herein.

[0030] [Fiber perpendicularity test] A 10.2 cm x 15.3 cm (4 in x 6 in) sample is cut with the long edge parallel to the machine direction of the web. A cross-sectional photograph is taken in the machine direction. Using the Select Angle Tool in ImageJ software, two vectors are drawn along the 15.3 cm side of the sample. The first line is drawn along the flat base parallel to the length of the sample, and the second line is drawn approximately parallel to the central third of a representative web fiber. Fiber perpendicularity is reported as the angle between the two lines. The line measurement is repeated so that the angles of at least 10 different fibers are measured. The net orientation of the fibers is calculated based on the measured angles.

[0031] 3 illustrates a cleaning article 100 according to an exemplary embodiment. The article 100 is comprised of a nonwoven web 50 having opposed first and second major surfaces 102, 104, which have been subjected to a densification process. As illustrated, the nonwoven web 50 includes a densified layer 106 and a non-densified layer 108. These layers extend in a similar manner and are bounded along the outer surface of the nonwoven web 50 by the first and second major surfaces 102, 104, respectively. The densified layer 106 and the non-densified layer 108 are integral parts of the nonwoven web 50, with the densified layer 106 having a higher density than the non-densified layer 108.

[0032] Densification of the nonwoven web 50 can be achieved by applying a coating to the nonwoven web 50 such that the coating penetrates into the voids of the nonwoven fibrous web 50. Densification can also be achieved by simultaneously applying heat and pressure to the nonwoven web 50 to create regions of heat-induced compression. In a preferred embodiment, both of these methods are used together to provide a nonwoven web 50 that includes regions of heat-induced compression and also has a coating received within the voids.

[0033] The coating applied to the nonwoven web 50 can be provided by applying a coating composition to the nonwoven web 50 and then curing it to form the densified layer 106. In some embodiments, the coating composition is a curable coating composition prepared from a reaction mixture of a curable binder resin and optional abrasive particles. Optionally, the abrasive particles may be organic abrasive particles.

[0034] In some embodiments, the coated nonwoven web may have a thickness of at least 0.5, 1, or 1.5 cm. In some embodiments, the coated nonwoven web may have a thickness of up to 10, 5, or 4 cm.

[0035] In some embodiments, the basis weight of the coated nonwoven web may be at least 100, 200, 300, 400, 500, or 600 grams per square meter (gsm). In some embodiments, the basis weight of the coated nonwoven web may be up to 3000, 2500, 2000, 1500, 1000, or 600 gsm. The basis weight may be affected by how much coating is applied.

[0036] A curable binder resin is used to bond the abrasive particles to the nonwoven web 50. In some examples, the curable binder is provided in the form of a curable binder precursor that is sufficiently flowable to coat the surface of the nonwoven web 50. Solidification of the binder precursor can be achieved by curing (e.g., polymerization and / or crosslinking), drying (e.g., removal of liquid), and / or cooling. The binder precursor may be an organic solvent-based, water-based, or 100% solids (i.e., substantially solvent-free) composition. Thermoplastic and / or thermosetting polymers or materials, as well as combinations thereof, can be used as binder precursors. After curing of the binder precursor, the curable coating is converted into a hardened coating.

[0037] In one embodiment, the binder precursor is a condensation-curable resin or an addition-polymerizable resin. In one embodiment, the binder precursor is a curable organic material. Examples of suitable binder resins include thermosetting resins. Examples of thermosetting resins include, but are not limited to, phenolic resins, urea-formaldehyde resins, urethane resins, melamine resins, epoxy resins, bismaleimide binders, vinyl ether resins, aminoplast resins with pendant α,β-unsaturated carbonyl groups, acrylate resins, acrylate-isocyanurate resins, isocyanurate resins, acrylate-urethane resins, acrylate-epoxy resins, alkyd resins, and mixtures thereof.

[0038] In one embodiment, the addition-polymerizable resin may be an ethylenically unsaturated monomer and / or oligomer. Other binders that can be used to adhere the coating, optionally including abrasive particles, to the nonwoven web 50 include, but are not limited to, glues, varnishes, polyurethane resins, radiation-curable crosslinked acrylate binders, and the like. In one embodiment, the coating composition comprises 10% to 90% by weight of resin binder and 90% to 10% by weight of organic abrasive particles, particularly 15% to 80% by weight of resin binder and 20% to 85% by weight of organic abrasive particles, and more particularly 20% to 65% by weight of resin binder and 35% to 80% by weight of organic abrasive particles.

[0039] The binder resin may further include one or more mild abrasives. Suitable examples of mild abrasives include, but are not limited to, talc, calcium carbonate, melamine formaldehyde, calcium silicate, pumice, kaolin, and clay. When included, the mild abrasives are used in an amount of up to 50% by dry weight of the binder resin, up to 30% by dry weight of the binder resin, or up to 15% by dry weight of the binder resin.

[0040] The binder resin formulation may further include a toughening agent. In one embodiment, the toughening agent is a polymer latex, for example, selected from vinyl acetate, vinyl chloride, ethylene, styrene-butyl acrylate, and vinyl esters of versatic acid, polymers, and copolymers. The glass transition temperature of the polymer used as a toughening agent is typically in the range of 0°C to 50°C.

[0041] Other materials may be added to the binder resin for special purposes, including, but not limited to, grinding aids, fibers, lubricants, wetting agents, surfactants, pigments, dyes, coupling agents, plasticizers, antistatic agents, antibacterial agents, suspending agents, etc. Examples of antistatic agents include graphite, carbon black, conductive polymers, humectants, vanadium oxide, etc.

[0042] The optional organic abrasive particles can be formed from a resin binder. The curable resin binder precursor imparts bulk material properties to the resulting organic abrasive and, if present, also functions to bind mild abrasive particles within the organic abrasive to form the organic abrasive particles. The binder may be derived from the cured binder precursor. The agglomerated abrasive particles may contain abrasive particles of the same or different particle sizes. The organic abrasive particles may have any shape or size, and may be precisely shaped or irregularly and randomly shaped. The organic abrasive particles may be precisely shaped particles, as described in International Patent Publication No. WO 2019 / 215571 (Mevissen et al.). For example, the precisely shaped particles may be any three-dimensional shape, such as, but not limited to, pyramids, cones, blocks, cubes, spheres, cylinders, rods, triangles, hexagons, squares, etc. Furthermore, any combination of abrasive particle shapes can be used in the provided cleaning articles. In one embodiment, the organic abrasive particles are triangular, precisely shaped particles having a length of 100-800 μm, a width of 100-800 μm, and a depth of 50-500 μm.

[0043] Other materials can be added to organic abrasive particles for special purposes, including, but not limited to, crosslinkers, plasticizers, mild abrasives, acid catalysts, surfactants, antibacterial agents, antifungal agents, magnetic compounds, and glitter. Crosslinkers enable crosslinking of binder precursors. Plasticizers are curable binder precursors that can be added to resin binder systems to promote plasticity and reduce brittleness. Mild abrasives contribute to the flexural modulus of the cured binder system and can also function as mild abrasives. Acid catalysts have the ability to catalyze reactions of binder precursors. Surfactants can adjust the surface tension of the formulation or function as cleaning agents. Antibacterial agents can impart antibacterial properties to cleaning products.

[0044] In one embodiment, the organic abrasive particles comprise 35-100% by weight of a resin binder, up to 15% by weight of a crosslinker, up to 65% by weight of a plasticizer, up to 65% by weight of a mild abrasive, up to 10% by weight of an acid catalyst, and up to 10% by weight of a surfactant. Specifically, the organic abrasive particles comprise 45-90% by weight of a resin binder, up to 10% by weight of a crosslinker, 5-30% by weight of a plasticizer, 5-45% by weight of a mild abrasive, up to 8% by weight of an acid catalyst, and up to 8% by weight of a surfactant. More specifically, the organic abrasive particles comprise 65-85% by weight of a resin binder, up to 8% by weight of a crosslinker, 5-20% by weight of a plasticizer, 10-30% by weight of a mild abrasive, up to 5% by weight of an acid catalyst, and up to 5% by weight of a surfactant.

[0045] The organic abrasive particles are produced by sequentially adding and mixing the components in a mixer. The components are then cured and ground to the desired size. In one embodiment, the organic abrasive particles are ground to a size in the range of 50 to 500 μm, particularly 100 to 500 μm.

[0046] Precision-shaped particles can generally be produced according to the process described in International Patent Publication No. WO 2019 / 215571 (Mevissen et al.). Typically, precision-shaped particles are produced by forming a mixture containing at least a binder precursor. The binder resin may further contain mild abrasives, toughening agents, and other materials added to the binder resin for special purposes, including, but not limited to, grinding aids, fibers, lubricants, wetting agents, surfactants, pigments, dyes, coupling agents, plasticizers, antistatic agents, antibacterial agents, and suspending agents. The mixture is coated into a precision-shaped cavity of a production tool, the binder precursor is at least partially cured, and the precision-shaped particles are then removed from the cavity of the production tool. The mixture can be formed using any known technique, such as high-shear mixing, air agitation, or tumbling. A vacuum can also be used during mixing to minimize air entrapment. The mixture may be introduced into the cavity of the production tool using techniques such as gravity feeding, pumping, die coating, or vacuum drop die coating.

[0047] The organic abrasive particles must be hard enough to adequately clean a surface while minimizing scratching of the surface. One measure of hardness is the Mohs hardness scale, which characterizes the scratch resistance of minerals through the ability of hard materials to scratch softer materials. In one embodiment, the organic abrasive particles used in a suitable coating composition have a Mohs hardness of 2.0 to 5.0, particularly 2.0 to 4.0, and more particularly 2.5 to 3.5.

[0048] Other materials, such as viscosity modifiers, surfactants, plasticizers, crosslinkers, defoamers, mild abrasives, abrasives, pigments, acid catalysts, fungicides, and antibacterial agents, can be added to the coating composition for special purposes. Viscosity modifiers can be used to adjust the viscosity of the formulation. Defoamers can be used to defoam the formulation. Pigments can be added to impart color to the formulation. Antibacterial agents can impart antibacterial properties to the article, and fungicides can impart antifungal properties to the article. In one embodiment, the coating composition may contain 5% to 90% by weight of a resin binder, 90% to 10% by weight of organic abrasive particles, up to 10% by weight of a viscosity modifier, up to 10% by weight of a surfactant, up to 50% by weight of a plasticizer, up to 20% by weight of a crosslinker, up to 5% by weight of a defoamer, up to 50% by weight of a mild abrasive, and up to 15% by weight of a pigment. In particular, the composition may comprise 15% to 80% by weight of a resin binder, 20% to 85% by weight of organic abrasive particles, up to 5% by weight of a viscosity modifier, up to 5% by weight of a surfactant, up to 30% by weight of a plasticizer, up to 10% by weight of a crosslinker, up to 3% by weight of an antifoaming agent, up to 25% by weight of a mild abrasive, and up to 10% by weight of a pigment. More particularly, the composition may comprise 20% to 65% by weight of a resin binder, 35% to 80% by weight of organic abrasive particles, up to 2% by weight of a viscosity modifier, up to 3% by weight of a surfactant, up to 6% by weight of a plasticizer, up to 6% by weight of a crosslinker, up to 1% by weight of an antifoaming agent, up to 15% by weight of a mild abrasive, and up to 5% by weight of a pigment.

[0049] When used in coating compositions, the organic abrasive particles are incorporated into nonwoven, lofty, open mats formed from randomly arranged fibers and thermally bonded with a binder slurry for use as cleaning articles such as scrubbing pads.

[0050] In manufacturing the provided cleaning articles, organic abrasive particles can be incorporated into the nonwoven web 50 by applying a coating composition containing the organic abrasive particles to the nonwoven web 50 or by applying a printed abrasive coating containing the organic abrasive particles to the nonwoven web 50.

[0051] In one method, the nonwoven web 50 is first impregnated with a binder resin. Impregnation of the nonwoven web 50 with the binder resin can be accomplished by any known method. In one embodiment, the binder resin is roll coated onto the nonwoven web 50, causing the binder resin to penetrate into the voids in the nonwoven web 50. Alternatively, or in combination, the binder resin can be spray coated onto a major surface of the nonwoven web 50, causing the binder resin to penetrate into the voids in the nonwoven web 50. The coated nonwoven web 50 is then dried, causing the binder resin to harden. A scrubbing layer can be applied to at least one major surface of the resulting pre-bonded nonwoven web by spray coating with a binder solution containing organic abrasive fragment particles. The coated nonwoven web 50 is then dried, causing the binder to harden, forming a strong abrasive coating on the nonwoven web 50.

[0052] During roll coating, the binder resin can be forced into the nonwoven web 50 using, for example, a pressure nip. The degree of penetration can be selected based on the nip pressure, the openness of the web, and the viscosity of the resin. The binder resin roll coated onto the nonwoven web 50 can penetrate at least 50%, 60%, 70%, 80%, 90%, or 100% of the thickness of the nonwoven web 50.

[0053] During spray coating, the binder resin is atomized and deposited on the surface of the nonwoven web 50. The degree of penetration can be selected based on the air pressure, the openness of the web, and the viscosity of the resin. Generally, the spray-coated binder resin can penetrate up to 5%, 10%, 15%, 20%, or 25% of the thickness of the nonwoven web 50.

[0054] A scrubbing layer can be coated onto one or both major surfaces of the nonwoven web 50. Spray coating can be used to enhance the durability of the nonwoven web 50 and also to provide additional functionality, such as scrubbing performance. A significant technical advantage of providing a separate scrubbing layer in situ is that no separate adhesive is required. Furthermore, this method eliminates the need to cast and laminate a separate scrubbing layer onto the nonwoven web. Eliminating unnecessary steps and materials leads to significant reductions in manufacturing costs.

[0055] However, in some embodiments, a separate scrubbing layer may be laminated to one or both major surfaces of the nonwoven web 50 to provide a multi-layer cleaning article. Lamination may be accomplished by heat sealing or using a suitable adhesive to join the scrubbing layer and the nonwoven web 50 together. This additional layer may be used to provide a specialized scrubbing surface and / or further enhance the overall durability of the cleaning article.

[0056] The scrubbing layer described above can be made from, but is not limited to, woven, knitted, nonwoven, or foam materials. The woven, knitted, or nonwoven materials can be made from natural fibers, synthetic fibers, or a combination of natural and synthetic fibers. In some embodiments, the wiping material is hydrophilic and can retain and store water.

[0057] In some embodiments, the scrubbing layer comprises a nonwoven web having a plurality of abrasive particles adhered to the surfaces of fibers within the nonwoven web. Optionally, the abrasive particles are incorporated by applying a foamed liquid make coat precursor to the fibers of the web, spraying a plurality of fine abrasive particles onto a first side of the web, and then curing the make coat precursor to adhere the abrasive particles to the web.

[0058] Alternatively, the abrasive slurry can be directly deposited on the substrate and cured. The abrasive coating can include any combination of a binder and organic and inorganic abrasive particles. Some abrasive particles have a Mohs hardness of 7 or greater and are dispersed in a binder, while other abrasive particles have a Mohs hardness in the range of 1 to 5 and can be dispersed in a binder. In some embodiments, the former abrasive particles have a median particle size of 20 to 100 μm, and the latter abrasive particles have a median particle size greater than 100 μm.

[0059] Examples of these and other separate scrubbing layers are described in U.S. Patent Publication Nos. 2009 / 0276971 (Nozari) and 2021 / 0212544 (Zu et al.), and U.S. Patent Nos. 5,863,305 (Beardsley et al.) and 6,017,831 (Beardsley et al.).

[0060] A similar effect can be achieved using another method, in which a cleaning article is formed when organic abrasive particles are incorporated into a printed abrasive coating, by coating nonwoven web 50 with a slurry containing organic abrasive grinding particles, similar to the process described in International Patent Publication No. WO 2015 / 123635 (Endle et al.).

[0061] The densified layer 106 preferably has sufficient solidity to impart the necessary web strength to withstand repeated water immersion and hand scrubbing, while providing acceptable compressibility, flexibility, and other handling characteristics. The solidity may be 0.05% to 20%, 0.1% to 15%, 0.2% to 10%, or in some embodiments, less than, equal to, or greater than: 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%. Additionally, the non-densified layer may be 0.05% to 20%, 0.1% to 15%, 0.2% to 10%, or may be less than, equal to, or greater than 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%.

[0062] The change in solidity can also be characterized by a corresponding change in web density. As a result of coating or heat-compressing the nonwoven web 50, the density of the densified layer 106 may be 10% to 1000%, 20% to 700%, 30% to 500%, or in some embodiments, less than, equal to, or greater than the density of the nonwoven web 108 (i.e., the nonwoven web precursor). Good: 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 100%, 150%, 200%, 250%, 300%, 350%, 400%, 450%, 500%, 550%, 600%, 650%, 700%, 750%, 800%, 850%, 900%, 950%, 1000%.

[0063] 3, densified layer 106 has a depth that extends approximately halfway through the overall thickness of nonwoven web 50. However, the relative thicknesses of densified layer 106 and non-densified layer 108 are not particularly limited. For example, the densified layer may extend across a depth of 1% to 100%, 50% to 100%, 75% to 100%, or in some embodiments, less than, equal to, or greater than 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% or less of the total thickness of the nonwoven web 50. In a preferred embodiment, the densified layer 106 extends across the entire thickness of the nonwoven web 50.

[0064] The presence of densifying layer 106 can significantly improve the durability of nonwoven web 50 when article 100 is used in household scrubbing applications. When scrubbing pads made from conventional nonwoven webs are soaked in soapy water and subjected to vigorous scrubbing against a surface, the fibers of the web tend to separate, disentangle, and ultimately disintegrate. Advantageously, densifying layer 106 allows nonwoven web 50 to be used directly as a kitchen or automobile cleaning scrubbing pad without covering it with a protective net or mesh. In other words, the outer surface of article 100 may be partially or entirely the same as the outer surface of nonwoven web 50. However, while not required, the provided cleaning article may be enclosed in such an encasement if desired.

[0065] FIG. 4 illustrates a cleaning article 200 made from a nonwoven web 50, similar to article 100. Article 200 differs from the previously described article 100 in that the nonwoven web 50 is densified through its entire thickness, such that a densified layer 206 comprises the entire article 200. This embodiment may provide the greatest durability improvement to the entire article 200, and further allows either the first major surface 202 or the second major surface 204 to be used as an effective, durable scrubbing surface. For example, FIG. 7 illustrates a cross section of an actual nonwoven web that has been densified by compressing it under heat and pressure, as previously described.

[0066] 5 shows a cleaning article 300 similar to article 200, but having a densified layer 306 whose first major surface 302 extends along a three-dimensional topological pattern and whose second major surface 304 remains flat. Although not shown, in some cases, densified layer 306 may be shaped so that both first and second major surfaces 302, 304 have a three-dimensional topological pattern.

[0067] The topological pattern may replicate a cellular pattern of raised and depressed regions, as shown in the examples and in Figures 8A-D. Such patterns may be represented as a grid pattern (e.g., the rectangular grid pattern of Figure 8B) or a staggered pattern (e.g., the quilted pattern of Figure 8C). Other patterns are contemplated, including discontinuous shapes and / or randomly distributed features. The replicated cellular features of the topological pattern may have a periodicity of 2 mm to 100 mm, 5 mm to 40 mm, or 10 mm to 25 mm, and in some embodiments, may be less than, equal to, or greater than the following values: 2 mm, 3, 4, 5, 7, 10, 12, 15, 17, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 mm.

[0068] Advantageously, the topological pattern of first major surface 302 results in the surface roughness of article 100 being manifested at two very different scales: that of the fiber spacing within nonwoven web 50, and that of the periodicity of the topological pattern. Because debris such as food and dirt on the surface to be cleaned can exist at very different size scales, a scrubbing pad having roughness at both fine and coarse size scales will be more effective at removing such debris than an identical pad having roughness only at the fine size scale.

[0069] FIG. 6 illustrates a method for manufacturing article 300. In this method, nonwoven web 350 is produced using an airlaid or vertical wrapping machine 360 ​​and then passed on an endless belt 362 through a heated oven 364, where a series of patterned roll tools emboss a topological pattern into nonwoven web 350. In some cases, these tools may be gear-driven, have identical alignment, and are configured to press nonwoven web 350 in the same position as it passes through. A permanent topological pattern can be imprinted into web 350 using an appropriate combination of heat and pressure at a temperature above the softening temperature of one or more of the polymeric components of nonwoven web 350. After exiting the oven, web 350 is wound onto take-up roll 368 for temporary storage suitable for subsequent processing, converting, or packaging.

[0070] Although not shown here, article 300 can also be processed using a batch process. For example, as described above, a wrapping machine can be used to produce a nonwoven web, trim it into individual members, and a topology plate made from copper or other metal can be heated to an appropriate temperature and pressed against the individual members to emboss a pattern. As described above, these individual members can be converted to smaller sizes for consumer use and undergo other processing steps as necessary to obtain the finished product.

[0071] 10 and 11 illustrate a cleaning assembly 470. Assembly 470 includes a cleaning article 400 having the properties described herein and a substrate 474 removably coupled to cleaning article 400 along attachment surface 472. Optionally, and as shown, the substrate is functional and includes a handle to enhance convenience when scrubbing a surface with the cleaning article. FIG. 10 illustrates assembly 470 in an assembled configuration, and FIG. 11 illustrates assembly 470 with cleaning article 400 partially removed from attachment surface 472, illustrating one example of the engagement between these components.

[0072] The cleaning article 400 and substrate 474 are removably attached along attachment surface 472. Attachment surface 472 is preferably integral with substrate 474, but may also be a separate layer permanently bonded to either article 400 or substrate 474. As another option, attachment surface 472 may be part of a separately manufactured shoe or other member that is permanently or removably coupled to the handle.

[0073] In the illustrated embodiment, attachment surface 472 includes a multitude of tiny hooks that can engage nonwoven fibers in article 400, thereby providing a detachable bond. The "hook and loop" type engagement between these structures allows article 400 to be removed from attachment surface 472 and easily discarded, while retaining these members while scrubbing the surface, without the need to disengage / unlatch any members from substrate 474. Advantageously, fiber loops present near a major surface of a vertical wrapping or airlaid nonwoven web (e.g., as shown in FIG. 2) can be particularly effectively engaged with appropriately sized hook structures.

[0074] Hook structures useful in "hook and loop" engagement mechanisms are known. Such hook structures may have a variety of sizes and shapes depending on the characteristics of the nonwoven fibrous web, such as fiber size and solidity. They are described in U.S. Patent Publication Nos. 2001 / 0016245 (Tuman et al.) and 2003 / 0009144 (Tanzer et al.), as well as U.S. Patent Nos. 5,392,498 (Goulait et al.) and 7,014,906 (Tuman et al.).

[0075] In addition to hook size and shape, other factors can affect performance. The spacing between hooks affects how deeply the hooks penetrate into the nonwoven region and engage with the loops. Placing the hooks too closely can hinder hook-and-loop engagement, while spacing the hooks too widely reduces the number of hooks that engage. The hooks may be oriented to promote engagement with loops in the nonwoven fibrous web. When pulling the article 400 away from the hooks, the required force tends to be stronger in the direction parallel to the hooks and weaker in the direction perpendicular to the hooks. In some embodiments, two or more different hook orientations are used on the attachment surface 472 to increase the overall tensile strength along multiple directions. For example, hooks angled along both the longitudinal and transverse directions may be preferable to hooks angled only in the longitudinal direction.

[0076] The attachment surface 472 may engage a densified layer of the article 400 or may engage a non-densified layer. The nature of the hook-and-loop engagement along the densified regions between the article 400 and the substrate 474 may be significantly different from the nature of the engagement along the non-densified regions. In particular, initial retention was found to be somewhat higher along the non-densified regions, but this retention tended to decrease rapidly with repeated engagement / disengagement cycles. On the other hand, along the densified regions, initial retention was often somewhat lower, but high retention was well maintained despite repeated hook engagement / disengagement. Densification appears to create a fibrous structure that is resistant to the disturbances associated with inserting and removing hooks from the attachment structure. [Example]

[0077] The objects and advantages of the present disclosure are further illustrated by the following non-limiting examples, although the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed as unduly limiting the present disclosure. Unless otherwise stated or apparent from the context, all parts, percentages, ratios, etc. in the examples and elsewhere in this specification are by weight. Where applicable, brand and trade names are in all capital letters. [Table 1-1] [Table 1-2]

[0078] <Test Method> [Immersion test] A tray was filled with water. The sample was dropped into the water-filled tray and the time it took for the sample to sink into the water was recorded. No additional force was applied.

[0079] [Hook and loop engagement test] A 10.2 cm x 15.3 cm (4 in x 6 in) sample was clamped to a flat testing platform using wooden frame blocks, leaving an exposed sample surface area of ​​8.9 cm x 10.2 cm (3.5 in x 4 in). A test head, consisting of a 5.08 cm x 5.08 cm (2 in x 2 in) square of hook material, was centered on the sample surface, and a 2.25 kg (5 lb) weight was placed on the test head for 3 seconds to facilitate hook engagement with the web sample. A tension frame was used to measure the maximum release force when pulling perpendicular to the web surface at 10 cm / min (3.94 in / min). The hook-loop engagement force was defined as the maximum load recorded during the test.

[0080] [Sponge Density] The length (l), width (w) and thickness (t) of the sample were measured using a comparator gauge. The volume (m 3 The sample was then weighed to obtain the dry weight (g) of the material to the nearest 0.001 g. Density was calculated by multiplying the dry weight (g) by the volume (m 3 ) was calculated by dividing by

[0081] [Compression test] A 5.08 cm x 5.08 cm (2 in x 2 in) sample was clamped to a tensile frame and compressed using a 10.2 cm x 10.2 cm (4 in x 4 in) compression foot at a rate of 10 cm / min (3.94 in / min). The sample was preconditioned by two compression cycles to 50% of its initial thickness. The sample was then compressed a third time to 50% of its initial thickness, and the maximum force required to compress the sample was recorded.

[0082] [Cleaning performance] A 10.2 cm (4 in) diameter, 18-gauge stainless steel panel was coated with a food-soil mixture consisting of 120 g whole milk, 120 g cream cheese, 20 g flour, and 100 g granulated sugar. The coated panel was baked in a 230°C oven for 14 minutes to ensure a final coating weight of less than 0.5 g. A 6.4 cm (2.5 in) diameter sample was inserted into the holder of a Schiefer Tester, and the coated food-soil panel was tested at 250 rpm under a 2.25 kg load for 75 cycles while water was dispensed onto the circular coated panel surface at a rate of 60 to 80 drops per minute. After 75 cycles, the weight loss of the panel was measured and the total mass (mg) of food soil removed was calculated.

[0083] [Durability] Samples were treated for a minimum of 30 minutes in heated soapy water at approximately 65° C. under vigorous mechanical agitation. Durability was assessed by visual observation of the materials.

[0084] [Preparation examples 1 to 5 (PE1 to PE5)] The amounts (wt %) shown in Table 2 were charged into a 18.93 liter (5 gallon) container and mixed under shear for 30 minutes. [Table 2]

[0085] [Examples 1 to 13 (EX1 to EX13) and Comparative Examples 1 to 5 (CE1 to CE5)] Nonwoven fibrous web samples were prepared using either airlaid or vertical wrapping techniques. In the airlaid process, nonwoven web samples (EX1-5, EX12-13, and CE4) were composed of pre-fabricated staple and crimped fibers. These fibers were obtained in the form of tightly packed "bales" and first passed through an opener to mix the fibers (structural and adhesive) by weight percentage. An example of a suitable opener is the Reiter Bale Opener (Bracker, France). The fibers were then individualized using a fiber opener. An example of a suitable fiber opener is the Hergeth Hollingsworth carding machine (Aachen, Germany). The fibers were then transported to the airlaid machine. An example of a suitable airlaid machine is the Rando Webber (Macedon, NY, USA). By optimizing the input parameters of the airlaid machine, it was possible to achieve a single angle of 60° to 90°, which resulted in the fibers in the nonwoven web being substantially oriented in the z-direction. The output from the nonwoven web samples (EX1-5, EX12-13, and CE4) prepared by the airlaid machine was up to about 2.5 cm thick and had basis weights ranging from about 200 gsm to about 500 gsm before densification or coating (web basis weight).

[0086] In the vertical lapping process, the blend of structural and adhesive fibers was first converted into a nonwoven web using standard fiber mixing and carding equipment known to those skilled in the art. The resulting nonwoven web was fed into a vertical lapping machine, which folded the web back and forth on itself to produce a nonwoven mat (EX6-11 and CE5), which had a vertically wrapped structure with high z-direction orientation. Examples of suitable vertical lapping machines are the V-Lap Vertical Lapping System (V-Lap PTY Ltd, Australia) or a Struto machine (Struto International Inc.). The nonwoven mat was then thermally bonded by passing it through a through-air oven. In some examples (EX6-8 and CE5), rolls of vertically wrapped web purchased from Structured Fibers Inc. were used for additional post-processing. Such vertical wrapping materials include those produced using the apparatus described in "A DEVICE FOR PERPENDICULAR STRATIFICATION OF PLANARY FIBROUS SHAPES" disclosed in International Publication No. WO 99 / 61693, those produced using the V-Lap Vertical Lapping System manufactured by V-Lap PTY Ltd of Australia (e.g., as described in International Publication No. WO 2006 / 092029, which is incorporated herein by reference), and those produced using the STRUTO material produced using the Struto system from Struto International Inc. (described in Russell SJ, Handbook of Nonwovens, Chapter 2.12, Woodhead Publishing Limited, Cambridge, England, 2007, which is incorporated herein by reference). Nonwoven web samples prepared by vertical wrapping have a thickness of up to about 2.5 cm and a basis weight of about 400 g / m before densification or coating. 2 ~about 600g / m 2 (web basis weight)

[0087] As shown in Table 3, the densification coating identified in the preparative example was applied to the particular sample using roll coating, spray coating, or both methods / techniques. In cases where both roll coating and spray coating were used, roll coating was performed first. The coating was dried by passing the sample through an oven twice at the specified temperature and time. The first pass dried the roll coat, and the second pass dried the spray coat. For samples with only one coating, two passes were performed to dry. For CE4, CE5, EX2, EX3, and EX6, the temperature for the first and second passes was 180°C, with a total time of 316 seconds. For EX1, the temperature for the first and second passes was 150°C, with a total time of 158 seconds. For the other examples and comparative examples, the temperature for the first pass was 177°C, the temperature for the second pass was 190°C, and the total time was 450 seconds. Thermal densification was performed by passing the sample through an oven twice at the specified temperature and time. The physical properties (e.g., thickness, basis weight, etc.) and densification details of the samples are also shown in Table 3. The densification pattern created for EX10 is shown in Figure 8B, and for EX11 is shown in Figure 8C. Figures 8A and 8D show other patterns envisioned for the cleaning article, but not embodied in the examples. [Table 3]

[0088] CE1 to CE5, EX1 to EX3 and EX6 were subjected to an immersion test, and the results are shown in Table 4. [Table 4]

[0089] Compression tests were carried out on CE1 to CE5, EX1 to EX3 and EX6 to EX8, and the results are shown in Table 5. [Table 5]

[0090] CE4 and EX2 were subjected to durability performance tests, and the results are shown in Figure 9. CE4 before the test is shown in Figure 9A, and after the test is shown in Figure 9B. EX2 before the test is shown in Figure 9C, and after the test is shown in Figure 9D.

[0091] EX13 was subjected to a hook and loop engagement test. The hook and loop engagement force (N) of EX13 was 11N.

[0092] A cleaning performance test was conducted on EX13. The cleaning performance (mg) of EX13 was 120mg.

[0093] All references, patents, and patent applications cited in this patent application are incorporated by reference in their entirety for all purposes. In the event of a conflict or inconsistency between any portion of an incorporated reference and this application, the foregoing description shall control. The foregoing description is provided to enable one skilled in the art to practice the claimed disclosure, but is not intended to limit the scope of the disclosure, which is defined by the claims and all equivalents thereof.

Claims

1. A nonwoven fibrous web having fibers substantially oriented along an interior portion thereof at an angle of between 45 degrees and 90 degrees relative to a major surface thereof. A cleaning article comprising: A cleaning article wherein the outer surface of the nonwoven fibrous web comprises a densified layer extending throughout the nonwoven fibrous web, the densified layer comprising a coating received within voids of the nonwoven fibrous web, areas of heat-induced compression, or a combination thereof.

2. 10. The cleaning article of claim 1, wherein the nonwoven fibrous web comprises a vertically wrapped nonwoven web.

3. 10. The cleaning article of claim 1, wherein the nonwoven fibrous web comprises an air-laid nonwoven web.

4. Nonwoven fibrous webs, including vertically stacked nonwoven webs A cleaning article comprising: A cleaning article wherein the outer surface of the cleaning article comprises a densified layer extending across the nonwoven fibrous web, the densified layer comprising either a coating received within voids in the nonwoven fibrous web, areas of heat-induced compression, or a combination thereof.

5. The cleaning article according to any one of claims 1 to 4, wherein the outer surface of the nonwoven fibrous web constitutes the outer surface of the cleaning article.

6. A cleaning article according to any one of claims 1 to 5, wherein the densified layer has a solidity of up to 20%.

7. The cleaning article of any one of claims 1 to 6, wherein the densified layer extends throughout the thickness of the nonwoven fibrous web.

8. The cleaning article of any one of claims 1 to 7, wherein the densified layer extends along a topological pattern.

9. The cleaning article of claim 8 , wherein the topological pattern comprises a grid pattern.

10. 10. The cleaning article of claim 8 or 9, wherein the topological pattern comprises discontinuous shapes.

11. The cleaning article according to any one of claims 8 to 10, wherein the topological pattern exhibits a periodicity of 2 mm to 100 mm along the lateral direction.

12. The cleaning article of any one of claims 1 to 11, wherein the nonwoven fibrous web comprises a blend of adhesive fibers and structural fibers.

13. 13. The cleaning article of claim 12, wherein both the adhesive fibers and the structural fibers are crimped.

14. 14. The cleaning article of claim 12 or 13, wherein the adhesive fiber comprises a bicomponent fiber including a support component and an adhesive component, the adhesive component comprising at least an outer portion of the bicomponent fiber.

15. 15. The cleaning article of any one of claims 1 to 14, further comprising a scrubbing layer extending over and in direct contact with the outer surface, the scrubbing layer comprising a cured binder resin having abrasive particles therein.

16. A method for manufacturing a cleaning article, comprising: providing a nonwoven fibrous web having fibers oriented substantially at angles between 45 degrees and 90 degrees along an interior portion thereof; densifying the nonwoven fibrous web to obtain a densified layer; wherein the densified layer is characterized by a density of 10% to 1000% of the solidity of the original undensified state, and an outer surface of the nonwoven fibrous web comprises the densified layer.

17. The densification of the nonwoven fibrous web is coating the nonwoven fibrous web with a curable composition; curing the curable composition; 17. The method of claim 16, comprising:

18. 18. The method of claim 17, wherein coating the nonwoven fibrous web with the curable composition comprises roll coating, spray coating, or a combination thereof.

19. 17. The method of claim 16, wherein densifying the nonwoven fibrous web comprises compressing the nonwoven fibrous web at a temperature above the softening temperature of the nonwoven fibrous web.

20. coating a reaction mixture of a curable binder resin and abrasive particles onto the exterior surface; curing the reaction mixture; The method of any one of claims 16 to 19, further comprising:

21. A cleaning article according to any one of claims 1 to 15, a substrate having an attachment surface removably associated with the cleaning article; A cleaning assembly comprising:

22. 22. The cleaning assembly of claim 21, wherein the substrate comprises a handle.

23. 23. The cleaning assembly of claim 21 or 22, wherein the attachment surface includes a plurality of hook structures that engage the nonwoven fibrous web.

24. 24. The cleaning assembly of claim 23, wherein the hook structures engage the nonwoven fibrous web along the densified layer.

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