Sanitary articles including polyurethane and methods thereof

Abstract

Sanitary articles of manufacture can include a portion up to an entirety of each sanitary article formed of polyurethane, incorporating the polyurethane, or covered with one or more layers of the polyurethane. The polyurethane can include a hard segment including hard-segment residues of a diisocyanate and a chain extender; a soft segment including soft-segment residues of a polyglycol; a cationic modifier incorporated into main chains of the polyurethane, side chains of the polyurethane, or both; and an anionic active agent ionically bonded to the cationic modifier, which anionic active agent provides antimicrobial or antifouling properties to the sanitary article. Optionally, the sanitary article can include an odorant dispersed in the polyurethane. The sanitary article can be configured for fixing to a physical location or remaining removable from the physical location. Such a physical location can include a bathroom or kitchen.

Description

Docket No.101672.0599PCT SANITARY ARTICLES INCLUDING POLYURETHANE AND METHODS THEREOF PRIORITY

[0001] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 537,595, filed September 11, 2023, which is incorporated by reference in its entirety into this application. FIELD

[0002] This application relates to sanitary articles of manufacture including a portion up to an entirety of each sanitary article formed of polyurethane, incorporating the polyurethane, or covered with one or more layers of the polyurethane. The polyurethane can include a main chain of a diisocyanate, a polyglycol, and a diol chain extender, which can also include at least one ionically-charged modifier into the main chain, a side chain, or both. The ionically-charged modifier can be cationic, having at least one functional moiety, which can be, for example, a quaternary ammonium moiety. Sanitary articles made therefrom have inherent antimicrobial or anti-fouling characteristics or can easily bond anionic active agents to provide desirable material properties, including antimicrobial, and anti-fouling. BACKGROUND

[0003] Maintaining the cleanliness and sanitation of fixtures as well as certain removable items in physical locations such as bathrooms and kitchens is of importance, especially when these locations are used by multiple people or guests. In the bathroom, for example, toilet and faucet handles are high-touch fixtures that can become breeding grounds for bacteria and viruses if not regularly disinfected. Similarly, in the kitchen, drawer, cabinet, and faucet handles require frequent cleaning to prevent the spread of foodborne illnesses. Removable items like floor mats and waste receptacles also need to be washed or replaced regularly to ensure they do not harbor harmful microbes. Ensuring these fixtures and removable items are sanitary not only promotes good health but also enhances the overall experience for people, making them feel comfortable and cared for in a clean environment.

[0004] Disclosed herein are sanitary articles of manufacture and methods that address the cleanliness and sanitation in various physical locations in need thereof.Docket No.101672.0599PCT SUMMARY

[0005] Disclosed herein is a sanitary article of manufacture including, in some embodiments, a portion up to an entirety of the sanitary article formed of polyurethane, incorporating the polyurethane, or covered with one or more layers of the polyurethane. The polyurethane includes a hard segment including hard-segment residues of a diisocyanate and a chain extender; a soft segment including soft-segment residues of a polyglycol; a cationic modifier incorporated into main chains of the polyurethane, side chains of the polyurethane, or both; and an anionic active agent ionically bonded to the cationic modifier, which anionic active agent provides antimicrobial or antifouling properties to the sanitary article. Optionally, the sanitary article can include an odorant dispersed in the polyurethane. The sanitary article is configured for fixing to a physical location or remaining removable from the physical location.

[0006] In some embodiments, the polyurethane includes the odorant dispersed therein.

[0007] In some embodiments, the odorant is a small-molecule organic compound.

[0008] In some embodiments, the odorant is a mixture of two or more small-molecule organic compounds.

[0009] In some embodiments, the odorant includes one or more functional groups selected from various alcohol, aldehyde, ketone, carboxylic acid, carboxylate, ester, amine, amide, or sulfur-containing functional groups. The one-or-more functional groups provide fragrance and enhanced water solubility of the odorant.

[0010] In some embodiments, the odorant includes the carboxylate functional group. The odorant is ionically bonded to the cationic modifier via the carboxylate functional group.

[0011] In some embodiments, the odorant includes one or more phytochemicals or synthetics thereof.

[0012] In some embodiments, the odorant includes one or more polyphenols, terpenoids, alkaloids, nitrogenous compounds other than alkaloids, or chemical degradants, chemical derivatives, or structural analogs thereof.

[0013] In some embodiments, the odorant confers fungal, bacterial, or viral resistance to the sanitary article, thereby complementing the anionic active agent in the antimicrobial or antifouling properties it provides to the sanitary article.Docket No.101672.0599PCT

[0014] In some embodiments, the sanitary article is a fixed article configured for fixing to a physical location.

[0015] In some embodiments, the fixed article is selected from a countertop, a faucet, a dispenser, a partition, a urinal or toilet flush valve, a urinal cartridge for water-free urinals, an assistance-providing grab bar, a baby diaper-changing station, a safety seat for children, a door handle, and mounted signage.

[0016] In some embodiments, the fixed article is selected from the door handle, a faucet handle of the faucet, a urinal or toilet handle respectively of the urinal or toilet flush valve, and the grab bar. Each of the door handle, the faucet handle, the urinal handle, the toilet handle, or the grab bar is independently of the polyurethane or covered with the one-or-more layers of the polyurethane.

[0017] In some embodiments, the fixed article is the dispenser. The dispenser is selected from a soap dispenser, a paper-towel dispenser, a toilet seat-cover dispenser, a toilet- paper dispenser, and a facial-tissue dispenser.

[0018] In some embodiments, a housing of the soap dispenser, the paper-towel dispenser, the toilet seat-cover dispenser, the toilet-paper dispenser, or the facial-tissue dispenser is of the polyurethane or covered with the one-or-more layers of the polyurethane. A dispensing button, lever, or wheel of the paper-towel dispenser is of the polyurethane or covered with the one-or-more layers of the polyurethane. A dispensing button or lever of the soap dispenser is of the polyurethane or covered with the one-or-more layers of the polyurethane.

[0019] In some embodiments, the fixed article is the partition. The partition is selected from a urinal partition, a toilet partition, and a shower partition of the polyurethane or covered with one or more layers of the polyurethane.

[0020] In some embodiments, the fixed article is the baby diaper-changing station or the safety seat for children. Each of the baby diaper-changing station or the safety seat is independently of the polyurethane or has one or more surfaces covered with the one-or-more layers of the polyurethane.Docket No.101672.0599PCT

[0021] In some embodiments, the sanitary article is a non-fixed article configured for remaining removable from a physical location.

[0022] In some embodiments, the non-fixed article is selected from a waste receptacle, a urinal screen, a toilet-rim cage, a toilet-seat handle for lifting or lowering a toilet seat without touching the toilet seat, a floor mat, a plunger, and temporary signage.

[0023] In some embodiments, the physical location is a bathroom or kitchen.

[0024] Also disclosed herein is a method of refreshing a sanitary article of manufacture. The method includes, in some embodiments, a solution-obtaining operation, a sanitary article- disposing operation, swelling operation, and a sanitary article-removing operation. The solution-obtaining operation includes obtaining a solution of an anionic active agent and an odorant. The anionic active agent provides antimicrobial or antifouling properties to the sanitary article, whether the sanitary article is configured for fixing to a physical location or remaining removable from the physical location. The sanitary article-disposing operation includes disposing the sanitary article in the solution. The sanitary article includes a portion up to an entirety of the sanitary article formed of polyurethane, incorporating the polyurethane, or covered with one or more layers of the polyurethane. The polyurethane include a hard segment including hard-segment residues of a diisocyanate and a chain extender; a soft segment including soft-segment residues of a polyglycol; and a cationic modifier incorporated into main chains of the polyurethane, side chains of the polyurethane, or both. The swelling operation includes allowing the sanitary article to swell, thereby allowing the anionic active agent and the odorant to diffuse into the sanitary article. At least the anionic active agent ionically bonds to the cationic modifier. The sanitary article-removing operation includes removing the sanitary article from the solution.

[0025] These and other features of the concepts provided herein will become more apparent to those of skill in the art in view of the accompanying drawings and following description, which describe particular embodiments of such concepts in greater detail. BRIEF DESCRIPTION OF DRAWINGS

[0026] FIG. 1 illustrates an assistance-providing grab bar and a toilet-paper dispenser in accordance with some embodiments.

[0027] FIG. 2 illustrates a urinal partition in accordance with some embodiments.Docket No.101672.0599PCT

[0028] FIG. 3 illustrates a soap dispenser in accordance with some embodiments.

[0029] FIG. 4 illustrates a urinal screen in accordance with some embodiments.

[0030] FIG. 5 illustrates a toilet mat in accordance with some embodiments.

[0031] FIG. 6 illustrates a waste receptacle in accordance with some embodiments.

[0032] FIG. 7 is a thermogravimetric analysis (“TGA”) curve, weight (%) versus temperature (° C) for an embodiment.

[0033] FIG.8 is a TGA curve, weight (%) versus temperature (° C) for an embodiment.

[0034] FIG. 9 is a TGA curve, weight (%) versus temperature (° C) for a reference embodiment. DESCRIPTION

[0035] Before some particular embodiments are disclosed in greater detail, it should be understood that the particular embodiments disclosed herein do not limit the scope of the concepts provided herein. It should also be understood that a particular embodiment disclosed herein can have features that can be readily separated from the particular embodiment and optionally combined with or substituted for features of any of a number of other embodiments disclosed herein.

[0036] 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 in connection with 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 one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily referring to the same embodiment of the invention. Furthermore, the particular features, structures, materials, or characteristics can be combined in any suitable manner in one or more embodiments.

[0037] Regarding terms used herein, it should also be understood the terms are for the purpose of describing some particular embodiments, and the terms do not limit the scope of the concepts provided herein. Ordinal numbers (e.g., first, second, third, etc.) are generally used to distinguish or identify different features or steps in a group of features or steps, and do notDocket No.101672.0599PCT supply a serial or numerical limitation. For example, “first,” “second,” and “third” features or steps need not necessarily appear in that order, and the particular embodiments including such features or steps need not necessarily be limited to the three features or steps. In addition, any of the foregoing features or steps can, in turn, further include one or more features or steps unless indicated otherwise. Labels such as “left,” “right,” “top,” “bottom,” “front,” “back,” and the like are used for convenience and are not intended to imply, for example, any particular fixed location, orientation, or direction. Instead, such labels are used to reflect, for example, relative location, orientation, or directions. Singular forms of “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise.

[0038] Polyglycols include, but are not limited to, polyalkylene glycol, polyester glycol, and polycarbonate glycol. A non-limiting specific example of polyalkylene glycol is polyether glycol. A polyether glycol is a moderate molecular weight oligomer derived from an alkylene oxide, containing both ether linkages and glycol termination.

[0039] A chain extender is a short chain (e.g., low molecular weight) branched or unbranched diol, diamine, or amino alcohol of up to 10 carbon atoms or mixtures thereof. Such hydroxyl- or amine-terminated compounds are used during polymerization to impart desired properties to a polymer.

[0040] An ionically-charged modifier is a compound exhibiting a charge that enhances a basic polyurethane structure of a diisocyanate; a diol chain extender; and a polyglycol. The ionically-charged modifier herein includes a cationic modifier, having one or more functional moieties (e.g., a quaternary ammonium moiety) that make the polyurethane cationic in nature to render the resulting sanitary article with desirable properties. The desired properties include passive reduction of bacterial biofilm colony formation due to inhibition of microbial growth by a cationic quaternary ammonium moiety and antifouling property due to ionic repulsion. The functional moieties of the cationic modifier include but are not limited to a quaternary ammonium moiety. The cationic modifier can be incorporated into a main chain, a side chain, or both. The cationic modifier can be delivered as a polyglycol, a diol chain extender, or as a diisocyanate.

[0041] Antimicrobial agents that can be used for bonding with cationic functional moieties of the polyurethane include any anionic antibiotics, for example, cloxacillin salt, cefoxitin salt, cefazolin salt, penicillin salt, or derivatives thereof. The skilled artisan willDocket No.101672.0599PCT recognize that other anionic biocides of either small molecules or macromolecules can also be used for bonding with cationic functional groups of the polyurethane.

[0042] A surface energy-modifying oligomer of moderate molecular weight, as described in WO 2020 / 068617 or WO 2020 / 068619, each of which is incorporated herein in its entirety, is an optionally included compound that enhances a basic polyurethane structure of a diisocyanate; a diol chain extender; a polyglycol; and a cationic modifier. Modifying oligomers, which are different from polyglycols and a cationic modifier, contain functional moieties (e.g., fluoroether or silicone) that migrate onto the polyurethane surface to render the resulting sanitary article with a modified surface energy (e.g., a lower surface energy) and additional desirable surface properties including antifouling properties. Modifying oligomers can have at least one, two, or more than two, alcohol moieties (C-OH). The alcohol moieties can be located along a main chain of the oligomer. The alcohol moieties can be located at an end of the oligomer. In a detailed embodiment, the oligomer terminates with an alcohol moiety.

[0043] Isocyanate index is defined as the molar ratio of the total isocyanate groups in the diisocyanate to the total hydroxyl or amino groups presented in polyols and extenders. In general, the polyurethane becomes harder with an increasing isocyanate index. There is, however, a point beyond which the hardness does not increase, and the other physical properties begin to deteriorate.

[0044] As used herein, the term “consists essentially of” means that the material does not contain any other components in amounts that can alter the properties of the polyurethane material.

[0045] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art.

[0046] Principles and embodiments disclosed herein generally relate to thermoplastic polyurethane (“TPU”) materials having improved properties, and methods of preparing and using them. Provided are sanitary articles that either have inherent antimicrobial or anti-fouling characteristics or can easily bond anionic active agents to provide desirable material properties, including antimicrobial and anti-fouling. Included with traditional polyurethane monomers is an ionically-charged modifier. Herein, the ionically-charged modifier is cationic, whose functional moieties (e.g., a quaternary ammonium moiety) can be introduced into soft segments of the TPU materials using polyglycols or optional surface energy-modifying oligomers withDocket No.101672.0599PCT cationic functionalities or hard segments of TPU materials using diol chain extenders or diisocyanates with cationic functionalities.

[0047] The sanitary articles include a polyurethane-based resin that is a reaction product of the following ingredients: a diisocyanate; a diol chain extender; a polyglycol; and a cationic modifier incorporated into a main chain of the polyurethane-based resin, as a side chain or both. Incorporation into main chain means that cationic functionalities (e.g., a quaternary ammonium moiety) are directly linked to the main and sides chains of the polyurethane; incorporation as a side chain means that there is at least one carbon chain spacer between cationic functionalities and the polyurethane main chain. The polyurethane-based resin includes a hard segment content in a range of from 25% to 75% by weight and a soft segment content of the resin in a range of from 75% to 25% by weight. In one or more embodiments, the polyurethane-based resin has an overall ion exchange capacity in a range of from 0.01 to 1 mmol / g.

[0048] In one or more embodiments, the cationic modifier is incorporated into the polyurethane-based resin in an amount greater than or equal to 0.01 wt. %, 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, or 4.5 wt. % of the overall composition of the polyurethane-based resin. In one or more embodiments, the cationic modifier is incorporated into the polyurethane-based resin in an amount less than or equal to 10 wt. %, 9.5 wt. %, 9.0 wt. %, 8.5 wt. %, 8.0 wt. %, 7.5 wt. %, 7.0 wt. %, 6.5 wt. %, or 6.0 wt. % of the overall composition of the polyurethane-based resin. In one or more embodiments, the cationic modifier is incorporated into the polyurethane-based resin in an amount ranging from greater than or equal to 0.01 to less than or equal to 10 wt. %, including values and subranges therebetween; including greater than or equal to 0.5 to less than or equal to 7.5 wt. %, greater than or equal to 1.0 to less than or equal to 6.0 wt. %, including values and subranges therebetween; or including greater than or equal to 0.01 wt. %, 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, or 4.5 wt. % to less than or equal to 10 wt. %, 9.5 wt. %, 9.0 wt. %, 8.5 wt. %, 8.0 wt. %, 7.5 wt. %, 7.0 wt. %, 6.5 wt. %, or 6.0 wt. % of the overall composition of the polyurethane-based resin.

[0049] The cationic modifier can include one or more quaternary ammonium functional moieties. A non-limiting example of the cationic modifier of a quaternary ammonium functional moiety is bis(2-hydroxyethyl)dimethylammonium chloride (“BHDAC").Docket No.101672.0599PCT

[0050] In one or more embodiments, the cationic modifier is incorporated as a side chain.

[0051] In one or more embodiments, the cationic modifier is incorporated into the main chain. Non-limiting examples of the cationic modifier incorporated into the main chain include BHDAC.

[0052] In one or more embodiments, the cationic modifier is incorporated into both a side chain and the main chain, as discussed herein.

[0053] In an embodiment, the polyurethane-based resin is a reaction product of a diisocyanate; a diol chain extender; a polyglycol; and BHDAC. In an embodiment, the polyurethane-based resin is a reaction product of a diisocyanate; a diol chain extender; a polyglycol; and a combination of two or more cationic modifiers.

[0054] In a detailed embodiment, the polyurethane-based resin is a reaction product of ingredients consisting essentially of 4,4′-diphenylmethane diisocyanate (“MDI”) as the diisocyanate; 1,4-butanediol as the diol chain extender; polytetramethylene ether glycol(s) as the polyglycols; and BHDAC as the cationic modifier.

[0055] In a detailed embodiment, the polyurethane-based resin is a reaction product of a diisocyanate; a diol chain extender; a polyglycol; a cationic modifier incorporated into a main chain, a side chain, or both of the polyurethane-based resin; and a surface energy-modifying oligomer (as described in WO 2020 / 068617 and WO 2020 / 068619) incorporated into a main chain, a side chain, or both of the polyurethane-based resin.

[0056] The polyurethane-based resins herein are synthesized by a conventional one- step copolymerization process. Catalyst or solvent can be used. The synthesis can also be achieved by a variety of other synthetic techniques with or without a catalyst or solvent. Through structural and compositional design, the resulting cationic polyurethane resins can potentially possess inherent antimicrobial or anti-fouling surface properties for various sanitary applications, due to inhibition of microbial growth by a cationic quaternary ammonium moiety and ionic repulsion.

[0057] Antimicrobial agents that can be used for bonding with cationic functional moieties of the polyurethane include any anionic antibiotics. Non-limiting examples of theDocket No.101672.0599PCT anionic antibiotics include cloxacillin salt, cefoxitin salt, cefazolin salt, penicillin salt, or derivatives thereof. The skilled artisan will recognize that other anionic biocides of either small molecules or macromolecules can also be used for bonding with cationic functional groups of the polyurethane. Ionic bonding of active agents can be achieved by solution imbibing technique or bulk mixing (e.g., thermal compounding or solvent mixing) technique. As a result, anionic antimicrobial agents become ionically bonded not only on cationic TPU surface but also in the bulk cationic TPU to render the resulting sanitary article desirable properties, including antimicrobial and anti-fouling properties. Polyurethanes

[0058] Polyurethane materials disclosed herein have enhanced surface properties, which can be tailored to fit different practical needs with respect to sanitary articles formed of these polyurethane materials.

[0059] TPUs suitable for sanitary articles are typically synthesized from three basic components, a diisocyanate, a polyglycol, and a chain extender, usually a low molecular weight diol, diamine, amino alcohol, or water. If the chain extender is a diol, the polyurethane consists entirely of urethane linkages. If the extender is water, amino alcohol, or diamine, both urethane and urea linkages are present, which results in a polyurethaneurea (“PUU”). Inclusion of an amine-terminated polyether to the polyurethane synthesis also results in a polyurethaneurea.

[0060] Polyurethane and polyurea chemistries are based on the reactions of isocyanates with other hydrogen-containing compounds, where isocyanates are compounds having one or more isocyanate group (-N=C=O). Isocyanate compounds can be reacted with water (H2O), alcohols (R-OH), amines (Rx-NH(3-x)), ureas (R-NH-CONH2), and amides (R-CONH2). Certain polyurethanes can be thermoplastic elastomers (“TPE”), whereas other compositions can be highly cross-linked.

[0061] Thermoplastic polyurethanes include two-phases or microdomains conventionally termed hard segments and soft segments, and as a result are often referred to as segmented polyurethanes. The hard segments, which are generally of high crystallinity, form by localization of the portions of the polymer molecules which include the diisocyanate and chain extender(s). The soft segments, which are generally either non-crystalline or of low crystallinity, form from the polyglycol or the optional amine-terminated polyether. The hard segment content is determined by the weight percent of diisocyanate and chain extender in theDocket No.101672.0599PCT polyurethane composition, and the soft segment content is the weight percent of polyglycol or polydiamine. The thermoplastic polyurethanes can be partly crystalline or partly elastomeric depending on the ratio of hard to soft segments. One of the factors which determine the properties of the polymer is the ratio of hard and soft segments. In general, the hard segment contributes to hardness, tensile strength, impact resistance, stiffness, and modulus while the soft segment contributes to water absorption, elongation, elasticity and softness.

[0062] Polyurethane materials can be used as raw materials for the sanitary articles via compounding, extrusion, coextrusion, or molding.

[0063] The polyurethanes can be produced by the reaction of a diisocyanate, a diol chain extender, at least one polyglycol, an ionically-charged modifier, and optionally, a surface energy-modifying oligomer. The polyurethane can have a hard segment content between 25% and 75% by weight, where a hard segment is the portion(s) of the polymer molecules which include the diisocyanate and the extender components, which are generally highly crystalline due to dipole-dipole interactions or hydrogen bonding. In contrast, the soft segments formed from the polyglycol portions and optionally the surface energy-modifying oligomers between the diisocyanate of the polymer chains and generally are either amorphous or only partially crystalline due to the characteristics of the polyglycol(s) and modifying oligomer(s). In an embodiment, the hard segment content can be in the range of from 25% to 75% and the soft segment content can be in the range of from 75% to 25%. Herein, the ionically-charged modifier is cationic, whose cationic functional moieties can be introduced into soft segments of the TPU materials using polyglycols or optional surface energy-modifying oligomers with cationic functionalities or hard segments of TPU materials using diol chain extenders or diisocyanates with cationic functionalities. Non-limiting examples of the cationic functional moieties include quaternary ammonium moieties. In an embodiment, ionically-charged modifier is introduced into the hard segments of the TPU material using diol chain extender with cationic functionalities such as BHDAC.

[0064] Polymerization of the polyurethane can be a one-step copolymerization process. The process can utilize a catalyst, solvent, other additives, or a combination thereof. The synthesis can also be achieved by a variety of other synthetic techniques with or without a catalyst or solvent.Docket No.101672.0599PCT

[0065] The diisocyanate can be selected from the group consisting of an aliphatic diisocyanate, alicyclic diisocyanate, and an aromatic diisocyanate. In various embodiments, the diisocyanate can be selected from the group consisting of MDI, toluene diisocyanate (“TDI”), isophorone diisocyanate (“IPDI”), methylene-bis(4-cyclohexylisocyanate) (“HMDI”), and combinations thereof.

[0066] The diol chain extender can be selected from the group consisting of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, and alicyclic glycols having up to 10 carbon atoms.

[0067] The polyglycol can be selected from the group consisting of polyalkylene glycol, polyester glycol, polycarbonate glycol, and combinations thereof. In an embodiment, the polyglycol includes the polyalkylene glycol. In an embodiment, the polyalkylene glycol includes a polytetramethylene ether glycol.

[0068] The polytetramethylene ether glycol can be of any desired molecular weight. The desired molecular weight is the molecular weight in the range of from 200 Da to 4000 Da, or 250 Da to 2900 Da. The polytetramethylene ether glycol (“PTMEG”) can be PTMEG250, PTMEG650, PTMEG1000, PTMEG1400, PTMEG1800, PTMEG2000, or PTMEG2900. PTMEG has the formula HO(CH2CH2CH2CH2-O-)nH, which can have an average value of n in the range of 3 to 40. A blend of two or more selected from PTMEG250, PTMEG650, PTMEG1000, PTMEG1400, PTMEG1800, PTMEG2000, and PTMEG2900 can be used. Reference to PTMEG250 means a polytetramethylene ether glycol having an average molecular weight in a range of 230 to 270 Da. Reference to PTMEG650 means a polytetramethylene ether glycol having an average molecular weight in a range of 625 to 675 Da. Reference to PTMEG1000 means a polytetramethylene ether glycol having an average molecular weight in a range of 950 to 1050 Da. Reference to PTMEG1400 means a polytetramethylene ether glycol having an average molecular weight in a range of 1350 to 1450 Da. Reference to PTMEG1800 means a polytetramethylene ether glycol having an average molecular weight in a range of 1700 to 1900 Da. Reference to PTMEG2000 means a polytetramethylene ether glycol having an average molecular weight in a range of 1900 to 2100 Da. Reference to PTMEG2900 means a polytetramethylene ether glycol having an average molecular weight in a range of 2825 to 2976 Da. In an embodiment, an average molecular weight of the combination is less than 1000 Da. In an embodiment, the polyol is a blend of two or more PTMEGs having the formula HO(CH2CH2CH2CH2-O-)nH, where n has an averageDocket No.101672.0599PCT value in the range of 3 to 40. In one or more embodiments, the polyols are a blend of two or more PTMEGs having the formula HO(CH2CH2CH2CH2-O-)nH, where n has an average value in the range of 3 to 40 and an average molecular weight of the combination being less than 1000 Da.

[0069] A further polyalkylene glycol can be polyethylene glycol (“PEG”) or polypropylene glycol (“PPG”). The PEG or PPG can include any desired molecular weight. The desired molecular weight is the average molecular weight in the range of from 200 Da to 8000 Da.

[0070] The polyurethane-based resin can further include a polyetheramine. Suitable polyetheramines include but are not limited to amine-terminated polyethers having repeating units of ethylene oxide, propylene oxide, tetramethylene oxide, or combinations thereof and having an average molecular weight in the range of about 230 to 4000 Da. Polyetheramines can have propylene oxide repeating units. Jeffamine® D4000 is a specific polyetheramine, a polyoxypropylene diamine, having an average molecular weight of about 4000 Da.

[0071] The ionically-charged modifier is cationic, containing cationic functional moieties (e.g., a quaternary ammonium moiety) that make the polyurethane cationic in nature. Resulting sanitary articles can advantageously have desirable surface properties including but not limited to antimicrobial or anti-fouling properties, due to inhibition of microbial growth by a cationic quaternary ammonium moiety and ionic repulsion.

[0072] Including an ionically-charged modifier such as a cationic modifier in the polyurethane resin to obviate a separate surface coating process can offer one or more of the following advantages: (i) simple cationic TPU copolymer composition with passive non- fouling surface, without leach-out concern of the active agents; (ii) no capital investment for coating process; (iii) much reduced manufacturing or conversion costs; or (iv) less environment, health and safety (“EHS”) impact.

[0073] Antimicrobial agents that can be used for bonding with cationic functional moieties of the polyurethane include any anionic antibiotics. Non-limiting examples of anionic antibiotics include cloxacillin salt, cefoxitin salt, cefazolin salt, penicillin salt, or derivatives thereof. In addition, the skilled artisan will recognize that other anionic biocides of either small molecules or macromolecules can also be used for bonding with cationic functional groups of the polyurethane.Docket No.101672.0599PCT

[0074] Should an antimicrobial bonding nonetheless be desired to achieve desirable material surface antimicrobial or anti-fouling properties, the technology herein has one or more of the following advantages: (i) ionic bonding of antimicrobial agents onto cationic TPU polymer substrates to achieve non-leaching or controlled release of active agents; (ii) polymer substrates already have cationic functionalities for bonding of active agents and no priming (e.g., chemical or plasma treatments) of polymer substrates is needed, which simplifies sanitary article manufacturing process and significantly reduce conversion costs; or iii) anionic antimicrobial agents are ionically bonded not only on cationic TPU surface but also in the bulk cationic TPU for potential continuous and long-term antimicrobial agent supply to device surface.

[0075] The cationic modifier can include one or more quaternary ammonium functional moieties. A non-limiting example of the cationic modifier with quaternary ammonium functional moiety includes BHDAC. The cationic modifier can include more than one functional moiety.

[0076] In one or more embodiments, the cationic modifier is incorporated as a side chain.

[0077] In one or more embodiments, the cationic modifier is incorporated into the main chain. In an embodiment, the cationic modifier incorporated into the main chain includes BHDAC.

[0078] In one or more embodiments, the cationic modifier is incorporated both as a side chain and into the main chain.

[0079] In one or more embodiments, the sanitary articles herein are effective to reduce bacterial biofilm. In one or more embodiments, the sanitary articles passively reduce bacterial biofilm formation due to inhibition of microbial growth by a cationic quaternary ammonium moiety and ionic repulsion.

[0080] The polyurethanes described herein can be fabricated into various solid shapes film, tubing, and other forms by conventional thermoplastic fabricating techniques including melt casting, compounding, extrusion, coextrusion, molding, etc. The polymer can have incorporated therein, as desired, conventional stabilizers, additives (e.g., a radiopaque filler), or processing aids. The amounts of these materials will vary depending upon the application ofDocket No.101672.0599PCT the polyurethane, but if present, are typically in amounts so in the range of from 0.1 to 50 weight percent of the final compound. Polyurethanes including surface energy-modifying oligomers

[0081] Optionally, the polyurethanes disclosed herein can further include surface energy-modifying oligomers to provide further surface enhancements as described in WO 2020 / 068617 and WO 2020 / 068619, each of which incorporated herein by reference in its entirety. An advantage of surface energy-modified polyurethane materials is that their non- sticking, hydrophobic surfaces can provide antimicrobial and anti-fouling properties.

[0082] The polyurethanes including surface energy-modifying oligomers can be produced by the reaction of a diisocyanate, a diol chain extender, at least one polyglycol, an ionically-charged modifier, and a surface energy-modifying oligomer. In an embodiment, modified polyurethanes include a hard segment content in the range of from 25% to 75% and a soft segment content in the range of from 75% to 25% by weight.

[0083] Polymerization of the polyurethane to include a surface energy-modifying oligomer can be a one-step or a two-step copolymerization process. The process can use a catalyst, solvent, other additives, or a combination thereof. The synthesis can also be achieved by a variety of other synthetic techniques with or without a catalyst or solvent.

[0084] The surface energy-modifying oligomers contain functional moieties that migrate onto the polyurethane surface to render the resulting sanitary article with desirable surface properties. Non-limiting examples of the surface energy-modifying oligomer include fluoroether, silicone, or a combination thereof. In one or more embodiments, the surface energy-modifying oligomers have at least one, two, or more than two alcohol moieties (C-OH).

[0085] A surface energy-modifying oligomer for the main chain can include a diol- containing perfluoropolyether.

[0086] In one or more embodiments, the diol-containing perfluoropolyether has the following structure, HO(CH2CH2O)pCH2CF2O(CF2CF2O)q(CF2O)rCF2CH2(OCH2CH2)pOH,Docket No.101672.0599PCT wherein total of values for p+q+r are such that the fluorine content of the oligomer can be in the range of from 55% to 60% by weight and the average molecular weight of the oligomer is in the range of from 1500 to 2200 Da.

[0087] An example diol-containing perfluoropolyether (“PFPE”) can be a commercial product sold under the trade name Fluorolink® E10-H, which is a di-alcohol-terminated, ethoxylated PFPE, with about a 1,700-Da average molecular weight and about 57% w / w fluorine content.

[0088] A surface energy-modifying oligomer as a side chain can include a monofunctional polysiloxane. In one or more embodiments, the monofunctional polysiloxane is a monodialcohol-terminated polydimethylsiloxane (“PDMS”) having the following structure,, wherein s can be in the range of from 5 to 200.

[0089] Mono-di-alcohol-terminated polydimethylsiloxanes can be commercial products such as those sold under the product codes MCR-C61, MCR-C62, and MCR-C63. MCR-C62 has an average molecular weight of 5000 Da (s in range of 62-63), MCR-C61 has an average molecular weight of 1000 Da (s in range of 8-9), and MCR-C63 has an average molecular weight of 15,000 Da (s in range of 197-198). In one or more embodiments, the surface energy-modifying oligomer for the side chain is MCR-C62. Bonding of active agents with polyurethane-based resins

[0090] In one or more embodiments, the polyurethane-based resin is bound to an anionic agent through ionic bonding. In various embodiments, the anionic agent includes an antimicrobial agent; however, in some embodiments the anionic agent can additionally or alternatively include the odorant set forth herein.

[0091] Antimicrobial agents that can be used for bonding with cationic functional moieties of the polyurethane include any anionic antibiotics. Non-limiting anionic antibioticsDocket No.101672.0599PCT include cloxacillin salt, cefoxitin salt, cefazolin salt, penicillin salt, and derivatives thereof. In addition, the skilled artisan will recognize that other anionic biocides of either small molecules or macromolecules can also be used for bonding with cationic functional groups of the polyurethane.

[0092] Ionic bonding of active agents can be achieved by solution imbibing technique, which includes disposing the polyurethane-based resin or a sanitary article produced therefrom into a solution (e.g., aqueous solution) including one or more anionic agents. Indeed, the solution can enable an anionic agent to diffuse into the polymer chains of the polyurethane- based resin or a sanitary article for ionically bonding with the cationic modifier. Alternatively, ionic bonding of active agents can be achieved by bulk mixing (e.g., thermal compounding or solvent mixing) technique. As a result, anionic antimicrobial are ionically bonded not only on cationic TPU surface but also in the bulk cationic TPU to render the resulting sanitary article with desirable properties, including antimicrobial and anti-fouling properties.

[0093] In one or more embodiments, the sanitary articles herein are effective to provide antimicrobial or anti-fouling activity. In one or more embodiments, the sanitary articles actively provide enhanced surface properties including antimicrobial or anti-fouling activity. General procedure for polyurethane synthesis

[0094] The polyurethanes discussed herein are prepared by a one-step copolymerization process using a pilot-scale polyurethane (“PU”) processor. No catalyst or solvent is used for this reaction. The polyglycol(s) (e.g., PTMEG), cationic modifier(s) (e.g., BHDAC, introduced as a cationic diol chain extender), and chain extender(s) (e.g., 1,4- butanediol) in the total amount of about 7.5 kg are charged into B tank (2.5-gallon full tank capacity with a recycle loop) of the PU processor with adequate mixing through a tank agitator at a set temperature until the solid cationic modifier is completely dissolved in the polyglycol- chain extender mixture. The diisocyanate (e.g., MDI, calculated amount to react out B tank diol mixture) is charged into A tank (2.5-gallon full tank capacity with a recycle loop) of the PU processor. During the reaction, both B tank and A tank materials are pumped through their individual feeding lines at controlled feed rates to achieve an isocyanate index of 1.0 to 1.1. In one or more embodiments, the isocyanate index is 1.02. Both the B and A streams are continuously injected through their respective injectors into an 8-cc mixing head with high rotor speed for adequate mixing and poured into silicone pans (covered with Teflon sheets).Docket No.101672.0599PCT The entire PU processor system, including A and B tanks, fill, feed, recycle, and drain lines, injectors and mixing head, is maintained at a temperature of 50-90° C (various zone temperature controls) and under vacuum of <100 mmHg during operation. The silicone pans filled with the PU reactants mixture are passed through a 150° F conveyor oven with 10-20 min of curing time to achieve complete reaction. The resulting yellow or white PU slab has a dimension of 7.7 in×3.5 in×0.3 in. The PU slabs are subsequently ground into granulated forms for downstream compounding and extrusion or coextrusion processes.

[0095] The PU granulates or chips are extruded into ribbon sheets for material property characterizations.

[0096] The PU ribbon sheets can be extruded either from a single copolymer composition or from a blend of two or more different PU compositions. Blending or compounding can allow for quick creation and characterization of new PU compositions using already existing PU copolymers. Even though the micro-domain structure and molecular weight distribution can be different using a direct copolymerization approach compared to a blending or compounding approach, it is expected that comparable material properties will result based on a comparable overall PU composition. In one or more embodiments, direct copolymerization approach can be used for preparation of cationic PU ribbon compositions.

[0097] Table I. Example formulations of polyurethane resins with the proviso that the ingredients total 100%.Docket No.101672.0599PCT Example polyurethane-based resins

[0098] Sanitary articles are formed from a polyurethane-based resin, which is a reaction product of the following ingredients: a diisocyanate; a diol chain extender; a polyglycol; and a cationic modifier including one or more quaternary ammonium functional groups, wherein the cationic modifier is incorporated into a main chain, a side chain, or both. In one or more embodiments, the polyglycol is one or more polyalkylene glycols, which can include a polytetramethylene ether glycol. The resulting polyurethane-based resins are random copolymers based on the ingredients. A hard segment content is in the range of from 25% to 75% by weight, and a soft segment content of the resin is in the range of from 75% to 25% by weight.

[0099] Using the following ingredients, various polymer chain segments (A)-(C) are expected, including the diisocyanate of MDI; the diol chain extender of 1,4-butanediol; the polyglycols of a PTMEG with average MW in the range of from 250 Da to 2900 Da (n=3−40); and the cationic modifier of BHDAC, which is introduced as a cationic diol chain extender and is part of the polyurethane hard segments. In one or more embodiments, the polyurethane-based resins are cationic polyurethane-based resins, which are random copolymers including the following chain segments of (A), (B) and (C):(A), wherein n is in the range of 3 to 40;(C).Docket No.101672.0599PCT Again, a hard segment content of the resin can be in the range of from 25% to 75% by weight, and a soft segment content of the resin can be in the range of from 75% to 25% by weight. Notably, the polyurethane-based resin can have an overall ion exchange capacity of 0.01 to 1 mmol / g.

[0100] In one or more embodiments, the polyurethane-based resins are cationic polyurethane-based resins optionally including a surface energy-modifying oligomer, which are random copolymers including various polymer chain segments (A)-(E) using the following ingredients: the diisocyanate of MDI; the diol chain extender of 1,4-butanediol; the polyglycols of a PTMEG with average MW in the range of from 250 Da to 2900 Da (n=3−40); the cationic modifier of BHDAC; and the surface energy-modifying oligomers, if present, of a diol- containing perfluoropolyether or a monofunctional polysiloxane. In one or more embodiments, the polyurethane-based resins are random copolymers including the following chain segments selected from (A), (B), (C), (D), and (E).(A), wherein n is in the range of 3 to 40;Docket No.101672.0599PCT(D), wherein the total of p+q+r is such that the fluorine content of the oligomer is in the range of from 55% by weight to 60% by weight and the average molecular weight of the oligomer is in the range of from 1500 to 2200 Da; and(E), wherein s is in the range of 5 to 200. Sanitary articles of polyurethane

[0101] FIGS. 1-6 illustrate various sanitary articles in accordance with some embodiments.

[0102] Each article of the one-or-more sanitary articles can be selected from at least a fixed article and a non-fixed or removable article found in a physical location, for example, a bathroom or kitchen, which physical location excepts a human body or that another type of animal. It should be understood that a portion of the fixed or non-fixed article up to an entirety of the article can be of the polyurethane disclosed herein. Alternatively, a portion of the fixedDocket No.101672.0599PCT or non-fixed article up to an entirety of the article can instead be covered with one or more layers of the polyurethane disclosed herein.

[0103] As to the fixed article, each article of the one-or-more sanitary articles can be further selected from at least a countertop, a faucet, a dispenser, a partition, a urinal or toilet flush valve, a urinal cartridge for water-free urinals, an assistance-providing grab bar 100, a baby diaper-changing station, a safety seat for children, a door handle, and mounted signage. In an example, an article of the one-or-more sanitary articles can be a faucet handle of the polyurethane, or a faucet handle covered with one or more layers of the polyurethane. In another example, an article of the one-or-more sanitary articles can be a dispenser selected from a soap dispenser 106, a paper-towel dispenser, a toilet seat-cover dispenser, a toilet-paper dispenser 102, and a facial-tissue dispenser. A housing 103 of the soap dispenser 106, the paper-towel dispenser, the toilet seat-cover dispenser, the toilet-paper dispenser 102, or the facial-tissue dispenser; a dispensing button, lever, or wheel of the paper-towel dispenser; a dispensing button or lever 108 of the soap dispenser 106, or the like can be of the polyurethane or covered with one or more layers of the polyurethane. In another example, an article of the one-or-more sanitary articles can be a partition selected from a urinal partition 104, a toilet partition, and a shower partition. The partition can be of the polyurethane, or one or more sides of the partition can be covered with one or more layers of the polyurethane. In another example, an article of the one-or-more sanitary articles can be a handle of a urinal or toilet flush valve, wherein the handle is of the polyurethane, or the handle is covered with one or more layers of the polyurethane. In another example, an article of the one-or-more sanitary articles can be a grab bar 100 of the polyurethane or a grab bar 100 covered with one or more layers of the polyurethane. In another example, an article of the one-or-more sanitary articles can be a baby diaper-changing station or a safety seat for children, wherein the baby diaper-changing station or safety seat is of the polyurethane, or one or more surfaces of the baby diaper-changing station or safety seat is covered with one or more layers of the polyurethane. In another example, an article of the one-or-more sanitary articles can be a door handle of the polyurethane, or a door handle covered with one or more layers of the polyurethane.

[0104] As to the non-fixed or removable article, each article of the one-or-more sanitary articles can be further selected from a waste receptacle 114, a urinal screen 110, a toilet-rim cage, a toilet-seat handle for lifting or lowering a toilet seat without touching the toilet seat, a floor mat, a plunger, and temporary signage (e.g., a fold-out wet-floor sign). In an example, anDocket No.101672.0599PCT article of the one-or-more sanitary articles can be a waste receptacle 114, wherein the waste receptacle 114 is of the polyurethane or one or more surfaces of the waste receptacle 114 including those of the lid is covered with one or more layers of the polyurethane. In another example, an article of the one-or-more sanitary articles can be a urinal screen 110 of the polyurethane, wherein the urinal screen 110 is optionally configured to include a scented insert. In another example, an article of the one-or-more sanitary articles can be a toilet-rim cage of the polyurethane, wherein the toilet-rim cage is optionally configured to include a scented insert. In another example, an article of the one-or-more sanitary articles can be a toilet-seat handle of the polyurethane or a toilet-seat handle covered with one or more layers of the polyurethane. In another example, an article of the one-or-more sanitary articles can be a floor mat selected from a urinal mat 112, a toilet mat, and an anti-fatigue mat. The floor mat can be of the polyurethane or covered with one or more layers of the polyurethane. In another example, an article of the one-or-more sanitary articles can be a toilet plunger, wherein a handle or a cup of the toilet plunger is independently of the polyurethane or covered with one or more layers of the polyurethane. That said, the toilet plunger can be integral, and, in such an embodiment, an entirety of the toilet plunger can be of the polyurethane.

[0105] Notwithstanding the foregoing, it should be understood the one-or-more sanitary articles are not limited to fixed articles or non-fixed or removable articles found in physical locations such as bathrooms or kitchens. Indeed, the one-or-more sanitary articles can be any article that benefits from being formed of the polyurethane, incorporating the polyurethane, or being covered with one or more layers of the polyurethane. That said, being that the one-or-more sanitary articles include the odorant, which, as set forth herein can be a terpenoid or the like, any article of the one-or-more sanitary articles should have limited dermal contact due the contact dermatitis-causing potential of the odorant. As such, medical devices such as catheters (e.g., central venous catheters, peripherally inserted central catheters, or the like) are excluded from the one-or-more sanitary articles disclosed herein.

[0106] During compounding, granulates of synthesized polyurethanes described herein are added into a twin-screw compounder simultaneously with any other compounding components or ingredients. The mix ratio can be controlled and adjusted by a gravimetric multiple-feeder system. The mixed polyurethane melt (conveying through multiple heating zones) continuously passes through a die, a quench tank, and is subsequently cut into regular-Docket No.101672.0599PCT sized pellets by a puller-pelletizer. The collected pellets are used to be fed into, for example, a hopper for molding sanitary articles or extruding sheets for covering the sanitary articles.

[0107] Sanitary articles formed from cationic polyurethane resins disclosed herein can potentially possess inherent antimicrobial or anti-fouling surface properties, due to inhibition of microbial growth by a cationic quaternary ammonium moiety and ionic repulsion.

[0108] Antimicrobial agents that can be used for bonding with cationic functional moieties of the polyurethane include any anionic antibiotics, for example, cloxacillin salt, cefoxitin salt, cefazolin salt, penicillin salt etc. In addition, the skilled artisan will recognize that other anionic biocides of either small molecules or macromolecules can also be used for bonding with cationic functional groups of the polyurethane. Ionic bonding of active agents can be achieved by solution imbibing technique or bulk mixing technique. In one or more embodiments, the bulk mixing technique includes a thermal compounding technique and a solvent mixing technique. As a result, anionic antimicrobial agents are ionically bonded not only on cationic TPU surface but also in the bulk cationic TPU to render the resulting sanitary articles with desirable properties, including antimicrobial and anti-fouling properties. Odorant

[0109] The odorant can be a small-molecule organic compound or a mixture of two or more such compounds respectively having a fragrance or bouquet of fragrances capable of at least temporarily binding to olfactory receptors of a human or another type of animal and, thereby, activating the olfactory receptors. The odorant can include one or more heteroatom- functionalized compounds independently having at least an alcohol, an aldehyde, a ketone, a carboxylic acid or carboxylate for ionically bonding to the cationic modifier like the anionic agent, an ester, an amine, an amide, or a sulfur-containing functional group, which provides fragrance and enhances solubility for at least the solution imbibing technique set forth herein. Such an odorant can include one or more polyphenols, terpenoids, alkaloids, nitrogenous compounds other than alkaloids, or chemical degradants, chemical derivatives, or structural analogs (e.g., homologs, functional analogs, etc.) thereof. In an example, the odorant can be a terpenoid, which is defined as a modified terpene including at least a functional group having one or more heteroatoms, and which terpenoid can be selected from at least a monoterpenoid, sesquiterpenoid, diterpenoid, triterpenoid, and tetraterpenoid. Notwithstanding the foregoing, the odorant need not include a heteroatom-functionalized compound if the odorant is paired with an emulsifier, surfactant, or complexing agent to enhance solubility for at least the solutionDocket No.101672.0599PCT imbibing technique set forth herein. In an example, the odorant can include a terpene, which is defined as a hydrocarbon derived from two or more isoprene units, and which can be selected from at least a monoterpene, sesquiterpene, diterpene, triterpene, and tetraterpene if paired with an emulsifier, surfactant, or complexing agent. Notably, the foregoing polyphenols, terpenes, terpenoids, alkaloids, and nitrogenous compounds other than alkaloids can be phytochemicals or synthetics thereof, many of which are produced by plants for resistance to fungi, bacteria, and viruses. Likewise, the odorant can, in addition to providing fragrance, confer fungal, bacterial, or viral resistance in each article of the one-or-more sanitary articles in which it is imbibed or otherwise incorporated. It should be understood that such fungal, bacterial, or viral resistance complements that provided by the anionic active agent(s) set forth herein, or, in the absence of the anionic active agent(s), supplants the fungal, bacterial, or viral resistance otherwise provided by the anionic active agent(s). EXAMPLES Example 1

[0110] Cationic TPU resins are made in accordance with Table 2 by the one-step copolymerization process (no catalyst or solvent) using a pilot-scale PU processor as described earlier in accordance with Example Formulation I-C shown above. Example formulations include MDI as an aromatic diisocyanate, a combination of PTMEGs with average molecular weight of 500-1000 Da), 1,4-butanediol as the chain extender, and BHDAC as the cationic modifier according to Table 2. No surface energy-modifying oligomer need be present. Reference polyurethane without a cationic modifier can be made as well. Table 2 shows both the benchmark reference and the cationic TPU copolymer compositions. Notably, the polyurethane-based resins can include the following chain segments selected from (A), (B), and (C).wherein n is in the range of 3 to 40;Docket No.101672.0599PCT

[0111] Q-PU-2, Q-PU-3 and Reference PU-A are prepared by direct copolymerization in the PU reactor, while Q-PU-1 is prepared by uniform blend of two different PUs (i.e., 35 / 65 wt. % blend of Q-PU-2 and Reference PU-A).

[0112] Table 3 shows gel temperatures and gel times for the copolymerization reactions according to Examples Q-PU-2, Q-PU-3, and Reference PU-A.Docket No.101672.0599PCT

[0113] As Table 3 shows, incorporation of the cationic modifier BHDAC (introduced as a cationic diol chain extender) during copolymerization at 0.96 wt. % does not change the reaction rate and polymerization gel time significantly; however, introduction of 2.51 wt. % of cationic modifier BHDAC increases the polymerization gel time to 61.8 sec, indicating slower reaction. Example 2

[0114] Calculation of Ion Exchange Capacity. The ion exchange capacity (mmol / gm) of cationic TPUs can be easily calculated based on the copolymer compositions as shown in Table 4.

[0115] For examples in Table 2, TPU slabs (dimension of about 7.7 in×3.5 in×0.3 in) are produced from the above-mentioned pilot-scale PU processor and conveyor oven curing system, which were subsequently ground into granulated forms and extruded into ribbon sheets for material physical property characterizations. The thickness of the ribbon sheets can be 0.007-0.010 in.

[0116] Tensile Property Testing. Tensile properties of both the reference and the cationic PU ribbons (thickness of 0.007-0.010 in.) are characterized using Instron. The testing is performed at room conditions (23° C, 50% RH, and >40 h equilibration time), which is provided in Table 5 (mean of 10 measurements for each data).Docket No.101672.0599PCT

[0117] Testing can also be performed at slightly elevated temperature (e.g., 37° C) under wet conditions (e.g., , water equilibration for 4 hours) as might be found in at least a kitchen, which is provided in Table 6 (mean of 10 measurements for each data). Soften ratio is defined according to the following Equation (1). Equation (1)Docket No.101672.0599PCT

[0118] Comparison of tensile properties of Reference PU-A with cationic TPUs Q-PU- 2 and Q-PU-3 at room conditions shows that with introduction of cationic modifier BHDAC as part of the chain extender hard segment, both material ultimate tensile strength and material stiffness (Young's modulus) is reduced, while material ultimate tensile strain does not change significantly.

[0119] Comparison of tensile properties of Reference PU-A with cationic TPUs Q-PU- 2 and Q-PU-3 at elevated temperature under wet conditions shows that with introduction of cationic modifier BHDAC as part of the chain extender hard segment, material ultimate tensile strength is reduced, while material ultimate tensile strain and material stiffness (Young's modulus) does not change significantly, which results in reduced material soften ratio.

[0120] Overall, after introduction of cationic modifier BHDAC, the novel cationic TPUs still exhibits desirable tensile properties for sanitary article applications.

[0121] Thermogravimetric Analysis. The reference and disclosed cationic TPU granulates or chips are analyzed using TA Instruments TGA Q500. For testing, 3 mg of eachDocket No.101672.0599PCT sample was heated from 25° C to 800° C at 10° C / min in nitrogen gas. FIGS.7 and 8 show the TGA curves of the cationic TPUs Q-PU-2 and Q-PU-3, respectively. FIG. 9 shows the TGA curve of the Reference PU-A. Table 7 shows the degradation temperatures (based on 1% and 5% weight losses) of both the reference and disclosed cationic TPU materials.

[0122] Table 7 shows that introduction and increase of cationic modifier BHDAC as part of the chain extender hard segment decreases material thermal degradation temperatures of the resulting cationic TPUs, presumably due to the thermal degradation of quaternary ammonium functional groups. This information is useful and can be referenced for compounding, ribbon, and tubing extrusion of the disclosed cationic TPU materials as lower thermal processing temperatures prevent potential cationic TPU copolymer thermal degradation.

[0123] Melt Flow Index. The reference and disclosed cationic TPU granulates or chips are characterized for melt flow indexes using a Zwick / Roell extrusion plastometer. The equipment has an extrusion barrel diameter of 9.55 mm (length of 170 mm) and a piston diameter of 9.48 mm (weight of 325 g). Five (5) g of each pre-dried (dried at 95-110° C for over 12 hours) sample are used to perform the test at 210° C with 5 kg of load weight and 300 seconds of preheat time. Table 8 shows the melt mass flow rate, melt volume flow rate, and melt density of both the reference and disclosed cationic TPU materials.Docket No.101672.0599PCT

[0124] Table 8 shows that introduction and increase of cationic modifier BHDAC as part of the chain extender hard segment increases the melt flow of the resulting cationic TPUs significantly. This information is useful and can be referenced for compounding, ribbon, and tubing extrusion of the disclosed cationic TPU materials as lower thermal processing temperatures achieve desirable melt flows.

[0125] Molecular Weight. The reference and disclosed cationic TPU granulates or chips are characterized for molecular weight using Gel Permeation Chromatography-Multi Angle Light Scatter (“GPC-MALS”). Samples are dissolved in N,N-dimethylformamide, centrifuged, and diluted to 5 mg / mL. They are injected (200 microliters volume) into a mobile phase of N,N-dimethylformamide with 0.1 M LiBr and passed through two (2) 300 mm Agilent 5 μm PLgel Mixed-C columns to separate them by molecular weight. Wyatt T-REX and Helios II detectors are used to measure light scattering and differential refractive index, respectively. Wyatt Astra is used to analyze the detector outputs and calculate molecular weight results. Polystyrene standards is used for calibration. Table 9 shows number average molecular weight (“Me”), weight average molecular weight (“Mw”), and polydispersity index (“PDI”) of both the reference and disclosed cationic TPU materials.Docket No.101672.0599PCT

[0126] Table 9 shows that with introduction of cationic modifier BHDAC as part of the chain extender hard segment, the resulting cationic TPU copolymer molecular weight is reduced compared to Reference PU-A, but still pretty high (Mn>10K Da) to provide material desirable tensile properties (as data shown in previous tensile property session); in addition, higher PDI is observed for these cationic TPUs.

[0127] While some particular embodiments have been disclosed herein, and while the particular embodiments have been disclosed in some detail, it is not the intention for the particular embodiments to limit the scope of the concepts provided herein. Additional adaptations or modifications can appear to those of ordinary skill in the art, and, in broader aspects, these adaptations or modifications are encompassed as well. Accordingly, departures can be made from the particular embodiments disclosed herein without departing from the scope of the concepts provided herein.

Claims

Docket No.101672.0599PCT CLAIMS What is claimed is:

1. A sanitary article of manufacture, comprising: a portion up to an entirety of the sanitary article formed of polyurethane, incorporating the polyurethane, or covered with one or more layers of the polyurethane, the polyurethane including: a hard segment including hard-segment residues of a diisocyanate and a chain extender; a soft segment including soft-segment residues of a polyglycol; a cationic modifier incorporated into main chains of the polyurethane, side chains of the polyurethane, or both; an anionic active agent ionically bonded to the cationic modifier, the anionic active agent providing antimicrobial or antifouling properties to the sanitary article; and, optionally, an odorant dispersed in the polyurethane, the sanitary article configured for fixing to a physical location or remaining removable from the physical location.

2. The sanitary article according to claim 1, wherein the polyurethane includes the odorant dispersed therein.

3. The sanitary article according to claim 2, wherein the odorant is a small- molecule organic compound.

4. The sanitary article according to claim 2, wherein the odorant is a mixture of two or more small-molecule organic compounds.

5. The sanitary article according to any of claims 2-4, wherein the odorant includes one or more functional groups selected from various alcohol, aldehyde, ketone, carboxylic acid, carboxylate, ester, amine, amide, or sulfur-containing functional groups, the one-or-more functional groups providing fragrance and enhanced water solubility of the odorant.Docket No.101672.0599PCT 6. The sanitary article according to claim 5, wherein the odorant includes the carboxylate functional group, the odorant ionically bonded to the cationic modifier via the carboxylate functional group.

7. The sanitary article according to any of claims 2-6, wherein the odorant includes one or more phytochemicals or synthetics thereof.

8. The sanitary article according to any of claims 2-7, wherein the odorant includes one or more polyphenols, terpenoids, alkaloids, nitrogenous compounds other than alkaloids, or chemical degradants, chemical derivatives, or structural analogs thereof.

9. The sanitary article according to any of claims 2-8, wherein the odorant confers fungal, bacterial, or viral resistance to the sanitary article, thereby complementing the anionic active agent in providing the antimicrobial or antifouling properties to the sanitary article.

10. The sanitary article according to any of the preceding claims, wherein the sanitary article is a fixed article configured for fixing to a physical location.

11. The sanitary article according to claim 10, wherein the fixed article is selected from a countertop, a faucet, a dispenser, a partition, a urinal or toilet flush valve, a urinal cartridge for water-free urinals, an assistance-providing grab bar, a baby diaper-changing station, a safety seat for children, a door handle, and mounted signage.

12. The sanitary article according to claim 11, wherein the fixed article is selected from the door handle, a faucet handle of the faucet, a urinal or toilet handle respectively of the urinal or toilet flush valve, and the grab bar, each of the door handle, the faucet handle, the urinal handle, the toilet handle, or the grab bar independently of the polyurethane or covered with the one-or-more layers of the polyurethane.

13. The sanitary article according to claim 11, wherein the fixed article is the dispenser, the dispenser selected from a soap dispenser, a paper-towel dispenser, a toilet seat- cover dispenser, a toilet-paper dispenser, and a facial-tissue dispenser.

14. The sanitary article according to claim 12, wherein a housing of the soap dispenser, the paper-towel dispenser, the toilet seat-cover dispenser, the toilet-paper dispenser, or the facial-tissue dispenser is of the polyurethane or covered with the one-or-more layers of the polyurethane; a dispensing button, lever, or wheel of the paper-towel dispenser is of theDocket No.101672.0599PCT polyurethane or covered with the one-or-more layers of the polyurethane; or a dispensing button or lever of the soap dispenser is of the polyurethane or covered with the one-or-more layers of the polyurethane.

15. The sanitary article according to claim 11, wherein the fixed article is the partition, the partition selected from a urinal partition, a toilet partition, and a shower partition of the polyurethane or covered with one or more layers of the polyurethane.

16. The sanitary article according to claim 11, wherein the fixed article is the baby diaper-changing station or the safety seat for children, each of the baby diaper-changing station or the safety seat independently of the polyurethane or having one or more surfaces covered with the one-or-more layers of the polyurethane.

17. The sanitary article according to any of claims 1-9, wherein the sanitary article is a non-fixed article configured for remaining removable from a physical location.

18. The sanitary article according to claim 17, wherein the non-fixed article is selected from a waste receptacle, a urinal screen, a toilet-rim cage, a toilet-seat handle for lifting or lowering a toilet seat without touching the toilet seat, a floor mat, a plunger, and temporary signage.

19. The sanitary article according to any of the preceding claims, wherein the physical location is a bathroom or kitchen.

20. A method of refreshing a sanitary article of manufacture, comprising: obtaining a solution of an anionic active agent and an odorant, the anionic active agent for providing antimicrobial or antifouling properties to the sanitary article, whether the sanitary article is configured for fixing to a physical location or remaining removable from the physical location; disposing the sanitary article in the solution, the sanitary article including a portion up to an entirety of the sanitary article formed of polyurethane, incorporating the polyurethane, or covered with one or more layers of the polyurethane, the polyurethane including: a hard segment including hard-segment residues of a diisocyanate and a chain extender; a soft segment including soft-segment residues of a polyglycol;Docket No.101672.0599PCT a cationic modifier incorporated into main chains of the polyurethane, side chains of the polyurethane, or both; allowing the sanitary article to swell, thereby allowing the anionic active agent and the odorant to diffuse into the sanitary article and at least the anionic active agent to ionically bond to the cationic modifier; and removing the sanitary article from the solution.

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