Antimicrobial coating composition

Abstract

Described herein are quaternary ammonium polymers with broad-spectrum antimicrobial properties that produce fast-acting, long-lasting, non-toxic, non-allergenic, colorless, transparent, and durable surface coatings that are resistant to water and common solvents. The surface coatings are easy and cost-effective to produce from readily available materials using versatile synthesis, allowing for a wide range of chemical variations. Such coatings are easily applied to a wide range of surfaces and materials without leaching of materials from the coating.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the interests of U.S. Provisional Patent Application No. 63 / 164,081, filed on 22 March 2021, which is incorporated herein by reference in its entirety.

[0002] Embodiments of this disclosure relate to broad-spectrum antimicrobial coating compositions and methods for using the same. More specifically, embodiments of this disclosure relate to quaternary ammonium polymers having broad-spectrum antibacterial and antiviral properties. [Background technology]

[0003] Infectious diseases, including influenza, kill millions of people worldwide every year and make hundreds of millions sick. In 2020, the world experienced a global pandemic caused by the highly contagious novel coronavirus, severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2).

[0004] SARS-CoV-2 coronavirus and other earlier viruses have been shown to be transmitted from person to person as airborne droplets and through contact with virus-contaminated surfaces. A 2020 study conducted at two major urban hospitals in the United States. 1 The study concluded that healthcare-associated infections decreased by 36% when frequently touched surfaces (keyboards, countertops, handrails, chairs, etc.) were coated with disinfectant. In fact, surface disinfection was adopted as a widespread health and safety practice during the COVID-19 pandemic, but antiviral coatings have limited effectiveness because their effects wear off quickly, making them costly and labor-intensive, requiring frequent reapplication.

[0005] Over the years, numerous antimicrobial polymers have been developed to provide more effective antibacterial / antiviral surface coatings. (Jarach et al., 2020) 2 A recent review highlights several different polymer approaches to this problem. These polymers include nanoparticles with bound or adsorbed drugs, nanoparticles with embedded antiviral metals, naturally occurring polymers such as chitosan, and silica particles with adsorbed quaternary ammonium salts and quaternary polyethyleneimine (PEI).

[0006] An optimal antimicrobial surface coating has the following characteristics: (i) broad-spectrum antimicrobial activity at a low minimum inhibition concentration (MIC), (ii) rapid action, (iii) long-lasting effect, (iv) non-toxic and non-allergenic, (v) no material leaching from the coating, (vi) acceptable color, transparency, and appearance as a surface coating, (vii) easy application to a wide range of surfaces and materials, (viii) produces a durable surface coating resistant to water, alcohol, and common solvents, and (ix) is easy and cost-effective to produce.

[0007] As recognized by the inventors of this application, prior art antimicrobial surface coatings lack many of the above-mentioned features. Therefore, there is a need for improved antimicrobial surface coating compositions. [Overview of the Initiative]

[0008] Embodiments of this technology provide antimicrobial surface coatings having three or more of the following properties: (i) broad-spectrum antimicrobial activity at a low minimum inhibitory concentration (MIC), (ii) rapid action, (iii) long-lasting, (iv) non-toxic and non-allergenic, (v) no material leaching from the coating, (vi) acceptable color, transparency, and appearance as a surface coating, (vii) easy application to a wide range of surfaces and materials, (viii) producing a durable surface coating resistant to water, alcohol, and common solvents, and (ix) easy and cost-effective to produce. In some embodiments, the antimicrobial surface coatings of this technology have four or more of these properties. In some embodiments, the antimicrobial surface coatings of this technology have five or more of these properties. In some embodiments, the antimicrobial surface coatings of this technology have six or more of these properties. In some embodiments, the antimicrobial surface coatings of this technology have seven or more of these properties. In some embodiments, the antimicrobial surface coatings of this technology have eight or more of these properties. In some embodiments, the antimicrobial surface coatings of this technology have nine or more of these properties. In some embodiments, the antimicrobial surface coating of this technology possesses all of these properties.

[0009] In one embodiment, the present specification provides an antimicrobial composition comprising a polymer, the polymer comprising a reaction product of a polyethyleneimine oligomer, a polyfunctional crosslinking agent, an alkylating agent, an optional monoisocyanate, and an optional catalyst, wherein the polyethyleneimine oligomer comprises an optionally substituted hydroxyethylene functional group that reacts with one or both of the optional monoisocyanate or the polyfunctional crosslinking agent, and the nitrogen atoms present in the polyethyleneimine oligomer are at least partially quaternized by the alkylating agent.

[0010] In some embodiments, The hydroxyethylene functional group is C 6 -C 10 C is optionally substituted with aryl and hydroxyl groups. 1 -C 6 C is optionally substituted with a substituent selected from any of the alkoxy groups. 1-C 6 Alkyl; C 1 -C 6 Alkoxy; C 1 -C 6 C optionally substituted with alkyl 6 -C 10 It is optionally substituted with aryl and carboxyl compounds. In some embodiments, the polyethyleneimine oligomer comprises a reaction product of polyethyleneimine and a monoepoxide. Monoepoxide is C 6 -C 10 C is optionally substituted with aryl and hydroxyl groups. 1 -C 6 C is optionally substituted with a substituent selected from any of the alkoxy groups. 1 -C 6 Alkyl; C 1 -C 6 Alkoxy; C 1 -C 6 C optionally substituted with alkyl 6 -C 10 It is optionally substituted with aryl and carboxyl compounds.In some embodiments, the monoepoxide is a C1-C6 alkyl epoxide. In some embodiments, the C1-C6 alkyl epoxide is selected from the group consisting of propyl epoxides, butyl epoxides, and hexyl epoxides. In some embodiments, the polyethyleneimine has a molecular weight of about 600 to about 270,000 daltons, preferably about 10,000 to about 200,000 daltons, and more preferably about 25,000 to about 120,000 daltons. In some embodiments, the polyethyleneimine is branched. In some embodiments, the polyethyleneimine is polybranched. In some embodiments, the polyethyleneimine has a primary to secondary to tertiary amine ratio of about 1:2:1 to about 1:1:1. In some embodiments, the polyethyleneimine has a primary to secondary to tertiary amine ratio of about 1:1:0.7. In some embodiments, the polyfunctional crosslinking agent is a polyisocyanate. In some embodiments, the polyisocyanate has an average isocyanate functional value of 2 to 5, preferably 3 or 4. In some embodiments, the polyisocyanate is prepared from a diisocyanate selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexylisocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (TMXDI), and trimethylhexamethylene diisocyanate (TMDI).In some embodiments, the polyisocyanate is selected from the group consisting of DESMODUR® N-3300, DESMODUR® N-100, DESMODUR® Z4470SN, WANNATE® T series polyisocyanate, and LUPRANATE® M series polyisocyanate. In some embodiments, at least 75% of the nitrogen atoms of the polyethyleneimine oligomer are quaternized by an alkylating agent. In some embodiments, the alkylating agent comprises one or more R2-LG, wherein each R2 is independently selected from hydroxy, C1-C6 alkoxy, carboxy, C6-C. 10 aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 aryl), and C1-C6 alkoxy optionally substituted with substituents selected from C1-C6 alkyl optionally substituted with substituents selected from hydroxy, and each LG is a leaving group. In some embodiments, the alkylating agent is benzyl halide or hexyl halide. In some embodiments, the monoisocyanate comprises one or more R3-NCO, wherein each R3 is independently (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10 aryl optionally substituted with 1 to 3 substituents independently selected from C6-C 20 alkyl, and (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c ) optionally substituted with 1 to 3 substituents independently selected from C6-C 10 aryl, wherein each R a is independently C1-C6 alkyl, each R b and each R cThe monoisocyanate is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3. In some embodiments, the monoisocyanate includes octyl isocyanate, octadecyl isocyanate, or a combination thereof. In some embodiments, at least 20%, preferably at least 45%, and more preferably at least 75% of the optionally substituted hydroxyethylene functional groups react with the monoisocyanate, and 25% or less, preferably 10% or less of the optionally substituted hydroxyethylene functional groups react with the polyisocyanate. In some embodiments, the polymer comprises a polyethyleneimine oligomer, a polyfunctional crosslinking agent, an alkylating agent, and an optionally selected catalyst reaction product in the absence of the monoisocyanate. In some embodiments, the optionally selected catalyst includes dibutyltin dilaurate or bismuth carboxylate.

[0011] In another embodiment, compound (IV): [ka] An antimicrobial composition comprising, in the formula, Each A is independent, [ka] and [ka] Or any two or more copolymers of them are selected, and each bond of A forms a carbamate bond, Each Y is independently H or -C(O)-NHR3, Each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 100 to 1000. Each R1 is Independently, hydrogen; C 6 -C 10 C is optionally substituted with aryl and hydroxyl groups. 1 -C 6 C is optionally substituted with a substituent selected from any of the alkoxy groups. 1 -C 6 Alkyl; C 1 -C 6 Alkoxy; C 1 -C 6 C optionally substituted with alkyl 6 -C 10 Selected from aryl and carboxyl, Each R2 independently comprises hydroxyl, C1-C6 alkoxy, carboxyl, and C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 Selected from C1-C6 alkyl groups optionally substituted with substituents selected from aryl groups and C1-C6 alkoxy groups optionally substituted with hydroxyl groups, Each R3 is independently (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Alkyl, (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C 10 Aryl, and (3) [ka] Selected from, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each R c These are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3, Each R4 is independently and optionally substituted with phenyl C1-C 10 Alkylene, or a 3- to 8-membered cycloalkyl ring, each X - The present invention provides an antimicrobial composition independently selected from the group consisting of acetic acid, halides, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, carbonic acid, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, as well as organically substituted derivatives thereof.

[0012] In some embodiments of compound (IV), at least 75% of R3, though not all, is independently a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Alkyl; as well as halogens, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C 10 Selected from the aryl group, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each R c R3 is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3. In some embodiments of compound (IV), each R3 is independently a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules are optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Selected from alkyl groups. In some embodiments of compound (IV), R3 is octyl, octadecyl, or a combination thereof. In some embodiments of compound (IV), each R3 is independently a halogen, a C1-C6 alkyl, and a -SiR a (OR b)( Ure c C6-C 10 Selected from aryl compounds. In some embodiments of compound (IV), R3 is [ka] That is the case.

[0013] In another embodiment, compound (V): [ka] An antimicrobial composition comprising, in the formula, Each A is independent, [ka] Or any two or more copolymers of them are selected, and each bond of A forms a carbamate bond, Each Y is independently H or -C(O)-NHR3, Each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 100 to 1000. Each R1 is Independently, hydrogen; C 6 -C 10 C is optionally substituted with aryl and hydroxyl groups. 1 -C 6 C is optionally substituted with a substituent selected from any of the alkoxy groups. 1 -C 6 Alkyl; C 1 -C 6 Alkoxy; C 1 -C 6 C optionally substituted with alkyl 6 -C 10 Selected from aryl and carboxyl, Each R2 independently comprises hydroxyl, C1-C6 alkoxy, carboxyl, and C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 Selected from C1-C6 alkyl groups optionally substituted with substituents selected from aryl groups and C1-C6 alkoxy groups optionally substituted with hydroxyl groups, Each R3 is independently (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Alkyl, (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C 10 Aryl, and (3) [Chemical formula] selected from, wherein each R a is independently C1-C6 alkyl, and each R b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3, each R4 is independently C1-C 10 alkylene optionally substituted with phenyl, or a 3- to 8-membered cycloalkyl ring, each X - is independently selected from the group consisting of acetic acid, halide, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, carbonic acid, silicic acid, hexafluorophosphate, hexafluoroantimonate, and borate, and their organic substituted derivatives, and an antibacterial composition is provided.

[0014] In some embodiments of compound (V), at least 75% but not all of R3 are independently selected from halogen, -SiR a (OR b )(ORc), and C6-C 10 alkyl optionally substituted with 1 to 3 substituents independently selected from aryl; and halogen, C1-C6 alkyl, and -SiR 20 alkyl optionally substituted with 1 to 3 substituents independently selected from (OR a (OR b )(OR c ) and aryl selected from C6-C 10 wherein each R a is independently C1-C6 alkyl, and each R b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3. In some embodiments of compound (V), each R3 is independently halogen, -SiR a (OR b )(OR c ), and C6-C 10 alkyl optionally substituted with 1 to 3 substituents independently selected from aryl and substituted with C6-C 20is selected from alkyl. In some embodiments of compound (V), R3 is octyl, octadecyl, or a combination thereof. In some embodiments of compound (V), each R3 is independently halogen, C1-C6 alkyl, and -SiR a (OR b)( OR c ) and is optionally substituted with 1 to 3 substituents independently selected from C6-C 10 aryl. In some embodiments of compound (V), R3 is [Chemical formula] .

[0015] In some embodiments of compound (IV) or compound (V), each R1 is independently C1-C6 alkyl. In some embodiments of compound (IV) or compound (V), each R2 is independently hydroxy, C1-C6 alkoxy, carboxy, C6-C 10 aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 aryl), and is optionally substituted with a substituent selected from C1-C6 alkoxy optionally substituted with hydroxy and is selected from C1-C6 alkyl. In some embodiments of compound (IV) or compound (V), each R2 is independently methyl, butyl, hexyl, benzyl, -CH2C(O)Ph, and -CH2C(O)OCH2CH3. In some embodiments of compound (IV) or compound (V), R4 is C1-C 10 alkylene optionally substituted with phenyl. In some embodiments of compound (IV) or compound (V), R4 is C1-C 10 alkylene. In some embodiments of compound (IV) or compound (V), R4 is a 3- to 8-member cycloalkyl ring.

[0016] In another aspect, herein, compound (VI), compound (VII), or compound (VIII): [Chemical formula] Or an antimicrobial composition comprising any two or more combinations thereof, or any two or more copolymers thereof, wherein, Each Y is independently H or -C(O)-NHR3, Each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 100 to 1000. Each R1 is Independently, hydrogen; C 6 -C 10 C is optionally substituted with aryl and hydroxyl groups. 1 -C 6 C is optionally substituted with a substituent selected from any of the alkoxy groups. 1 -C 6 Alkyl; C 1 -C 6 Alkoxy; C 1 -C 6 C optionally substituted with alkyl 6 -C 10 Selected from aryl and carboxyl, Each R2 independently comprises hydroxyl, C1-C6 alkoxy, carboxyl, and C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 Selected from C1-C6 alkyl groups optionally substituted with substituents selected from aryl groups and C1-C6 alkoxy groups optionally substituted with hydroxyl groups, Each R3 is independently (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Alkyl, and (2) halogens, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C 10 Selected from the aryl group, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each R cThese are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3, each X - The present invention provides an antimicrobial composition independently selected from the group consisting of acetic acid, halides, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, carbonic acid, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, as well as organically substituted derivatives thereof.

[0017] In some embodiments of compound (VI), compound (VII), or compound (VIII), each R1 is independently a C1-C6 alkyl group. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R2 is independently a hydroxy, C1-C6 alkoxy, carboxy, or C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 The substituents are selected from C1-C6 alkyl groups optionally substituted with substituents selected from C1-C6 alkoxy groups optionally substituted with aryl groups and hydroxyl groups. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R2 is independently selected from methyl, butyl, hexyl, benzyl, -CH2C(O)Ph, and -CH2C(O)OCH2CH3. In some embodiments of compound (VI), compound (VII), or compound (VIII), at least 75% but not all of R3 are independently halogens, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Alkyl; as well as halogens, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C 10 Selected from the aryl group, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each Rc R3 is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R3 is independently a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules are optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Selected from alkyl groups. In some embodiments of compound (VI), compound (VII), or compound (VIII), R3 is octyl, octadecyl, or a combination thereof. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R3 is independently a halogen, a C1-C6 alkyl, and -SiR a (OR b)( Ure c C6-C 10 Selected from the list.

[0018] In another embodiment, the antimicrobial surface coating of the present technology comprises a mono-urethane-substituted alkyl quaternary polyethyleneimine (PEl)-A (MUA-Q-PEI-A) formed by reacting at least one monoisocyanate with a hydroxyl alkyl quaternary PEI (Mono-Urethane substituted Alkyl Quaternary Polyethyleneimine (PEl)-A, HA-Q-PEI). In some embodiments, 20% to 100% of the hydroxyl groups of HA-Q-PEI are converted to urethane groups by reacting with at least one monoisocyanate. In some embodiments, 50% to 95% of the hydroxyl groups of HA-Q-PEI are converted to urethane groups by reacting with at least one monoisocyanate. In some embodiments, the monoisocyanate is selected from alkyl-, alkylaryl-, arylalkyl-, or aryl-monoisocyanate. In some embodiments, the monoisocyanate is a blend of octyl isocyanate and octadecyl isocyanate. In some embodiments, the molar ratio of octyl isocyanate to octadecyl isocyanate is 1 / 9 to 5 / 5. In some embodiments, the molar ratio of octyl isocyanate to octadecyl isocyanate is 2 / 8 to 4 / 6. In some embodiments, the monoisocyanate is a fluoro or organosilicon-substituted monoisocyanate. In some embodiments, the polyethyleneimine has an average molecular weight of 600 to 1,000,000. In some embodiments, the polyethyleneimine has an average molecular weight of 25,000 to 270,000. In some embodiments, the polyethyleneimine is linear, branched, polybranched polyethyleneimine, or a blend thereof. In some embodiments, MUA-Q-PEI-A has a counterion selected from halides, sulfuric acid, sulfonic acid, phosphoric acid, carbonic acid, and borate. In some embodiments, the counterion is a chloride, bromide, iodide, or sulfuric acid.In some embodiments, the reagent HA-Q-PEI is formed by reacting polyethyleneimine with a monoepoxide and quaternizing it with a quaternizing agent. In some embodiments, the monoepoxide is an alkyl epoxide. In some embodiments, the alkyl epoxide is selected from propyl, butyl, or hexyl epoxides. In some embodiments, the alkyl epoxide is a propyl epoxide. In some embodiments, the quaternizing agent is an alkyl halide or an arylalkyl halide. In some embodiments, the quaternizing agent is a benzyl halide or a hexyl halide.

[0019] In another embodiment, the antimicrobial surface coating of the present technology comprises a crosslinked polyurethane alkyl quaternary PEI-B (PUA-Q-PEI-B) formed by crosslinking the above-mentioned HA-Q-PEI with at least one polyisocyanate. In some embodiments, the polyisocyanate has an average isocyanate functional value of 2 to 5. In some embodiments, the polyisocyanate has an average isocyanate functional value of 3 to 4. In some embodiments, the polyisocyanate is prepared from a diisocyanate selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylenediphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexyl isocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (TMXDI), or trimethylhexamethylene diisocyanate (TMDI). In some embodiments, the polyisocyanate is an isocyanate-terminated cap oligomer prepared from a polyfunctional isocyanate and a polyol. In some embodiments, the polyol is selected from polyester polyols, polyether polyols, polysiloxane polyols, polycaprolactone polyols, or polybutadiene polyols.

[0020] In another embodiment, the antimicrobial surface coating of the present technology comprises a crosslinked polyurethane alkyl quaternary PEI-C (PUA-Q-PEI-C), which is formed by reacting at least one polyisocyanate with HA-Q-PEI. In some embodiments, the polyisocyanate has an average isocyanate functional value of 2 to 5. In some embodiments, the polyisocyanate has an average isocyanate functional value of 3 to 4. In some embodiments, the polyisocyanate is prepared from a diisocyanate selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylenediphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexyl isocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (TMXDI), or trimethylhexamethylene diisocyanate (TMDI). In some embodiments, the polyisocyanate is an isocyanate-terminated cap oligomer prepared from a polyfunctional isocyanate and a polyol. In some embodiments, the polyol is selected from polyester polyols, polyether polyols, polysiloxane polyols, polycaprolactone polyols, or polybutadiene polyols.

[0021] In another embodiment, the Technology provides an antimicrobial coating, coating fluid, or spray fluid comprising any of the antimicrobial compositions described above. In some embodiments, HA-Q-PEI, MUA-Q-PEI-A, PUA-Q-PEI-B, or PUA-Q-PEI is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible. In some embodiments, the coating fluid or spray fluid is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible. In some embodiments, the device, apparatus, or accessory is selected from filters, air purifiers, masks, or other personal protection devices (PPDs), respiratory devices, etc. In some embodiments, the device, apparatus, or accessory is selected from keyboards, keypads, mice, remote controllers, touchscreens, telephones, or displays, or any device integrating any of the aforementioned components.

[0022] In another embodiment, the technology provides a personal care aid comprising one of the above-described coatings, coating fluids, or spray fluids. In some embodiments, the coating fluid or spray fluid is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible.

[0023] In another embodiment, a method for sterilizing a surface is provided herein, comprising applying a composition described herein. In another embodiment, a method for reducing antimicrobial growth on a surface is provided herein, comprising applying a composition described herein. In another embodiment, a method for preventing antimicrobial growth on a surface is provided herein, comprising applying a composition described herein. In some embodiments, the method further comprises forming a coating solution containing the composition. In some embodiments, the method further comprises directing the coating solution onto a surface and providing a coating on the surface by applying the coating solution to the surface.

[0024] Other embodiments are also described and enumerated herein.

[0025] For illustrative purposes, specific embodiments of this technology are shown in the drawings described below. However, it should be understood that this technology is not limited to the exact arrangement, dimensions, and fixtures shown. These are the drawings below. [Brief explanation of the drawing]

[0026] [Figure 1] The structure of the resulting hydroxyalkyl quaternary PEI (HA-Q-PEI) polymer after the reaction with initial polyethyleneimine (PEI) and alkyl epoxide, followed by quaternization with an alkylating agent, is shown. [Figure 2] The structure of mono-urethane-substituted alkylquaternary PEI-A (MUA-Q-PEI-A) obtained after reaction of the initial HA-Q-PEI with one or a blend thereof of hydrophobic monoisocyanates is shown. [Figure 3] The structure of mono-urethane-substituted alkyl quaternary PEI-A100 (MUA-Q-PEI-A100), in which 100% of the free hydroxyl groups have reacted, is shown. [Figure 4] This provides one of the structures of crosslinked polyurethane alkyl quaternary PEI-B (PUA-Q-PEI-B). [Figure 5] This provides one of the structures of a crosslinked polymer network of polyurethane alkyl quaternary PEI-C (PUA-Q-PEI-C). [Figure 6A-6B] The RT-qPCR test is shown, with Figure 6A illustrating the test plate setup and Figure 6B illustrating the QuantStudio3 PCR procedure. [Figure 7] The test plate used to evaluate the antiviral properties of composition (III) is shown. [Modes for carrying out the invention]

[0027] Here, the subject invention is described with reference to the drawings, and similar reference numerals are used throughout to refer to similar elements. In the following description, many specific details are described for illustrative purposes and to provide a full understanding of the Art. However, it may be apparent that the Art can be carried out without these specific details. In other cases, well-known structures and devices are shown in the form of block diagrams to facilitate the description of the Art. To provide a substantial understanding of the Art, it should be understood that specific aspects, modes, embodiments, variations, and features of the Art are described below at varying levels of detail.

[0028] definition For convenience, the meanings of some terms and phrases used in this specification, the examples, and the appended claims are provided below. Unless otherwise stated or implied by the context, the following terms and phrases have the meanings provided below. The definitions are provided to aid in describing specific embodiments and are not intended to limit the subject matter claimed, as the scope of this art is limited only by the claims. Unless otherwise expressly stated, all technical and scientific terms used herein have the same meanings as commonly understood by those skilled in the art. In the event of any apparent conflict between the use of a term in the art and its definition provided herein, the definition provided herein shall prevail.

[0029] As used herein and in the appended claims, the singular forms "a," "an," and "the" refer to multiple objects unless the context makes this clear. For example, a reference to "a cell" includes a combination of two or more cells, etc.

[0030] Where used herein, the terms “approximately” or “about” with respect to a value or parameter are generally interpreted to include a number that falls within the range of 5%, 10%, 15%, or 20% (greater than or less than) the possible value, unless otherwise stated or the context makes clear (except when such a number is less than 0% or greater than 100%). A reference to “approximately” or “about” a value or parameter includes (and describes) embodiments relating to that value or parameter. For example, a reference to “about X” includes a description of “X.”

[0031] As used herein, the term "or" means "and / or". As used herein in phrases such as "A and / or B", the term "and / or" is intended to include A and B, A or B, A (alone), and B (alone). Similarly, as used in phrases such as "A, B, and / or C", the term "and / or" is intended to include each of the following embodiments: A, B, and C; A, B, or C; A or C; A or B; B or C; A and C; A and B; B and C; A (alone); B (alone); and C (alone).

[0032] As used herein, the term “including” means that other elements may be present in addition to the defined elements presented. The use of “including” indicates inclusion, not limitation.

[0033] The term "consisting of" refers to the compositions, methods, and their respective components described herein, excluding any elements not enumerated in the description of the embodiments.

[0034] As used herein, the term “essentially derived from” refers to elements necessary for a given embodiment. The term permits the presence of additional elements that do not substantially affect the basic and novel or functional features of that embodiment of the Art.

[0035] As used herein, “aryl” refers to a fully aromatic carbocyclic (all-carbon) ring. An “aryl” group may consist of two or more fused rings (rings sharing two adjacent carbon atoms). If the aryl group is a fused ring system, the ring connected to the rest of the molecule is fully aromatic. Other rings in the fused ring system may or may not be fully aromatic. Examples of aryl groups include, but are not limited to, the radicals of benzene, naphthalene, and azulene.

[0036] As used herein, “alkyl” refers to a hydrocarbon group that is fully saturated (without double or triple bonds) in a linear or branched chain. The alkyl groups of the compounds disclosed herein may contain 1 to 15 carbon atoms. The alkyl groups herein may have 1 to 4 carbon atoms, 1 to 5 carbon atoms, 1 to 6 carbon atoms, 1 to 7 carbon atoms, 1 to 8 carbon atoms, 1 to 9 carbon atoms, 1 to 10 carbon atoms, 1 to 11 carbon atoms, 1 to 12 carbon atoms, 1 to 13 carbon atoms, 1 to 14 carbon atoms, or 1 to 15 carbon atoms. As used herein, C1-C6 alkyl represents an alkyl group having 1 to 6 carbon atoms, C1-C4 alkyl represents an alkyl group having 1 to 4 carbon atoms, and C1-C3 alkyl represents an alkyl group having 1 to 3 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, t-butyl, amyl, t-amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

[0037] As used herein, “alkoxy” refers to the alkyl group as defined above, which is attached to the parent molecule via an oxy group (-O-). As used herein, C1-C6 alkoxy refers to an alkoxy group containing 1 to 6 carbon atoms, and C1-C3 alkoxy refers to an alkoxy group containing 1 to 3 carbon atoms. Typical examples of alkoxys include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy, tert-butoxy, pentyloxy, and hexyloxy.

[0038] Where used herein, unless otherwise specified, “independently selected” means that each of the specified bases is independently selected from the list of subsequent species.

[0039] The terms "statistically significant" or "significantly significant" refer to statistical significance, which generally means a difference of two standard deviations (2SD) or more.

[0040] The terms “reduce,” “reduced,” “decrease,” or “inhibit” are all used herein to mean a reduction of a statistically significant amount. In some embodiments, “reduce,” “decrease,” or “decrease,” or “inhibit” typically mean a reduction of at least 10% compared to a reference level (e.g., the absence of a given treatment or drug), and may include reductions of, for example, at least about 10%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99%, or greater. As used herein, “decrease” or “inhibit” does not include complete inhibition or reduction compared to a reference level. “Complete inhibition” is 100% inhibition compared to a baseline level. The reduction may preferably be reduced to a level that is acceptable as being within the normal range for a given non-disabled individual.

[0041] The terms “increased,” “enhance,” “strengthen,” or “activate” are all used herein to mean an increase of a statically significant amount. In some embodiments, the terms “increased,” “enhance,” or “activate” may mean an increase of at least 10% compared to a reference level, e.g., at least about 20%, or at least about 30%, or at least about 40%, or at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90%, or up to 100%, including 100%, or any increase between 10% and 100% compared to a reference level, or an increase of at least about 2 times, or at least about 3 times, or at least about 4 times, or at least about 5 times, or at least about 10 times compared to a reference level, or any increase between 2 times and 10 times or more. In the context of markers or symptoms, “increase” is a statistically significant increase of such level.

[0042] As used herein, the term “quaternary ammonium polymer antiviral composition” generally refers to a family of quaternary ammonium polymer compositions in which the tertiary nitrogen moiety is quaternized using an alkylating agent such as benzyl chloride.

[0043] As used herein, the term "polyethylenemine" generally refers to a family of polymers containing primary, secondary, and tertiary amino groups, such as PEI 70 kDa (also known as average molecular weight).

[0044] As used herein, the term “monoisocyanate” generally refers to a family of naturally hydrophobic monoisocyanates, such as alkyl, aryl, alkylaryl, or arylalkyl monoisocyanates, preferably monoisocyanates having ≥6, more preferably ≥8 carbon atoms. Useful examples include, but are not limited to, octadecyl isocyanates, dodecyl isocyanates, and octyl isocyanates.

[0045] As used herein, the term "polyisocyanate" generally refers to, but is not limited to, a family of polyisocyanates containing two or more isocyanate-reactive groups, such as DESMODUR® N3300 and N100 (produced by Covestro Deutschland AG in Leverkusen, Germany), which are aliphatic polyisocyanates based on HDI (hexamethylene diisocyanate) trimers, or DESMODUR® Z4470SN (produced by Covestro Deutschland AG in Leverkusen, Germany), which is a polyfunctional polyisocyanate based on IPDI (isophorone diisocyanate).

[0046] As used herein, the term “antimicrobial” is generally used to indicate that a composition or coating of a portion of a surface kills at least a certain level of pathogenic bacteria. For example, antimicrobial may be used to indicate biosuppressive efficacy, a reduction in the bactericidal level (3 logs, or 99.9%) in at least one organism, or a reduction in the disinfectant level (5 logs, or 99.999%) in at least one organism, or sterilization (no detectable organisms). Pathogenic bacteria, or microorganisms, may include any species of bacteria, viruses, fungi including molds and yeasts, or spores. Thus, antimicrobial as used herein includes antiviral, antibacterial, and antifungal properties.

[0047] As used herein, the terms “residual antimicrobial,” “residual self-sterilizing,” and “self-decontaminating surface” are used interchangeably to describe a surface that, once coated with an antimicrobial coating composition and the composition dries on the surface as a thin film, maintains antimicrobial efficacy under certain conditions for a specific period of time. The coated surface may maintain residual antimicrobial efficacy indefinitely, or the coating may eventually “wear away” and lose its residual antimicrobial efficacy. Antimicrobial coating compositions may function as contact disinfectants, bacteriostatic materials, disinfectants, or sterilizers (e.g., as liquid antimicrobial agents applied to contaminated surfaces), and may also have the ability to leave a residual antimicrobial coating on a surface that, once dried or cured, can continue to inactivate new microorganisms that come into contact with the coated surface. In various embodiments, a coating composition may not be antimicrobial until it dries or cures on a surface, but is still referred to as an antimicrobial coating composition due to its ability to produce a residual antimicrobial coating on the surface. Antimicrobial coating compositions for use in various embodiments may provide residual antimicrobial efficacy on a surface, meaning that microorganisms subsequently inoculated onto the coated surface, or otherwise coming into contact with the coated surface, may experience cell death, destruction, or inactivation. The residual antimicrobial effects enabled by the coatings described herein are not limited by any particular mechanism of action, nor is such a theory provided. For example, antimicrobial effects measured on a surface may result from intracellular mutation, inhibition of certain cellular processes, cell wall rupture, or inactivation of organisms not described, such as viruses. Other antimicrobial effects may include inhibiting the reproduction of organisms or inhibiting the ability of organisms to accumulate in biofilms.

[0048] As used herein, the term “antimicrobial coating composition” refers to a chemical composition comprising at least one chemical species used to produce a residual antimicrobial coating on a surface after the composition has been applied and subsequently dried, allowed to dry, or cured in some way. The term is also used to refer to a liquid composition that can be used as a disinfectant spray (disinfectant or bactericide) because the composition can subsequently dry to an antimicrobial coating. The term is also extended to include compositions that can be applied sequentially (e.g., above or below) or simultaneously with the application of an antimicrobial coating composition to assist in bonding the residual antimicrobial coating to the surface, improve the durability of the overall coating, and / or provide a catalytic effect or some kind of enhancement or synergistic effect with the residual antimicrobial coating, including an antimicrobial activator. For the sake of simplification herein, each of several compositions used sequentially or concurrently to produce an overall residual antimicrobial coating on a portion of a surface is referred to as an “antimicrobial coating composition” even if one or more of the compositions used for coating do not have identifiable antimicrobial activity or the activator is unclear. Antimicrobial coating compositions may contain pure 100% activated species or may be solutions or suspensions of a single chemical species in a solvent. In other embodiments, compositions may contain complex mixtures of chemicals, some of which may undergo chemical reactions (such as hydrolysis and auto-condensation) within the composition to produce identifiable or unidentifiable reaction products. For example, monomeric species in an antimicrobial coating composition may be partially or completely polymerized or copolymerized to produce polymers, including homopolymers and copolymers, having distributions of molecular weight, comonomer ratio, or molecular architecture in solution prior to the coating process using the composition. In other embodiments, chemical components in an antimicrobial coating composition may chemically react, implant, or form interpenetrating networks on the surface or interphase to which the composition is applied, such as while the composition is drying and concentrating on a surface or while the coating composition is curing by various methods.In various embodiments, the solution containing the polymer distribution may be further polymerized or cured, such as to longer chain lengths or to form polymer networks, while the solution dries on the surface. Antimicrobial coating compositions for use in various embodiments may further comprise any number and combination of inert excipients, such as solvents, buffers, acids, alkalis, surfactants, emulsifiers, stabilizers, UV absorbers, thickeners, free radical initiators, fillers, pigments or colorants, and catalysts.

[0049] As used herein, the term “homopolymer” has its usual meaning in organic chemistry for molecules having repeated and identical monomer units. For simplicity, unless otherwise specified, the term homopolymer herein includes smaller oligomers, i.e., dimers, trimers, tetramers, dendrimers, dendrons, etc. For example, homopolymer distributions herein may include dimers or more, or trimers or more, as shown. In some cases, homopolymer chain length distributions may be clearly defined and characterized, while in others, the distribution may be uncharacterizable and remain unknown. The term copolymer herein includes random copolymers, block copolymers, graft copolymers, interpolymer complexes, interpenetration networks, etc., and blends thereof.

[0050] As used herein, the term “weight %” has the usual meaning of the weight percentage (%) of a component in a chemical composition based on the total weight of the “as prepared” composition. For example, an aqueous composition containing 1 weight % of an amine “based on the total weight of the composition” is equivalent to a composition containing 99.0 grams of water and 1.0 gram of amine. Weight % in a composition refers to the weight % of the active substance unless otherwise specified. “As prepared” means that the written composition refers to what it looks like when added to a mixing vessel and does not refer to what a particular component may ultimately become in the mixture after a reaction, such as hydrolysis or polymerization of the components.

[0051] Unless otherwise defined herein, scientific and technical terms used in connection with this application shall have meanings generally understood by those skilled in the art to which this disclosure belongs. It should be understood that the Art is not limited to the specific methodologies, protocols, and reagents described herein, and that these are subject to change. The technical terms used herein are for the sole purpose of describing specific embodiments and are not intended to limit the scope of the Art as defined solely by the claims. For definitions of general terms in immunology and molecular biology, please refer to The Merck Manual of Diagnosis and Therapy. 3 , The Encyclopedia of Molecular Cell Biology and Molecular Medicine 4 , Molecular Biology and Biotechnology: a Comprehensive Desk Reference 5 Immunology 6 Janeway's Immunobiology 7 Lewin's Genes XI 8 , Molecular Cloning: A Laboratory Manual 9 , Basic Methods in Molecular Biology 10 , Laboratory Methods in Enzymology 11 ,Current Protocols in Molecular Biology(CPMB) 12 ,Current Protocols in Protein Science(CPPS) 13 , and Current Protocols in Immunology (CPI) 14 It can be seen in this.

[0052] Other terms are defined herein within the descriptions of various aspects of this technology.

[0053] Antibacterial coating Surfaces of objects that come into direct or indirect contact with humans and animals are exposed to high microbial loads and have a demonstrable impact on the transmission of diseases and infections. The antimicrobial coatings of this technology can be applied to virtually any surface and can significantly reduce the microbial load, making them particularly useful. Surfaces that can be treated with antimicrobial coatings include, but are not limited to, interior and exterior building components such as handrails, fixtures, fixture knobs, pull handles, and grips; parts such as faucet handles in kitchens, washrooms, bathrooms, toilets, personal items, telephones, computers, door handles, counters, furniture, walls, ticket machines, and high-touch areas (e.g., building lounges, public payment systems, public transport systems); and other hard-to-clean / hard-to-access areas such as machinery and HVAC systems. Furthermore, these coatings can be applied to medical devices and accessories, implants and instruments, laboratory equipment, factories, water purification equipment, hospitals, schools / childcare facilities, airports, restaurants, gyms, and more.

[0054] Bacteria of particular concern include, but are not limited to, Staphylococcus aureus (Staph), Escherichia coli (E. coli), Methicillin-Resistant Staphylococcus aureus (MRSA), and Vancomycin-Resistant Enterococcus faecalis and Enterobacter aerogenes (VRE). Staph is a group of more than 30 strains that cause many different types of infections, including skin infections, foodborne illnesses, and bloodborne illnesses. Most strains of E. coli are harmless and are part of the healthy gut microbiota. However, some strains can cause a variety of illnesses, including pneumonia, urinary tract infections, diarrhea, and meningitis. Some strains of E. coli can cause nausea, vomiting, and fever. MRSA is a type of bacteria that causes infections in different parts of the body. It is relatively more difficult to treat than most other strains of Staph due to its antibiotic resistance. It can cause serious skin, bloodstream, lung, or urinary tract infections. VRE is a type of bacteria called Enterococci, and as its name suggests, it has developed resistance to many antibiotics, particularly vancomycin. These bacteria can cause serious infections, especially in people who are already sick, weak, and / or immunocompromised. VRE can cause bloodstream infections (sepsis), urinary tract infections, pneumonia, cardiac infections (endocarditis), or meningitis.

[0055] Viruses of particular concern include, but are not limited to, influenza A and B viruses, respiratory syncytial viruses, adenoviruses, rhinoviruses, and coronaviruses (229E, HKU1, NL63, OC43, and more recently, SARS-CoV-2), and these viruses have been shown to have long survival periods on many surfaces. For example, recent studies on airports... 15The detection of pathogenic viral nucleic acids indicated viral surface contamination at multiple sites associated with high contact rates, suggesting a potential risk in standard passenger pathways on airport premises. These viruses can cause serious infections, particularly in people who are already ill, weakened, and / or immunocompromised.

[0056] In the chemical coatings industry, a 99.9% reduction in bacteria or viruses translates to a three-digit reduction (i.e., 3log) in microbial risk. However, there are several physical and chemical requirements that must be met for an antimicrobial coating to be a fully effective and widely applicable antiviral / antibacterial / antifungal agent and surface coating. These properties include: 1. High antibacterial activity against a broad spectrum of viruses, bacteria, and fungi. 2. Extremely fast-acting, it kills over 99.9% of viruses with a contact time of less than 10 minutes and kills bacteria overnight. 3. Long-term durability: Maintains at least 98% bacterial or viral killing efficiency after 100 days of storage under ambient conditions or 72 hours of storage at 40°C / 85%RH humidity. 4. Non-toxic and non-allergenic, based on recognized standard testing procedures. 5. The material will not leach over time or when exposed to typical liquids used for cleaning. 6. The surface coating is visibly colorless and transparent. 7. It is easy to apply to a wide range of surfaces and materials by painting, spraying, dipping, or other commonly used application methods. 8. A durable surface coating that is resistant to peeling or visible degradation from the surface upon contact with water, alcohol, and common solvents. 9. It is easy and cost-effective to produce from readily available materials. 10. It is produced by a highly versatile synthesis, and a wide range of chemical variations are available to fine-tune its properties (i.e., solubility, etc.) for different applications.

[0057] To the knowledge of the inventors, no antimicrobial coating that meets most or all of these requirements is yet available. Many existing antimicrobial coatings tend to degrade over time and lose their effectiveness as contamination is repeated.

[0058] Conventional coating products that claim to provide antibacterial properties include PAINTGUARD / PAINTSHIELD® from Sherwin Williams Company (Cleveland, Ohio), ALESTA® AM and ALESTA® Ralguard from Axalta (Philadelphia, PA), and SILVERSAN® from PPG Industrial Coatings (Pittsburgh, PA). However, while these products generally claim 99.9% effectiveness, it takes more than 5 hours after application to reach maximum efficiency. Furthermore, existing solutions tend to degrade over time, so their active performance falls below 90% after re-contamination (i.e., repeated exposure to pathogens in combination with regular environmental exposure and / or prolonged scrubbing / washing). With only 90% protection, bacteria and germs have the ability to grow and respire, eventually proliferating to a point where existing pathogens on the substrate layer can survive, thereby reducing the effectiveness of these coatings.

[0059] Antimicrobial polymers have been reported for implants containing metals such as silver. 16 These formulations suffer from the fact that the embedded antimicrobial agent may leach out over time, causing the polymer coating to lose its antimicrobial activity. Furthermore, such formulations are not entirely satisfactory, as they only result in a 3-log reduction that cannot completely inhibit bacterial regrowth. This lack of effectiveness may be due to the fact that silver is used in insufficient amounts and / or is unevenly dispersed throughout the composition, leading to mismatch of antimicrobial particles within the composition / coating and ultimately an ineffective distribution.

[0060] Park et al. (2006) 17 We reported antimicrobial polymers prepared by reacting polyethyleneimine with a hydrophobic long-chain hydrocarbon alkylating agent, followed by quaternization by methylation. These polymers possess antibacterial and antiviral activity as surface coatings, but the coatings are not colorless, lack durability, and are not resistant to contact with water and other common solvents that surfaces may come into regular contact with.

[0061] Many speculate that the antiviral activity of quaternary ammonium polymers is due to the interaction between hydrophobic quaternary ammonium groups and the viral load film, causing the destruction of the film that inactivates viruses and other microorganisms. Indeed, many active ingredients in commercially available antiviral surface sprays are low molecular weight quaternary ammonium surfactant-like materials, and while they are assumed to work by this mechanism, they do not form long-lasting, durable surface coatings.

[0062] Researchers have reported acrylic or methacrylic copolymers having quaternary ammonium functional groups that possess antimicrobial activity. 18、19 However, these do not produce durable, water-resistant, and solvent-resistant coatings, and some exhibit a degree of toxicity.

[0063] Several researchers have reported antimicrobial polyurethane polymers containing quaternary ammonium functional groups. 20、21、22 However, these have several drawbacks. Some are water-soluble and therefore unsuitable for durable surface coatings. Others have not reported testing for coating durability or material toxicity. Some are somewhat expensive and quite redundant to synthesize, requiring up to four synthesis steps, including amine blocking and deblocking reactions.

[0064] Gao et al. (2007) 23The synthesis and antibacterial activity of polymers synthesized by alkylating polyethyleneimine with propyl epoxide and then quaternizing it with benzyl chloride were reported. These polymers were reported to be highly antibacterial with a short contact time of 4 minutes; however, they are water-soluble and therefore unsuitable for producing durable surface coatings. Furthermore, no tests for viral and toxic effects were reported for these polymers.

[0065] Although antimicrobial quaternary ammonium compounds and polymers have been previously known, simple coatings of these materials are either not optically transparent, do not exhibit high antimicrobial properties, or are not durable. The simple step of crosslinking the coating to achieve durability is insufficient to achieve all of these properties simultaneously.

[0066] This technology involves polymers The specific polymer chemistry of this technology is novel and new in that it involves the development of non-trivial chemical modifications to the basic polyethyleneimine quaternary ammonium polymer structure to optimize the overall properties of the polymer by controlling the molecular weight of the polymer, the properties of the polymer quaternary ammonium groups, the use of hydroxyalkylated PEI hydroxyl groups to fine-tune the hydrophilic-hydrophobic properties of the polymer through partial reactions with selected monoisocyanates, and by controlling the type and degree of polymer crosslinking to produce coatings that have the above properties and, more specifically, exhibit both high antimicrobial efficiency and good durability simultaneously.

[0067] In one embodiment, several novel quaternary ammonium polymers that substantially satisfy all of the requirements listed above are provided herein. A general process for producing these polymers begins with reacting polyethyleneimine (PEI) with an alkyl epoxide in a one-pot reaction, followed by quaternization with an alkylating agent, to produce polymers with the general structure shown in Figure 1, referred to as hydroxyalkyl quaternary PEI (HA-Q-PEI). These polymers are generally water-soluble or water-dispersible.

[0068] In the second step, the polymer is reacted with one or a blend thereof of hydrophobic monoisocyanates, in one case less than 100% of the free hydroxyl groups, to obtain the polymer shown in Figure 2, which is called mono-urethane-substituted alkyl quaternary PEI-A (MUA-Q-PEI-A).

[0069] In an alternative embodiment, 100% of the free hydroxyl groups are reacted to obtain the polymer shown in Figure 3, referred to as mono-urethane-substituted alkyl quaternary PEI-A100 (MUA-Q-PEI-A100). Both of these polymers (A and A100) are generally water-insoluble and, in some embodiments, are suitable for surface coatings.

[0070] In other embodiments, to produce a more durable surface coating, a MUA-Q-PEI-A type polymer is dissolved in a solvent with a polyisocyanate and coated onto the surface, so that some of the remaining unreacted free hydroxyl groups react with the polyisocyanate to form a highly durable crosslinked polyurethane alkyl quaternary PEI-B (PUA-Q-PEI-B) coating after drying (see Figure 4).

[0071] In yet another embodiment, the surface coating can be produced by applying a solution of HA-Q-PEI type polymer together with polyisocyanate to create a crosslinked polymer polyurethane alkyl quaternary PEI-C (PUA-Q-PEI-C), as shown in Figure 5.

[0072] The synthesis of these antimicrobial polymers is relatively easy using only commercially available materials. It will be understood that this novel family of antimicrobial polymers and the general methods for preparing them offer considerable versatility for tuning and fine-tuning their physical and chemical properties, as well as their antimicrobial properties, for a wide range of surfaces and applications. Examples of variables available for this fine-tuning include, but are not limited to, the molecular weight of the PEI, whether the PEI is linear, branched, or polybranched, the ratio of primary, secondary, and tertiary amines, the R group on the epoxide used, the alkylating agent used for PEI quaternization, the degree of quaternization, the monoisocyanate used, the percentage (including 0%) of hydroxyl groups reacted with the monoisocyanate, the polyisocyanate used, and the degree of crosslinking. It will also be understood that other means of crosslinking besides the use of polyisocyanates may be used.

[0073] Some embodiments of the technology described herein can be defined according to any of the following numbered paragraphs: 1. An antimicrobial composition comprising monourethane-substituted alkyl quaternary polyethyleneimine (PEl)-A (MUA-Q-PEI-A), wherein MUA-Q-PEI-A is formed by reacting at least one monoisocyanate with hydroxylalkyl quaternary PEI (HA-Q-PEI). 2. The antimicrobial composition according to paragraph 1, wherein 20% to 100% of the hydroxyl groups of HA-Q-PEI are converted to urethane groups by reaction with at least one monoisocyanate. 3. The antimicrobial composition according to paragraph 1, wherein 50% to 95% of the hydroxyl groups of HA-Q-PEI are converted to urethane groups by reaction with at least one monoisocyanate. 4. The antimicrobial composition according to any one of paragraphs 1 to 3, wherein the monoisocyanate is selected from the group comprising alkyl-, alkylaryl-, arylalkyl-, and aryl-monoisocyanates. 5. The antimicrobial composition according to any one of paragraphs 1 to 3, wherein the monoisocyanate is a blend of octyl isocyanate and octadecyl isocyanate. 6. The antimicrobial composition according to paragraph 5, wherein the molar ratio of octyl isocyanate to octadecyl isocyanate is 1 / 9 to 5 / 5. 7. The antimicrobial composition according to paragraph 5, wherein the molar ratio of octyl isocyanate to octadecyl isocyanate is 2 / 8 to 4 / 6. 8. The antimicrobial composition according to any one of paragraphs 1 to 3, wherein the monoisocyanate is a fluoro or organosilicon-substituted monoisocyanate. 9. An antimicrobial composition according to any one of paragraphs 1 to 3, wherein the polyethyleneimine has an average molecular weight of 600 to 1,000,000. 10. An antimicrobial composition according to any one of paragraphs 1 to 3, wherein the polyethyleneimine has an average molecular weight of 25,000 to 270,000. 11. The antimicrobial composition according to any one of paragraphs 1 to 3, wherein the polyethyleneimine is linear, branched, polybranched polyethyleneimine, or a blend thereof (i.e., a combination of two or more thereof). 12. The antimicrobial composition according to any one of paragraphs 1 to 3, wherein MUA-Q-PEI-A has a counterion selected from the group consisting of halides, sulfuric acid, sulfonic acid, phosphoric acid, carbonic acid, and borate. 13. The antimicrobial composition according to paragraph 12, wherein the counterion is chloride, bromide, iodide, or sulfuric acid. 14. The antimicrobial composition according to paragraph 1, wherein the reactant HA-Q-PEI is formed by reacting polyethyleneimine with a monoepoxide and quaternizing it with a quaternizing agent. 15. The antimicrobial composition according to paragraph 14, wherein the monoepoxide is an alkylepoxide. 16. The antimicrobial composition according to paragraph 15, wherein the alkyl epoxide is selected from the group consisting of propyl epoxide, butyl epoxide, and hexyl epoxide. 17. The antimicrobial composition according to paragraph 15, wherein the alkyl epoxide is a propyl epoxide. 18. The antimicrobial composition according to paragraph 14, wherein the quaternizing agent is an alkyl halogen or an aryl alkyl halogen. 19. The antimicrobial composition according to paragraph 14, wherein the quaternizing agent is benzyl halogenate or hexyl halogenate. 20. An antimicrobial composition comprising a crosslinked polyurethane alkyl quaternary PEI-B (PUA-Q-PEI-B), wherein PUA-Q-PEI-B is formed by crosslinking MUA-Q-PEI described in paragraph 1 with at least one polyisocyanate. 21. The antimicrobial composition according to paragraph 20, wherein the polyisocyanate has an average isocyanate functional value of 2 to 5. 22. The antimicrobial composition according to paragraph 20, wherein the polyisocyanate has an average isocyanate functional value of 3 to 4. 23. The antimicrobial composition according to any one of paragraphs 20 to 22, wherein the polyisocyanate is prepared from a diisocyanate selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylenediphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexyl isocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (TMXDI), and trimethylhexamethylene diisocyanate (TMDI). 24. The antimicrobial composition according to any one of paragraphs 20 to 22, wherein the polyisocyanate is an isocyanate-terminated cap oligomer prepared from a polyfunctional isocyanate and a polyol. 25. The antimicrobial composition according to paragraph 24, wherein the polyol is selected from the group consisting of polyester polyols, polyether polyols, polysiloxane polyols, polycaprolactone polyols, and polybutadiene polyols. 26. An antimicrobial composition comprising crosslinked polyurethane alkyl quaternary PEI-C (PUA-Q-PEI-C), wherein PUA-Q-PEI-C is formed by reacting at least one polyisocyanate with HA-Q-PEI. 27. The antimicrobial composition according to paragraph 26, wherein the polyisocyanate has an average isocyanate functional value of 2 to 5. 28. The antimicrobial composition according to paragraph 26, wherein the polyisocyanate has an average isocyanate functional value of 3 to 4. 29. An antimicrobial composition according to any one of paragraphs 26 to 28, wherein the polyisocyanate is prepared from a diisocyanate selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylenediphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexyl isocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (TMXDI), and trimethylhexamethylene diisocyanate (TMDI). 30. The antimicrobial composition according to paragraph 29, wherein the polyisocyanate is an isocyanate-terminated capped oligomer prepared from a polyfunctional isocyanate and a polyol. 31. The antimicrobial composition according to paragraph 29, wherein the polyol is selected from the group consisting of polyester polyols, polyether polyols, polysiloxane polyols, polycaprolactone polyols, and polybutadiene polyols. 32. An antimicrobial coating, coating fluid, or spray fluid comprising any one of the compositions described in paragraphs 1 to 31. 33. The antimicrobial coating, coating fluid, or spray fluid according to paragraph 32, wherein HA-Q-PEI, MUA-Q-PEI-A, PUA-Q-PEI-B, or PUA-Q-PEI-C is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible. 34. Devices, equipment, apparatus, or accessories comprising the coating, coating fluid, or spray fluid described in paragraph 32. 35. A device, apparatus, apparatus, or accessory as described in paragraph 34, wherein the coating fluid or spray fluid is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible. 36. The device, apparatus, apparatus, or accessory described in paragraph 34 or 35, wherein the device, apparatus, apparatus, or accessory is selected from the group consisting of filters, air purifiers, and masks. 37. The device, apparatus, apparatus, or accessory described in paragraph 34 or 35, wherein the device, apparatus, apparatus, or accessory is selected from the group consisting of keyboards, keypads, mice, remote controllers, touchscreens, telephones, and displays. 38. Personal care products comprising the coating, coating fluid, or spray fluid described in paragraph 32. 39. The personal care product according to paragraph 38, wherein the coating fluid or spray fluid is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible.

[0074] In another embodiment, the Specified provides a polymer comprising, essentially comprising, or consisting of a reaction product of a polyethyleneimine oligomer, a polyfunctional crosslinking agent, an alkylating agent, an optional monoisocyanate, and an optional catalyst, wherein the polyethyleneimine oligomer comprises an optionally substituted hydroxyethylene functional group that reacts with one or both of the optional monoisocyanate or polyfunctional crosslinking agent, and the nitrogen atoms present in the polyethyleneimine oligomer are at least partially quaternized by the alkylating agent.

[0075] Hydroxyethylene functional groups on polyethyleneimine oligomers can be introduced by the reaction of polyethyleneimine with a monoepoxide. Therefore, a secondary and / or primary amine on polyethyleneimine is alkylated with a monoepoxide to form a hydroethylene functional group.

[0076] The hydroxyethylene functional group is C 6 -C 10 C is optionally substituted with aryl and hydroxyl groups. 1 -C 6 C is optionally substituted with a substituent selected from any of the alkoxy groups. 1 -C 6 Alkyl; C 1 -C 6 Alkoxy; C 1 -C 6 C optionally substituted with alkyl6 -C 10 It can be optionally substituted with aryl and carboxyl compounds. In some embodiments, the hydroxyethylene functional group is C6-C 10 It is substituted with a C1-C6 alkyl group that is optionally substituted with an aryl group. In some embodiments, the hydroxyethylene functional group is substituted with a C1-C6 alkyl group that is optionally substituted with a C1-C6 alkoxy group, and the C1-C6 alkoxy group is optionally substituted with a hydroxyl group. In some embodiments, the hydroxyethylene functional group is substituted with a C1-C6 alkyl group that is optionally substituted with a C1-C6 alkoxy group, and the C1-C6 alkoxy group is optionally substituted with a C1-C6 alkoxy group. In some embodiments, the hydroxyethylene functional group is substituted with a C1-C6 alkyl group that is optionally substituted with a C1-C6 alkoxy group, and the C1-C6 alkoxy group is optionally substituted with a C6-C 10 Optionally substituted with aryl, C6-C 10 The aryl group is optionally substituted with a C1-C6 alkyl group. In some embodiments, the hydroxyethylene functional group is optionally substituted with a C1-C6 alkyl group, which is optionally substituted with a C1-C6 alkoxy group, and the C1-C6 alkoxy group is optionally substituted with a carboxyl group. In some embodiments, the hydroxyethylene functional group is substituted with a C1-C6 alkyl group.

[0077] Polyethyleneimine oligomers contain, are essentially, or may contain reaction products of polyethyleneimine and monoepoxide. Monoepoxide is C 6 -C 10 C is optionally substituted with aryl and hydroxyl groups. 1 -C 6 C is optionally substituted with a substituent selected from any of the alkoxy groups. 1 -C 6 Alkyl; C 1 -C 6 Alkoxy; C 1 -C 6 C optionally substituted with alkyl 6 -C 10 It is optionally substituted with aryl and carboxyl compounds. In some embodiments, the monoepoxide is C6-C 10It is substituted with a C1-C6 alkyl group that is optionally substituted with an aryl group. In some embodiments, the monoepoxide is substituted with a C1-C6 alkyl group that is optionally substituted with a C1-C6 alkoxy group, and the C1-C6 alkoxy group is optionally substituted with a hydroxyl group. In some embodiments, the monoepoxide is substituted with a C1-C6 alkyl group that is optionally substituted with a C1-C6 alkoxy group, and the C1-C6 alkoxy group is optionally substituted with a C1-C6 alkoxy group. In some embodiments, the monoepoxide is substituted with a C1-C6 alkyl group that is optionally substituted with a C1-C6 alkoxy group, and the C1-C6 alkoxy group is optionally substituted with a C6-C 10 Optionally substituted with aryl, C6-C 10 The aryl group is optionally substituted with a C1-C6 alkyl group. In some embodiments, the monoepoxide is optionally substituted with a C1-C6 alkyl group that has been optionally substituted with a C1-C6 alkoxy group, and the C1-C6 alkoxy group is optionally substituted with a carboxyl group. In some embodiments, the monoepoxide is a C1-C6 alkyl epoxide. In some embodiments, the C1-C6 alkyl epoxide is selected from the group consisting of propyl epoxides, butyl epoxides, and hexyl epoxides.

[0078] Polyethyleneimines can have molecular weights ranging from approximately 600 to approximately 270,000 daltons, or any range in between. These include 600, 800, 1000, 5000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000, 60000, 65000, 70000, 75000, 80000, 85000, 90000, 95000, 100000, 105000, 110000, 115000, 120000, 125000, 130000, 135000, 140000, 145000, and 1 The molecular weights include 50,000, 155,000, 160,000, 165,000, 170,000, 175,000, 180,000, 185,000, 190,000, 195,000, 200,000, 205,000, 210,000, 215,000, 220,000, 225,000, 230,000, 235,000, 240,000, 245,000, 250,000, 255,000, 260,000, 265,000, or 270,000 daltons, or any value in between. In some embodiments, polyethyleneimine has a molecular weight of about 10,000 to about 200,000 daltons. In some embodiments, polyethyleneimine has a molecular weight of about 25,000 to about 120,000 daltons. Polyethyleneimine may be branched or polybranched.

[0079] In some embodiments, polyethyleneimine has a primary to secondary to tertiary amine ratio of about 1:2:1 to about 1:1:1. In some embodiments, polyethyleneimine has a primary to secondary to tertiary amine ratio of about 1:1:0.7.

[0080] The polyfunctional crosslinking agent may be a polyisocyanate. In some embodiments, the polyisocyanate has an average isocyanate functional value of 2 to 5. This includes average isocyanate functional values ​​of 2, 3, 4, or 5. In some embodiments, the polyisocyanate has an average isocyanate functional value of 3 or 4.

[0081] Polyisocyanates can be prepared from diisocyanates selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylenediphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexyl isocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (TMXDI), and trimethylhexamethylene diisocyanate (TMDI).

[0082] In some embodiments, the polyisocyanate is selected from the group consisting of DESMODUR® N-3300, DESMODUR® N-100, DESMODUR® Z4470SN, WANNATE® T-series polyisocyanates, and LUPRANATE® M-series polyisocyanates. DESMODUR® N-3300 and DESMODUR® N-100 are aliphatic polyisocyanates based on HDI (hexamethylene diisocyanate) trimer. DESMODUR® Z4470SN is a polyfunctional polyisocyanate based on IPDI (isophorone diisocyanate). WANNATE® T-series polyisocyanates are toluene diisocyanate (TDI)-based aromatic polyisocyanates. LUPRANATE® M-series polyisocyanates are aromatic polyisocyanates based on 4,4-diphenylmethane diisocyanate (MDI).

[0083] At least 75% of the nitrogen atoms of polyethyleneimine oligomers can be quaternized by alkylating agents. This includes 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100% of the nitrogen atoms of polyethyleneimine oligomers that have been quaternized by alkylating agents.

[0084] The alkylating agent comprises, essentially consists of, or may consist of one or more R2-LG groups, where each R2 is independently hydroxyl, C1-C6 alkoxy, carboxyl, or C6-C6. 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 The LGs are selected from C1-C6 alkyl groups optionally substituted with substituents selected from aryl, C1-C6 alkoxy, and hydroxyl, respectively, where each LG is a leaving group. As used herein, “leaving group” refers to halides (e.g., chlorides, bromides, or iodides), sulfonates (e.g., mesylates, tosylates, triflates, nonaflates), fluorosulfates, or acetates. In some embodiments, each R2 is independently hydroxyl, C1-C6 alkoxy, carboxyl, or C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 The alkylating agent is selected from C1-C6 alkyl groups optionally substituted with substituents selected from aryl and hydroxyl-substituted C1-C6 alkoxy groups. In some embodiments, the alkylating agent is benzyl halogen or hexyl halogen. In some embodiments, the alkylating agent is hexyl halogen. In some embodiments, the alkylating agent is benzyl halogen.

[0085] Monoisocyanates contain, essentially consist of, or may consist of one or more R3-NCOs, where each R3 is independently (1) a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Alkyl, and (2) halogens, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C 10Selected from the aryl group, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each R c These are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3. In some embodiments, the monoisocyanate comprises one or more R3-NCOs, where each R3 is independently a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules are optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Selected from alkyl groups. In some embodiments, the monoisocyanate comprises one or more R3-NCO groups, where each R3 is independently a halogen, a C1-C6 alkyl group, and a -SiR group. a (OR b )(OR c C6-C 10 Selected from the aryl group, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each R c These are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3. In some embodiments, the monoisocyanate includes octyl isocyanate, octadecyl isocyanate, or a combination thereof.

[0086] In some embodiments, at least 20% of the optionally substituted hydroxyethylene functional groups react with the monoisocyanate, and 25% or less of the optionally substituted hydroxyethylene functional groups react with the polyisocyanate. This includes 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, Includes 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% or more but less than 100%. In some embodiments, at least 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 5 8, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% or more but less than 100% react with the monoisocyanate. In some embodiments, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1% or less but greater than 0% of the optionally substituted hydroxyethylene functional groups react with the polyisocyanate. In some embodiments, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2% or less, or 1% or less but greater than 0%, of the optionally substituted hydroxyethylene functional groups react with the polyisocyanate.

[0087] In some embodiments, 100% of the optionally substituted hydroxyethylene functional groups react with the polyisocyanate.

[0088] In some embodiments, the polymer comprises, consists essentially of, or consists of the reaction product of a polyethyleneimine oligomer, a polyisocyanate, an alkylating agent, and optionally a catalyst, in the absence of a monoisocyanate.

[0089] The catalyst can comprise, consist essentially of, or consist of dibutyltin dilaurate or bismuth carboxylate. In some embodiments, the catalyst comprises, consists essentially of, or consists of dibutyltin dilaurate. In some embodiments, the catalyst comprises, consists essentially of, or consists of bismuth carboxylate.

[0090] In another aspect, herein, compound (IV):

Chemical formula

Chemical formula

Chemical formula

[0091] In another aspect, as used herein, compound (V): [Chemical formula] is a polymer, wherein each A is independently [Chemical formula] or selected from any two or more copolymers thereof, and the bond of each A forms a carbamate bond each Y is independently H or -C(O)-NHR3 each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 100 to 1000 each R1 is Independently, hydrogen; C 6 -C 10 C is optionally substituted with aryl and hydroxyl groups. 1 -C 6 C is optionally substituted with a substituent selected from any of the alkoxy groups. 1 -C 6 Alkyl; C 1 -C 6 Alkoxy; C 1 -C 6 C optionally substituted with alkyl 6 -C 10 Selected from aryl and carboxyl, each R2 is independently C1-C6 alkyl optionally substituted with a substituent selected from hydroxy, C1-C6 alkoxy, carboxy, C6-C 10 aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 aryl), and C1-C6 alkoxy optionally substituted with hydroxy each R3 is independently (1) C6-C a (OR b )(OR c ) and C6-C 10 alkyl optionally substituted with 1 to 3 substituents independently selected from aryl, (2) halogen, C1-C6 alkyl, and -SiR 20 alkyl, (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(ORc C6-C 10 Aryl, and (3) [ka] Selected from, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each R c These are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3, Each R4 is independently and optionally substituted with phenyl C1-C 10 Alkylene, or a 3- to 8-membered cycloalkyl ring, each X - The present invention provides polymers independently selected from the group consisting of acetic acid, halides, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, carbonic acid, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, as well as organically substituted derivatives thereof.

[0092] In some embodiments of compound (IV) or compound (V), at least 75% but not all of R3 is independently a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Alkyl; as well as halogens, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C 10 Selected from the aryl group, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each R cThese are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3. This includes 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% or more, but not all of R3, independently of halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Alkyl; as well as halogens, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C 10 Selected from the aryl group, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each R c These are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3.

[0093] In some embodiments of compound (IV) or compound (V), each R3 is independently a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules are optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Selected from alkyl. In some embodiments of compound (IV) or compound (V), each R3 is C6-C 20 Selected independently from alkyl. In some embodiments of compound (IV) or compound (V), R3 is octyl, octadecyl, or a combination thereof. In some embodiments of compound (IV) or compound (V), each R3 is independently halogen, C1-C6 alkyl, and -SiR a (OR b)( Ure cC6-C 10 Selected from the list.

[0094] In some embodiments of compound (IV), R3 is [ka] That is the case.

[0095] In some embodiments of compound (V), R3 is [ka] That is the case.

[0096] In some embodiments of compound (IV) or compound (V), each R1 is independently a C1-C6 alkyl group.

[0097] In some embodiments of compound (IV) or compound (V), each R2 is independently hydroxy, C1-C6 alkoxy, carboxy, C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 The substituents are selected from C1-C6 alkyl groups optionally substituted with substituents selected from aryl groups and C1-C6 alkoxy groups optionally substituted with hydroxyl groups. In some embodiments of compound (IV) or compound (V), each R2 is independently selected from C1-C6 alkyl groups optionally substituted with hydroxyl groups. In some embodiments of compound (IV) or compound (V), each R2 is independently selected from C1-C6 alkyl groups optionally substituted with C1-C6 alkoxy groups. In some embodiments of compound (IV) or compound (V), each R2 is independently selected from C1-C6 alkyl groups optionally substituted with carboxyl groups. In some embodiments of compound (IV) or compound (V), each R2 is independently selected from C6-C 10Selected from C1-C6 alkyl groups optionally substituted with aryl groups. In some embodiments of compound (IV) or compound (V), each R2 is independently selected from C1-C6 alkyl groups optionally substituted with C1-C6 alkoxy groups, where the C1-C6 alkoxy groups are optionally substituted with hydroxyl groups. In some embodiments of compound (IV) or compound (V), each R2 is independently selected from -C(O)O(C1-C6 alkyl) or -C(O)-(C6-C 10 Selected from C1-C6 alkyl groups optionally substituted with aryl groups. In some embodiments of compound (IV) or compound (V), each R2 is independently selected from methyl, butyl, hexyl, benzyl, -CH2C(O)Ph, and -CH2C(O)OCH2CH3. In some embodiments of compound (IV) or compound (V), R2 is hexyl or benzyl. In some embodiments of compound (IV) or compound (V), R2 is hexyl. In some embodiments of compound (IV) or compound (V), R2 is benzyl.

[0098] In some embodiments of compound (IV) or compound (V), R4 is a C1-C molecule optionally substituted with phenyl. 10 It is an alkylene. In some embodiments of compound (IV) or compound (V), R4 is C 1- C 10 It is an alkylene. In some embodiments of compound (IV) or compound (V), R4 is a 3- to 8-membered cycloalkyl ring.

[0099] In another embodiment, compound (VI), compound (VII), or compound (VIII): [ka] Or a polymer comprising, essentially, or consisting of any two or more combinations thereof, or any two or more copolymers thereof, in the formula, Each Y is independently H or -C(O)-NHR3, Each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 100 to 1000. Each R1 is Independently, hydrogen; C 6 -C 10 C is optionally substituted with aryl and hydroxyl groups. 1 -C 6 C is optionally substituted with a substituent selected from any of the alkoxy groups. 1 -C 6 Alkyl; C 1 -C 6 Alkoxy; C 1 -C 6 C optionally substituted with alkyl 6 -C 10 Selected from aryl and carboxyl, Each R2 independently comprises hydroxyl, C1-C6 alkoxy, carboxyl, and C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 Selected from C1-C6 alkyl groups optionally substituted with substituents selected from aryl groups and C1-C6 alkoxy groups optionally substituted with hydroxyl groups, Each R3 is independently (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Alkyl, and (2) halogens, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C 10 Selected from the aryl group, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each R c These are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3, each X - The present invention provides polymers independently selected from the group consisting of acetic acid, halides, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, carbonic acid, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, as well as organically substituted derivatives thereof.

[0100] In some embodiments of compound (VI), compound (VII), or compound (VIII), each R1 is independently a C1-C6 alkyl group.

[0101] In some embodiments of compound (VI), compound (VII), or compound (VIII), each R2 is independently hydroxy, C1-C6 alkoxy, carboxy, C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 The substituents are selected from C1-C6 alkyl groups optionally substituted with substituents selected from aryl groups and C1-C6 alkoxy groups optionally substituted with hydroxyl groups. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R2 is independently selected from C1-C6 alkyl groups optionally substituted with hydroxyl groups. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R2 is independently selected from C1-C6 alkyl groups optionally substituted with C1-C6 alkoxy groups. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R2 is independently selected from C1-C6 alkyl groups optionally substituted with carboxyl groups. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R2 is independently selected from C6-C 10 Selected from C1-C6 alkyl groups optionally substituted with aryl groups. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R2 is independently -C(O)O(C1-C6 alkyl) or -C(O)-(C6-C 10Selected from C1-C6 alkyl groups optionally substituted with aryl groups. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R2 is independently selected from C1-C6 alkyl groups optionally substituted with C1-C6 alkoxy groups, where the C1-C6 alkoxy groups are optionally substituted with hydroxyl groups. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R2 is independently selected from methyl, butyl, hexyl, benzyl, -CH2C(O)Ph, and -CH2C(O)OCH2CH3. In some embodiments of compound (VI), compound (VII), or compound (VIII), R2 is hexyl or benzyl. In some embodiments of compound (VI), compound (VII), or compound (VIII), R2 is hexyl. In some embodiments of compound (VI), compound (VII), or compound (VIII), R2 is benzyl.

[0102] In some embodiments of compound (VI), compound (VII), or compound (VIII), each R3 is independently a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules are optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Selected from alkyl. In some embodiments of compound (VI), compound (VII), or compound (VIII), each R3 is independently C6-C 20 Selected from alkyl groups. In some embodiments of compound (VI), compound (VII), or compound (VIII), R3 is octyl, octadecyl, or a combination thereof. In some embodiments of compound (VI), compound (VII), or compound (VIII), R3 is independently halogen, C1-C6 alkyl, and -SiR a (OR b)( Ure c C6-C 10 Selected from the list.

[0103] In some embodiments of compound (VI), compound (VII), or compound (VIII), at least 75% but not all of R3 is independently a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Alkyl; as well as halogens, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C 10 Selected from the aryl group, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each R c These are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3. This includes 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% or more, but not all of R3, independently of halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C molecules optionally substituted with 1 to 3 substituents independently selected from the aryl group. 20 Alkyl; as well as halogens, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C 10 Selected from the aryl group, in the formula, each R a These are independently C1-C6 alkyl groups, and each R b and each R c These are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3.

[0104] For compound (IV), compound (V), compound (VI), compound (VII), or compound (VIII), each X - These are independently selected from the group consisting of acetic acid, halides, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, carbonic acid, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, and their organically substituted derivatives. As used herein, and unless otherwise specified, “organically substituted derivative” refers to an anion in which a sulfur atom, phosphorus atom, boron atom, silicon atom, or carbonyl group is substituted with either an alkyl group or an aryl group. Non-limiting examples include methyl sulfate, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethylsulfonic acid, and trifluoroacetic acid.

[0105] In another embodiment, antimicrobial compositions comprising, essentially comprising, or consisting of the polymers disclosed herein are provided. In some embodiments, the polymer comprises, essentially comprising, or consisting of compound (IV). In some embodiments, the polymer comprises, essentially comprising, or consisting of compound (V). In some embodiments, the polymer comprises, essentially comprising, or consisting of compound (VI), compound (VII), or compound (VIII), or any two or more combinations thereof, or any two or more copolymers thereof.

[0106] In another embodiment, the Specified herein provides antimicrobial coatings, coating fluids, or spray fluids comprising, essentially, or consisting of antimicrobial compositions described herein. In some embodiments, the coating fluid or spray fluid is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible. In some embodiments, the coating fluid or spray fluid is water-soluble or water-dispersible. In some embodiments, the coating fluid or spray fluid is alcohol-soluble or alcohol-dispersible.

[0107] In another embodiment, this specification provides devices, apparatus, devices, or accessories comprising antimicrobial coatings, coating fluids, or spray fluids described herein. Non-limiting examples of devices, apparatus, devices, or accessories include filters, air purifiers, masks, or other personal protective devices (PPDs), respiratory devices, etc. Other non-limiting examples include keyboards, keypads, mice, remote controllers, touchscreens, telephones, and displays, or any device integrating any of the aforementioned components.

[0108] In another embodiment, the Specified Provisions provide personal care products comprising coatings, coating fluids, or spray fluids as described herein. Non-limiting examples of personal care products include facial tissues, hand soaps, and cleansing pads.

[0109] How to use In another embodiment, this specification provides a method for sterilizing a surface, which includes, essentially comprises, or consists of applying a composition disclosed herein to the surface.

[0110] In another embodiment, this specification provides a method for reducing (e.g., minimizing) antimicrobial growth on a surface, which includes, essentially, or consists of applying a composition disclosed herein to the surface. In some embodiments, the method includes forming a coating solution containing a composition according to any embodiment described herein. The method further includes directing the coating solution to the surface via an applicator (e.g., a sprayer) and providing a coating on the surface by applying the coating solution to the surface.

[0111] In another embodiment, this specification provides a method for preventing the growth of antimicrobial growth on a surface, which includes, essentially comprises, or consists of applying a composition disclosed herein to the surface.

[0112] In some embodiments of the above-described methods, the coating step includes, essentially, or consists of spraying or brushing the surface with the composition. In some embodiments of the above-described methods, the coating step includes, essentially, or consists of immersing the surface in a coating solution containing the composition according to any embodiment described herein. In some embodiments of the above-described methods, the coating step includes, essentially, or consists of applying the composition to the surface by an electrostatic process.

[0113] The description of embodiments of this disclosure is not intended to be exclusive or to limit to any form exactly as disclosed herein. Specific embodiments and examples of this disclosure are described herein for illustrative purposes, but various equivalent modifications are possible within the scope of this disclosure, as will be recognized by those skilled in the art. For example, while method steps or functions are presented in a given order, alternative embodiments may perform the functions in a different order, or the functions may be performed substantially simultaneously. The teachings of this disclosure provided herein may be applied to other procedures or methods where appropriate. Further embodiments may be provided by combining the various embodiments described herein. Aspects of this disclosure may be modified, as needed, to adopt compositions, functions, and concepts of the above-mentioned references and uses in order to provide further embodiments of this disclosure. Furthermore, several modifications may be made to the protein structure without affecting the type or amount of biological or chemical action, taking into consideration biological functional equivalence. These and other modifications may be made to this disclosure in light of the detailed description. All such modifications are intended to be included within the scope of the appended claims.

[0114] Any particular element of any of the embodiments described above can be combined with or replaced by elements of other embodiments. Furthermore, while the advantages associated with specific embodiments of this disclosure are described in the context of those embodiments, other embodiments may also demonstrate such advantages, and not all embodiments are required to demonstrate advantages that fall within the scope of the Art.

[0115] The techniques described herein are further illustrated by the following examples, which should not be construed as further limitations. Methods and materials similar to or equivalent to those described herein may be used in the practice or testing of this disclosure, but preferred methods and materials are described below. [Examples]

[0116] The present technology, as commonly described today, will be more readily understood by referring to the following examples, the first three of which describe general synthetic procedures for synthesizing HA-Q-PEI polymers, reacting them with monoisocyanates to produce MUA-Q-PEI-A polymers, and preparing crosslinked MUA-Q-PEI-B polymer coatings. These are included solely for illustrative purposes of specific aspects and embodiments of the present technology and are not intended to limit the present technology.

[0117] Example 1 Synthesis of Hydroxypropylquaternary Ammonium PEI For the purposes of the chemicals described herein, the ratio of primary, secondary, and tertiary amines in branched PEI is assumed to be 1:2:1, as reported in the literature. 24、25 .

[0118] The procedure used is essentially the same as that described in Gao et al. (2007). 26 As shown below, the structure of polymer compound (I) is intended to be an approximation showing that most of the primary and secondary amines react with epoxides, and most of the tertiary amines are quaternized by alkylation with benzyl chloride. [ka]

[0119] 3.33 g of 70 kDa PEI solution (assuming 30% PEI in water, 1 g mw = 43.1 g / mol, 23.2 mmol) was added to a 25 mL two-necked flask under nitrogen and cooled to 0°C. 5.4 g (92.8 mmol) of propylene oxide was added dropwise to this mixture at 0–3°C. After the addition was complete, the reaction mixture was stirred at 0–3°C for 7 hours. The temperature of the reaction mixture was then raised to 35°C, and the unreacted propylene oxide was distilled (approximately 3.60 mL). 11.75 g (10.6 mL, 92.8 mmol) of benzyl chloride was added to the resulting solution, and the reaction mixture was heated at 50°C for 30 hours. The reaction mixture was extracted with diethyl ether (3 × 20 mL) to remove unreacted benzyl chloride, residual propylene oxide, and any oleophilic by-products or impurities. The aqueous phase was separated, vaporized under vacuum, and dried by freeze-drying, leaving compound (I) as a transparent solid (2.85 g). The product was characterized by proton NMR and infrared (IR) spectroscopy.

[0120] Example 2: Process of reaction between hydroxypropyl quaternary ammonium PEI and monoisocyanate (approximately 85% of free OH groups) As shown below, the structure of the polymer product is intended to be an approximation indicating that the majority of the hydroxyl groups (approximately 85% molar equivalent) react with the monoisocyanate blend to form a urethane, while some hydroxyl groups remain unreacted. [ka]

[0121] The concentration of reactive hydroxyl groups (mmol / gram of dry polymer) was determined by titrating a known amount (grams) of dry HA-Q-PEI polymer with a known excess amount (grams, mmol) of octasdecyl isocyanate. The proportion of monoisocyanate consumed in the reactant was monitored using infrared (IR) spectroscopy, at 2263 cm⁻¹. -1 This was determined by monitoring the decrease in the isocyanate peak. From the percentage decrease in this peak, the number of millimoles of isocyanate consumed was estimated. This value corresponded to the number of millimoles of polymer hydroxyl groups that reacted with the isocyanate. In this way, the hydroxyl group concentration of the polymer (mmole reactive hydroxyl groups / g dry polymer) was calculated and then used in subsequent reactions to determine the amount of monoisocyanate required to functionalize a specific percentage of reactive hydroxyl groups in the polymer, thereby fine-tuning the hydrophilic / hydrophobic properties of the polymer.

[0122] Using the procedure described in Example 1, 2.0 g (2.27 mmol, assuming a molecular weight of 881 g / mol per polymer unit cell) of hydroxypropyl quaternary ammonium PEI compound (I) was prepared, then dried under vacuum at 60°C for 2 hours, followed by storage overnight in a drying oven at room temperature. To the dried polymer, 13.8 g of t-butyl alcohol and 9.2 g of dimethylacetamide were added. The resulting mixture was stirred under nitrogen until the polymer was completely dissolved. Both of these solvents were thoroughly dried using a molecular sieve of 4 Å before use. A mixture of 1.6 g (5.41 mmol) of octadecyl isocyanate and 0.36 g (2.32 mmol) of octyl isocyanate was added dropwise to the polymer solution. This mixture totaled 7.73 mmol of monoisocyanate, corresponding to approximately 85% of the available hydroxyl groups. The reaction mixture became slightly cloudy. The resulting reaction mixture was stirred under nitrogen at room temperature for 12 hours. The resulting reaction mixture was filtered through a PTFE filter (1 μm) to obtain 20.83 grams of compound (II) as a 12.19% solid solution. IR spectroscopy showed a new peak expected to correspond to the urethane carbonyl, and no residual isocyanate peak was observed.

[0123] In some embodiments, after the reaction with monoisocyanate was complete, the reaction mixture was added to water to precipitate the MUA-Q-PEI-A product. This product was isolated, washed with water to remove any water-soluble impurities, and then dried for use in the next step. This water precipitation step was useful in removing any water-soluble impurities that could contribute to toxicity.

[0124] Example 3: Process for crosslinking and coating reaction of octadecyl / octazil urethane quaternary ammonium PEI As shown below, the structure of polymer compound (III) is intended to be an approximation indicating that some of the unreacted hydroxyl groups in compound (II) reacted with the polyisocyanate to form urethane crosslinks. [ka] TIFF0007887060000024.tif141157

[0125] Using the procedure described in Example 2, 20 g of octadecyl / octyl urethane quaternary ammonium PEI was prepared, to which 1.25 g of Desmodur N3300 (50% solution in anhydrous acetone) and 0.18 g of a 1% solution of dibutyltin dilaurate in dry toluene were added. The resulting mixture was thoroughly mixed and immediately coated onto corona-pretreated white PET (2 mil, Milenex 339) supported on a stainless steel plate using a #36 Meyer rod. The coated film was heated in an oven at 60°C for 30 minutes without vacuum. This dried film was used to measure antimicrobial activity. IR spectroscopy showed no residual isocyanates.

[0126] It should be noted that the above crosslinking procedure was also carried out without the dibutyltin dilaurate catalyst, and the resulting dried film provided a reasonable coating, although its durability was slightly lower than that obtained when the catalyst was used.

[0127] It will also be understood that several variations, including but not limited to those described below, may be used in the processes described above to adjust the physical, chemical, and mechanical properties of the polymer to suit a range of possible applications, as needed: ● Different average molecular weight PEIs and PEIs with different degrees of branching. ●Other epoxides besides propyl epoxide. ● Different quaternary groups other than benzyl. ● The degree of hydroxyalkylation and quaternization can be varied. ● The degree of oligomer formation in hydroalkylation reactions with alkyl epoxides. ● Different monoisocyanates can be used, and these may be a single monoisocyanate or a blend of monoisocyanates. ●The reaction with the monoisocyanate that forms the urethane can be modified so that less than 100% of the hydroxyl groups react, or so that 100% of the hydroxyl groups react. ●Other polyisocyanates besides N3300 can be used for crosslinking. ● Different solvents can be used for the chemical reaction depending on the solubility of the PEI-derived polymer, which may be affected by the above-mentioned variations. ● Reactants other than monoisocyanates and polyisocyanates can be used for reactions with hydroxyl groups and for crosslinking.

[0128] Example 4 Evaluation of the antiviral activity of polymers and / or their coatings This study was conducted to evaluate the antiviral activity of the polymer coating of this technology. All samples and accessories used in the evaluation were first disinfected by either high-temperature autoclaving, alcohol washing, or irradiation in a UV laminar chamber.

[0129] First, adenovirus (108 PFU / mL, plaque-forming units, MOI=100, co-infection) was administered in phosphate-buffered water (PBS) in a 2 × 10⁻¹⁶ solution. 7 The solution was diluted to PFU / ml. Then, 0.1 mL of the diluted virus solution was deposited onto the disinfected sample.

[0130] Antiviral activity was determined by two different methods: (i) the human cell (HuH7) method, and (ii) the quantitative reverse transcription polymerase chain reaction (RT-qPCR) method.

[0131] (i) Human cell (HuH7) method HuH7 is a type of human hepatocyte cell line that can be grown in a laboratory for research purposes. According to the website huh7.com, it is "a cancer cell line derived from well-differentiated hepatocytes, originally taken from a liver tumor in a 57-year-old Japanese man in 1982."

[0132] To evaluate antiviral activity, 0.1 mL of adenovirus in Dulbecco's Modified Eagle Medium (DMEM) + 10% fetal bovine serum (FBS) was dropped onto the coating and onto a control substrate, and left on the coating for 30 minutes. The virus / culture mixture was transferred to a petri dish containing HuH7 cells (human hepatocytes) in the culture medium. The residual virus on the coating was rinsed twice with 0.1 mL of culture medium and liquid combined with the virus solution in the petri dish. The petri dish was transferred to a CO2 incubator and incubated at 37°C for 48 hours at approximately 95% relative humidity and 5% CO2 concentration to amplify the signal.

[0133] Once incubation was complete, visible light and fluorescence microscopy images of the virus / cell samples were taken to determine the population of viruses and living / dead cells. For the positive control, 0.1 mL of virus in the culture medium was directly transferred to a petri dish containing HuH7 cells in the culture medium.

[0134] (ii) RT-qPCR method RT-qPCR is used in a variety of applications, including pathogen detection, gene expression analysis, RNAi validation, microarray validation, genetic testing, and disease research.

[0135] Sample preparation The culture medium (DMEM, high sucrose, pyruvate; ThermoFisher, catalog number: 11995040) was removed from the refrigerator and prepared in a 37°C water bath for 30 minutes.

[0136] Preparation of virus solution: A typical number of viruses in the stock is 5 lambda (5 x 10) per tube. 8 ) Add 1 mL of DMEM medium to the virus tube, and mix the tube uniformly with a vortex mixer for 5 to 10 seconds, then 5 × 10 8 A viral fluid with a concentration of / mL was prepared. The viral solution was then incubated in DMEM medium for antiviral testing, with a concentration of 5 × 10⁶ units. 7 It was further diluted to / mL.

[0137] RT-qPCR procedure for coating: The coated film was immersed in 99% alcohol for 1 second. Excess alcohol was removed from the surface. The film was then air-dried in a new petri dish for 15-20 minutes. Then, 100 μL of diluted virus solution (5 × 10⁶) was added. 6 The solution ( / mL) was dropped onto a dry film. The Petri dish was covered to allow the virus to remain in contact with the film for the desired contact time. In some experiments, the contact time was reduced to a minimum of 30 seconds. The virus solution was transferred from the film to an Eppendorf tube. The film was then rinsed twice with 50 μL of 1X PBD, and the rinse fluid was combined with the Eppendorf tube. The total volume of the test solution was 200 μL, and it was ready for DNA extraction.

[0138] RT-qPCR procedure for aqueous solutions: 100 μL of the test sample is mixed with 100 μL of diluted viral fluid in an Eppendorf tube (5 × 10⁻¹⁰⁶). 7 Add to the mixture (5 × 10 / mL) 6 The viral load was shaken on a shaker for 30 minutes. DNA was extracted using a Novogene DNA kit according to the specified extraction procedure.

[0139] RT-qPCR test: Each sample was tested in a four-tube strip. The components listed in Table 1 were thoroughly mixed in Eppendorf tubes. [Table 1] [Table 2]

[0140] As illustrated in Figure 6A, 10 μL of the premix was added to each cavity of the test plate, three samples were taken for each coating, and each sample was tested in a four-component sequence. Therefore, a total of 12 tests were performed for each coating.

[0141] The plate was centrifuged to confirm that all the premix fluid had flowed to the bottom of the cavities. As illustrated in Figure 6B, the plate was inserted into an Applied Biosystems QuantStudio3 (ThermoFisher) to determine the number of cycle thresholds (CTs) for calculating antiviral efficiency. A quantitative RT-PCR method may also be performed. Antiviral efficiency is quantitatively calculated from the number of CTs. For instructions on using the QuantStudio3 PCR procedure, see https: / / www.youtube.com / watch?v=udy7iskkZwE and https: / / www.youtube.com / watch?v=PjgwDhN63Zc.

[0142] test Qualitative cell viability test of the coating: The coating was placed in a petri dish, and 100 μL of DMEM medium was dropped onto the coating. The petri dish was then covered for 30 minutes. The medium on the film was then measured in 500 μL of medium, with 8 × 10⁶ cells in each fraction, as shown in Figure 7. 4 The cells were transferred to a cell plate containing [number] cells. The film was rinsed twice with 50 μL of DMEM medium, and the rising fluid was combined with the previously used test fluid at the same location in the plate. A total of 200 μL of test fluid was added to 500 μL of cells / medium. The cell plate was incubated in a 37°C / 95%RH CO2 incubator for 48–96 hours, after which cell proliferation and morphology were observed under a visible microscope. Dead cells floated or suspended in the medium, while live cells remained fixed to the bottom of the plate. This test was intended to evaluate the contact cytotoxicity of the polymer film. If this test shows some degree of cytotoxicity, the actual mechanism of cell death is not given, although cell death due to the extraction of chemicals from the coating is one possibility.

[0143] Qualitative cell viability test of polymer solutions or dispersions: 100 μL of polymer solution or dispersion and 100 μL of DMEM medium were added to an Eppendorf container and thoroughly mixed in a shaker for 30 minutes. In the case of polymer films, the fixed area of ​​the film was cut and dispersed in the medium for the test. The test fluid was transferred to a cell plate, and cells were grown in a 37°C / 95%RH CO2 incubator for 48-96 hours. Cell growth and morphology were recorded under a visible microscope.

[0144] Qualitative antiviral efficiency test of polymer film: 100 μL of virus solution (5 × 10 7 The virus solution was dropped onto the polymer film in a Petri dish. The Petri dish was covered for 30 minutes. The virus solution was then added to 500 μL of culture medium in each fraction, with 8 × 10⁶ units of the solution added. 4 The cells were transferred to a cell plate containing the specified number of cells (see Figure 7). The film was then rinsed twice with 50 μL of DMEM medium, and the rising fluid was combined with the previously used test fluid at the same location in the plate. The total volume of the test fluid was 200 μL. The cell plate was then incubated in a 37°C / 95%RH CO2 incubator for 48–96 hours. Finally, cell morphology and fluorescence were recorded under a UV microscope.

[0145] Qualitative antiviral efficiency test of polymer solution or dispersion: 100 μL of virus solution (5 × 10 7 The polymer solution or dispersion (8 × 10 / mL) and 100 μL were added to the Eppendorf container and shaken thoroughly in a shaker for 30 minutes. The test mixture was then mixed with 8 × 10 units of medium in 500 μL of each fraction. 4 The cells were added to a cell plate containing individual cells. The cell plate was then incubated in a 37°C / 95%RH CO2 incubator for 48–96 hours. Finally, cell morphology and fluorescence were recorded under a UV microscope.

[0146] Experimental Results - Antiviral Activity and Toxicity of Coating with Crosslinked Polymer Compound (III) As described above, the coating of cross-linked polymer compound (III), prepared and tested, killed >99.9% of adenoviruses with a contact time of only 30 seconds. Furthermore, compound (III) was nontoxic to HuH7 cells. The compound (III) coating was essentially colorless, transparent, durable to contact with water and alcohol, and exhibited excellent adhesion to various substrates such as PET and metal plates. Similar highly efficient antiviral activity and non-toxicity were observed with the compound (II) polymer coating, which was also essentially colorless and transparent, although it had slightly inferior durability to water and alcohol compared to the compound (III) coating.

[0147] The following examples further illustrate the advantages and versatility of this technology.

[0148] Example 5: Aqueous solution antiviral efficiency of HA-Q-PEI polymers having various PEI molecular weights, quaternary nitrogen groups, and anion counterions against adenovirus. The following formula: [ka] Various HA-Q-PEIs (hydroxyalkyl quaternary PEIs) were prepared using a procedure similar to that described in Example 1, and their antiviral (AV) efficiency against adenoviruses described in Example 4 was analyzed. Selected data are shown in Table 2 (R1 = methyl group for each polymer). These results demonstrate high antiviral efficiency across the PEI molecular weight range using various nitrogen quaternization groups (R2) and anion counterions (X-). [Table 3]

[0149] Example 6: Aqueous solution antiviral efficiency of HA-Q-PEI polymers with various PEI molecular weights against adenovirus. The following formulas have various molecular weights: [ka] Additional HA-Q-PEI polymers (R1=methyl, R2=hexyl, X=bromide) were prepared using a procedure similar to that described in Example 1, and their antiviral (AV) efficacy against adenoviruses described in Example 4 was analyzed. Selected data are shown in Table 3. [Table 4]

[0150] These results demonstrate that the solution antiviral efficiency against adenovirus for this series of HA-Q-PEI polymers increases with increasing PEI molecular weight, leveling off at a maximum of >99% in the range of 25,000–270,000.

[0151] While these HA-Q-PEI polymers exhibit high solution-based antiviral efficiency, their high water solubility makes them unsuitable for the direct fabrication of durable, water-resistant surface coatings. Coating durability against solvents such as water and ethanol is highly desirable, as it maintains antimicrobial efficiency and significantly reduces the need for frequent re-sterilization of surfaces even after cleaning.

[0152] Example 7 Adenovirus antiviral efficiency of PUA-Q-PEI-C coating as a function of weight percentage of N100 crosslinking agent used The following formula: [ka] The coating of the PUA-Q-PEI-C polymer was performed using a procedure similar to that described in Example 2, replacing the octadecyl / octyl urethane quaternary ammonium PEI with HA-Q-PEI (PEI: molecular weight = 70,000 (branched), R1 = methyl, R2 = hexyl, X = bromide), and the crosslinking agent Z (DESMODUR® N100): [ka] The preparations were made by varying the amount of [ingredient].

[0153] The antiviral efficacy of these PUA-Q-PEI-C polymers against adenoviruses (as described in Example 4) was investigated. Selected data are shown in Table 4. [Table 5]

[0154] Crosslinking the HA-Q-PEI coating to form a polyurethane PUA-Q-PEI-C polymer coating improved the water and ethanol resistance of the coating (data not shown), but as can be seen from this example, this is associated with a significant decrease in antiviral efficiency due to the increase in the amount of crosslinking.

[0155] Example 8 Antiviral efficiency of HA-Q-PEI polymer aqueous solution and MUA-Q-PEI-A and MUA-Q-PEI-A100 polymers against adenovirus as a non-crosslinked coating. The following formula: [ka] MUA-Q-PEI-A polymer (R3=C 18 Alkyl or C8 alkyl groups were prepared from HA-Q-PEI (PEI: molecular weight = 70,000 (branched), R1 = methyl, R2 = benzyl) and a monoisocyanate mixture (7:3 mixture ratio of octadecyl isocyanate to octyl isocyanate), and approximately 90% of the HA-Q-PEI hydroxyl groups reacted with the monoisocyanate mixture (see a similar protocol in Example 2). MUA-Q-PEI-A100 polymers were prepared similarly, and approximately 100% of the HA-Q-PEI hydroxyl groups reacted with the monoisocyanate mixture. Films of these MUA-Q-PEI-A and MUA-Q-PEI-A100 polymers were examined for their antiviral efficiency against adenovirus, as described in Example 4. These results are shown in Table 5. [Table 6]

[0156] These results indicate that the high solution antiviral efficiency of the HA-Q-PEI polymer was maintained and / or increased after reaction with the monoisocyanate mixture, forming coatings of MUA-Q-PEI-A and MUA-Q-PEI-A100 polymers. These results also demonstrate that the coating exhibits >99% antiviral efficiency even with a short contact time of 30 seconds.

[0157] Example 9 Antiviral efficiency and coating durability of PUA-Q-PEI-B coating against adenovirus as a function of the amount (weight percent) of N3300 polyisocyanate crosslinking agent used. The following formula: [ka] PUA-Q-PEI-B polymer (R3=C 18 Alkyl or C8 alkyl groups were prepared using a procedure similar to that described in Example 3. In particular, HA-Q-PEI (prepared from PEI: molecular weight = 25,000 (multi-branched), R1 = methyl, R2 = hexyl, X = bromide) was reacted with a monoisocyanate mixture (a mixture of octadecyl isocyanate and octyl isocyanate in a ratio of 7:3), and the remaining hydroxyl groups were crosslinked with various amounts of crosslinking agent Z (DESMODUR® N3300): [ka] Before the reaction, approximately 90% of the HA-Q-PEI hydroxyl groups were reacted with a monoisocyanate mixture.

[0158] These PUA-Q-PEI-B polymer coatings were evaluated for their antiviral efficiency against adenovirus, water resistance, and ethanol resistance (as described in Example 4). The general procedure for measuring water and ethanol resistance was to immerse a centrally cross-cut coated sample in water or ethanol for 10 minutes, followed by gently wiping the sample with a cotton swab. Undamaged coatings passed the test. Selected data are shown in Table 6. [Table 7]

[0159] This data suggests that crosslinking agents are necessary to achieve good durability, and that for these samples, there was an optimal range of crosslinking agent levels where antiviral efficiency was >99%, and an optimal range beyond which antiviral efficiency significantly decreased.

[0160] Example 10: Retention of high coating antiviral efficiency over extended time and under more extreme environmental conditions. The following formula: [ka] PUA-Q-PEI-B polymer (R3=C 18 Alkyl) was prepared using a procedure similar to that described in Example 3. In particular, HA-Q-PEI (prepared from PEI: molecular weight = 70,000 (branched), R1 = methyl, R2 = benzyl, X = chloride) was reacted with octadecyl isocyanate, and approximately 85% of the hydroxyl groups of HA-Q-PEI were reacted with octadecyl isocyanate before the remaining hydroxyl groups were reacted with the crosslinking agent Z (DESMODUR® N3300).

[0161] After coating and drying, the coating was optically clear, passed water and ethanol durability tests (protocol described in Example 9), was non-toxic to human liver cells, and showed a 99.9% antiviral efficiency against adenovirus after 30 seconds of contact (protocol described in Example 4).

[0162] After storing the coating under ambient conditions for 105 days, the coating still exhibited an antiviral efficiency of over 98%, and after storing it at 40°C / 85%RH for 72 hours, the coating showed an antiviral efficiency of >99.73%. Furthermore, these results were shown to be independent of the level of crosslinking agent used, ranging from 1.62 to 7.61 weight percent.

[0163] In contrast, commercially available LIVINGUARD® face masks showed an antiviral efficiency against adenovirus of only 44% after 1 minute of contact and only 72% after 20 minutes of contact. When subjected to the same prolonged and harsh conditioning tests, the efficiency of LIVINGUARD® face masks decreased to 0% after 20 minutes of contact after 105 days of storage under ambient conditions, and further decreased from 72% to just 16% after 72 hours of storage at 40°C / 85%RH.

[0164] For comparison, several commercially available products were tested using the antiviral and toxicity testing procedures, as well as the durability testing procedures described above.

[0165] In contrast to the coatings of this technology, the quaternary PEI polymers shown below did not form a colorless, transparent, durable, water- and alcohol-resistant coating, and exhibited only moderate antiviral activity. The two latex quaternary polymers shown below showed antiviral activity but were toxic to HuH7 cells. [ka]

[0166] Mundex-W and Mundex-LK (from Munditech, Germany) are two "self-disinfecting polymer emulsions" for surface treatment. Both were found to have very weak antiviral properties against adenovirus. Unexpectedly, the water-based Mundex-W did not provide a durable, water-resistant or alcohol-resistant surface coating. The solvent-based Mundex-LK provided a more hydrophobic coating, but its water- or alcohol-resistant properties were only slight. Furthermore, both were found to be toxic to HuH7 cells.

[0167] Example 11: Evaluation of the antibacterial and antifungal activity of the additional coating of this technology. The following formula: [ka] PUA-Q-PEI-B polymer (R3=C 18 Alkyl or C8 alkyl groups were prepared using a procedure similar to that described in Example 3. In particular, HA-Q-PEI (prepared from PEI: molecular weight = 25,000 (multi-branched) or 600 (branched), R1 = methyl, R2 = hexyl, X = bromide) was reacted with a monoisocyanate mixture (7:3 ratio of octadecyl isocyanate to octyl isocyanate), and approximately 75% of the HA-Q-PEI hydroxyl groups were reacted with octadecyl isocyanate before the remaining hydroxyl groups were reacted with various amounts of crosslinking agent Z (DESMODUR® N100).

[0168] The antibacterial and antifungal efficacy of these PUA-Q-PEI-B polymer coatings was evaluated. Selected data are shown in Table 7. [Table 8] † Antimicrobial efficiency evaluated at 35°C using the PN-EN ISO22196:2011 standard. ‡Antimicrobial efficiency evaluated at 25°C using the PN-EN ISO21702:2019 standard. * PEI molecular weight = 25,000 daltons (multi-branched) ** PEI molecular weight = 600 daltons (branched), A = Staphylococcus aureus (MRSA), B = Pseudomonas aeruginosa, C = Candida albicans, D = Clostridium difficile, E = Influenza A virus H3N2, F = Influenza A virus H1N1, G = Human coronavirus 220E

[0169] Example 12: Evaluation of the antibacterial and antifungal activity of the coating of this technology. Similar high-efficiency antiviral activity and non-toxicity were observed in coatings of common types of polymers of compound (II) and compound (III), with various substituents on the PEI, as shown below: polymer (2), fully reacted polymer (2), and polymer (3): [ka] It changes in TIFF0007887060000044.tif136159, and in the formula, R1 = independently of hydrogen, alkyl, alkylaryl, arylalkyl, aryl, alkyloxy, carboxy, hydroxyalkyloxyalkyl, and preferably methyl. R2 = independently of alkyl, arylalkyl, carboxyalkyl, hydroxyalkyl, alkoxyalkyl, hydroxyalkyloxyalkyl, and preferably benzyl, methyl, hexyl, ethyl acetate, ethyl butyrate, and acetophenone. R3 = independently of alkyl, alkylaryl, aryl, arylalkyl, fluoro, or organosilicon substitution, and preferably C8H 17 or C 18 H 37 Long-chain alkyl groups such as R4 = Independently, alkylenes including cyclic alkylenes, C6H 12 , C7H6, C10 H 17 , C 13 H 10 , or C 13 H 18 Alkylphenylenes such as C6H 12 , X- = chloride, bromide, iodide, sulfuric acid, phosphoric acid, borate, etc., and preferably an anionic counterion for quaternary ammonium ions such as chloride, bromide, and sulfuric acid.

[0170] The percentage of hydroxyl groups converted to monoisocyanates in polymer (2) may be in the range of 20% to 100%, preferably 50% to 95%. The monourethane-functionalized polymer (2), fully reacted (2), and (3) may be derived from the reaction of one or more monoisocyanates or a blend thereof, and preferably a blend of octyl isocyanate and octadecyl isocyanate in a molar ratio in the range of 1 / 9 to 5 / 5, preferably 2 / 8 to 4 / 6. The crosslinked portions shown in polymer (3) are derived from polyisocyanate alkyl diisocyanate trimers such as hexamethylene diisocyanate trimers (HDI). Other possible crosslinking agents include, but are not limited to, polyisocyanates having an average isocyanate functional value of 2 to 5, preferably isophorone diisocyanate (IPDI), toluene isocyanate (TDI), methylene isocyanate (MDI), dicyclohexylmethane-4,4'-diisocyanate (DMDI), and polyisocyanates derived from other di-, tri-, and polyisocyanates. The weight percentage of polyisocyanate to the partially monourethane functionalized polymer (2) for forming the crosslinked polymer (3) is preferably in the range of 1% to 30%, more preferably in the range of 3% to 10%. The PEI polymer backbone may be linear, branched, or polybranched, and preferably has an average molecular weight (average Mw) in the range of 0.6 to 1,000 kDa, more preferably in the range of 25 to 270 kDa.

[0171] The hydroxyalkyl quaternary ammonium PEI polymers of type (I) prepared as described above are typically water-soluble. Generally, they exhibited high antiviral efficiency in solution. Some of these polymers tested showed some level of toxicity to HuH7 cells, while others were non-toxic depending on the properties of their substituents and counterions.

[0172] Sample preparation and testing methods To evaluate the antibacterial activity of the polymer coatings of this disclosure, the polymer coatings were prepared as described above for antiviral testing. All samples and accessories used for evaluation were first disinfected by either high-temperature autoclaving, alcohol washing, or irradiation in a UV laminar chamber.

[0173] The test protocol used to determine antibacterial and antifungal activity is the procedure described in ASTM-E2149-13a, which was a standard test method for determining the antimicrobial activity of antimicrobial agents under dynamic contact conditions.

[0174] Test results When the cross-linked polymer compound (III) coating was prepared and tested on the bacterium E. coli as described above, at least 99.9% of the bacteria were killed after overnight incubation at 37°C. Furthermore, as previously stated, compound (III) was nontoxic to HuH7 cells.

[0175] Similar high-efficiency antibacterial activity and non-toxicity were observed in coatings of common types of polymers of compound (II) and compound (III), with various substituents on the PEI altered as described above.

[0176] Similar highly efficient antibacterial activity was observed against other bacteria, including Staphylococcus aureus, Pseudomonas aeruginosa, Klebsiella pneumoniae, Andida albicans, Salmonella enterica, and Streptococcus pneumoniae, as well as against the fungus Aspergillus niger.

[0177] In conclusion, the novel antimicrobial polymers of this technology produce surface coatings exhibiting the following properties: (i) high antimicrobial activity against viruses, bacteria, and fungi; (ii) rapid action; (iii) long-lasting effect; (iv) non-toxic and non-allergenic; (v) no material leaching from the coating; (vi) colorless and transparent as a surface coating; (vii) easy application to a wide range of surfaces and materials; (viii) durable surface coating resistant to water and common solvents; and (ix) easy and cost-effective production. Therefore, these novel antimicrobial polymers represent an improved class of antimicrobial polymers.

[0178] References: 1 Ellingson, KD, et al. (2020). “Urban Hospital Study - Antimicrobial Surface Coating.” Clinical Infectious Diseases, 71(8):1807-1813. 2 Jarach, N., et al., (2020). “Polymers in the Medical Antiviral Front-Line”. Polymers, 12(8):1727. 3 THE MERCK MANUAL OF DIAGNOSIS AND THERAPY, (2011).19 th Edition, published by Merck Sharp & Dohme Corp., (ISBN 978-0-911910-19-3). 4 THE ENCYCLOPEDIA OF MOLECULAR CELL BIOLOGY AND MOLECULAR MEDICINE, Robert S. Porter et al.(eds.), published by Blackwell Science Ltd., 1999-2012 (ISBN 9783527600908). 5 MOLECULAR BIOLOGY AND BIOTECHNOLOGY: A COMPREHENSIVE DESK REFERENCE, (1995).Robert A. Meyers (ed.), published by VCH Publishers, Inc.(ISBN 1-56081-569-8). 6 IMMUNOLOGY, (2006).Werner Luttmann, published by Elsevier. 7 JANEWAY’S IMMUNOBIOLOGY, (2014).Kenneth Murphy, Allan Mowat, Casey Weaver (eds.), Taylor & Francis Limited, (ISBN 0815345305, 9780815345305). 8 LEWIN’S GENES XI, (2014). published by Jones & Bartlett Publishers (ISBN-1449659055). 9 Michael Richard Green and Joseph Sambrook, (2012).MOLECULAR CLONING: A LABORATORY MANUAL, 4th ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y., USA (ISBN 1936113414). 10Davis et al., (2012).BASIC METHODS IN MOLECULAR BIOLOGY, Elsevier Science Publishing, Inc., New York, USA (ISBN044460149X). 11 LABORATORY METHODS IN ENZYMOLOGY: DNA, (2013).Jon Lorsch (ed.) Elsevier (ISBN 0124199542). 12 CURRENT PROTOCOLS IN MOLECULAR BIOLOGY (CPMB), (2014).Frederick M. Ausubel (ed.), John Wiley and Sons (ISBN 047150338X, 9780471503385). 13 CURRENT PROTOCOLS IN PROTEIN SCIENCE (CPPS), (2005).John E. Coligan (ed.), John Wiley and Sons, Inc. 14 CURRENT PROTOCOLS IN IMMUNOLOGY (CPI) (2003).Coligan, J.E., et al., (eds.)John Wiley and Sons, Inc.(ISBN 0471142735, 9780471142737). 15 Ikonen, N., et al., (2018).“Deposition of respiratory virus pathogens on frequently touched surfaces at airports.”BMC Infectious Diseases, 18(437):1-8. 16Geczi, Z., et al., (2018).“Antimicrobial Silver-Polyethyleneimine Polylactic Acid Polymer Composite Film for Coating Methacrylate-Based Denture Surfaces.”J.of Nanomaterials, 2018(6):1-9. 17 Park, D., et al., (2006).“One-Step, Painting-Like Coating Procedures To Make Surfaces Highly and Permanently Bactericidal.”Biotechnology Prog.22(2):584-589. 18 Xue, Y. and Xiao, H. (2015).“Antibacterial / Antiviral Property and Mechanism of Dual-Functional Quaternized Pyridinium-Type Copolymer.”Polymers, 7(11):2290-2303. 19 U.S.Patent No.5,783,502, “Virus Inactivating Coatings.”(Issued July 21, 1998). 20 Nurdin, N., et al., (1993).“Biocidal Polymers Active By Contact.II.Biological Evaluation of Polyurethane Coatings with Pendent Quaternary Ammonium Salts.”J.of Applied Polymer Science, 50:663-670. 21Chung, S., et al., (2016).“Antimicrobial Nanostructural Polyurethane Scaffolds.”Ch.17 in ADVANCES IN POLYURETHANE BIOMATERIALS, Cooper S.L. and Guan, J.(eds.), Elsevier Ltd. 22 Park, D., et al., (2013).“Antiviral and Antibacterial Polyurethanes of Various Modalities.”Appl.Biochem.Biotechnol., 169:1134-1146. 23 Gao, B., et al., (2007).“Studies on the Preparation and Antibacterial Properties of Quaternized Polyethyleneimine.”J.Biomaterials Science, Polymer Edition, 18(5):531-544. 24 Klibanov, A., et al., (2006).“One-Step Painting-Like Coating Procedures to make Surfaces Highly and Permanently Bactericidal.”Biotechnol.Prog., 22(2):584-589. 25 Gao, B., et al., (2007).“Studies on the Preparation and Antibacterial Properties of Quaternized Polyethyleneimine.”J.Biomaterials Science, Polymer Edition, 18(5):531-544. 26 Id.

[0179] All patents and other publications, including references to literature, issued patents, published patent applications, and concurrently pending patent applications, are expressly incorporated herein by reference for the purpose of describing and disclosing methodologies described in such publications that may be used, for example, in connection with the technology described herein. These publications are provided only for disclosures prior to the filing date of this application. Nothing in this regard should be construed as acknowledging that there are no prior rights to such disclosures, either by prior invention or for any other reason. All statements regarding dates or expressions relating to the content of these documents are based on information available to the applicant and do not constitute any endorsement of the accuracy of the dates or content of these documents.

[0180] The description in the aforementioned document is considered sufficient to enable those skilled in the art to practice the embodiments and aspects of this invention. Since the examples are intended to be merely illustrative of one aspect, the embodiments and aspects of this invention are not limited in scope by the provided examples, and other functionally equivalent embodiments are within the scope of this disclosure. In addition to those shown and described herein, various modifications will be apparent to those skilled in the art from the foregoing description and are included in the appended claims. The advantages and objectives described herein are not necessarily encompassed by each embodiment. Those skilled in the art will be able to recognize or confirm many equivalents to specific embodiments described herein using only routine experimentation. Such equivalents are intended to be included in the following claims. [Sequence Listing Free Text]

[0181] Sequence ID 1 is a description of the artificial sequence: a synthetic primer. Sequence ID 2 is an artificial sequence description: a synthetic primer.

Claims

1. Compound (IV): 【Chemistry 1】 An antimicrobial composition comprising, in the formula, Each A acts independently, 【Chemistry 2】 Or any two or more copolymers of them are selected, and the bonds of each A form a carbamate bond, Each Y independently corresponds to H or -C(O)-NHR ３ And, Each n is an integer independently selected from 1 to 3000. Each R1 is independently hydrogen; C1-C6 alkyl groups optionally substituted with substituents selected from C6-C10 aryl and hydroxylated C1-C6 alkoxy groups; C1-C6 alkoxy; C6-C10 aryls optionally substituted with C1-C6 alkyls; and Selected from carboxyl, Each R ２ is independently hydroxy, C １ -C ６ -alkoxy, carboxy, C ６ -C １０ -aryl, -C(O)O(C １ -C ６ -alkyl), -C(O)-(C ６ -C １０ -aryl), and C １ -C ６ -alkoxy optionally substituted with a substituent selected from hydroxy-substituted C １ -C ６ -alkyl, and is selected from Each R ３ However, independently, (1) halogen, -SiR ａ (OR ｂ ) ( OR ｃ ), and C ６ -C １０ C is optionally substituted with 1 to 3 substituents independently selected from the aryl group. ６ -C ２０ Alkyl, (2) halogen, C １ -C ６ Alkyl and -SiR ａ (OR ｂ ) ( OR ｃ C is optionally substituted with 1 to 3 substituents independently selected from ). ６ -C １０ Aryl, and (3) 【Transformation 3】 Selected from, in the formula, each R ａ However, independently, C １ -C ６ It is alkyl, and each R ｂ and each R ｃ However, independently, C １ -C ６ Alkyl and -Si(C) １ -C ６ Alkyl) ３ Selected from, Each R ４ However, independently, C is optionally substituted with phenyl. １ -C １０ Alkylene, or a cycloalkyl ring with 3 to 8 members, Each X － An antimicrobial composition independently selected from the group consisting of acetic acid, halides, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, carbonic acid, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, and their organically substituted derivatives.

2. Compound (V): 【Chemistry 4】 An antimicrobial composition comprising, in the formula, Each A acts independently, 【Transformation 5】 Or any two or more copolymers of them are selected, and the bonds of each A form a carbamate bond, Each Y independently corresponds to H or -C(O)-NHR ３ And, Each n is an integer independently selected from 1 to 3000. Each R1 is independently hydrogen; C1-C6 alkyl groups optionally substituted with substituents selected from C6-C10 aryl and hydroxylated C1-C6 alkoxy groups; C1-C6 alkoxy; C6-C10 aryls optionally substituted with C1-C6 alkyls; and Selected from carboxyl, Each R ２ However, independently, hydroxy, C １ -C ６ Alkoxy, carboxy, C ６ -C １０ Ariel, -C(O)O(C １ -C ６ Alkyl), -C(O)-(C ６ -C １０ C(aryl), and C(hydroxy) optionally substituted. １ -C ６ C is optionally substituted with substituents selected from alkoxys. １ -C ６ Selected from alkyl groups, Each R ３ However, independently, (1) halogen, -SiR ａ (OR ｂ ) ( OR ｃ ), and C ６ -C １０ C is optionally substituted with 1 to 3 substituents independently selected from the aryl group. ６ -C ２０ Alkyl, (2) halogen, C １ -C ６ Alkyl and -SiR ａ (OR ｂ ) ( OR ｃ C is optionally substituted with 1 to 3 substituents independently selected from ). ６ -C １０ Aryl, and (3) 【Transformation 6】 Selected from, in the formula, each R ａ However, independently, C １ -C ６ It is alkyl, and each R ｂ and each R ｃ However, independently, C １ -C ６ Alkyl and -Si(C) １ -C ６ Alkyl) ３ Selected from, Each R ４ However, independently, C is optionally substituted with phenyl. １ -C １０ Alkylene, or a cycloalkyl ring with 3 to 8 members, Each X － An antimicrobial composition independently selected from the group consisting of acetic acid, halides, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, carbonic acid, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, and their organically substituted derivatives.

3. The foregoing R ３ Although not all, at least 75% of them are independently a halogen, -SiR ａ (OR ｂ )(OR ｃ ), and C ６ -C １０ An optionally substituted C ６ -C ２０ alkyl with 1 to 3 substituents independently selected from aryl; and a halogen, C １ -C ６ alkyl, and an optionally substituted C ａ (OR ｂ )(OR ｃ ) with 1 to 3 substituents independently selected from aryl; wherein each R ６ -C １０ is independently a C ａ -C １ alkyl, each R ６ and each R ｂ are independently selected from C ｃ -C １ alkyl and -Si(C ６ -C １ -C ６ alkyl) ３ The antibacterial composition according to claim 1 or 2.

4. Each R ３ However, independently, halogen, -SiR ａ (OR ｂ ) ( OR ｃ ), and C ６ -C １０ C is optionally substituted with 1 to 3 substituents independently selected from the aryl group. ６ -C ２０ Selected from alkyl groups, or each R ３ However, independently, halogen, C １ -C ６ Alkyl and -SiR ａ (OR ｂ ) ( OR ｃ C is optionally substituted with 1 to 3 substituents independently selected from ). ６ -C １０ An antimicrobial composition according to claim 1 or 2, selected from aryls.

5. R ３ but, 【Transformation 7】 The antibacterial composition according to claim 1.

6. R ３ but, 【Transformation 8】 The antibacterial composition according to claim 2.

7. Each R １ However, independently, C １ -C ６ The antimicrobial composition according to claim 1 or 2, wherein the component is alkyl.

8. Each R ２ However, independently, methyl, butyl, hexyl, benzyl, -CH ２ C(O)Ph and -CH ２ C(O)OCH ２ CH ３ An antimicrobial composition according to claim 1 or 2, selected from the above.

9. R ４ However, C １ -C １０ The antimicrobial composition according to claim 1 or 2, wherein the antimicrobial composition is alkylene.

10. An antimicrobial coating comprising the composition according to claim 1 or 2.

11. A coating fluid comprising the composition according to claim 1 or 2.

12. A device comprising the coating fluid described in claim 11.

13. The device according to claim 12, wherein the device is selected from the group consisting of a keyboard, keypad, mouse, remote controller, touchscreen, telephone, and display.

14. The device according to claim 12 or 13, wherein the coating fluid is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible.

15. An apparatus comprising the antimicrobial coating described in claim 10.

16. The apparatus according to claim 15, wherein the apparatus is selected from the group consisting of a filter, an air purifier, and a mask.

17. A method for sterilizing a surface, reducing the growth of antimicrobial agents on the surface, or preventing the growth of antimicrobial agents on the surface, comprising applying the composition described in claim 1 or 2 to the surface.

18. The method according to claim 17, further comprising forming a coating solution containing the composition.

19. The method according to claim 18, further comprising directing the coating solution toward the surface and providing a coating to the surface by applying the coating solution to the surface.

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