EP4658145A1

EP4658145A1 - Abrasive article

Info

Publication number: EP4658145A1
Application number: EP24703632.0A
Authority: EP
Inventors: Myhanh T. Truong; Jing Zhang
Original assignee: 3M Innovative Properties Co
Current assignee: 3M Innovative Properties Co
Priority date: 2023-02-03
Filing date: 2024-01-31
Publication date: 2025-12-10
Also published as: JP2026504426A; WO2024161328A1; KR20250142883A; CN120641016A

Abstract

Provided is a cleaning article (100) that includes a filler (108) and a netting (104) wrapped around the filler. The netting (104) includes interwoven threads defining a plurality of openings, and has first and second opposed major surfaces. An abrasive composite (210) is disposed on the first major surface, where the abrasive composite includes grit particles dispersed in an organic binder. The provided cleaning article displays significantly improved scouring performance over conventional non-scratch scour pads while avoiding damage to the substrate to be cleaned.

Description

ABRASIVE ARTICLE

Field of the Invention

Provided are cleaning articles, and more particularly, cleaning articles that are useful as cleaning articles in household kitchen and bath applications.

Background

Cleaning articles are widely used to clean surfaces such as household surfaces, including those in the home as well as vehicular surfaces. The cleaning article is generally used with water and a soap or detergent, with a scouring surface of the cleaning article being used to clean a surface. Such surfaces include dishes, utensils, glasses, pots, pans, grills, walls, floors, countertops, and vehicular surfaces and windows.

Scouring materials are produced in many forms, including non-woven webs (for example, the low density non-woven abrasive webs described in U.S. Patent No. 2,958,593 (Hoover et al.)). Following manufacture, a web of scouring material may be cut into individual pieces of a size suitable for hand use (for example, the individual rectangular pads described in U.S. Patent No. 2,958,593 (Hoover et al.)) or it may be left to the end user to divide the web into pieces of a convenient size when required (as described, for example, in International Patent Publication No. WO 2000/006341 (Mateos et al.) and U.S. Patent No. 5,712,210 (Windisch et al.)). Examples of non-scratch cleaning articles are sold under the trade name SCOTCH-BRITE by 3M Company of Saint Paul, Minnesota. A particular non-scratch cleaning article is the SCOTCH-BRITE DOBIE brand Cleaning Pad by 3M Company of Saint Paul, Minnesota, composed of polyurethane foam pad and enclosed in a netting or mesh.

Summary

Opportunities remain for improvements in scouring performance, particularly for non-scratch cleaning articles. Provided is a wrapped cleaning article having a mildly abrasive surface formed from a binder resin and granulated plastic cleaning media dispersed therein. The provided cleaning article yielded a significant scouring performance advantage over conventional scouring pads. Further, this construction can incorporate a high-loft filler, such as a fibrous non-woven web, for enhanced sustainability and performance advantages.

In one aspect, a cleaning article is provided. The cleaning article comprises: a filler; and a netting wrapped around the filler, the netting comprising interwoven threads defining a plurality of openings, and having first and second opposed major surfaces; and an abrasive composite disposed on the first major surface, the abrasive composite comprising grit particles dispersed in an organic binder.

In a second aspect, a method of cleaning a substrate is provided, the method comprising: scrubbing the cleaning article against the substrate to remove a contaminant therefrom without visibly scratching the substrate.

In a third aspect, a method of making a cleaning article is provided, the method comprising: providing a netting comprising interwoven threads defining a plurality of openings and having an exposed major surface; coating the exposed major surface with an abrasive composite slurry comprised of grit particles dispersed in an organic binder precursor; curing the organic binder precursor to obtain a cured abrasive composite; and wrapping and securing the netting around the filler to obtain the cleaning article whose outer surface comprises the cured abrasive composite.

Brief Description of the Drawings

FIG. 1 is a plan view of a cleaning article in assembled form according one exemplary embodiment;

FIG. 2 is a plan view of the cleaning article of FIG. 1 in partially disassembled form;

FIG. 3 is an enlarged view of a component of the cleaning article of FIGS. 1-2.

Repeated use of reference characters in the specification and drawings is intended to represent the same or analogous features or elements of the disclosure. It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art, which fall within the scope and spirit of the principles of the disclosure. The figures may not be drawn to scale. Detailed Description

As used herein, the terms “preferred” and “preferably” refer to embodiments described herein that can afford certain benefits, under certain 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.

As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a” or “the” component may include one or more of the components and equivalents thereof known to those skilled in the art. Further, the term “and/or” means one or all of the listed elements or a combination of any two or more of the listed elements. It is noted that the term “comprises”, and variations thereof do not have a limiting meaning where these terms appear in the accompanying description. Moreover, “a,” “an,” “the,” “at least one,” and “one or more” are used interchangeably herein. Relative terms such as left, right, forward, rearward, top, bottom, side, upper, lower, horizontal, vertical, and the like may be used herein and, if so, are from the perspective observed in the particular drawing. These terms are used only to simplify the description, however, and not to limit the scope of the invention in any way.

Reference throughout this specification to “one embodiment,” “certain embodiments,” “one or more embodiments” or “an embodiment” means that a particular feature, structure, material, or characteristic described relating to the embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrases such as “in one or more embodiments,” “in certain embodiments,” “in some embodiments” or “in an embodiment” in various places throughout this specification are not necessarily referring to the same embodiment of the invention.

Described herein are cleaning articles useful for household cleaning applications, such as cleaning dishes as well as other surfaces such as countertops, walls, shower curtains, and automotive surfaces. The construction of the cleaning article can provide various performance and environmental related advantages. FIGS. 1 and 2 are photographs directed to an exemplary cleaning article, hereinafter designated by the numeral 100. The cleaning article 100 has an outwardfacing major surface 102 comprised of a netting 104. As visible in the partially disassembled view of FIG. 2, the netting 104 is wrapped around a filler 108, shown partially received therein. The netting 104 has a mesh structure with interwoven threads that define a plurality of openings 106. The netting 104 has first and second opposed major surfaces, where the first major surface is coplanar with the major surface 102 of the overall cleaning article 100 and functions as a scrubbing surface.

FIG. 3 is an enlarged micrograph showing additional features on the netting 204 of a cleaning article 200 not visible in FIGS. 1 and 2. As depicted in FIG. 3, the netting 204 has the form of a grid with contiguous diamond-shaped openings. An abrasive composite 210 is disposed on an exposed major surface 202 of the cleaning article 200. For clarity, the major surface 202 includes surfaces of the netting 204 that face various directions and may not be coplanar with the page in FIG. 3 (i.e., the plane of the netting 204). Here, the major surface 202 represents those surfaces having normal vectors with a positive, or outward-facing, component perpendicular to the plane of the netting 204.

The abrasive composite 210 includes a plurality of grit particles 214 dispersed in an organic binder 212. At least some of the grit particles 214 can be exposed at the surface, or at least protrude outwardly from the surface, as shown. The abrasive composite 210 can be disposed on only the first major surface 202 or on both the exposed major surface 202 and the inward-facing second major surface (not visible).

While not intended to be exhaustive, further aspect of the cleaning articles 100, 200 are presented in the sections below.

The coating of the abrasive composition on the netting can be continuous or discontinuous. In some embodiments, the abrasive composition is not coated over the entire outward -facing major surface of the netting but over less than 100 percent, less than 90 percent, less than 80 percent, or even less than 70 percent of the outward-facing major surface of the netting. The abrasive composition can be coated onto the netting based on a two-dimensional pattern. The two-dimensional pattern can be a replicated pattern. The replicated pattern can have discontinuous coated regions surrounded by continuous uncoated regions, or discontinuous uncoated regions surrounded by continuous coated regions. Both coated and uncoated regions can be discontinuous — for example, the netting can be coated with a series of parallel stripes of the abrasive composition, extending from one end of the cleaning article to its opposite end.

While the cleaning article in FIGS. 1 and 2 is rectangular in shape, the cleaning article in general can take any shape that facilitates handling of the cleaning article by a user. For example, the cleaning article can have a round or hexagonal shape in plan view.

In various embodiments, the fdler is a fibrous filler. Optionally, at least one of the fibrous filler and the netting is composed of a sustainable material. In some embodiments, both the fibrous filler and the netting are composed of sustainable materials. Filler materials need not be particularly restricted. Non-fibrous fillers are also possible, for example, such as fillers made from open-cell polymeric foams and other conventional sponge materials.

The fibrous filler can be a three-dimensional web of entangled fibers that are bonded to one another at their mutual contact points by a bicomponent fiber, conjugate fibers and/or low melting fiber acting as the binder component. One function of the nonbonded fibrous filler is to absorb liquid. In some embodiments, the fibrous filler has an absorption rate of at least 10 times the dry weight of the fibrous filler, particularly 15 times the dry weight of the fibrous filler, more particularly 20 times the dry weight of the fibrous filler, and most particularly 30 times the dry weight of the fibrous filler.

Advantageously, fibrous fillers can require less material to absorb the same or more liquid than other materials currently on the market for absorbing liquid, such as foam. Because the fibrous filler requires less material, the cleaning article can be made at lower cost and is more sustainable than other current products in the market. In some embodiments, the fibrous filler has a density of from 10 kg/m³ to 30 kg/m³, or in some embodiments, less than, equal to, or greater than 10 g/m³, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 g/m³.

Related to the above density ranges, the undensified layer can have any suitable solidity, such as a solidity of from 0.05 percent to 20 percent, from 0.1 percent to 15 percent, from 0.2 percent to 10 percent, or in some embodiments, less than, equal to, or greater than 0.05 percent, 0.1, 0.2, 0.5, 0.7, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 15, 17, or 20 percent.

The fibrous filler can also have a lower compression force than other materials used to absorb liquid currently in the market. Thus, the fibrous filler requires less compression force to squeeze liquid out of the fibrous filler, resulting in easier rinsing and quicker drying time. In some embodiments, the fibrous filler has a compression of 9 Kgf or less, particularly 4 Kgf or less, and more particularly 2 Kgf or less.

In some embodiments, the fiber deniers range between 2 denier and 1000 denier, particularly between 2 denier and 100 denier, and more particularly between 3 denier and 15 denier. In some embodiments, the staple fiber lengths are between 30 mm and 120 mm, particularly between 40 mm and 100 mm, and more particularly between 50 mm and 60 mm.

Sustainable materials for the fibrous material can be biodegradable, recyclable, compostable, or made from recycled material. Examples of suitable, sustainable materials that the fibrous filler can be composed of include, but are not limited to: natural fibers, naturally derived fibers, recycled synthetic fibers, and biodegradable synthetic fibers. Examples of naturally derived fibers, including naturally derived fibers from renewable resources, include, but are not limited to: rayon, rayon from bamboo, polylactide (PLA), and combinations thereof. Examples of recycled synthetic fibers include, but are not limited to, recycled polyethylene terephthalate (PET), recycled nylon, combinations thereof, and can also include post-industrial and/or post-consumer material.

Examples of biodegradable synthetic fibers include, but are not limited to: viscous and melt processable fibers such as polylactic acid (PLA), polybutylene succinate (PBS), polyglycolic acid, polyester amide, dimer acid polyamide, polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), blends of PLA/PBS, blends of PLA/dimer acid polyamide, blends of PBS/dimer acid polyamide, blends of PHA/PHB, blends of PHA/PLA, blends of PHA/PBS, any of the aforementioned resins with a hydrophilic surfactant agent compounded into the polymer matrix, and combinations thereof. Examples of hydrophilic surfactants include, but are not limited to: polyoxyethylene coconut monoethanolamide, sodium salt of butanedioic acid, sulfo-, l,4-bis(2 -ethylhexyl) ester, and blends of these surfactants in a ratio of 50:50.

In some embodiments, the fibrous filler is a non-woven web. The non-woven filler can be made through an air-laid process or through a vertical lapping process. In the airlaid process, the non-woven filler is composed of staple fibers that are crimped for enhanced loft. In some embodiments, the fibers have a length of between 1 inch and 3 inches. These fibers can be provided in a tightly packed bale and run through an opener. An example of a suitable opener is a Reiter Bale Opener (Bracker, France). The fibers are then individualized in fiber opening equipment. An example of a suitable fiber opening equipment is a Hergeth Hollingsworth carding machine (Aachen, Germany). The fibers are then conveyed to an air-laid machine. An example of a suitable air-laid machine is a Rando Webber (Macedon, NY). In some embodiments, the output from the air-laid machine can range in basis weight of from 25 g/m² to 2500 g/m² at thicknesses of up to 7.6 cm (3 inches).

In the vertical lapping process, very thick, low-density webs with good compression resistance can be produced. This is achieved by creating vertical “struts” by taking a very flat web and folding it into vertical pleats. Vertical lapping equipment can be provided, for example, by Struto (Jihlava, Czech Republic). The vertical lapping equipment output can have thicknesses of between 0.5 inches and 2 inches.

Optionally, other materials can be added to the fibrous filler for special purposes, including, but not limited to: grinding aids, lubricants, wetting agents, surfactants, pigments, dyes, colorants, fillers, fragrances, coupling agents, plasticizers, mild abrasives, cross-linkers, antistatic agents, antioxidants, antimicrobial agents, anti-fungal agents, particles, and suspending agents. The materials can be added for functional purposes or aesthetic purposes. For example, dyes, colorants, fragrances and particles can serve aesthetic purposes.

Additional options and advantages associated with useful non-woven webs are described in International Patent Publication No. WO 2020/157659 (Truong, et al.) The netting functions primarily to clean or scour debris from a surface. The netting surrounds the fibrous filler and provides a flexible, abrasive surface useful for removing debris when contacted and rubbed against a surface while also being breathable. This also enables liquids to be absorbed and rinsed from the fibrous filler.

The netting can include a plurality of filaments and a plurality of monofilaments overlapping each other, n some embodiments, the monofilaments and filaments can form a twisted structure. The netting includes a backbone structure and a network structure in the backbone structure. The backbone structure of the netting formed by the plurality of filaments and the plurality of monofilaments, and the network structure of the netting is formed by the plurality of filaments. The plurality of filaments are disposed to be extended in different predetermined directions and cross with each other, and thereby form the backbone structure. That is, the backbone structure may be formed into contiguous polygonal shapes.

The netting may be folded and wrapped around the fibrous filler by any known method to those of skill in the art. Any terminal edges of the netting can be sealed along opposing edges by stitching as shown in FIGS. 1 and 2, or alternatively by welding or bonding through an adhesive. Preferably the netting completely surrounds the fibrous filler such that the filler is fully encapsulated within. Optionally, one edge of the netting sleeve can be resealable, allowing the filler to be removed and replaced by a user. The filler not only provides a scrubbing surface but also protects the relatively softer filler material from abrasion and degradation over repeated use.

While not required, the netting may be coupled to the non-bonded fibrous filler using adhesives, clamps, sealing, sewing, or welding. In some embodiments, the netting is in the form of a sleeve that is folded and wrapped around the fibrous filler and sewn to itself to secure the filler within the netting, as shown in FIG. 1. The netting can be composed of any material known in the art capable of being formed into a flexible lattice structure and used to scour a substrate. Scouring ability may be enhanced by the material used or the form, shape and cut of the netting material. For example, the netting can include gaps, grooves, protrusions, or other textures to optimize scouring for a given cleaning application.

The provided cleaning article is preferably non-scratching, meaning that it does not scratch the surface being cleaned. In these embodiments, the netting has a roughness sufficient to sufficiently clean a surface while minimizing any scratching of the surface. In some embodiments, the cleaning article has a Schiefer scratch rating of 3.5 or less, 3 or less, 2.5 or less, or 2 or less.

In some embodiments, the netting is composed of a sustainable material. That is, the netting may be biodegradable, recyclable, compostable, or made of recycled material. In some embodiments, the netting can be made from recycled plastic such as plastic bottles. Examples of suitable, sustainable materials that the netting can be composed of include, but are not limited to: natural fibers, naturally derived fibers, recycled synthetic fibers, or biodegradable synthetic fibers. Natural fibers, including naturally derived fibers from renewable resources, can include bamboo, sisal, flax, hemp, rayon, rayon from bamboo, polylactide (PLA), and combinations thereof. Examples of recycled synthetic fibers include, but are not limited to, recycled polyester (such as recycled polyethylene terephthalate), recycled nylon, combinations thereof, and can also include post-industrial and/or post-consumer material. Examples of biodegradable synthetic fibers include, but are not limited to: viscose and melt processable fibers such as polylactic acid (PLA), polybutylene succinate (PBS), polyglycolic acid, polyester amide, dimer acid polyamide, polyhydroxyalkanoate (PHA), Poly hydroxy butyrate (PHB), a blend of PLA/PBS, a blend of PLA/Dimer acid polyamide, a blend of PBS/dimer acid polyamide, a blend of PHA/PHB, a blend of PHA/PLA, a blend of PHA/PBS, all the afore mentioned resins with a hydrophilic surfactant agent compounded into the polymer matrix, and combinations thereof. Examples of hydrophilic surfactants include, but are not limited to: polyoxyethylene coconut monoethanolamide, sodium salt of butanedioic acid, sulfo-, l,4-bis(2 -ethylhexyl) ester, and a blend of these surfactants in a ratio of 50:50.

In a preferred embodiment, the abrasive composite is a composite structure comprising grit particles retained in a binder. The binder is preferably an organic binder. The abrasive composite can be made by curing or otherwise hardening a precursor slurry comprised of the grit particles dispersed within a curable organic binder precursor. The organic binder precursor is curable to obtain a thermoset polymer.

Organic binder precursors include curable phenol formaldehyde, acrylate monomers, (meth)acrylated urethanes, (meth)acrylated epoxies, ethylenically-unsaturated free-radically polymerizable compounds, aminoplast derivatives having pendant alpha, beta-unsaturated carbonyl groups, isocyanurate derivatives having at least one pendant acrylate group, and isocyanate derivatives having at least one pendant acrylate group) vinyl ethers, and mixtures and combinations thereof.

(Meth)acrylated urethanes include di(meth)acrylate esters of hydroxyl -terminated isocyanate-extended polyesters or polyethers. Examples of commercially available acrylated urethanes include those available as CMD 6600, CMD 8400, and CMD 8805 from Cytec Industries, West Paterson, New Jersey. (Meth)acrylated epoxies include di(meth)acrylate esters of epoxy resins such as the diacrylate esters of bisphenol A epoxy resin. Examples of commercially available acrylated epoxies include those available as CMD 3500, CMD 3600, and CMD 3700 from Cytec Industries. Ethylenically-unsaturated free -radically polymerizable compounds include both monomeric and polymeric compounds that contain atoms of carbon, hydrogen, and oxygen, and optionally, nitrogen and the halogens. Oxygen or nitrogen atoms or both are generally present in ether, ester, urethane, amide, and urea groups. Ethylenically- unsaturated free -radically polymerizable compounds typically have a molecular weight of less than 4,000 g/mole and are typically esters made from the reaction of compounds containing a single aliphatic hydroxyl group or multiple aliphatic hydroxyl groups and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and the like.

Examples of ethylenically-unsaturated free-radically polymerizable compounds include methyl methacrylate, ethyl methacrylate, styrene, divinylbenzene, vinyl toluene, ethylene glycol diacrylate, ethylene glycol methacrylate, hexanediol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, glycerol triacrylate, pentaerythritol triacrylate, pentaerythritol methacrylate, and pentaerythritol tetraacrylate. Other ethylenically unsaturated resins include monoallyl, polyallyl, and polymethallyl esters and amides of carboxylic acids, such as diallyl phthalate, diallyl adipate, and N,N- diallyladipamide. Still other nitrogen containing compounds include tris(2 -acryloyloxyethyl) isocyanurate, l,3,5-tris(2-methyacryloxyethyl)-s-triazine, acrylamide, N- methylacrylamide, N,N -dimethylacrylamide, N-vinylpyrrolidone, and N-vinylpiperidone.

Useful aminoplast resins have at least one pendant alpha, beta-unsaturated carbonyl group per molecule or oligomer. These unsaturated carbonyl groups can be acrylate, methacrylate, or acrylamide type groups. Examples of such materials include N- (hydroxymethyl)acrylamide, N,N'-oxydimethylenebisacrylamide, ortho- and para- acrylamidomethylated phenol, acrylamidomethylated phenolic novolac, and combinations thereof. These materials are further described in U.S. Patent Nos. 4,903,440 and 5,236,472 (both to Kirk et al.).

Isocyanurate derivatives having at least one pendant acrylate group and isocyanate derivatives having at least one pendant acrylate group are further described in U.S. Patent No. 4,652,274 (Boettcher et al.). An example of one isocyanurate material is the triacrylate of tris(hydroxyethyl) isocyanurate.

Compounds that generate a free-radical source if exposed to actinic electromagnetic radiation (e.g., ultraviolet or visible electromagnetic radiation) are generally termed photoinitiators. Examples of photoinitiators include benzoin and its derivatives such as a-methylbenzoin; a-phenylbenzoin; a-allylbenzoin; a-benzylbenzoin; benzoin ethers such as benzil dimethyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether; acetophenone and its derivatives such as 2-hydroxy-2-methyl-l- phenyl-1 -propanone and 1 -hydroxy cyclohexyl phenyl ketone; 2-methyl-l-[4- (methylthio)phenyl] -2-(4-morpholinyl)- 1 -propanone; and 2-benzyl-2-(dimethylamino)- 1 - [4-(4-morpholinyl)phenyl] - 1 -butanone .

Other useful photoinitiators include, for example, pivaloin ethyl ether, anisoin ethyl ether, anthraquinones (e.g., anthraquinone, 2-ethylanthraquinone, 1- chloroanthraquinone, 1,4-dimethylanthraquinone, 1 -methoxyanthraquinone, or benzanthraquinone), halomethyltriazines, benzophenone and its derivatives, iodonium salts and sulfonium salts, titanium complexes such as bis(.eta..sub.5-2,4-cyclopentadien-l- yl)-bis[2,6-difluoro-3-(lH-pyrrol- -l-yl)phenyl]titanium; halonitrobenzenes (e.g., 4- bromomethylnitrobenzene), mono- and bis-acylphosphines. Combinations of photoinitiators may be used. One or more spectral sensitizers (e.g., dyes) may be used in conjunction with the photoinitiator(s), for example, in order to increase sensitivity of the photoinitiator to a specific source of actinic radiation.

An initiator, such as a photoinitiator, can be present in any amount effective to cure the curable binder precursor. Typical amounts range from 0. 1 percent to 5 percent, or in some embodiments, less than, equal to, or greater than 0.1 percent, 0.2, 0.3, 0.4, 0.5, 0.7, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 percent of the overall weight of the organic binder, although greater and lesser amounts may also be used.

In some embodiments, silane treatment can help promote adhesion between the binder and certain grit particles. To promote an association bridge between the organic binder and the grit particles, a silane coupling agent may be included in a slurry of grit particles and organic binder precursor; typically in an amount of from 0.01 percent to 5 percent by weight, from 0.01 percent to 3 percent by weight, or from 0.01 percent to 1 percent by weight, although other amounts may also be used, depending on the size and composition of the grit particles.

Silane coupling agents can include, for example, methacryloxypropylsilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3,4- epoxy cyclohexylmethyltrimethoxy silane, y-glycidoxypropyltrimethoxy silane, and y- mercaptopropyltrimethoxysilane, allyltriethoxysilane, diallyldichlorosilane, divinyldiethoxysilane, and meta, para-styrylethyltrimethoxysilane, dimethyldiethoxysilane, dihydroxydiphenylsilane, triethoxy silane, trimethoxysilane, triethoxysilanol, 3 -(2-aminoethylamino)propyltrimethoxysilane, methyltrimethoxysilane, vinyltriacetoxysilane, methyltriethoxysilane, tetraethyl orthosilicate, tetramethyl orthosilicate, ethyltriethoxysilane, amyltriethoxysilane, ethyltrichlorosilane, amyltrichlorosilane, phenyltrichlorosilane, phenyltriethoxysilane, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, and mixtures thereof.

Optionally, the organic binder precursor (and hence also the organic binder) may optionally contain additives such as, for example, colorants, grinding aids, fdlers, wetting agents, dispersing agents, light stabilizers, and antioxidants.

For consumer household applications, such as kitchen and bath applications, the grit particles are preferably organic in nature. Useful organic grit particles have sufficient hardness and surface roughness to function as a gentle scrubbing surface in a scouring process that will not damage softer substrates. To provide both adequate scouring performance while avoiding damage to surfaces to be cleaned, the grit particles can have a Mohs hardness of from 1 to 5, from 1 to 4, from 2 to 3, or in some embodiments, less than, equal to, or greater than 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5.

Organic grit particles are typically polymeric particles, shaped organic particles, shaped inorganic particles, and combinations thereof. Polymeric particles can be made from a polyolefin, polycarbonate, poly(meth)acylate, polyester, polyurea, melamine, or copolymer or blend thereof.

Shaped particles can be composed of molded polymer or polymer composite materials. The shaped particles described herein can include any suitable material or combination of materials. For example, the shaped particles can include a reaction product of a polymerizable mixture including one or more polymerizable resins. The one or more polymerizable resins are chosen from a phenolic resin, a urea formaldehyde resin, a urethane resin, a melamine resin, an epoxy resin, a bismaleimide resin, a vinyl ether resin, an aminoplast resin (which may include pendant alpha, beta unsaturated carbonyl groups), an acrylate resin, an acrylated isocyanurate resin, an isocyanurate resin, an acrylated urethane resin, an acrylated epoxy resin, an alkyd resin, a polyester resin, a drying oil, or mixtures thereof. The polymerizable mixture can include any number of optional additives such as a plasticizer, an acid catalyst, a cross-linker, a surfactant, a mild- abrasive, a pigment, a catalyst or an antibacterial agent.

The predetermined shape can be replicated, for example, from a mold cavity used to form a shaped grit particle. In embodiments where the shaped grit particles are formed in mold cavity, the predetermined geometric shape may substantially replicate the mold cavity used to form the shaped abrasive particle. Shaped grit particles may also replicate a shape of a die in examples where a shaped grit particle is formed through extrusion. Shaped grit particles may also replicate a shape found in a program, for example a computer-aided-design (CAD) program, if shaped grit particles are formed through an additive manufacturing process. Here, shaped grit particles do not refer to randomly sized crushed grit particles formed, for example, by a mechanical crushing operation.

Examples of shaped abrasive particles are described in U.S. Patent No. 8,142,531 (Adefris et al.), where shaped abrasive particles were obtained by molding abrasive sol gel in equilateral triangle-shaped polypropylene mold cavities. For non-scratching applications, relatively softer shaped abrasive particles can also be used, as described in U.S. Patent Publication No. 2021/122959 (Mevissen et al.).

The grit particles can have a number average particle diameter of from 50 micrometers to 1000 micrometers, 100 micrometers to 500 micrometers, 150 micrometers to 400 micrometers, or in some embodiments, less than, equal to, or greater than 50 micrometers, 60, 70, 80, 90, 100, 110, 120, 150, 170, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1000 micrometers.

The grit particles can have any suitable coating weight. It is preferred for coating weight to be in a range where adequate flexibility is preserved in the coated netting while providing mechanical and/or adhesive securement of the grit particles on the organic binder. The grit particles can have a coating weight of from 10 gsm to 200 gsm, 15 gsm to 175 gsm, 20 gsm to 150 gsm, or in some embodiments, less than, equal to, or greater than 10 gsm, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400, 450, or 500 gsm. In some embodiments, the grit particles can comprise 10 to 70 percent by weight, or in some embodiments, less than, equal to, or greater than 10 percent by weight, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or 70 percent by weight, in each case relative to the overall weight of the abrasive composite. Further details applicable to the provided abrasive composite are described in International Patent Publication No. WO 2021/111327 (Liu et al.)

The cleaning products according to the present disclosure can be made, for example, by a method comprising the following sequential, and optionally consecutive, steps.

First, the netting is coated with an abrasive composite precursor slurry to coat one or both major surfaces of the netting, such as by spray coating, roll coating, or dip coating. If desired, the precursor slurry can coat the entirety of the one or both major surfaces. Alternatively, the netting could be masked such that the precursor slurry only coats a portion of one or both major surfaces of the netting. In some embodiments, the coating can be applied according to a two-dimensional pattern, providing a replicated pattern of abrasive islands, or inversely, non-abrasive islands. Given that the netting itself has a plurality of openings, the abrasive -coated regions may be limited to areas where unmasked areas overlap with the struts of the netting.

Second, as an optional step, the composite assembly can be ultrasonically vibrated to ensure good coating of the threads by the abrasive composite precursor slurry. Suitable ultrasonic devices are well-known in the art and may include, for example, commercially available sonication generators equipped with a horn, knife, blade, or plat. As used herein, the term “ultrasonic” refers to vibrational frequency above 20,000 Hz. Examples of commercially available suitable ultrasonic devices include those available from Branson Ultrasonics, Danbury, Connecticut.

Finally, the curable binder precursor can be exposed to sufficient actinic electromagnetic radiation to cause curing. Suitable sources of actinic (e.g., ultraviolet and/or visible) electromagnetic radiation are well-known in the art and include, for example, low-, medium-, and/or high-pressure mercury lamps, lasers, microwave driven lamps, and xenon flash lamps. Exposure conditions will typically depend on the lamp type, intensity, and duration of exposure, and are within the capability of those skilled in the art. For some initiators, curing can also be induced chemically or by application of heat. Curing produces a finished cleaning article in which an abrasive composite with a scrubbing surface is provided on an outer-facing major surface of the cleaning article.

The finished cleaning article can be used in any of a number of household and commercial cleaning applications. Advantageously, the cleaning article can be rubbed against relatively soft substrates in an oscillating or circular scouring motion to remove a contaminant therefrom without risk of visibly scratching the substrate. Substrates for the cleaning article include non-stick cookware surfaces, laminated sinks, countertops, painted surfaces, and other surfaces that can be prone to scratching. Common household items that could benefit from the provided cleaning articles include dishes, utensils, glasses, pots, pans, grills, walls, floors, countertops, and vehicles.

As a further option, the nonabrasive mesh type backing can include of loops which are knitted into the backside of the abrasive articles allowing hoop-and-loop attachment system, enabling the cleaning article to be attached to a separate cleaning tool.

EXAMPLES

Objects and advantages of this disclosure are further illustrated by the following non-limiting examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure. Unless otherwise noted, parts, percentages, ratios, etc. in the Examples are by weight. Where applicable, brand names and trademarked names are set out in all caps.

Table 1: Materials

Test Methods

Cleaning Efficacy

Cleaning efficacy testing was performed in a generally similar manner as the Food Soil Removal Test Method described in the examples of U.S. Pat. No. 5,626,512 (Palaikis et al). A 10.1 cm 18-gauge stainless steel panel was coated with a food soil mixture made up of 120 grams whole milk, 120 grams cream cheese, 20 grams flour, and 100 granulated sugars. The coated panel was baked in an oven at 230°C for 14 minutes. The above coating and curing process was repeated three times to achieve a uniform coat on the panel. Acceptable food soil coating weight should be at least equal to 0.25-0.45 grams. The coated panel was then wet with 4% aqueous dish soap solution and secured to the lower turntable of a Schiefer Abrasion Tester from Frazier Co. of Hagerstown, MD, United States. A 6.3 cm sample was placed on the food soil coated panel. Sample cleaning articles were saturated with water, centered, and fastened against the upper turntable in the Schiefer Abrasion Tester. A force of 2.27 kg was applied for either 50 or 75 cycles until the coated panel was clean. A cleaning rate efficacy as grams per 100 seconds (g/100 sec) and a percentage of food soil removal were calculated and recorded. The percentage of food soil removal was determined by dividing the weight (in grams) of how much food soil content was removed after 50 or 75 cycles testing by the initial weight (in grams) and multiplying by 100.

Scratch Evaluation

Schiefer scratch testing was performed to evaluate the relative abrasiveness of a sample cleaning article. The test was performed in a generally similar manner as the Schiefer Cut Test described in the examples of U.S. Pat. No. 5,626,512 (Palaikis et al). Sample cleaning articles were cut into a circular sample (8.25 cm in diameter). The test was conducted with the sample rotating at 250 rpm for 5000 revolutions under a load of 2.25 kg with water applied to the surface of the circular acrylic work piece (10.16 cm in diameter) at a rate of 40-60 drops per minute. Results are provided as a visual rating, or an average of a visual rating of three samples, from 1 to 5 defining the scratch patterns remaining on the acrylic disk. The Schiefer scratch visual ratings are defined as 1) no visible scratches, 2) light scratches, 3) light scratches with well-defined patterning, 4) heavy scratches covering portions of the entire workpiece, and 5) heavy scratches covering the entire workpiece.

Examples 1 - 4 (EXI - EX4) and Comparative Examples 1 - 10 (CE1 - CE10)

Coating compositions (Cl - C4) were made by shear mixing quantities as defined in Table 2 (in weight percent) together for one hour until homogenous.

Table 2: Coating Compositions (weight percent)

Cleaning article samples were made by spraying coating the compositions onto Netting 1 or Netting 2 and wrapping the coated netting around a fibrous filler. The basis weight of the added coating was between 160 gsm and 325 gsm. Sample constructions are defined in Table 3. The fibrous filler was made by a vertical stacking nonwoven process with PET fiber.

Table 3 : Cleaning Article Samples

Samples underwent Cleaning Efficacy and Scratch Evaluation Testing, and the results are represented in Table 4 (75 cycles), Table 5 (50 Cycles), and Table 6. Comparative Example 1 (CE1) was Netting 2 without a coating composition applied. Comparative Example 2 (CE2) was a non-scratch cleaning pad from H-E-B of San Antonio, Texas, United States. Comparative Example 3 (CE3) was a SCOUR DADDY ARMORTEC brand Mesh Scouring Pad from Scrub Daddy of Pennsauken, NJ, United States. Comparative Example 4 (CE4) was a SCOTCH-BRITE DOBIE brand Pad from 3M Company, St. Paul, MN, United States. Comparative Example 5 (CE5) was a SCOTCH-BRITE brand Non-Scratch Scour Pad from 3M Company. Comparative Example 6 (CE6) was a SCOTCH-BRITE brand Non-Scratch Scrub Sponge from 3M Company. Comparative Example 7 (CE7) was a SCOTCH-BRITE brand Stainless Steel Scrubbing Pad from 3M Company. Comparative Example 8 (CE8) was a SCOTCH- BRITE brand Power Scrub from 3M Company. Comparative Example 9 (CE9) was a SCOUR DADDY brand steel mesh from Scrub Daddy. Comparative Example 10 (CE10) was an XTRACT brand Net Disc 310W, Grade 320 from 3M Company. Comparative Examples 1 - 9 performed similarly (i.e., rating of 2) to Examples 1 - 4 with respect to the Scratch Evaluation Test.

Table 4: Cleaning Efficacy Test Results (75 Cycles) Table 5: Cleaning Efficacy Test Results (50 Cycles)

Table 6: Scratch Evaluation Test Results

All cited references, patents, and patent applications in the above application for letters patent are herein incorporated by reference in their entirety in a consistent manner. In the event of inconsistencies or contradictions between portions of the incorporated references and this application, the information in the preceding description shall control. The preceding description, given in order to enable one of ordinary skill in the art to practice the claimed disclosure, is not to be construed as limiting the scope of the disclosure, which is defined by the claims and all equivalents thereto.

Claims

CLAIMS: What is claimed is:

1. A cleaning article comprising: a filler; and a netting wrapped around the filler, the netting comprising interwoven threads defining a plurality of openings, and having first and second opposed major surfaces; and an abrasive composite disposed on the first major surface, the abrasive composite comprising grit particles dispersed in an organic binder.

2. The cleaning article of claim 1, wherein the grit particles comprise organic grit particles.

3. The cleaning article of claim 2, wherein the organic grit particles comprise a polyolefin, polycarbonate, poly(meth)acylate, polyester, polyurea, melamine, or copolymer or blend thereof.

4. The cleaning article of claim any one of claims 1 - 3, wherein the grit particles are shaped particles.

5. The cleaning article of any one of claims 1 - 4, wherein the grit particles have a number average particle diameter of from 50 micrometers to 1000 micrometers.

6. The cleaning article of claim 5, wherein the grit particles have a number average particle diameter of from 150 micrometers to 400 micrometers.

7. The cleaning article of any one of claims 1 - 6, wherein the grit particles have a coating weight of from 10 gsm to 500 gsm.

8. The cleaning article of claim 7, wherein the grit particles have a coating weight of from 100 gsm to 300 gsm.

9. The cleaning article of any one of claims 1 - 8, wherein the grit particles are from 10 percent to 70 percent by weight relative to the overall weight of the abrasive composite.

10. The cleaning article of any one of claims 1 - 9, wherein the organic binder comprises a thermoset polymer.

11. The cleaning article of claim 10, wherein the thermoset polymer is made by polymerizing phenol formaldehyde, acrylate monomers, (meth)acrylated urethanes, (meth)acrylated epoxies, ethylenically-unsaturated free-radically polymerizable compounds, aminoplast derivatives having pendant alpha, beta-unsaturated carbonyl groups, isocyanurate derivatives having at least one pendant acrylate group, isocyanate derivatives having at least one pendant acrylate group) vinyl ethers, or mixture or combination thereof.

12. The cleaning article of any one of claims 1 - 11, wherein the netting, fdler, or both comprise a material that is biodegradable, recyclable, or made from a recycled material.

13. The cleaning article of any one of claims 1 - 12, wherein the fdler comprises a fibrous non-woven web.

14. The cleaning article of claim 13, wherein the fibrous non-woven web comprises an air-laid non-woven web, vertically lapped non-woven web, or combination thereof.

15. The cleaning article of claim 13 or 14, wherein the fibrous non-woven web comprises recycled polyester.

16. The cleaning article of any one of claims 1 - 15, wherein the filler comprises fibers having a denier of from 2 to 1000.

17. The cleaning article of any one of claims 1 - 16, wherein the filler has a density of from 10 kg/m³ to 30 kg/m³.

18. A method of cleaning a substrate, the method comprising: scrubbing the cleaning article of any one of claims 1 - 17 against the substrate to remove a contaminant therefrom without visibly scratching the substrate.

19. The method of claim 18, wherein the substrate comprises a dish, utensil, glass, pot, pan, grill, wall, floor, countertop, or vehicle.

20. A method of making a cleaning article, the method comprising: providing a netting comprising interwoven threads defining a plurality of openings and having an exposed major surface; coating the exposed major surface with an abrasive composite slurry comprised of grit particles dispersed in an organic binder precursor; curing the organic binder precursor to obtain a cured abrasive composite; and wrapping and securing the netting around the filler to obtain the cleaning article whose outer surface comprises the cured abrasive composite.