ARTICLES CONTAINING A CROSSLINKED POLYMER CONTAINING GUANIDINYL AND USES THEREOF
Patent Information
- Application Number
- MX2022000792
- Authority / Receiving Office
- MX · MX
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2019-08-07
- Filing Date
- 2022-01-19
- Publication Date
- 2026-02-25
- Estimated Expiration
- 2040-07-23
AI Technical Summary
Existing articles with cationic coatings, such as cloths and filters, suffer from inefficient manufacturing processes due to undesirable polymer washing, leading to residue on surfaces and inadequate microorganism removal, particularly from surfaces contaminated with persistent organisms like C. difficile spores.
A cationic coating containing a cross-linked guanidinyl-containing polymer is bonded to a substrate, using a guanidinyl-containing polymer cross-linked with an amine-reactive polyepoxy compound, ensuring minimal residue and effective microorganism removal, with at least 99% elimination and less than 0.2% transfer to a second surface.
The cross-linked polymer coating effectively removes microorganisms from surfaces while minimizing residue, enhancing manufacturing efficiency and reducing recontamination risks, particularly effective against C. difficile spores.
Abstract
Description
ARTICLES CONTAINING A CROSSLINKED POLYMER CONTAINING GUANIDINIL AND ITS USES Background of the Invention Microorganisms are known to persist on surfaces for extended periods. Many of these organisms require only about 10–100 individuals to cause infection. Good hygiene practices, such as handwashing and surface disinfection, are proven methods for eliminating or reducing the transmission of these pathogenic microorganisms and significantly impacting public health. Daily use of disinfectant cleaners, including quaternary ammonium compounds or alcohol-based cleaners, is effective in destroying most microorganisms, but some bacteria, such as Clostridium difficile spores, are unaffected by these chemicals.Bleach and peracetic acid-based chemicals are frequently used to eliminate other persistent organisms; however, these chemicals are not commonly used due to their corrosive properties and associated health problems, such as skin and nasal irritation. Reducing the transmission of these organisms without the use of chemical disinfectants is highly desirable. Ref. 330661 Articles such as cloths are known to incorporate a crosslinked polymer; however, many exhibit undesirable polymer washout, leading to inefficient manufacturing processes and reduced article effectiveness. Insufficient crosslinking of the coating polymers can result in undesirable residue of polymer and crosslinking agent remaining on surfaces that come into contact with the article. Summary of the Invention This description pertains to an article, such as a filter or cloth, containing a cationic coating, and to methods for using the article. The cationic coating includes a crosslinked guanidinyl-containing polymer. The coating does not readily separate from the substrate. As a result, minimal or no residue of the cationic coating remains on surfaces after cleaning with the cloths, for example. In one embodiment, the article includes: a substrate; a cationic coating bonded to the substrate, wherein the cationic coating includes a guanidinyl-containing polymer crosslinked to the substrate; wherein the guanidinyl-containing polymer is of the following Formula (I): Polymer R4 R3N R4 II N--u--Nen where: R3 is an H, C1-C12 (hetero)alkyl, C5-C12 (hetero)aryl, or polymer; each R4 is independently H, C1-C12 (hetero)alkyl, or C5-C12 (hetero)aryl; each R5 is H, C1-C12 (hetero)alkyl, C5-C12 (hetero)aryl, or N(R4)2; the polymer is a residue of an aminopolymer chain; m is 1 or 2; yx is an integer of at least 1; and wherein the guanidinyl-containing polymer is crosslinked with an amine-reactive polyepoxy compound having dangling -OH groups (e.g., glycerol diglycidyl ether). In certain preferred embodiments, the article is a cloth. Cloths are useful for removing microorganisms from a surface contaminated with microorganisms and also for reducing recontamination of the cleaned surface with the removed microorganisms or the transfer of removed microorganisms to another surface. Advantageously, when placed in contact with an area of a surface contaminated with microorganisms, cloths can remove at least 99 percent of the microorganisms in the area. The removed microorganisms adhere to the cloth, and no more than 0.2 percent of the removed microorganisms are transferred from the cloth to a second surface when the cloths come into contact with a second surface or with the previously cleaned surface. In another embodiment, the method is a method for removing a contaminant from a contaminated surface, wherein the method includes bringing the article in the form of a cloth into contact with a liquid in the presence of an area of the contaminated surface, wherein the contaminated surface is a solid surface. As used in this description, the term polymer includes a homopolymer, copolymer, terpolymer, and the like. Polymer in Formula (I) refers to all portions of the polymer containing guanidinyl except for the x groups of Formula (I) or R3 if it is a residue of an aminopolymer chain. As used in the present description, the term guanidinyl refers to a group of the formula — NR3—C(=NR4) — NR4R5. As used herein, alkyl refers to a monovalent radical of an alkane and includes linear, branched, and cyclic alkyl groups, as well as unsubstituted and substituted alkyl groups. Unless otherwise stated, alkyl groups typically contain 1 to 20 carbon atoms, or 1 to 12 carbon atoms. Examples of alkyl, as used herein, include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and norbornyl, and the like. The term heteroalkyl refers to an alkyl group containing 1–3 heteroatoms such as nitrogen, oxygen, or sulfur. The term (hetero)alkyl refers to both alkyl and heteroalkyl groups. As used herein, alkylene refers to a divalent radical of an alkane and includes linear, branched, and cyclic alkylene groups, both unsubstituted and substituted. Unless otherwise stated, alkylene groups typically contain from 1 to 20 carbon atoms. Examples of alkylene, as used herein, include, but are not limited to, methylene, ethylene, n-propylene, n-butylene, n-pentylene, isobutylene, t-butylene, isopropylene, n-octylene, n-heptylene, ethylhexylene, cyclopentylene, cyclohexylene, cycloheptylene, adamantine, and norbornylene, and the like. As used in this description, aryl is a monovalent radical of an aromatic group containing 5–12 atoms in the ring and may contain optional fused rings, which can be saturated, unsaturated, or aromatic. Examples of carbocyclic aryl groups include phenyl, naphthyl, biphenyl, phenantrile, and anthracil. The term heteroaryl refers to an alkyl group containing 1–3 heteroatoms such as nitrogen, oxygen, or sulfur and may contain fused rings. Examples of heteroaryl groups include pyridyl, furanyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, indolyl, benzofuranyl, and benzothiazolyl. The term (hetero)aryl refers to both aryl and heteroaryl groups. As used in this description, arylene is a divalent radical of an aromatic group containing 5–12 atoms in the ring and may contain optional fused rings, which may be saturated, unsaturated, or aromatic. Examples of arylene groups that are carbocylic include phenylene, naphthylene, biphenylene, phenanthrylene, and anthracylene. As used in this description, "contact in the presence of a liquid" generally refers to contacting a cloth with a surface (e.g., a surface contaminated with microorganisms), where the cloth and / or the surface is wetted with a liquid in an area where the surface and the cloth come into contact with each other. The liquid typically includes at least 10 percent water by weight and may include up to 100 percent water by weight, relative to the total weight of the liquid. As used in this description, the term "bonded," with reference to the cationic coating (e.g., the guanidinyl-containing polymer in the cationic coating) bonded to the substrate, means that the cationic coating cannot be removed without destroying the substrate. For example, the cationic coating may be chemically bonded to the substrate or crosslinked around the substrate fibers in such a way that the coating cannot be removed by flaking, dissolving in water, or using an organic solvent. The term microorganism refers to bacteria (including Gram-positive and Gram-negative bacteria), fungi (e.g., yeasts), molds, protozoa, viruses (including non-enveloped and enveloped viruses), bacterial endospores, and similar organisms, and combinations thereof. In some forms, microorganisms include bacterial endospores. In this description, the term "comprises" and variations thereof do not have a limiting meaning when they appear in the description and claims. Such terms shall be understood to imply the inclusion of a mentioned step or element or group of steps or elements, but not the exclusion of any other step or element or group of steps or elements. "Consisting of" is understood to include, and be limited to, what follows the phrase "consisting of." Accordingly, the phrase "consisting of" indicates that the listed elements are required and mandatory, and that no other elements may be present. "Consisting essentially of" means that it includes any of the elements listed after the phrase and limits other elements that do not interfere with or contribute to the activity or action described in the description to the listed elements.However, the phrase "essentially consists of" indicates that the listed elements are necessary or mandatory, but that other elements are optional and may or may not be present depending on whether or not they materially affect the activity or action of the listed elements. Any of the elements or combinations of elements mentioned in this description with open expressions (e.g., "comprise" and their derivatives) are also considered to be mentioned with closed expressions (e.g., "consist of" and their derivatives) and with partially closed expressions (e.g., "essentially consist of" and their derivatives). The words "preferred" and "preferably" refer to variations of the description that may provide certain benefits under certain circumstances. However, other claims may also be preferred under the same or different circumstances. Furthermore, the description of one or more preferred claims does not imply that other claims are not useful and is not intended to exclude other claims from the scope of the description. In this application, terms such as a, an, and the are not intended to refer to only a single entity but include the general class of which a specific example may be used for illustrative purposes. The terms a, an, and the are used interchangeably with the term at least one. The phrases at least one of and comprises at least one of followed by a list refer to any of the items in the list and any combination of two or more items in the list. As used in the present description, the term or is generally used in its usual sense which includes and / or, unless the content clearly indicates otherwise. The term and / or means one or all of the elements mentioned or a combination of any two or more of the elements mentioned. Furthermore, in this description, it is assumed that all figures are modified by the term "approximately" and, in certain cases, preferably by the term "exactly." As used in this description in relation to a measured quantity, the term "approximately" means that the variation in the measured quantity would be expected by someone skilled in the art of making the measurement and exercising a level of attention appropriate to the purpose of the measurement and the precision of the measuring equipment used. In this description, "up to" a number (e.g., up to 50) includes the number (e.g., 50). Furthermore, in the present description, narratives of numerical intervals by endpoints include all numbers included within that interval, as well as the endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). As used in this description, the term room temperature refers to a temperature of 20°C to 25°C or 22°C to 25°C. The term in the interval or within an interval (and similar statements) includes the boundary values of the stated interval. The groupings of alternative elements or modalities described herein are not to be construed as limitations. Each member of the group may be referenced and claimed individually or in any combination with other members of the group or other elements found therein. It is envisaged that one or more members of a group may be included in, or removed from, a group for reasons of convenience and / or patentability. When such inclusion or removal occurs, the description herein shall be deemed to contain the modified group that, consequently, satisfies the written description of all Markush groups used in the appended claims. When a group appears more than once in a formula described herein, each group is selected independently, whether or not it is specifically indicated. For example, when more than one group R appears in a formula, each group R is selected independently. References throughout this description to an embodiment, certain embodiments, or some embodiments, etc., mean that a particular function, configuration, composition, or feature described in relation to the embodiment is included in at least one embodiment of the invention. Therefore, the occurrence of such phrases in various places throughout this description does not necessarily refer to the same embodiment of the invention. Furthermore, the particular functions, configurations, compositions, or features may be combined in any suitable manner in one or more embodiments. The foregoing summary of this description is not intended to describe every embodiment or implementation of the present invention. The description provided below shows more specifically the illustrative embodiments. Guidance is provided in several sections throughout this application by way of lists of examples. These examples can be used in various combinations. In each case, the aforementioned list serves only as a representative group and should not be construed as an exhaustive list. Therefore, the scope of this description should not be limited to the specific illustrative structures described herein, but rather extends at least to the structures described by the language of the claims and their equivalents.Any of the elements positively mentioned in this description as alternatives may be explicitly included in the claims or excluded from the claims, in any combination desired. Although various theories and mechanisms may have been analyzed herein, in no case shall such analyses be used to limit the claimed subject matter. Brief Description of the Figures Figure 1 is a schematic profile view of a specific modality of an article of the present description. Figure 2 is a graphical representation of the results of nonwoven fabric sheets from the example of glycerol diglycidyl ether (GDGE) and comparative examples (butanediol diglycidyl ether (BUDGE), ethylene glycol diglycidyl ether (EDGE), and poly(ethylene glycol) diglycidyl ether (PEGDGE)) washed according to the wash removal test, where the results for the percentage of wash removal of the coating are reported as the average value obtained from three replicates. Figure 3 is a graphical representation of the results of the non-woven fabric sheets of an example (GDGE) and the comparative example (BUDGE) washed according to the wash removal test, where the results for the percentage of coating wash are reported as the average value obtained from three replicates. Figure 4 is a graphical representation of the static bonding capacity results of nonwoven fabric sheets from an example (GDGE), comparative examples (BUDGE, EDGE and PEGDEGE), and an uncoated control washed according to the wash removal test, and then exposed according to the static bonding capacity test to tartrazine. Figures 5-6 are graphical representations of the removal and cross-contamination of microorganisms from surfaces using non-woven fabric sheets of an example (GDGE), comparative example (BUDGE) and an uncoated control according to the test method for the removal of microorganisms from a surface contaminated with microorganisms and contamination by transfer, where the results are reported as the mean value obtained from three replicates. Detailed Description of the Invention This description pertains to an article, such as a filter or cloth, containing a cationic coating, and to methods for using the article. The coated article includes a substrate and a cationic coating bonded to the substrate. The cationic coating includes a guanidinyl-containing polymer that is crosslinked and optionally covalently bonded to the substrate. In one embodiment, the article includes: a substrate; a cationic coating bonded to the substrate, wherein the cationic coating includes a guanidinyl-containing polymer crosslinked to the substrate; wherein the guanidinyl-containing polymer is of the following Formula (I): Polymer R3 wherein: R3 is an H, C1-C12 (hetero)alkyl, C5-C12 (hetero)aryl, or polymer; each R4 is independently H, C1-C12 (hetero)alkyl, or C5-C12 (hetero)aryl; each R5 is H, C5-C12 (hetero)alkyl, C5-C12 (hetero)aryl, or N(R4)2; the polymer is a residue of an aminopolymer chain; m is 1 or 2; yx is an integer of at least 1; and wherein the guanidinyl-containing polymer is crosslinked with an amine-reactive polyepoxy compound having dangling -OH groups (e.g., glycerol diglycidyl ether). In certain preferred forms, the article is a cloth. Wipes are useful for removing microorganisms from a contaminated surface and also for reducing recontamination of the cleaned surface with the removed microorganism or the transfer of removed microorganisms to another surface. Advantageously, when placed in contact with an area of a surface contaminated with microorganisms, wipes can remove at least 99 percent of the microorganisms in the area. The removed microorganisms adhere to the wipe, and no more than 0.2 percent of the removed microorganisms are transferred from the wipe to a second surface when the wipes come into contact with a second surface or with the previously cleaned surface. Figure 1 is a schematic profile view of an illustrative embodiment of Article 200 comprising a substrate 210 and a cationic coating layer 220 disposed on a first principal surface of the substrate 210. Article 200 further comprises a coating layer 222 disposed on a second principal surface of the substrate 210 opposite the first principal surface of the substrate 210. In some embodiments, the coating layer 222 may include the same cationic coating composition used in the cationic coating layer 220, although this is not a requirement, and the coating layer 222 may alternatively include other coating compositions. In certain embodiments, only one principal surface of the substrate has a cationic coating layer disposed on it. In other embodiments, the article includes a cationic coating layer surrounding a substrate. In some other configurations, a cationic coating can be applied to the surface of a substrate, or distributed throughout at least a portion of the substrate. That is, the cationic coating can penetrate the substrate. For example, if the substrate is a sponge, the cationic coating can be applied to the surface of the substrate and distributed throughout all or any portion of it. In other examples, if the substrate includes fibers, the cationic coating can surround the fibers or any portion of them. The cationic coating includes a polymer containing guanidinyl. The guanidinyl group can be located anywhere in the polymer. In most embodiments, the guanidinyl group is part of a pendant group attached to the polymer backbone. However, in some embodiments, the guanidinyl group is part of the polymer backbone. As used in this description, the term guanidinyl refers to a group of the formula —NR3—C(=NR4) —NR4R5. If the guanidinyl group is part of a pendant group, the R3 group refers to hydrogen, C1-C12 (hetero)alkyl, or C5-C12 (hetero)aryl. Alternatively, R3 may refer to the polymer, which is a residue of the aminopolymer chain, when the nitrogen to which it is attached is part of the main polymer chain. Each R4 group is independently hydrogen, C1-C22 (hetero)alkyl, or C5-C12 (hetero)aryl. The R5 group is hydrogen, C1-C12 (hetero)alkyl, C5-C12 (hetero)aryl, or a group of formula —N(R4)2. The guanidinyl group can be part of a biguanidinyl group which has the formula —NR3—C (=NR4) —NR4— C (=NR4) — NR4R5 where the groups R3, R4, and R5 are the same as defined above. Most guanidinyl-containing polymers have more than one guanidinyl group. The number of guanidinyl groups can vary depending on the method used to prepare the polymer. For example, the number of guanidinyl groups may depend on the choice of amino-containing polymer precursor (i.e., aminopolymer precursor) selected to react with a suitable guanylating agent. In some embodiments, the variable x can be up to 10,000, up to 5,000, up to 1,000, up to 500, up to 100, up to 80, up to 60, up to 40, up to 20, or up to 10. The guanidinyl-containing polymer of Formula (I) is frequently the reaction product of an amino-containing polymer precursor (i.e., aminopolymer precursor) and a suitable guanylating agent. In certain embodiments, the articles described herein include at least 0.1 percent by weight of the guanidinyl-containing polymer, based on the total weight of the article. In certain embodiments, the articles described herein include up to 10 percent by weight of the guanidinyl-containing polymer, based on the total weight of the article. This amount is typically used for a cloth, although larger amounts may be used for a filter. Amino-containing polymer precursor The amino-containing polymer used as a precursor polymer (i.e., amino precursor polymer or simply aminopolymer) to prepare a guanidinyl-containing polymer of Formula (I) can be represented by the following Formula (II): Polymer —N(R3)H. The amino-containing polymer can be a linear polymer or a branched polymer. However, as mentioned above, the amino-containing polymer typically has many —N(R3)H groups, but Formula (II) shows them only for the purpose of illustrating the discussion. The —N(R3)H groups can be primary or secondary amino groups and can be part of a pendant group or part of the main chain of the aminopolymer precursor. Amino-containing polymer precursors can be synthesized or can be naturally occurring biopolymers.Suitable amino-containing polymer precursors can be prepared by chain-growth polymerization procedures or growth steps with amino-containing monomers. These monomers can also be copolymerized with other monomers lacking an amino-containing group. Furthermore, amino-containing polymers can be obtained by grafting primary or secondary amine groups using an appropriate grafting technique. In some embodiments, useful amino-containing polymer precursors are water-soluble or water-dispersible polyamines. As used herein, the term water-soluble refers to a material that can dissolve in water. Solubility is typically at least 0.1 gram per milliliter of water. As used herein, the term water-dispersible refers to a material that is not soluble in water but can be emulsified or suspended in water. If desired, various combinations of amino-containing polymer precursors can be used. Examples of amino-containing polymer precursors suitable for use, which are prepared by chain-growth polymerization, include, but are not limited to, polyvinylamine, poly(N-methylvinylamine), polyallylamine, polyallylmethylamine, polydialylamine, poly(4-aminomethylstyrene), poly(4-aminomethylstyrene), poly(acrylamide-co-aminopropylacrylamide), and poly(acrylamide-co-amino ethyl methacrylate). Examples of amino-containing polymer precursors suitable for use, which are prepared by growth-step polymerization, include, but are not limited to, polyethyleneimine, polypropyleneimine, polylysine, polyaminoamides, and polydimethylamine-epichlorohydrinethylenediamine. Other polymer precursors containing useful amino groups with primary or secondary amino terminals include, but are not limited to, dendrimers (hyperbranched polymers) formed from polyamidoamine (PAMAM) and polypropyleneimine. Illustrative dendrimeric materials formed from PAMAM are commercially available under the trade name STARBURST (PAMAM) dendrimer (e.g., generation 0 with 4 primary amino groups, generation 1 with 8 primary amino groups, generation 2 with 16 primary amino groups, generation 3 with 32 primary amino groups, and generation 4 with 64 primary amino groups) from Aldrich Chemical (Milwaukee, WI). Dendrimeric materials formed from polypropyleneimine are commercially available under the trade name DAB-Am from Aldrich Chemical.For example, DAB-Am-4 is a generation 1 polypropyleneimine tetraamine dendrimer with 4 primary amino groups, DAB-Am-8 is a generation 2 polypropyleneimine octaamine dendrimer with 8 primary amino groups, DAB-Am-16 is a generation 3 polypropyleneimine hexadecaamine with 16 primary amino groups, DAB-Am-32 is a generation 4 polypropyleneimine dotriacontaamine dendrimer with 32 primary amino groups, and DAB-Am-64 is a generation 5 polypropyleneimine tetrahexacontaamine dendrimer with 64 primary amino groups. Examples of polymer precursors containing suitable amino groups that are biopolymers include chitosan as well as starch grafted with reagents such as methylaminoethyl chloride. Still other examples of amino-containing polymer precursors include polyacrylamide homo or copolymers and polyacrylate homo or copolymers containing amino, prepared with a monomeric composition containing an amino-containing monomer, such as an aminoalkyl(meth)acrylate, (meth)acrylamidoalkylamine, and diallylamine. For some items, preferred amino-containing polymer precursors (i.e., aminopolymer precursors or simply aminopolymers) include polyaminoamide, polyamidoamine, polyethyleneimine, polypropyleneimine, polyvinylamine, polyallylamine, polydialylamine, and mixtures of these. In certain forms, the amino-containing polymer precursor is a polyethyleneimine. Suitable commercially available amino-containing polymer precursors include, but are not limited to, polyamidoamines available under the trade names ANQUAMINE (e.g., ANQUAMINE 360, 401, 419, 456, and 701) from Air Products and Chemicals (Allentown, PA), polyethyleneimine polymers available under the trade name LUPASOL (e.g., LUPASOL FG, PR 8515, Waterfree, P, and PS) from BASF Corporation (Resselaer, NY), polyethyleneimine polymers such as those available under the trade name CORCAT P-600 from EIT Company (Lake Wylie, SC), and polyamide resins such as those available from Cognis Corporation (Cincinnati, OH) under the trade name VERSAMID series of resins formed by reacting a dimerized unsaturated fatty acid with alkylene polyamines. Guanylation agents Guanidinyl-containing polymers can be prepared by reacting an amino-containing polymer precursor (i.e., an aminopolymer precursor) with one or more guanylating agents. The number of amino groups available for guanylation (and crosslinking) can be determined by the amine equivalent weight of the amino-containing polymer precursor, or the polymer repeating unit. Such amino groups can be primary, secondary, tertiary, or even quaternary. Typically, at least 0.1 mol%, at least 0.5 mol%, at least 1 mol%, at least 2 mol%, at least 10 mol%, at least 20 mol%, at least 30 mol%, at least 40 mol%, or at least 50 mol% of the amino groups in the amino-containing polymer precursor are reacted with the guanylating agent. Up to 95 mol%, up to 90 mol%, up to 80 mol%, up to 70 mol%, up to 60 mol%, up to 50 mol%, or up to 25 mol% of the amino groups can be reacted with the guanylating agent. For example, the guanylating agent can be used in sufficient quantities to functionalize 0.1 to 95 mol⁻¹, 0.5 to 90 mol⁻¹, 1 to 90 mol⁻¹, 1 to 80 mol⁻¹, 1 to 60 mol⁻¹, 2 to 50 mol⁻¹, or 2 to 25 mol⁻¹ of the amino groups in the amino-containing polymer. Typically, the primary amino groups react with the guanylating agent, although some secondary amino groups may also react. To allow crosslinking, there are unreacted amino groups from the amino-containing polymer precursor that remain in the guanidinyl-containing polymer. In certain embodiments, where the aminopolymer is polyethyleneimine, no more than (or less than) 25 mol% of the amino groups of the aminopolymer receive guanidinyl functional groups. In certain embodiments, where the aminopolymer is polyethyleneimine, no more than (or less than) 20 mol% of the amino groups of the aminopolymer receive guanidinyl functional groups. In certain embodiments, where the aminopolymer is polyethyleneimine, no more than (or less than) 15 mol% of the amino groups of the aminopolymer receive guanidinyl functional groups. If desired, various combinations of guanylation agents can be used. Known guanylating agents for reaction with an amino-containing polymer precursor include, but are not limited to, cyanamide; O-alkylisourea salts such as O-methylisourea sulfate, O-methylisourea hydrogen sulfate, O-methylisourea acetate, O-ethylisourea hydrogen sulfate, and O-ethylisourea hydrochloride; chloroformamidine hydrochloride; 1-amidin-1,2,4-triazole hydrochloride; 3,5-dimethylpyrazol-1-carboxamidine nitrate; pyrazol-1-carboxidine hydrochloride; N-amidinopyrazol-1-carboxidine hydrochloride; and carbodiimides such as dicyclohexylcarbodiimide, N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide, and diisopropylcarbodiimide. The amino-containing polymer precursor can also be acylated with guanidino functional carboxylic acids, such as guanidinoacetic acid and 4-guanidinobutyric acid, in the presence of activating agents, such as EDC (N-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride), or EEDQ (2-ethoxy-l-ethoxycarbonyl-l,2-dihydroquinoline). Furthermore, the guanidinyl-containing polymer can be prepared by alkylation with chloroacetone guanyl hydrazone, as described in U.S. Patent No. 5,712,027 (Ali et al.) . Guanylation agents for the preparation of biguanide-containing polymers include sodium dicyanamide, dicyandiamide, and substituted cyanoguanidines such as N3-p-chlorophenyl-N1-cyanoguanidine, N3-phenyl-N1-cyanoguanidine, N3-alpha-naphthyl-N1-cyanoguanidine, N3-methyl-N1-cyanoguanidine, N3,N3-dimethyl-N1-cyanoguanidine, N3-(2-hydroxyethyl)-N1-cyanoguanidine, and N3-butyl-N1-cyanoguanidine. Alkylene- and arylenobiscyanoguanidines can be used to prepare functional biguanide polymers by chain-extension reactions. The preparation of cyanoguanidines and biscyanoguanidines is described in detail in Rose, FL and Swain, GJ Chem Soc., 1956, pp. 4422-4425. Other useful guanylation reagents are those described by Alan R. Katritzky et al., Comprehensive Organic Functional Group Transition, Vol. 6, p. 640. The guanidinyl-containing polymer formed by the reaction of an amino-containing polymer precursor and a guanylating agent will have dangling or catenary guanidinyl groups of Formula (III). R4 N R4 In the Formula (III), the R3 and R40 groups, and the m variables are the same as those defined previously. The wavy line attached to the N(R3) group shows the attachment position of the group to the rest of the polymeric material. In most embodiments, i.e., when R3 is not a polymer, the Formula (III) group is a pendant group of the polymer containing guanidinyl. Optional ligands In some formulations, it can be advantageous to react the amino-containing polymer precursor to provide other ligands or groups besides the guanidinyl-containing group. For example, it may be useful to include a hydrophobic ligand, an ionic ligand, or a hydrogen-bonding ligand. This can be particularly advantageous for eliminating certain microorganisms during the cleaning of a surface contaminated with them. Additional ligands can be readily incorporated into amino-containing polymers by well-known alkylation or acylation procedures. For example, the amino groups of amino-containing polymer precursors can be reacted using halide, sulfonate, and sulfate displacement reactions, or by epoxide ring-opening reactions. Useful alkylating agents for these reactions include, for example, dimethyl sulfate, butyl bromide, butyl chloride, benzyl bromide, dodecyl bromide, 2-chloroethanol, bromoacetic acid, 2-chloroethyltrimethylammonium chloride, styrene oxide, glycidyl hexadecyl ether, glycidyltrimethylammonium chloride, and glycidyl phenyl ether.Useful acylating agents include, for example, acid chlorides and anhydrides such as benzoyl chloride, acetic anhydride, succinic anhydride, and decanoyl chloride, and isocyanates such as trimethylsilylisocyanate, phenyl isocyanate, butyl isocyanate, and butyl isothiocyanate. In such embodiments, from 0.1 to 20 mol-%, preferably from 2 to 10 mol-%, of the amino groups of the amino-containing polymer precursors may be alkylated and / or acylated. Crosslinking agents and methods for preparing articles The guanidinyl-containing polymer can be crosslinked. The amino-containing polymer precursor can be crosslinked before reaction with the guanylating agent. Alternatively, the guanidinyl-containing polymer can be crosslinked by reacting a crosslinking agent with the remaining amino groups of the amino-containing polymer precursor after reaction with the guanylating agent. Suitable crosslinking agents include amine-reactive polyepoxy compounds (e.g., di- and triepoxy compounds) with dangling -OH groups. Examples include glycerol diglycidyl ether, sorbitol diglycidyl ether, diglycidyl ether of diglycerol, diglycidyl ether of diglycerol, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, trimethylol propane diglycidyl ether, and trimethylol ethane diglycidyl ether. Various combinations of crosslinking agents may be used if desired. A preferred crosslinking agent is glycerol diglycidyl ether. Typically, a guanylated aminopolymer is combined with a crosslinking agent, applied to a substrate (e.g., coated onto a substrate) in a liquid (e.g., water), and allowed to dry. Upon drying, the guanylated aminopolymer crosslinks. In certain embodiments, the substrate is subsequently washed to remove the uncrosslinked polymer. Details of such procedures can be found in the Examples section. U.S. Patents Nos. 9,758,547 (Rasmussen et al.) and 10,087,405 (Swanson et al.) describe the use of a guanidinyl-containing polymer crosslinked with butanediol diglycidyl ether (BUDGE) and ethylene glycol diglycidyl ether (EDGE) around the fibers of a nonwoven fabric. These materials were washed prior to use but showed extensive polymer washout in subsequent experiments. The cationic coating described herein, with its distinct crosslinking chemistry, demonstrates significantly reduced washout compared to coatings that include BUDGE or EDGE crosslinking agents. A lower residual polymer level in leachables / extractables allows for a reduced-cost manufacturing process, typically by eliminating a washing step otherwise used to produce a commercial product.Larger capacity items can be manufactured with less input coating material, which can further reduce manufacturing costs. Furthermore, the items described herein are better suited for use in the food service industry, which requires low levels of residual components on both direct and indirect food contact surfaces. Typically, at least 5 mol%, at least 10 mol%, or at least 15 mol% of the amino groups of the amine-containing polymer precursor are reacted with the crosslinking agent (whether reacted before or after guanylation of the precursor). Up to 95 mol%, up to 90 mol%, up to 80 mol%, up to 70 mol%, up to 60 mol%, up to 50 mol%, up to 40 mol%, or up to 30 mol% of the amino groups of the amine-containing polymer precursor are reacted with the crosslinking agent (whether reacted before or after guanylation of the precursor). The number of amino groups available for crosslinking (guanylation) can be determined by the amine equivalent weight of the amino-containing polymer precursor, or polymer repeating unit. These amino groups can be primary, secondary, tertiary, or even quaternary. Therefore, the percentage of crosslinking and the percentage of guanylation are calculated based on the original amine equivalent weight. A person skilled in the technique can determine the maximum for each, depending on the aminopolymer structure. For example, with polyethyleneimine (PEI), where 25% of the amine groups are tertiary, only 75% of the amine groups (primary and secondary) are available for guanylation and crosslinking. If all the primary amines are guanylated before crosslinking, only secondary amines remain for crosslinking. Substrates, articles and methods of use The substrates, articles, and methods of use of these articles can be found, for example, in U.S. Patents Nos. 9,758,547 (Rasmussen et al.) and 10,087,405 (Swanson et al.). Articles (e.g., cloths and filters) are provided comprising a substrate and a cationic coating disposed on a surface of the substrate, distributed over at least a portion of the substrate, or both. The cationic coating includes the guanidinyl-containing polymer that is bonded to the substrate by crosslinking and optionally grafted (i.e., covalently bonded) to the substrate. In certain modalities, the substrate is selected from fibers, particles, glass bubbles, membranes, sponges, woven fabrics, non-woven fabrics, and combinations thereof. In certain forms, the substrate is not porous. In certain embodiments, the substrate is porous. In such embodiments, the cationic coating is disposed on a surface of the porous substrate, distributed over at least a portion of the porous substrate, or both. Examples of porous substrates include a sponge, a woven fabric, a non-woven fabric, or a combination thereof. In certain embodiments, the guanidinyl-containing polymer is brought into contact with the substrate prior to crosslinking and crosslinks in the presence of the substrate. When the substrate includes fibers (e.g., the substrate includes a woven or nonwoven fabric), the crosslinked guanidinyl-containing polymer may surround the fibers. The fibers and the crosslinked guanidinyl-containing polymers may be intermingled in such a way that separation is not possible by a technique such as stripping or dissolving, or by any other technique without destroying the fabric. In certain embodiments, the substrate is formed from a material selected from poly(meth)acrylates, poly(meth)acrylamides, polyolefins, poly(isoprenes), poly(esters), poly(butadienes), fluorinated polymers, chlorinated polymers, polyamides, polyimides, polyethers, poly(ether sulfones), poly(sulfones), poly(vinyl acetates), vinyl acetate copolymers, poly(phosphacenes), poly(vinyl esters), poly(vinyl ethers), poly(vinyl alcohols), poly(carbonates), polyurethanes, cellulosic materials, and combinations thereof. During use, when it comes into contact with a target biological species, a complex is formed that includes the guanidinyl-containing polymer and the target biological species. The target biological species can be a nearly neutral or negatively charged biological species. In certain modalities, the target biological species is selected from biomacromolecules and microbiological species. In certain modalities, the biomacromolecules are selected from proteins, enzymes, nucleic acids, endotoxins, and combinations thereof. In certain modalities, the biological species is selected from bacteria, viruses, cells, cellular debris, spores, and combinations thereof. In certain modalities, the cells are selected from prokaryotes, eukaryotes, and combinations thereof. In certain modalities, the biological species is derived from a cell culture or a fermentation process. In certain modalities, the spores include bacterial endospores. In certain embodiments, the article is a cloth. These cloths can be used in a method for removing a contaminant. In certain embodiments, a method for removing a contaminant from a contaminated surface includes contacting the cloth, in the presence of a liquid, with an area of the contaminated surface, where the contaminated surface is a solid surface. The liquid may include water, a water-miscible organic solvent, or a mixture of these. In some methods, the contaminant is a microorganism. In some methods, at least 99 percent of microorganisms are eliminated from an area. In certain embodiments, the article, when it comes into contact with a surface area contaminated with microorganisms in the presence of the liquid and then comes into contact with a second surface, transfers no more than 0.2 percent of the microorganisms from the article to the second surface. In certain configurations, the article is a filter, which can be used in standard filtration methods. Configurations Modality 1 is an article comprising: a substrate; a cationic coating bonded to the substrate, wherein the cationic coating comprises a guanidinyl-containing polymer crosslinked to the substrate; wherein the guanidinyl-containing polymer is of the following Formula (I): Polymer wherein: R3 is an H, (hetero)alkyl C1-C12, (hetero)aryl C5C12, or polymer; each R4 is independently H, (hetero)alkyl C1-C12, or (hetero)aryl C5-C12; each R5 is H, (hetero)alkyl Ci-Ci2, (hetero)aryl C5-C12, or N(R4)2, the polymer is a residue of an aminopolymer chain; m is 1 or 2; and x is an integer of at least 1; and wherein the guanidinyl-containing polymer is crosslinked with an amine-reactive polyepoxy compound having dangling -OH groups. Modality 2 is the article of modality 1, wherein the guanidinyl-containing polymer is crosslinked by reaction of at least 5 mol-% (at least 10 mol-% or at least 15 mol-%) of the amino groups of an aminopolymer precursor with the amine-reactive polyepoxy compound having dangling -OH groups. Mode 3 is the article of mode 1 or 2, wherein the guanidinyl-containing polymer is crosslinked by the reaction of up to 95 mol-% (up to 90 mol-%, up to 80 mol-%, up to 70 mol-%, up to 60 mol-%, up to 50 mol-%, up to 40 mol-% or up to 30 mol-%) of the amino groups of an aminopolymer precursor with the amine-reactive polyepoxy compound having dangling -OH groups. Modality 4 is the article of any of the above modalities wherein the amine-reactive polyepoxy compound having dangling -OH groups is selected from the group of glycerol diglycidyl ether, sorbitol diglycidyl ether, diglycidyl ether of diglycerol, diglycidyl ether of diglycerol, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, trimethylol propane diglycidyl ether, trimethylol ethane diglycidyl ether, and combinations thereof. Modality 5 is the article of modality 4, wherein the amine-reactive polyepoxy compound having dangling OH groups is glycerol diglycidyl ether. Modality 6 is the article of any of the above modalities, wherein the guanidinyl-containing polymer is cross-linked to the substrate and covalently bonded to the substrate. Modality 7 is the article of any of the above modalities in which at least 0.1 mol-% (at least 0.5 mol-%, at least 1 mol-%, at least 2 mol-%, at least 10 mol-%, at least 20 mol-%, at least 30 mol-%, at least 40 mol-%, or at least 50 mol-%) of the amino groups of an aminopolymer precursor receive guanidinyl functional groups. Mode 8 is the article of any of the above modes in which up to 95 mol-% (up to 90 mol-%, up to 80 mol-%, up to 70 mol-%, up to 60 mol-%, up to 50 mol-%, or up to 25 mol-%) of the amino groups of an aminopolymer precursor receive guanidinyl functional groups. Modality 9 is the article of any of the above modalities where x is up to 10,000, up to 5,000, up to 1,000, up to 500, up to 100, up to 80, up to 60, up to 40, up to 20, or up to 10. Modality 10 is the article of any of the above modalities in which the R3 group refers to hydrogen, C1-C12 (hetero)alkyl, or C5-C12 (hetero)aryl. Modality 11 is the article of any of the above modalities in which the aminopolymer is selected from the group of polyaminoamide, polyamidoamine, polyethyleneimine, polypropyleneimine, polyvinylamine, polyallylamine, polydialylamine, and mixtures thereof. Modality 12 is the article of modality 11, where the aminopolymer is polyethyleneimine. Modality 13 is the article of modality 12, wherein no more (or less) 25 molar percent of the amino groups of the polyethyleneimine precursor receive guanidinyl functional groups. Modality 14 is the article of modality 13, wherein no more (or less) 20 molar percent of the amino groups of the polyethyleneimine precursor receive guanidinyl functional groups. Modality 15 is the article of modality 14, wherein no more (or less) 15 molar percent of the amino groups of the polyethyleneimine precursor receive guanidinyl functional groups. Modality 16 is the article of any of modalities 1 to 15, wherein the guanidinyl groups of the aminopolymer are pendants of the aminopolymer chain. Modality 17 is the article of any of modalities 1 to 15, wherein the guanidinyl groups of the aminopolymer are in the aminopolymer chain. Modality 18 is the article of any of the above modalities, wherein the guanidinyl-containing polymer is a reaction product of a guanylating agent and an amino-containing polymer precursor. Modality 19 is the article of any of the above modalities, wherein the guanidinyl-containing polymer is present in an amount of at least 0.1 percent by weight, based on the total weight of the article. Modality 20 is the article of any of the above modalities, wherein the guanidinyl-containing polymer is present in an amount of up to 10 percent by weight (for a cloth, although larger amounts may be used for a filter), based on the total weight of the article. Modality 21 is the article of any of the above modalities in which the substrate is selected from fibers, particles, glass bubbles, membranes, sponges, woven fabrics, non-woven fabrics and combinations thereof. Modality 22 is the article of any of modalities 1 through 21 where the substrate is not porous. Modality 23 is the composition of any of modalities 1 through 21 where the substrate is porous. Modality 24 is the article of modality 23, where the cationic coating is arranged on a Modality 29 is the article of modality 28, where the target biological species is selected from biomacromolecules and microbiological species. Modality 30 is the article of Modality 29, where biomacromolecules are selected from proteins, enzymes, nucleic acids, endotoxins and combinations thereof. Modality 31 is the article of modality 29, where the target biological species is selected from bacteria, viruses, cells, cell debris, spores, and combinations thereof. Modality 32 is the article of Modality 31, where the cells are selected from prokaryotes, eukaryotes, and combinations of these. Modality 33 is the article of modality 31 or 32, where the biological species is derived from a cell culture or fermentation process. Modality 34 is the article of modality 31 where the spores comprise bacterial endospores. Modality 35 is the article of any of modalities 23 to 34, which is a filter. Modality 36 is the article of any of modalities 23 to 34 that is a cloth. Mode 37 is a method for removing a contaminant from a contaminated surface; the method comprises bringing the article of Mode 36 into contact, in the presence of a liquid, with an area of the contaminated surface, wherein the contaminated surface is a solid surface. Modality 38 is the method of modality 37, wherein the liquid comprises water, a water-miscible organic solvent, or a mixture of these. Modality 39 is the method of modality 37 or 38, where the contaminant is a microorganism. Mode 40 is the method of mode 39, where at least 99 percent of microorganisms are eliminated from an area. Mode 41 is the method of any of modes 37 to 40, wherein the article, when brought into contact with a surface area contaminated with microorganisms in the presence of the liquid and then comes into contact with a second surface, transfers no more than 0.2 percent of the microorganisms from the article to the second surface. EXAMPLES The objectives and advantages of this description are further illustrated by the following examples, but the particular materials and quantities cited in the examples, as well as other conditions and details, should not be interpreted as unduly limiting this description. Unless otherwise stated, all parts, percentages, ratios, etc., in the examples and throughout the rest of the description are expressed by weight, and all reagents used in the examples are obtained from, or available from, general chemical suppliers such as, for example, Sigma-Aldrich, St. Louis, MO, or can be synthesized by conventional methods. The following abbreviations are used in this section: mi = milliliter, min = minute, h = hour, s = second, g = gram, mg = milligram, m = meter, centimeter = cm, mm = millimeter, pm = micrometer or micron, °C = degrees Celsius, °F = degrees Fahrenheit, N = Newton, oz = ounce, mW / cm² = milliwatts per square centimeter. Unless otherwise stated, all parts, percentages, ratios, etc., in the examples and throughout the rest of the description are by weight. Materials Abbreviations Description and Source Milli-Q Water Deionized water, filtered to 18 megaohm from a MilliQ Synthesis A10 system, obtained from Millipore, Waltham, MA BUDGE 1,4-Butanediol diglycidyl ether, obtained from TCI America, Portland, OR GDGE Glycerol diglycidyl ether (technical grade), obtained from Sigma-Aldrich Company, St. Louis, MO PEGDGE Poly(ethylene glycol) diglycidyl ether (500 Mn average), obtained from Sigma-Aldrich Company EGDGE Ethylene glycol diglycidyl ether (mixture), obtained from TCI America G-PEI Guanylated polyethyleneimine (described in Preparatory Examples 1-7) SONTARA 8004 Nonwoven fabric sheet (PET, 60 g / m2), obtained from Jacob Holm Group, Basel, Switzerland Testing methods Wash elimination test Three pre-weighed G-PEI coated nonwoven sheets (10 in (25.4 cm) by 12 in (30.5 cm)) were placed in a 1000 ml polypropylene bottle. Each sheet was prepared using the same example method. Deionized water (800 ml) was added to the bottle, and the bottle was capped. For the first wash cycle, the bottle was placed on an orbital shaker (Lab-Line Instruments Incorporated, Melrose Park, IL) at 150 revolutions per minute (rpm) for 15 minutes. The water was then discarded and replaced with fresh deionized water. The wash cycle was repeated two more times, using fresh deionized water for each wash cycle. After three water wash cycles, the nonwoven sheets were removed from the bottle and dried at 110 °C for 30 minutes. Each washed sheet and The dried material was weighed and the amount of coating remaining on the sheet was calculated.The percentage of the washed coating was calculated for each sheet according to Equation 1 (where A = calculated amount of coating on the sheet before the washing procedure and B = calculated amount of coating on the sheet after the washing and drying procedure). Equation 1: Percentage of washed coating = 100 * [1 ινΐΛ / a / zuzz / uuu i (B / A)]. The mean value for percentage of washed coating (n=3) was determined with the standard deviation. Static binding capacity assay to tartrazine Tartrazine (5 mL of 1.0 mg / mL solution in MilliQ water) was added to a 15 mL conical tube containing a 25 mm diameter disc of coated nonwoven fabric. The sample was incubated for 22 hours at room temperature while centrifuged in a tube vortex mixer (Thermo Scientific; Waltham, MA) set at 20 rpm. A tenfold dilution of the supernatant was prepared in a 96-well Costar assay plate (Corning Incorporated, Corning, NY) with MilliQ water and transferred (150 µL) to a 96-well clear UV-STAR microplate (Greiner Bio-One North America Incorporated, Monroe, NC). The tartrazine standard series was prepared by 2-fold dilutions from 100 µg / ml to 0.78 µg / ml using milliQ water. The standards were added (150 µl) to the microplate containing the diluted samples. A water-only control was added as both a standard (0 µg / ml tartrazine) and a blank.Absorbance (255 nanometers (nm) and 425 nm wavelength) was measured using a SPECTRAMAX M5 plate reader (Molecular Devices, San Jose, CA). The standard curve (absorbance at 255 nm) was used to determine the static tartrazine binding capacity (SBC) of the coated nonwoven fabric discs by calculating the total amount of tartrazine bound to a disc divided by the surface area of the disc (surface area of a 2.5 cm diameter disc = 4.91 cm²). The SBC was reported as the mean value of three replicates. This test provides an indication of the amount of polymer coated onto a substrate. Test method for eliminating microorganisms from a surface contaminated by microorganisms and contamination transfer The test method was performed as described in U.S. Patent No. 10,087,405 (Swanson et al.) with a 4x load weight of sterile distilled water used to moisten each cloth. Preparatory Example 1. 25% guanylated polyethyleneimine (25% G-PEI) Polyethyleneimine (PEI), 70,000 MW (obtained from Polysciences, Warrington, PA; 75 grams of a 30.5 wt% solution in water (0.532 amine equivalents) were loaded into a 500 mL polypropylene bottle. O-Methylisourea hemisulfate (16.38 grams, 0.133 equivalents) was dissolved in deionized water (100 mL), and the resulting solution was poured into the bottle containing PEI. The bottle was sealed and placed on a mechanical roller to mix the contents at room temperature for approximately 22 hours. NMR spectroscopy analysis indicated the conversion to the desired product, which has 25% PEI amine groups (primarily primary amine groups) converted to guanidines. Concentrated hydrochloric acid was used to titrate the mixture to approximately pH 7 (measured using pH paper). The percentage of solids was determined to be 20.5% using an Ohaus moisture balance (model number MB35, obtained from Ohaus Corporation, Parsippany, NJ). Preparatory Example 2.20% guanylated polyethyleneimine (20% G-PEI). The same procedure reported in Preparatory Example 1 was followed, except that 13.30 g of O-methylisourea hemisulfate dissolved in 75 mL of deionized water was used to prepare PEI in which 20% of the amine groups were converted to guanidines. The percentage of solids was determined to be 23.0%. Preparatory Example 3. 15% guanylated polyethyleneimine (15% G-PEI) The same procedure reported in Preparatory Example 1 was followed, except that 9.83 g of O-methylisourea hemisulfate dissolved in 50 mL of deionized water was used to prepare PEI in which 15% of the amine groups were converted to guanidines. The percentage of solids was determined to be 26.0%. Preparatory Example 4. 10% guanylated polyethyleneimine (10% G-PEI) Polyethyleneimine (PEI) was loaded, 70,000 MW (50 grams of 6. A 30.0 wt% solution in water (0.349 amine equivalents) was prepared in a 125 mL polypropylene bottle. O-Methylisourea hemisulfate (4.29 g, 0.0349 equivalents) was dissolved in deionized water (40 mL), and the resulting solution was poured into the bottle containing PEI. The bottle was sealed and placed on a mechanical roller to mix the contents at room temperature for approximately 22 hours. NMR spectroscopy analysis indicated the conversion to the desired product, which has 10% of the PEI amine groups (mainly primary amine groups) converted to guanidines. Concentrated hydrochloric acid was used to titrate the mixture to approximately pH 7 (measured using pH paper). The percentage of solids was determined to be 23.55%. Preparatory example 5. 5% guanylated polyethyleneimine (5% G-PEI) The same procedure reported in Preparatory Example 4 was followed, except that 2.14 grams (g) of O-methylisourea hemisulfate dissolved in 40 ml of deionized water were used to prepare PEI in which 5% of the amine groups were converted to guanidines. The percentage of solids was determined to be 22.85%. Preparatory Example 6. 2.5% guanylated polyethyleneimine (2.5% G-PEI) The same procedure was followed as reported in the Preparatory Example 4 with the exception that 1.07 g of O-methylisourea hemisulfate dissolved in 40 ml of deionized water was used to prepare PEI in which 2.5% of the amine groups were converted to guanidines. The percentage of solids was determined to be 21.7%. Preparatory Example 7. 1% guanylated polyethyleneimine (1% G-PEI) The same procedure reported in Preparatory Example 4 was followed, except that 0.429 g of O-methylisourea hemisulfate dissolved in 40 mL of deionized water was used to prepare PEI in which 1% of the amine groups were converted to guanidines. The percentage of solids was determined to be 21.2%. Example 1. Nonwoven fabric coated with 25% G-PEI crosslinked with GDGE A 25% portion of guanylated polyethyleneimine from Preparatory Example 1 (4.88 g) was diluted to 25 g with deionized water in a polypropylene bottle and mixed. GDGE (0.47 g) was added to a polypropylene bottle, diluted to 25 g with deionized water, and mixed. The contents of the two bottles were combined and mixed to form a coating formulation. A sheet of SONTARA 8004 nonwoven fabric (10 in (25.4 cm) x 12 in (30.5 cm)) was weighed before coating. The coating formulation (15 ml) was pipetted onto the nonwoven fabric sheet inside a plastic bag. The bag was sealed, and the coating formulation was pressed through the nonwoven fabric sheet using a hand roller so that the sheet was evenly coated. The coated fabric sheet was removed from the plastic bag, placed on a clean aluminum tray, and then dried at 110°C for 20 minutes.The dry coated sheet was weighed and the amount of coating on the sheet was calculated and recorded. Example 2. Nonwoven fabric coated with 20% G-PEI crosslinked with GDGE The same procedure was followed as reported in Example 1 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 4.35 g of the 20% guanylated polyethyleneimine of Preparatory Example 2. Example 3. Nonwoven fabric coated with 15% G-PEI crosslinked with GDGE The same procedure was followed as reported in Example 1 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 3.85 g of the 15% guanylated polyethyleneimine of Preparatory Example 3. Example 4. Nonwoven fabric coated with 10% G-PEI crosslinked with GDGE The same procedure reported in Example was followed with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 4.25 g of the 10% guanylated polyethyleneimine of Preparatory Example 4. Example 5. Nonwoven fabric coated with 5% G-PEI crosslinked with GDGE The same procedure was followed as reported in Example 1 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 4.38 g of the 5% guanylated polyethyleneimine of Preparatory Example 5. Example 6. Nonwoven fabric coated with 2.5% G-PEI crosslinked with GDGE The same procedure was followed as reported in Example 1 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 4.61 g of the 2.5% guanylated polyethyleneimine of Preparatory Example 6. Example 7. Nonwoven fabric coated with 1% G-PEI crosslinked with GDGE The same procedure was followed as reported in Example 1 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 4.72 g of the 1% guanylated polyethyleneimine of Preparatory Example 7. Example 8. Nonwoven fabric coated with 20% G-PEI crosslinked with GDGE (0.5% G-PEI by weight of coating formulation) A 20% portion of guanylated polyethyleneimine from Preparatory Example 2 (4.35 g) was diluted to 25 g with deionized water in a polypropylene bottle and mixed. GDGE (0.47 g) was added to a polypropylene bottle, diluted to 25 g with deionized water, and mixed. Each GDGE and G-PEI solution was diluted 4 times with deionized water. The contents of the two bottles were combined and mixed to form a coating formulation. The coating procedure described in Comparative Example 1 was followed. The coating formulation contained 0.5% G-PEI by weight. Example 9. 20% G-PEI coated nonwoven fabric crosslinked with GDGE (0.1% G-PEI by weight of coating formulation) A 20% portion of guanylated polyethyleneimine from Preparatory Example 2 (4.35 g) was diluted to 25 g with deionized water in a polypropylene bottle and mixed. GDGE (0.47 g) was added to a polypropylene bottle, diluted to 25 g with deionized water, and mixed. Each GDGE and G-PEI solution was diluted 20-fold with deionized water. The contents of the two bottles were combined and mixed to form a coating formulation. The coating procedure described in Comparative Example 1 was followed. The coating formulation contained 0.1% G-PEI by weight. Comparative Example 1. 25% G-PEI-coated nonwoven fabric crosslinked with BUDGE A 25% portion of guanylated polyethyleneimine from Preparatory Example 1 (4.88 g) was diluted to 25 g with deionized water in a polypropylene bottle and mixed. BUDGE (0.46 g) was added to a polypropylene bottle, diluted to 25 g with deionized water, and mixed. The contents of the two bottles were combined and mixed to form a coating formulation. A sheet of SONTARA 8004 nonwoven fabric (10 in (25.4 cm) x 12 in (30.5 cm)) was weighed before coating. The coating formulation (15 ml) was pipetted onto the nonwoven fabric sheet inside a plastic bag. The bag was sealed, and the coating formulation was pressed through the nonwoven fabric sheet using a hand roller so that the sheet was evenly coated. The coated fabric sheet was removed from the plastic bag, placed on a clean aluminum tray, and then dried at 110°C for 20 minutes.The dry coated sheet was weighed and the amount of coating on the sheet was calculated and recorded. Comparative example 2. Nonwoven fabric coated with 20% G-PEI crosslinked with BUDGE The same procedure was followed as reported in Comparative Example 1 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 4.35 g of the 20% guanylated polyethyleneimine of Preparatory Example 2. Comparative example 3. Nonwoven fabric coated with 15% G-PEI crosslinked with BUDGE The same procedure was followed as reported in the Comparative Example 1 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 3.85 g of the 15% guanylated polyethyleneimine of Preparatory Example 3. Comparative example 4. Nonwoven fabric coated with 10% G-PEI crosslinked with BUDGE The same procedure was followed as reported in the Comparative Example 1 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 4.25 g of the 10% guanylated polyethyleneimine of Preparatory Example 4. Comparative example 5. Nonwoven fabric coated with 5% G-PEI crosslinked with BUDGE The same procedure was followed as reported in the Comparative Example 1 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 4.38 g of the 5% guanylated polyethyleneimine of Preparatory Example 5. Comparative example 6. Non-woven fabric coated with G-PEI 2.5% crosslinked with BUDGE The same procedure was followed as reported in Comparative Example 1 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 4.61 g of the 2.5% guanylated polyethyleneimine of Preparatory Example 6. Comparative example 7. Nonwoven fabric coated with 1% G-PEI crosslinked with BUDGE The same procedure was followed as reported in Comparative Example 1 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 4.72 g of the 1% guanylated polyethyleneimine of Preparatory Example 7. Comparative example 8. Nonwoven fabric coated with 25% G-PEI crosslinked with EGDGE A 25% portion of guanylated polyethyleneimine from Preparatory Example 1 (4.88 g) was diluted to 25 g with deionized water in a polypropylene bottle and mixed. EGDGE (0.40 g) was added to a polypropylene bottle, diluted to 25 g with deionized water, and mixed. The contents of both bottles were combined and mixed to form a coating formulation. The coating procedure described in Comparative Example 1 was followed. Comparative example 9. Non-woven fabric coated with % G-PEI crosslinked with EGDGE The same procedure was followed as reported in Comparative Example 8 with the exception that the 25% guanylated polyethyleneimine from Preparatory Example 1 was replaced with 4.35 g of the 20% guanylated polyethyleneimine from Preparatory Example 2. Comparative example 10. Non-woven fabric coated with 15% G-PEI crosslinked with EGDGE The same procedure was followed as reported in Comparative Example 8 with the exception that the 25% guanylated polyethyleneimine from Preparatory Example 1 was replaced with 3.85 g of 15% guanylated polyethyleneimine from Preparatory Example 3. Comparative example 11. Nonwoven fabric coated with 25% G-PEI crosslinked with PEGDGE A 25% portion of guanylated polyethyleneimine from Preparatory Example 1 (4.88 g) was diluted to 25 g with deionized water in a polypropylene bottle and mixed. PEGDGE (1.15 g) was added to a polypropylene bottle, diluted to 25 g with deionized water, and mixed. The contents of both bottles were combined and mixed to form a coating formulation. The coating procedure described in Comparative Example 1 was followed. Comparative example 12. Nonwoven fabric coated with % G-PEI crosslinked with PEGDGE The same procedure was followed as reported in Comparative Example 11 with the exception that the 25% guanylated polyethyleneimine of Preparatory Example 1 was replaced with 4.35 g of the 20% guanylated polyethyleneimine of Preparatory Example 2. Comparative example 13. Nonwoven fabric coated with 15% G-PEI crosslinked with PEGDGE The same procedure was followed as reported in Comparative Example 11 with the exception that the 25% guanylated polyethyleneimine from Preparatory Example 1 was replaced with 3.85 g of 15% guanylated polyethyleneimine from Preparatory Example 3. Comparative example 14. Nonwoven fabric coated with 20% G-PEI crosslinked with BUDGE (0.5% G-PEI by weight of coating formulation) A 20% portion of guanylated polyethyleneimine from Preparatory Example 2 (4.35 g) was diluted to 25 g with deionized water in a polypropylene bottle and mixed. BUDGE (0.46 g) was added to a polypropylene bottle, diluted to 25 g with deionized water, and mixed. Each BUDGE and G-PEI solution was diluted 4 times with deionized water. The contents of the two bottles were combined and mixed to form a coating formulation. The coating procedure described in Comparative Example 1 was followed. The coating formulation contained 0.5% G-PEI by weight. Comparative example 15. Nonwoven fabric coated with 20% G-PEI crosslinked with BUDGE (0.1% G-PEI by weight of coating formulation) A 20% portion of guanylated polyethyleneimine from Preparatory Example 2 (4.35 g) was diluted to 25 g with deionized water in a polypropylene bottle and mixed. BUDGE (0.46 g) was added to a polypropylene bottle, diluted to 25 g with deionized water, and mixed. Each BUDGE and G-PEI solution was diluted 20-fold with deionized water. The contents of the two bottles were combined and mixed to form a coating formulation. The coating procedure described in Comparative Example 1 was followed. The coating formulation contained 0.1% G-PEI by weight. Example 10. Washout test of nonwoven fabrics coated with G-PEI The coated nonwoven sheets from Examples 1-3, Comparative Examples 1-3, and Comparative Examples 8-13 were washed according to the wash-out test method. The results for the percentage of coating washed off are reported in Table 1 and Figure 2 as the mean value obtained from three repetitions. Articles coated with G-PEI crosslinked with diglycidyl ether of glycerol (GDGE) have less wash-out of the coating from the nonwoven sheet (i.e., greater coating retention on the nonwoven sheet) after washing compared to the use of BUDGE, EGDGE, and PEGDGE. Table 1 Sample % of washed coating Coating description (n=3) Mean value Standard deviation Example 1 G-PEI at 25% with GDGE 50.8 3.7 Example 2 G-PEI at 20% with GDGE 41.0 1.4 Example 3 G-PEI at 15% with GDGE 36.6 1.9 Comparative example 1 G-PEI at 25% with BUDGE 92.7 1.8 Comparative example 2 G-PEI at 20% with BUDGE 88.6 2.4 Comparative example 3 G-PEI at 15% with BUDGE 94.4 4.8 Comparative example 8 G-PEI at 25% with EGDGE 92.8 2.9 Comparative example 9 G-PEI at 20% with EGDGE 77.3 6.1 Comparative example 10 G-PEI at 15% with EGDGE 68.8 7.9 Comparative example 11 G-PEI at 25% with PEGDGE 96.5 0.8 Comparative example 12 G-PEI at 20% with PEGDGE 89.8 1.6 Comparative example 13 G-PEI at 15% with PEGDGE 85.6 2.3 Example 11. Washout test of nonwoven fabrics coated with G-PEI The coated nonwoven sheets of Examples 4-7 and Comparative Examples 4-7 were washed according to the wash-out test method. The results for the percentage of coating washed off are reported in Table 2 and Figure 3 as the mean value obtained from three repetitions. Articles coated with GPEI crosslinked with diglycidyl glycerol ether (GDGE) have less wash-out of the coating from the nonwoven sheet (i.e., greater coating retention on the nonwoven sheet) after washing compared to using BUDGE for crosslinking. Table 2 % of washed coating Sample Coating Description (n=3) Mean Value Standard Deviation Example 4 G-PEI at 10% with GDGE 35.8 3.7 Example 5 G-PEI at 5% with GDGE 25.9 4.1 Example 6 G-PEI at 2.5% with GDGE 19.6 2.6 Example 7 G-PEI at 1% with GDGE 19.1 3.8 Comparative Example 4 G-PEI at 10% with BUDGE 44.5 5.8 Comparative Example 5 G-PEI at 5% with BUDGE 40.9 4.6 Comparative Example 6 G-PEI at 2.5% with BUDGE 35.1 1.8 Comparative Example 7 G-PEI at 1% with BUDGE 40.4 4.9 Example 12. Static bonding capacity to tartrazine of nonwoven fabrics coated with G-PEI The coated nonwoven fabric sheets from Examples 1-3 and Comparative Examples 8-13 were washed according to the wash removal test method. An uncoated nonwoven fabric sheet was also washed and served as an experimental control. Each fabric sheet was exposed to a 1 mg / ml tartrazine dye solution according to the Tartrazine Static Binding Capacity Test described in the Test Method section. The static binding capacity results are shown in Table 3 and Figure 4. The washed nonwoven fabrics exposed to tartrazine showed that the GDGE-crosslinked G-PEI had a significantly higher static binding capacity (SBC) compared to the BUDGE, EGDGE, and PEGDGE crosslinks.These results indicate a greater binding capacity due to higher levels of crosslinked polymer matrix using GDGE compared to other polyglycidyl ethers after coating and washing steps. Table 3 inaLa / a / zuzz / uuu i. Sample Coating Description Tartrazine SBC (mg / cm2, n=3) Mean Value Standard Deviation Control Uncoated SONTARA 8004 Fabric Sheet 0.0256 0.0004 Example 1 25% G-PEI with GDGE 0.3366 0.0099 Example 2 20% G-PEI with GDGE 0.5425 0.0643 Example 3 15% G-PEI with GDGE 0.5480 0.0594 Comparative Example 1 25% G-PEI with BUDGE 0.0477 0.0060 Comparative Example 2 20% G-PEI with BUDGE 0.0748 0.0278 Comparative Example 3 15% G-PEI with BUDGE 0.0783 0.0128 Comparative example 8 G-PEI at 25% with EGDGE 0.0979 0.0245 Comparative example 9 G-PEI at 20% with EGDGE 0.1306 0.0372 Comparative example 10 G-PEI at 15% with EGDGE 0.2456 0.0260 Comparative example 11 G-PEI at 25% with PEGDGE 0.0308 0.0208 Comparative example 12 G-PEI at 20% with PEGDGE 0.1156 0.0380 Comparative example 13 G-PEI at 15% with PEGDGE 0.1625 0.0082 Example 13. Elimination and transfer of microorganisms with nonwoven fabrics coated with G-PEI The coated nonwoven fabric sheets from Examples 8-9 and Comparative Examples 14-15 were evaluated as wipes for removing microorganisms from surfaces using the test method for microorganism removal from a surface contaminated with microorganisms and contamination transfer described in the test method section. An uncoated nonwoven fabric sheet was also evaluated as an experimental control. The results for removal and cross-contamination of C. sporogenes spores, ATCC no. 3584, from surfaces using coated nonwoven fabric sheets as wipes are reported in Tables 4-5 and Figures 5-6. The results are reported as the mean value obtained from three replicates. Evaluation of Examples 1-3 and Comparative Example 3 as cloths showed no difference in the removal of bacterial spores from a surface (data not shown). These examples were coated from a 2% solution G-PEI by weight with sufficient crosslinking agent to react with 20% of the amines. Reducing the initial polymer and crosslinking agent concentrations by 4 times (0.5% G-PEI by weight solution) and 20 times (0.1% GPEI by weight solution) showed that Examples 8-9 had greater bacterial spore removal and reduced surface-to-surface spore transfer compared to Comparative Examples 14-15. The results show a distinct advantage to using GDGE for crosslinking at low polymer concentrations. Table 4 ινΐΛ / a / zuzz / uuu i Sample Description Log10 reduction of C. sporogenes spores from a surface (n=3) Standard deviation Mean Control Uncoated SONTARA 8004 film 0.5% G-PEI at 20% with GDGE 0.1% G-PEI at 20% with GDGE 0.5% G-PEI at 20% with BUDGE 0.1% G-PEI at 20% with BUDGE 1.35 0.14 Example 8 3.12 0.12 Example 9 2.56 0.15 Comparative example 14 2.37 0.17 Comparative example 15 1.72 0.14 Table 5 Sample Description % of C. sporogenes spore transfer from a contaminated cloth to a clean surface (n=3) Mean Value Standard Deviation Control Uncoated SONTARA 8004 Sheet 2.37 0.60 Example 8 0.5% of 20% G-PEI with GDGE 0.04 0.02 Example 9 0.1% of 20% G-PEI with GDGE 0.15 0.08 Comparative Example 14 0.5% of 20% G-PEI with BUDGE 0.21 0.13 Comparative Example 15 0.1% of 20% G-PEI with BUDGE 1.80 0.77 The complete descriptions of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were incorporated individually. To the extent of any conflict or discrepancy between this document as written and the exposition in any document incorporated by reference herein, this document as written shall prevail. Various modifications and alterations to this description will be evident to those skilled in the art, without departing from the scope and spirit of this description.It should be understood that the present description is not intended to be unduly limited to the illustrative modalities and examples set forth herein, and that such examples and modalities are presented for illustrative purposes only, and therefore the scope of the description is limited only by the claims set forth herein as follows. It is hereby stated that, as of this date, the best method known to the applicant for putting the aforementioned invention into practice is that which is clear from the present description of the invention.
Claims
Having described the invention as above, the following claims are claimed as property:
1. An article, characterized in that it comprises: a substrate; a cationic coating bonded to the substrate, wherein the cationic coating comprises a guanidinyl-containing polymer crosslinked to the substrate; wherein the guanidinyl-containing polymer is of the following Formula (I): R3 is a C1-C12 H, (hetero)alkyl, C5-C12 (hetero)aryl, or polymer; each R4 is independently C1-C12 H, (hetero)alkyl, or C5-C12 (hetero)aryl; each R5 is C1-C12 H, (hetero)alkyl, C5-C12 (hetero)aryl, or N(R4)2; the polymer is a residue of an aminopolymer chain; mes 1 or 2; yx is an integer of at least 1; and wherein the guanidinyl-containing polymer is crosslinked with an amine-reactive polyepoxy compound having dangling -OH groups.
2. The article according to claim 1, characterized in that the guanidinyl-containing polymer is crosslinked by the reaction of at least 5 mol-% of the amino groups of an aminopolymer precursor with the amine-reactive polyepoxy compound having dangling -OH groups.
3. The article according to claim 1 or 2, characterized in that the guanidinyl-containing polymer is crosslinked by the reaction of up to 50 mol-% of the amino groups of an aminopolymer precursor with the amine-reactive polyepoxy compound having dangling -OH groups.
4. The article according to any of the preceding claims, characterized in that the amine-reactive polyepoxy compound having dangling -OH groups is selected from the group of glycerol diglycidyl ether, sorbitol diglycidyl ether, diglycidyl ether of diglycerol, diglycidyl ether of diglycerol, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, trimethylol propane diglycidyl ether, trimethylol ethane diglycidyl ether, and combinations thereof.
5. The article according to claim 4, characterized in that the amine-reactive polyepoxy compound having dangling -OH groups is glycerol diglycidyl ether.
6. The article according to any of the preceding claims, characterized in that at least 0.1 mol% of the amino groups of an aminopolymer precursor receive guanidinyl functional groups.
7. The article in accordance with any of the preceding claims, characterized in that up to 95 mol-% of the amino groups of an aminopolymer precursor receive guanidinyl functional groups.
8. The article according to any of the preceding claims, characterized in that the aminopolymer is selected from the group of polyaminoamide, polyamidoamine, polyethyleneimine, polypropyleneimine, polyvinylamine, polyallylamine, polydiallylamine, and mixtures thereof.
9. The article according to claim 8, characterized in that the aminopolymer is polyethyleneimine.
10. The article according to claim 9, characterized in that no more than 25 mol-% of the amino groups of a polyethyleneimine precursor receive guanidinyl functional groups.
11. The article according to any of the preceding claims, characterized in that the substrate is formed from a material selected from poly(meth)acrylates, poly(meth)acrylamides, polyolefins, poly(isoprenes), poly(butadienes), fluorinated polymers, chlorinated polymers, poly(esters), polyamides, polyimides, polyethers, poly(ether 67 sulfones), poly(sulfones), poly(vinyl acetates), vinyl acetate copolymers, poly(phosphacenes), poly(vinyl esters), poly(vinyl ethers), poly(vinyl alcohols), poly(carbonates), polyurethanes, cellulosic materials, and combinations thereof.
12. The article in accordance with any of the preceding claims, characterized in that the substrate is porous.
13. The article according to claim 12, characterized in that the cationic coating is disposed on a surface of the porous substrate, distributed along at least a portion of the porous substrate, or both.
14. The article according to claim 12 or 13, characterized in that it is a cloth.
15. A method for removing a contaminant from a contaminated surface, characterized in that it comprises bringing the cloth according to claim 14 into contact, in the presence of a liquid, with an area of the contaminated surface, wherein the contaminated surface is a solid surface.