HALS as an Antibacterial Additive in the Free Radical System

Abstract

The present invention provides a curable composition containing a (meth)acrylate-functionalized compound and a HALS, and relates to a method for protecting the surface of a substrate by applying the composition to the surface of the substrate, curing the composition, and converting the HALS to a haloamine by treatment with a halogenating agent. The present invention also relates to a curable composition containing a HALS, a cured composition containing a haloamine, and the use of a HALS for obtaining an antibacterial coating on the surface of a substrate.

Description

Technical Field

[0001] The present invention provides a curable composition containing a (meth)acrylate-functionalized compound and a HALS. The composition is applied to the surface of a substrate, the composition is cured, and the surface of the substrate is protected by converting the HALS to a haloamine by treatment with a halogenating agent. The present invention also relates to a curable composition containing a HALS, a cured composition containing a haloamine, and the use of a HALS for obtaining an antibacterial coating on the surface of a substrate.

Background Art

[0002] Hindered amine light stabilizers (HALS) are low-cost, low-toxicity light stabilizers and heat stabilizers, and are used in a wide range of commercially available materials (e.g., thermoplastic polymers, emulsions, and paints), and can be further chemically modified to achieve different functions. In the presence of a halogenating agent, HALS can be converted to N-halo-hindered amines (halamines) (Macromolecules 2005, 38, 8116-8119, Chem. Rev. 2017, 117, 4806-4862) that exhibit antibacterial properties against both Gram-negative and Gram-positive bacteria. For example, the N-chlorination of the hindered amine light stabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (TINUVIN® 770) by reaction with sodium dichloroisocyanurate has been described, and the resulting N-chlorinated compound has been incorporated into polyester-based paints (Progress in Organic Coatings 99 (2016) 330-336). U.S. Patent No. 7,998,886 describes a fiber product containing a plurality of yarns, the yarns containing a HALS or a haloamine compound disposed on their outer surfaces and / or dispersed within the yarns. U.S. Patent No. 7,399,793 describes a UV-curable resin mixture containing a HALS that is sprayed and cured on a panel to provide a protective clearcoat composition, but does not disclose the antibacterial activity of the coating produced according thereto.

[0003] In particular, when the surface also has weather resistance (for example, a surface having light resistance and heat resistance), there is a need for an easy and cost-effective method of providing an antibacterial surface that can recharge the antibacterial properties of the surface as needed. The present invention provides a curable composition containing a (meth)acrylate-functionalized compound and a HALS, applying the composition to a substrate surface, curing the composition, and achieving these purposes by converting the HALS into a haloamine. SUMMARY OF THE INVENTION

[0004] One aspect of the present invention is a method for protecting the surface of a substrate, comprising: - applying a curable composition containing a (meth)acrylate-functionalized compound and a hindered amine light stabilizer (HALS) to the surface of the substrate; - curing the curable composition to provide a cured composition; - treating the cured composition with a halogenating agent to halogenate the HALS present in the cured composition; and - optionally, removing the residual halogenating agent. The method comprises.

[0005] Another aspect of the present invention is a method of treating a cured composition with a halogenating agent to halogenate the HALS present in the cured composition, wherein the cured composition comprises a cured product of a curable composition containing HALS and a (meth)acrylate-functionalized compound.

[0006] Another aspect of the present invention is a curable composition containing a (meth)acrylate-functionalized compound and a HALS, wherein the total amount of HALS in the composition is at least 3% by weight, preferably at least 6% by weight, based on the weight of the composition.

[0007] Another aspect of the present invention is a cured composition containing an N-halo-hindered amine, which is obtained by (a) curing the curable composition according to the present invention; and (b) then converting the HALS into an N-halo-hindered amine by treating the HALS with a halogenating agent.

[0008] Another aspect of the present invention is the use of at least one HALS, at least one (meth)acrylate functionalized compound and at least one halogenating agent for obtaining an antibacterial coating on the surface of a substrate.

[0009] The figures provided herein are illustrative of embodiments of the invention and are not intended, however, to limit the scope of the invention described herein otherwise.

Brief Description of the Drawings

[0010]

Figure 1

Embodiments for Carrying Out the Invention

[0011] Curable Composition The present invention relates to a curable composition. The curable composition may be applied to the surface of a substrate and then cured and subsequently treated with a halogenating agent.

[0012] The curable composition comprises a (meth)acrylate functionalized compound and a hindered amine light stabilizer (HALS), as detailed below. The curable composition may further comprise one or more additives, as detailed below.

[0013] (Meth)acrylate Functionalized Compound The curable composition contains a (meth)acrylate-functionalized compound. The curable composition may contain a mixture of (meth)acrylate-functionalized compounds.

[0014] (Meth)acrylate-functionalized compounds are different from HALS. Thus, (meth)acrylate-functionalized compounds may not have a hindered amine moiety. Preferably, the curable composition substantially does not contain (meth)acrylate-functionalized compounds having a secondary amino group other than HALS. Even more preferably, the curable composition substantially does not contain (meth)acrylate-functionalized compounds having an amino group other than HALS.

[0015] (Meth)acrylate-functionalized compounds can be described as compounds having one or more (meth)acrylate functional groups per molecule. As used herein, the term "(meth)acrylate" refers to both methacrylate (-O-C(=O)-C(CH3)=CH2) and acrylate (-O-C(=O)-CH=CH2) functional groups. (Meth)acrylate-functionalized compounds suitable for use in the present invention generally have at least one carbon-carbon double bond that is alpha to an ester group (compounds containing at least one alpha, beta-unsaturated ester moiety), particularly carbon-carbon double bonds capable of participating in a reaction initiated by a free radical reaction or anionic reaction, particularly a reaction initiated by exposure to UV energy, visible light or an electron beam. Such reactions can result in polymerization or curing in which the (meth)acrylate-functionalized compound becomes part of a polymer matrix or polymer chain. In various embodiments of the present invention, (meth)acrylate-functionalized compounds may contain 1, 2, 3, 4, 5 or more (meth)acrylate functional groups per molecule. Combinations of multiple (meth)acrylate-functionalized compounds containing different numbers of (meth)acrylate groups can be utilized in the curable compositions of the present invention.

[0016] Thus, the curable composition of the present invention can undergo free radical and / or anionic polymerization (curing) by exposure to, for example, UV energy, visible light or an electron beam, and thus contains one or more (meth)acrylate functionalized compounds that provide a cured composition.

[0017] (The (meth)acrylate functionalized compound may be an oligomer or a monomer, or a combination of oligomers and / or monomers.)

[0018] The curable composition may contain a (meth)acrylate functionalized monomer. The curable composition may contain a mixture of (meth)acrylate functionalized monomers.

[0019] (The (meth)acrylate functionalized monomer may have a molecular weight of less than 600 g / mol, particularly 100 - 550 g / mol, more specifically 200 - 500 g / mol.)

[0020] (The (meth)acrylate functionalized monomer may have 1 - 6 (meth)acrylate groups, particularly 1 - 3 (meth)acrylate groups.)

[0021] (The (meth)acrylate functionalized monomer may contain a mixture of (meth)acrylate functionalized monomers having different functionalities. For example, the (meth)acrylate functionalized monomer may contain a (meth)acrylate functionalized monomer containing a single acrylate or methacrylate group per molecule (referred to herein as a "mono(meth)acrylate functionalized compound") and a (meth)acrylate functionalized monomer containing two or more, preferably two or three acrylate and / or methacrylate groups per molecule.)

[0022] The curable composition may contain a mono(meth)acrylate functionalized monomer. The mono(meth)acrylate functionalized monomer advantageously functions as a reactive diluent and can reduce the viscosity of the composition.

[0023] Examples of suitable mono(meth)acrylate-functionalized monomers include, but are not limited to, mono-(meth)acrylate esters of aliphatic alcohols (the aliphatic alcohol may be linear or branched and may be a monoalcohol, dialcohol or polyalcohol, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono-(meth)acrylate esters of cycloaliphatic or heterocyclic alcohols; mono-(meth)acrylate esters of aromatic alcohols (e.g., phenols (including alkylated phenols)); mono-(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); mono(meth)acrylate esters of oligomeric or polymeric glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol and polypropylene glycol; mono(meth)acrylate esters of monoalkyl ethers of glycol or oligoglycol; caprolactone mono(meth)acrylate; and their alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives; and combinations thereof.

[0024] The following compounds are specific examples of mono(meth)acrylate-functionalized monomers suitable for use in curable compositions: methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; isodecyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2- and 3-hydroxypropyl (meth)acrylate; 4-hydroxybutyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2- and 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; benzyl (meth)acrylate; phenol (meth)acrylate; nonylphenyl (meth)acrylate; cyclic trimethylolpropane (meth)acrylate; isobornyl (meth)acrylate; tricyclodecanemethanol (meth)acrylate; tert-butylcyclohexyl (meth)acrylate; trimethylcyclohexyl (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; polyethylene glycol monomethyl ether (meth)acrylate; hydroxyethyl-butylurethane (meth)acrylate; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate;(2-Ethyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate; 1,3-dioxan-5-yl (meth)acrylate; (1,3-dioxolan-4-yl)methyl (meth)acrylate; glycerol carbonate (meth)acrylate and its alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives; and combinations thereof.;

[0025] The curable composition may include a (meth)acrylate-functionalized monomer containing two or more (meth)acrylate functional groups per molecule.

[0026] Examples of suitable (meth)acrylate-functionalized monomers containing two or more (meth)acrylate groups per molecule include acrylates and methacrylate esters of polyhydric alcohols (organic compounds containing two or more, for example 2 to 6, hydroxyl groups per molecule).Specific examples of suitable polyhydric alcohols include ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, neopentyl glycol, 2,4-diethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornenedimethanol, norbornanedimethanol, tricyclodecanedimethanol, tricyclodecanedimethanol, bisphenol A, B, F or S, hydrogenated bisphenol A, B, F or S, trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane), triethylolpropane, pentaerythritol, di(pentaerythritol), glycerol, di-, tri- or tetraglycerol, polyglycerol, di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly(ethylene glycol-co-propylene glycol), alditol (i.e., erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, glucitol, fucitol or iditol), dianhydrohexitol (i.e., isosorbide, isomannide or isoidide), tris(2-hydroxyethyl) isocyanurate, polybutadiene polyol, and their alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives, derivatives obtained by ring-opening polymerization of lactones (e.g., la ε-caprolactone) initiated with one of the above polyols; and combinations thereof.Such polyhydric alcohols may be fully or partially esterified (using (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.) as long as they contain at least two (meth)acrylate functional groups per molecule.

[0027] Exemplary (meth)acrylate-functionalized monomers containing two or more (meth)acryloyloxy groups per molecule include bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4-butanediol di(meth)acrylate; 1,5-pentanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate; 1,8-octanediol di(meth)acrylate; 1,9-nonanediol di(meth)acrylate; 1,10-decanediol di(meth)acrylate; 1,12-dodecanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-1,4-dimethanol di(meth)acrylate; tricyclodecane dimethanol di(meth)acrylate; metal di(meth)acrylate; modified metal di(meth)acrylate; glyceryl di(meth)acrylate; glyceryl tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; di(trimethylolpropane) diacrylate; di(trimethylolpropane) triacrylate;Di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) tetraacrylate; di(pentaerythritol) pentaacrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and combinations thereof may be mentioned.;

[0028] The total amount of (meth)acrylate-functionalized monomers in the curable composition may be 0.1 to 97% by weight, 1 to 95% by weight, 5 to 93% by weight, 10 to 90% by weight, 15 to 85% by weight, 20 to 80% by weight, 25 to 75% by weight, based on the weight of the curable composition. In one embodiment, the total amount of (meth)acrylate-functionalized monomers in the curable composition is 10 to 97% by weight, 15 to 97% by weight, 20 to 97% by weight, 25 to 97% by weight, 30 to 97% by weight, 35 to 97% by weight, 40 to 97% by weight, 45 to 97% by weight, 50 to 97% by weight, 55 to 97% by weight, 60 to 97% by weight, 65 to 97% by weight, 70 to 97% by weight, 75 to 97% by weight, 80 to 97% by weight, 85 to 97% by weight or 90 to 97% by weight, based on the weight of the curable composition. Alternatively, the total amount of (meth)acrylate-functionalized monomers in the curable composition may be 0.1 to 50% by weight, 1 to 50% by weight, 5 to 50% by weight, 10 to 50% by weight, 15 to 50% by weight, 20 to 50% by weight, 25 to 50% by weight, 30 to 50% by weight, based on the weight of the curable composition.;

[0029] The curable composition may contain a (meth)acrylate-functionalized oligomer. The curable composition may contain a mixture of (meth)acrylate-functionalized oligomers.;

[0030] (Meth)acrylate-functionalized oligomers may be selected, among other attributes, to increase the flexibility, strength and / or modulus of elasticity of the cured polymer prepared using the curable composition.;

[0031] (Meth)acrylate-functionalized oligomers may have from 1 to 18 (meth)acrylate groups, particularly 2 to 6 (meth)acrylate groups, more specifically 2 to 6 acrylate groups.

[0032] (Meth)acrylate-functionalized oligomers may have a number average molecular weight of 600 g / mol or more, particularly 800 to 15,000 g / mol, more specifically 1,000 to 5,000 g / mol.

[0033] In particular, (meth)acrylate-functionalized oligomers may be selected from the group consisting of (meth)acrylate-functionalized urethane oligomers (which may also be referred to as "urethane (meth)acrylate oligomers", "polyurethane (meth)acrylate oligomers" or "carbamate (meth)acrylate oligomers"), (meth)acrylate-functionalized epoxy oligomers (which may also be referred to as "epoxy (meth)acrylate oligomers"), (meth)acrylate-functionalized polyether oligomers (which may also be referred to as "polyether (meth)acrylate oligomers"), (meth)acrylate-functionalized polydiene oligomers (which may also be referred to as "polydiene (meth)acrylate oligomers"), (meth)acrylate-functionalized polycarbonate oligomers (which may also be referred to as "polycarbonate (meth)acrylate oligomers"), (meth)acrylate-functionalized polyester oligomers (which may also be referred to as "polyester (meth)acrylate oligomers") and (meth)acrylate-functionalized (meth)acrylic oligomers (which may also be referred to as "(meth)acrylic (meth)acrylate oligomers"), and mixtures thereof.

[0034] Preferably, the curable composition comprises a (meth)acrylate-functionalized oligomer selected from (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyether oligomers, (meth)acrylate-functionalized polyester oligomers, and mixtures thereof. More preferably, the curable composition comprises a (meth)acrylate-functionalized urethane oligomer, and even more preferably an acrylate-functionalized urethane oligomer.

[0035] Advantageously, the curable composition comprises a (meth)acrylate-functionalized urethane oligomer having two (meth)acrylate groups, and more preferably an acrylate-functionalized urethane oligomer having two acrylate groups.

[0036] Exemplary polyester (meth)acrylate oligomers include the reaction product of (meth)acrylic acid (or its synthetic equivalents such as (meth)acryloyl chloride, (meth)acrylic anhydride or (meth)acrylic acid esters) and a hydroxyl-terminated polyester polyol. The reaction process may be carried out such that all or essentially all of the hydroxyl groups of the polyester polyol are (meth)acrylated, especially when the polyester polyol is bifunctional. The polyester polyol can be produced by the polycondensation reaction of a polyhydroxyl-functionalized component (especially a diol) and a poly(carboxylic acid)-functionalized compound (especially a dicarboxylic acid and an anhydride). The polyhydroxyl-functionalized compound and the poly(carboxylic acid)-functionalized compound can each have a linear, branched, alicyclic or aromatic structure and can be used individually or as a mixture.

[0037] Examples of suitable epoxy (meth) acrylates include reaction products of (meth) acrylic acid (or its synthetic equivalents such as (meth) acryloyl chloride or (meth) acrylic anhydride) with an epoxy resin containing at least one epoxide group (in particular, at least one group selected from glycidyl ethers, glycidyl esters and mixtures thereof). Epoxy resins are in particular bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolak resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinyl epoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis(3,4-epoxycyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, 1,Polyethers polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as 6 - hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of aliphatic long - chain dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxybutyl stearate, epoxyoctyl stearate, epoxidized linseed oil, epoxidized polybutadiene, etc. can be selected.,

[0038] Suitable polyether (meth)acrylate oligomers include, but are not limited to, the condensation reaction products of (meth)acrylic acid (or its synthetic equivalents such as (meth)acryloyl chloride, (meth)acrylic anhydride or (meth)acrylic acid esters) and hydroxyl - terminated polyether polyols (e.g., polyethylene glycol, polypropylene glycol, polytetramethylene glycol and their copolymers). Suitable polyether polyols can be linear or branched substances containing ether bonds and terminal hydroxyl groups. Polyether polyols can be prepared by ring - opening polymerization of cyclic ethers such as tetrahydrofuran and / or alkylene oxides (e.g., ethylene oxide and / or propylene oxide) with starting molecules. Suitable starting molecules include water, polyhydroxyl - functionalized materials, polyester polyols and amines.,

[0039] Suitable urethane (meth)acrylate oligomers include, but are not limited to, those based on at least one polyol, at least one polyisocyanate, and at least one hydroxyl-functionalized (meth)acrylate.

[0040] The urethane (meth)acrylate oligomer can be prepared by reacting a polyisocyanate (e.g., an aliphatic, cycloaliphatic, and / or aromatic diisocyanate or triisocyanate) with a polyol (e.g., a polyester polyol, a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, a polyorganosiloxane polyol, or a polydiene polyol such as a polybutadiene polyol, or a combination thereof) to form an isocyanate-functionalized oligomer, and then reacting this with a hydroxyl-functionalized (meth)acrylate (such as hydroxyethyl (meth)acrylate) to provide terminal (meth)acrylate groups. For example, the polyurethane (meth)acrylate oligomer can contain 2, 3, 4, or more (meth)acrylate functional groups per molecule. As is known in the art, other addition sequences can also be implemented to prepare the polyurethane (meth)acrylate. For example, the hydroxyl-functionalized (meth)acrylate can first be reacted with the polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, which can then be reacted with the polyol. Alternatively, all the components can be combined and reacted simultaneously.

[0041] Suitable acrylic (meth)acrylate oligomers include oligomers that can be described as substances having an oligomeric acrylic backbone functionalized with one or more (meth)acrylate groups (which may be at the ends of the oligomer or pendant to the acrylic backbone). The acrylic backbone can be a homopolymer, random copolymer, or block copolymer composed of repeating units of acrylic monomers. The acrylic monomers can be any monomer (meth)acrylate such as C1-C6 alkyl (meth)acrylate, as well as functionalized (meth)acrylates such as (meth)acrylates having hydroxyl, carboxylic acid, and / or epoxy groups. The acrylic (meth)acrylate oligomers can be prepared using any procedure known in the art, for example, by oligomerizing monomers, at least a part of which is functionalized with hydroxyl, carboxylic acid, and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomer intermediate, and then reacting this with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functional groups.

[0042] The total amount of (meth)acrylate-functionalized oligomer in the curable composition can be 0.1 to 97 wt%, 1 to 95 wt%, 5 to 93 wt%, 10 to 90 wt%, 15 to 85 wt%, 20 to 80 wt%, 25 to 75 wt% based on the weight of the curable composition. In one embodiment, the total amount of (meth)acrylate-functionalized oligomer in the curable composition is 10 to 97 wt%, 15 to 97 wt%, 20 to 97 wt%, 25 to 97 wt%, 30 to 97 wt%, 35 to 97 wt%, 40 to 97 wt%, 45 to 97 wt%, 50 to 97 wt%, 55 to 97 wt%, 60 to 97 wt%, 65 to 97 wt%, 70 to 97 wt%, 75 to 97 wt%, 80 to 97 wt%, 85 to 97 wt% or 90 to 97 wt% based on the weight of the curable composition. Alternatively, the total amount of (meth)acrylate-functionalized oligomer in the curable composition can be 0.1 to 50 wt%, 1 to 50 wt%, 5 to 50 wt%, 10 to 50 wt%, 15 to 50 wt%, 20 to 50 wt%, 25 to 50 wt%, 30 to 50 wt% based on the weight of the curable composition.

[0043] In one embodiment, the curable composition contains an amine-modified acrylate or a thiol-modified acrylate. The ethylenically unsaturated compound can contain a mixture of an amine-modified acrylate or a thiol-modified acrylate. Alternatively, the curable composition may substantially not contain an amine-modified acrylate or a thiol-modified acrylate.

[0044] The amine-modified acrylate (each thiol-modified acrylate) is obtained by reacting an acrylate-functionalized compound with an amine-containing compound (each thiol-containing compound). The amine-modified acrylate (each thiol-modified acrylate) contains at least one remaining acrylate group (i.e., an acrylate group that did not react with the amine-containing compound (each thiol-containing compound)) and / or at least one (meth)acrylate group that may not be reactive with a primary or secondary amine (each thiol).

[0045] The acrylate-functionalized compound may be the acrylate-functionalized monomer and / or acrylate-functionalized oligomer defined above.

[0046] The amine-containing compound contains a primary or secondary amino group and optionally a tertiary amino group. The thiol-containing compound contains a thiol group (-SH). The amine-containing compound may contain two or more primary and / or secondary amino groups. The thiol-containing compound may contain two or more thiol groups. The amine-containing compound may be selected from monoethanolamine (2-aminoethanol), 2-ethylhexylamine, octylamine, cyclohexylamine, sec-butylamine, isopropylamine, diethylamine, diethanolamine, dipropylamine, dibutylamine, 2-(methylamino)ethanol-1,2-methoxyethylamine, bis(2-hydroxypropyl)amine, diisopropylamine, dipentylamine, dihexylamine, bis(2-ethylhexyl)amine, 1,2,3,4-tetrahydroisoquinoline, N-benzylmethylamine, morpholine, piperidine, dioctylamine, and di-cocoamine, dimethylaminopropylamine, dimethylaminopropylaminopropylamine, 1,4-bis(3-aminopropyl)piperazine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(3-aminopropyl)piperazine, aniline, and optionally substituted benzocaine (ethyl-4-aminobenzenate).

[0047] Examples of commercially available amine-modified acrylates include CN3705, CN3715, CN3755, CN381, and CN386, all of which are available from Arkema. The polymer type or multi-amino type is also suitable.

[0048] The curable composition may contain 0 wt% to 25 wt%, particularly 2.5 wt% to 20 wt%, more particularly 5 to 15 wt% of amine-modified acrylate based on the total weight of the composition.

[0049] In a particularly preferred embodiment, the (meth)acrylate-functionalized compound of the curable composition is one or more (meth)acrylate-functionalized oligomers containing two or more (meth)acrylate groups per molecule, selected from the group consisting of (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyether oligomers, (meth)acrylate-functionalized polyester oligomers, and mixtures thereof, optionally combined with one or more (meth)acrylate-functionalized monomers having 1 to 6 (meth)acrylate groups per molecule.

[0050] Preferably, the total amount of the (meth)acrylate-functionalized compound in the curable composition can be 0.1 to 97 wt%, 1 to 95 wt%, 5 to 93 wt%, 10 to 90 wt%, 15 to 85 wt%, 20 to 80 wt%, 25 to 75 wt% based on the weight of the curable composition. In one embodiment, the total amount of the (meth)acrylate-functionalized compound in the curable composition can be 10 to 97 wt%, 15 to 97 wt%, 20 to 97 wt%, 25 to 97 wt%, 30 to 97 wt%, 35 to 97 wt%, 40 to 97 wt%, 45 to 97 wt%, 50 to 97 wt%, 55 to 97 wt%, 60 to 97 wt%, 65 to 97 wt%, 70 to 97 wt%, 75 to 97 wt%, 80 to 97 wt%, 85 to 97 wt% or 90 to 97 wt% based on the weight of the curable composition. Alternatively, the total amount of the (meth)acrylate-functionalized compound in the curable composition can be 0.1 to 50 wt%, 1 to 50 wt%, 5 to 50 wt%, 10 to 50 wt%, 15 to 50 wt%, 20 to 50 wt%, 25 to 50 wt%, 30 to 50 wt% based on the weight of the curable composition.

[0051] The curable composition may contain an ethylenically unsaturated compound other than the (meth)acrylate-functionalized compound. Examples of such compounds include allyl-functionalized compounds, vinyl-functionalized compounds, alkenes (e.g., 1,1-diester-1-alkene, 1,1-diketo-1-alkene, 1-ester-1-keto-1-alkene, 1,1-diamide-1-alkene, 1-amide-1-keto-1-alkene, 1-amide-1-ester-1-alkene and / or itaconate) and combinations thereof.

[0052] The relative proportions of the (meth)acrylate-functionalized compound and the ethylenically unsaturated compound other than the (meth)acrylate-functionalized compound can be varied as appropriate depending on the particular components selected and the properties of the desired curable composition and the cured composition obtained therefrom. For example, the total weight of the ethylenically unsaturated compound (including the (meth)acrylate-functionalized compound) in the curable composition can be 0.1 to 97 wt%, 1 to 95 wt%, 5 to 93 wt%, 10 to 90 wt%, 15 to 85 wt%, 20 to 80 wt%, 25 to 75 wt% based on the weight of the curable composition. In particular, the total weight of the ethylenically unsaturated compound (including the (meth)acrylate-functionalized compound) in the curable composition can be 10 to 97 wt%, 15 to 97 wt%, 20 to 97 wt%, 25 to 97 wt%, 30 to 97 wt%, 35 to 97 wt%, 40 to 97 wt%, 45 to 97 wt%, 50 to 97 wt%, 55 to 97 wt%, 60 to 97 wt%, 65 to 97 wt%, 70 to 97 wt%, 75 to 97 wt%, 80 to 97 wt%, 85 to 97 wt% or 90 to 97 wt% based on the weight of the curable composition.

[0053] HALS The curable composition of the present invention further comprises a hindered amine light stabilizer (also referred to as HALS). The curable composition may contain a mixture of HALS.

[0054] Using the HALS of the curable composition described herein, the composition can be cured and then the HALS can be converted to an N-halo-hindered amine (haloamine) to provide an antibacterial coating on a substrate.

[0055] The prior art has focused on haloamines as monomers that can be pre-reacted on a polymer, as opposed to the use of HALS as a "non-reactive" additive. In an exemplary embodiment, the HALS used in the present invention is an established additive used in photocurable resins to improve weather resistance and UV degradation. However, for the purposes of the present invention, the HALS does not pre-react with the curable composition prior to polymerization, and haloamines are formed during the halogenation step after curing has occurred.

[0056] The HALS can be any suitable secondary hindered amine compound (i.e., a hindered amine compound having a hydrogen atom bonded to the nitrogen atom of the amine group). As used herein, the term "hindered amine" refers to a compound or moiety in which the carbon atom adjacent to the nitrogen atom of the amine group does not have a hydrogen atom directly bonded thereto. Thus, the HALS has at least one nitrogen atom bonded to one hydrogen atom and two carbon atoms, and the carbon atom does not have a hydrogen atom directly bonded thereto. Preferably, the carbon atom adjacent to the nitrogen atom of the hindered amine compound or moiety is not a carbonyl carbon (i.e., a carbon atom to which an oxygen atom is double-bonded).

[0057] The haloamine can be the hindered amine as defined above in which the amine group is substituted with a halogen atom, particularly a chlorine, bromine, or iodine atom. The haloamine can be obtained by substituting the hydrogen atom bonded to the amine group of the HALS with a halogen atom (e.g., by a halogenation reaction).

[0058] The HALS and haloamine can have any suitable molecular weight. Typically, the HALS and haloamine have a molecular weight of about 2,500 atomic mass units or less, preferably about 2,000 atomic mass units or less, or about 1,000 atomic mass units or less, or about 500 atomic mass units or less.

[0059] In the curable composition of the present invention (i.e., before the curing step), the HALS and haloamine are preferably not in a polymerized form, i.e., they do not contain a plurality of repeating units derived from the polymerization of HALS or a haloamine containing a polymerizable carbon-carbon double bond. More preferably, each of the HALS and haloamine contains a single hindered amine moiety per molecule.

[0060] In an exemplary embodiment, the HALS contains a functional group that reacts the HALS during the curing process. In another exemplary embodiment, the HALS does not contain a functional group that crosslinks the HALS during the curing process.

[0061] In an exemplary embodiment, the HALS can be added to a monomer, oligomer, or a combination of both, and then the resulting composition can be transported off-site for curing to provide an antibacterial resin such as a coating.

[0062] Suitable HALS include, but are not limited to, the hindered amines disclosed in International Publication No. WO 2007 / 050245 (which is incorporated herein by reference in its entirety). Exemplary chemical structures of the hindered amines disclosed in International Publication No. WO 2007 / 050245 are shown below: TIFF2025519422000001.tif197170TIFF2025519422000002.tif59170wherein R1, R2, R3 and R4 are independently selected from the group consisting of C1-C4 alkyl groups; R5 is selected from the group consisting of a hydrogen atom, an alkyl group, an alkylamine group, a cyclic amine group, an amide group, a cyclic amide group, an isocyanate group, a hydroxyl group, an ether group, an ester group, and combinations thereof; R6 and R7 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an amine group, an amide group, and combinations thereof; R9, R 11 , R 12 and R 14 are independently selected from the group consisting of C1-C4 alkyl groups; R 10 and R 13is independently selected from the group consisting of an alkyl group, an aryl group, an amine group, an amide group, and combinations thereof; R 15 and R 16 are independently selected from the group consisting of C1-C4 alkyl groups; R 17 is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an amine group, an amide group, and combinations thereof; R 18 , R 19 , R 20 and R 21 are independently selected from the group consisting of C1-C4 alkyl groups; R 22 is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an amine group, an amide group; R 44 is C 11 -C 20 alkyl group; X is a hydrogen atom.

[0063] In various exemplary embodiments, suitable HALS include, but are not limited to, 2,2,6,6-tetramethylpiperidine; 4-chloro-2,2,6,6-tetramethylpiperidine; 4-bromo-2,2,6,6-tetramethylpiperidine; 2,2,6,6-tetramethyl-piperidin-4-ol; 4-isocyanato-2,2,6,6-tetramethylpiperidine; N-butyl-2,2,6,6-tetramethylpiperidin-4-amine; 4,4-bis[(tert-butyl)dioxy]-2,2,6,6-tetramethylpiperidine; N,N-bis-(2,2,6,6-tetramethyl-piperidin-4-yl)-propane-1,3-diamine; N,N-bis-(2,2,6,6-tetramethyl-piperidin-4-yl)-hexane-1,6-diamine; N 1-(2,2,6,6-Tetramethyl-piperidin-4-yl)-hexane-1,6-diamine; 2,2,6,6-tetramethylpiperidin-4-yl benzoate; bis(2,2,6,6-tetramethyl-4-piperidyl) succinate; 3-dodecyl-1-(2,2,6,6-tetramethyl-piperidin-4-yl)-pyrrolidine-2,5-dione; 1,5-dioxa-spiro[5.5]undecane-3,3-dicarboxylic acid bis(2,2,6,6-tetramethyl-piperidin-4-yl) ester; 2,6-bis-(2,2,6,6-tetramethyl-piperidin-4-yl)-hexahydro-2,3a,4a,6,7a,8a-hexaaza-cyclopenta[def]fluorene-4,8-dione; N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-diformyl-1,6-diaminohexane; 2,2,6,6-tetramethyl-4-piperidinecarboxylic acid 1,4-cyclohexanediylbis(methylene) ester; 2,2,6,6-tetramethyl-piperidin-4-yl methacrylate; methyl-[3-(2,2,6,6-tetramethyl-piperidin-4-yloxy)-propyl]-silane diol; N-(2,2,6,6-tetramethyl-piperidin-4-yl) stearamide; bis(2,2,6,6-tetramethyl-piperidin-4-yl) sebacate; bis(1,2,2,6,6-pentamethyl-piperidin-4-yl) sebacate; methyl-1,2,2,6,6-pentamethyl-piperidin-4-yl sebacate; 4-hydroxy-2,2,6,6-tetramethyl-piperidin-4-carboxylic acid; heptadecanoic acid 2,2,6,6-tetramethyl-piperidin-4-yl ester; N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-piperidin-4-yl)-formamide; N,N'-bis(1,1,3,3-tetramethylbutyl)-2,9,15,22-tetrakis(2,2,6,6-tetramethyl-piperidin-4-yl)-2,9,11,13,15,22,24,26,27,28-decaazatricyclo[21.3.1.1 10,14Octacosa-1(27),10,12,14(28),23,25-hexaene-12,25-diamine; Poly[(6-morpholino-s-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-piperidin-4-yl)imino]-hexamethylene[(2,2,6,6-tetramethyl-piperidin-4-yl)imino)]]; CYASORB® UV-3853; Poly[(6-morpholino-s-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-piperidin-4-yl)imino]-hexamethylene[(2,2,6,6-tetramethyl-piperidin-4-yl)imino)]]; N-phenylnaphthalen-1-amine; N-phenylnaphthalen-2-amine; Bis-[4-(1-phenyl-ethyl)-phenyl]-amine; N-(1,3-dimethylbutyl)-N'-phenylbenzene-1,4-diamine; 4-methylphenyl(4-anilinophenyl)amidosulfite; 2,2-dimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,3,3-tetramethyl-1,2,3,4-tetrahydroquinoline, 2,2,3,3,4-pentamethyl-1,2,3,4-tetrahydroquinoline; and combinations thereof are included.

[0064] A preferred HALS is TINUVIN® 770 (bis(2,2,6,6,-tetramethyl-4-piperidyl) sebacate) manufactured by BASF.

[0065] In an exemplary embodiment, the HALS is present in the curable composition in an amount such that the cured resin composition exhibits antibacterial properties when the HALS is converted to an N-halo hindered amine by treatment with a halogenating agent, for example, converted to an N-chloro hindered amine (NCHA) by treatment with a chlorinating agent, or converted to an N-bromo hindered amine by treatment with a brominating agent, for example, or converted to an N-iodo hindered amine by treatment with an iodinating agent. In an exemplary embodiment, the halogenating agent is an aqueous solution of a hypohalite (e.g., a hypochlorite containing about 0.001 wt% to about 1 wt% hypochlorite, e.g., an aqueous hypochlorite solution containing sodium hypochlorite) or another diluted oxidizing halogenating solution.

[0066] In an exemplary embodiment, the total amount of HALS in the curable composition is at least 3 wt%, particularly at least 4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, or at least 8 wt% based on the total weight of the curable composition. In an exemplary embodiment, the total amount of HALS in the curable composition is 3 to 30 wt%, particularly 3 to 25 wt%, 3 to 20 wt%, 3 to 15 wt%, 3 to 10 wt%, 4 to 30 wt%, 4 to 25 wt%, 4 to 20 wt%, 4 to 15 wt%, 4 to 10 wt%, 5 to 30 wt%, 5 to 25 wt%, 5 to 20 wt%, 5 to 15 wt%, 5 to 10 wt%, 6 to 30 wt%, 6 to 25 wt%, 6 to 20 wt%, 6 to 15 wt%, 6 to 10 wt%, 7 to 30 wt%, 7 to 25 wt%, 7 to 20 wt%, 7 to 15 wt% or 7 to 10 wt% based on the total weight of the curable composition.

[0067] In one embodiment of the present invention, the HALS may be capable of forming a covalent bond within the cured composition (in other words, the HALS may be capable of reacting with a (meth)acrylate functionalized compound during the curing of the composition). In particular, the HALS may be an ethylenically unsaturated HALS.

[0068] In another embodiment, the HALS may not be able to form a covalent bond within the curable composition (in other words, the HALS may not be able to react with the (meth)acrylate functionalized compound during the curing of the composition). In particular, the HALS may be a non-ethylenically unsaturated HALS.

[0069] In one embodiment of the present invention, the HALS can form a covalent bond within the curable composition, and the total amount of HALS in the curable composition is 10 to 30% by weight, 12.5 to 30% by weight, 15 to 30% by weight, or 20 to 30% by weight based on the total weight of the curable composition. In another embodiment, the HALS cannot form a covalent bond within the curable composition, and the total amount of HALS in the curable composition is 3 to 15% by weight, 3 to 12% by weight, 3 to 10% by weight, or 4 to 10% by weight based on the total weight of the curable composition. In another embodiment, the HALS cannot form a covalent bond within the curable composition, and the total amount of HALS in the curable composition is 6 to 15% by weight, 6 to 12% by weight, or 6 to 10% by weight based on the total weight of the curable composition.

[0070] In one embodiment of the present invention, the HALS may be capable of crosslinking within the curable composition. In particular, the HALS may be a polyethylene unsaturated HALS, i.e., a HALS containing two or more ethylenically unsaturated functional groups such as vinyl, allyl, and (meth)acrylate. More specifically, the HALS may be a poly(meth)acrylate-containing HALS.

[0071] The total amount of poly(meth)acrylate-containing HALS in the curable composition may be at least 10% by weight, particularly 10 to 30% by weight, 12.5 to 30% by weight, 15 to 30% by weight, or 20 to 30% by weight based on the total weight of the curable composition.

[0072] In one embodiment of the present invention, the HALS may be capable of forming a covalent bond within the curable composition without preferably being crosslinked to the curable composition. For example, the coating may be crosslinked, but not by the HALS compound, and may simply react to become part of the coating. In particular, the HALS may be a monoethylenically unsaturated HALS, i.e., an HALS containing a single ethylenically unsaturated functional group such as vinyl, allyl, and (meth)acrylate. More specifically, the HALS may be a mono(meth)acrylate-containing HALS. An example of a suitable mono(meth)acrylate-containing HALS is 2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate. Even more specifically, the mono(meth)acrylate-containing HALS is 2,2,6,6-tetramethyl-4-piperidyl methacrylate.

[0073] The total amount of mono(meth)acrylate-containing HALS in the curable composition may be at least 10% by weight, particularly 10 - 30% by weight, 12.5 - 30% by weight, 15 - 30% by weight, or 20 - 30% by weight based on the total weight of the curable composition.

[0074] In one embodiment of the present invention, the HALS may not be able to form a covalent bond within the curable composition. In particular, the HALS may be a non-ethylenically unsaturated HALS, i.e., an HALS lacking any ethylenically unsaturated functional groups such as vinyl, allyl, and (meth)acrylate. More specifically, the non-ethylenically unsaturated HALS may be bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770).

[0075] The total amount of non-ethylenically unsaturated HALS in the curable composition may be at least 3% by weight, particularly 3 - 15% by weight, 3 - 12% by weight, 3 - 10% by weight, or 4 - 10% by weight based on the total weight of the curable composition.

[0076] Additive The curable composition may further contain one or more additives including, but not limited to, a photoinitiator, an antioxidant, an ultraviolet absorber, a light stabilizer, a foam inhibitor, a solvent, a flow or leveling agent, a colorant, an adhesion promoter, a pigment, a dispersant (wetting agent), a slip additive, a filler, a thixotropic agent, a matting agent, a thermoplastic resin such as an acrylic resin that does not contain a free radical polymerizable functional group, a wax, or other various additives including any of the additives conventionally used in coating, sealing, adhesive, molding or ink technology.

[0077] In certain embodiments of the present invention, the curable composition described herein contains at least one photoinitiator. A photoinitiator can be considered any type of substance that forms species that initiate the reaction and curing of the polymerizable organic substances present in the curable composition upon exposure to irradiation (e.g., actinic radiation).

[0078] A free radical polymerization initiator is a substance that forms free radicals when irradiated. The use of free radical photoinitiators is particularly preferred. Non-limiting types of free radical photoinitiators suitable for use in the curable composition of the present invention include, for example, benzoin, benzoin ether, acetophenone, benzyl, benzyl ketal, anthraquinone, phosphine oxide, α-hydroxy ketone, phenylglyoxylate, α-amino ketone, benzophenone, thioxanthone, xanthone, acridine derivatives, phenazine derivatives, quinoxaline derivatives and triazine compounds.

[0079] Suitable photoinitiators include those that can generate free radicals when exposed to the necessary irradiation such as UV energy. In an exemplary embodiment, the photoinitiator includes an acylphosphine oxide (e.g., Irgacure® 819, Lucirin® TPO and Lucirin® TPO-L); a benzyl ketal (e.g., Irgacure 651); an alpha-hydroxy phenyl ketone, such as Irgacure 184 or Darocur 1173) or mixtures thereof.

[0080] The amount of photoinitiator can vary as appropriate depending on, among other factors, the photoinitiator(s) selected, the amount and type of polymerizable species present in the curable composition, the irradiation source, and the irradiation conditions used. However, typically, the amount of photoinitiator can be from 0.05 wt% to 5 wt%, preferably from 0.1 wt% to 2 wt%, based on the total weight of the curable composition.

[0081] Suitable solvents are any solvents that dissolve all other components in the curable composition and include aliphatic or aromatic hydrocarbons (e.g., hexane, toluene, or xylene), alcohols (e.g., ethanol or propylene glycol), esters (e.g., ethyl acetate, n-butyl acetate), ketones (e.g., acetone, methyl isobutyl ketone, or methyl ethyl ketone), and ethers (e.g., propylene glycol methyl ether or dimethoxyethane). However, in other embodiments, the curable composition of the present invention may be formulated to be solvent-free, i.e., contain no optional non-reactive volatile substances (substances having a boiling point of 150 °C or less at atmospheric pressure). For example, the curable composition of the present invention may contain little or no non-reactive solvent, e.g., less than 10% or less than 5% or less than 1% or even less than 0% non-reactive solvent based on the total weight of the curable composition.

[0082] Suitable adhesion promoters include silanes, titanates, zirconates, and polyolefins.

[0083] Suitable wetting agents include alkoxylated surfactants, silicone surfactants, sulfosuccinates, and fluorinated polyacrylates.

[0084] Suitable ultraviolet absorbers include benzophenone (such as benzophenone and hydroxybenzophenone), benzotriazole (such as hydroxyphenylbenzotriazole), hydroxyphenyltriazine (such as oxanilide), and thioxanthone.

[0085] Generally speaking, when the curable composition of the present invention is stored for a period of time before use, it is desirable to include one or more stabilizers in order to provide appropriate storage stability and shelf life. As used herein, the term "stabilizer" means a compound or substance that delays or prevents the reaction or curing of (meth)acrylate functional groups present in the composition in the absence of actinic radiation. However, it would be advantageous to select the amount and type of stabilizer such that the composition remains curable when exposed to actinic radiation (i.e., the stabilizer does not interfere with the radiation curing of the composition). Typically, effective stabilizers for the purposes of the present invention are classified as free radical stabilizers (i.e., stabilizers that function by inhibiting free radical reactions).

[0086] Any of the stabilizers known in the art related to (meth)acrylate functionalized compounds can be utilized in the present invention. Quinones represent a particularly preferred type of stabilizer that can be used in the context of the present invention. As used herein, the term "quinone" includes both quinones and hydroquinones, as well as their ethers, such as monoalkyl, monoaryl, monoaralkyl, and bis(hydroxyalkyl) ethers of hydroquinone. Hydroquinone monomethyl ether is an example of a suitable stabilizer that can be utilized.

[0087] The concentration of the stabilizer in the curable composition varies depending on the particular stabilizer or combination of stabilizers selected for use, as well as the desired degree of stabilization and the sensitivity of the components in the curable composition to decomposition in the absence of the stabilizer. However, typically, the curable composition is formulated to contain 50 to 5000 ppm of the stabilizer.

[0088] Method for protecting the surface of a substrate The present invention relates to a method for protecting the surface of a substrate. The method of the present invention includes a coating step, a curing step, and a halogenation step, as detailed below. The method of the present invention may further include an optional step of removing residual halogenating agent.

[0089] In one embodiment of the present invention, the coating step, the curing step, and the halogenation step may be repeated so that the substrate contains two or more layers of the curable composition.

[0090] The method of the present invention can be used to provide a protective coating on the surface of a substrate. The protective coating can advantageously exhibit one or more (or two or more, or three or more, or four or more) of the following properties: microbial resistance (or antibacterial property), light resistance, heat resistance, impact resistance, scratch resistance, and chemical resistance. Preferably, the protective coating is a microbial resistance (or antibacterial) protective coating.

[0091] The protective coating may be a clear coat coating.

[0092] The protective coating may have a thickness in the range of 5 to 250 μm, such as 5 to 225 μm, such as 5 to 200 μm, such as 5 to 175 μm, such as 5 to 150 μm.

[0093] Coating step The method of the present invention includes the step of applying the above-described curable composition to the surface of a substrate.

[0094] The curable composition can be applied to the substrate surface by any known conventional method, such as spraying, brushing, sponging, knife coating, roller coating, casting, drum coating, dipping, curtain coating, screen printing or other methods of image transfer, coating transfer, etc. and combinations thereof. Indirect coating using a transfer process can also be used.

[0095] In one embodiment, the curable composition can be applied directly to a substrate or on one or more of a primer, a basecoat system, or other suitable layers to achieve the desired final appearance and properties. For example, the curable composition can be applied on an aqueous basecoat or a solvent-based basecoat. Preferably, the curable composition is not grafted onto the substrate (i.e., there is no covalent or ionic bond between the substrate and the curable composition). Thus, the substrate does not need to be pretreated to generate grafting sites before the curable composition is applied thereon.

[0096] The substrate can be any commercially relevant substrate such as a high surface energy substrate or a low surface energy substrate (such as a metal substrate or a plastic substrate, respectively). The substrate can include one or more of metal, paper, cardboard, paperboard, glass, plastic (such as thermoplastic resins such as polyolefins, polycarbonates, acrylonitrile butadiene styrene (ABS) and blends thereof), composite materials, wood, leather, carbon fiber glass, non-woven fabric, ceramic (such as granite, marble), pigment coating, concrete, and combinations thereof. Preferably, the substrate includes one or more of metal, paper, cardboard, paperboard, glass, plastic (such as thermoplastic resins such as polyolefins, polycarbonates, acrylonitrile butadiene styrene (ABS) and blends thereof), composite materials, wood, leather, carbon fiber glass, ceramic (such as granite, marble), pigment coating, concrete, and combinations thereof. More preferably, the substrate includes one or more of metal, glass, plastic (such as thermoplastic resins such as polyolefins, polycarbonates, acrylonitrile butadiene styrene (ABS) and blends thereof), composite materials, carbon fiber glass, ceramic (such as granite, marble), pigment coating, concrete, and combinations thereof. Even more preferably, the substrate is a non-cellulose substrate.

[0097] In one embodiment of the present invention, the curable composition may be applied to the surface of a substrate so as to provide a dry film thickness in the range of 5 to 250 μm, for example 5 to 225 μm, for example 5 to 200 μm, for example 5 to 175 μm, for example 5 to 150 μm.

[0098] Curing step The method of the present invention includes a step of curing the above curable composition to provide a cured composition.

[0099] The curing of the curable composition according to the present invention can be carried out by any suitable method such as free radical, cationic and / or anionic polymerization, preferably free radical polymerization. One or more initiators such as free radical initiators (e.g., photoinitiators or peroxide initiators) may be present in the curable composition.

[0100] Curing can be accelerated or promoted by supplying energy to the curable composition, for example by exposing the composition to an irradiation source such as visible light, UV energy and / or an electron beam. Thus, the cured composition can be regarded as the reaction product of the curable composition formed by curing.

[0101] The curing step of the method of the present invention may include one of (1) exposing the curable composition to UV energy and / or visible light; (2) exposing the curable composition to an electron beam, (3) initiating polymerization using redox-generated radicals; (4) initiating polymerization by using heat-generated radicals, or a combination thereof. Preferably, the curing step of the method of the present invention includes one of (1) exposing the curable composition to UV energy and / or visible light,; or (2) exposing the curable composition to an electron beam.

[0102] The curable composition of the present invention is particularly well-suited for curing using LED (light emitting diode) curing (e.g., UV LED curing using irradiation from a UV LED device) and for use in high-speed coating (such as coating).

[0103] The plurality of layers of the composition according to the present invention may be applied to the substrate surface; the plurality of layers may be cured simultaneously (e.g., by exposure to a single dose of irradiation), or each layer may be cured continuously before the application of an additional layer of the composition.

[0104] The curable composition can be cured by exposing the composition to actinic radiation, particularly UV energy and / or visible light.

[0105] In particular, the curable composition can be cured by exposing the curable composition to UV energy. The UV energy can be in the range of 200 - 400 nm. The UV energy can be for a period of 1 second to 30 minutes, for example, 1 second to 10 minutes, at an irradiance level of 0.01 - 10 W / cm 2 , for example, 1 - 10 W / cm 2 and can be provided by one or more UV lamps that deliver an irradiance level.

[0106] More particularly, the curable composition can be cured by exposing the curable composition to UVC energy, UVB energy, UVA energy and / or visible light. In an exemplary embodiment, the curable composition is cured with a UV energy source that utilizes only UVA / UVB energy or UVA energy and is essentially free of UVC energy. In an exemplary embodiment, the curable composition is cured with high energy irradiation in the range of 0.01 - 10 W / cm 2 . Possible light sources include, but are not limited to, natural outdoor lights, black lights, fluorescent lights, LEDs, or high pressure mercury lamps.

[0107] The curable composition can be cured by exposing the curable composition to an electron beam. In one embodiment, the electron beam may be provided by an E - BEAM service device that delivers 2 megarads of energy.

[0108] The curable composition may be cured by free radical polymerization.

[0109] In particular, the curable composition can be cured by initiating polymerization using heat-generated radicals (also referred to as thermal curing). For example, the curable composition can include a radical initiator such as a peroxide initiator that is activated by heating. Examples of suitable peroxide initiators include, but are not limited to, hydrogen peroxide, benzoyl peroxide, or t-butyl hydroperoxide.

[0110] Alternatively, the curable composition can be cured by initiating polymerization using redox-generated radicals (also referred to as two-step redox curing). For example, the curable composition can include a radical initiator (e.g., the above peroxide) and a reducing agent (e.g., tertiary amines such as N,N-dimethylaniline, N-(4-methoxyphenyl)pyrrolidine, and N-phenyldiethanolamine, sodium sulfite, sodium metabisulfite). The radical initiator may be activated by the reducing agent.

[0111] Preferably, the curable composition does not cure by thermal curing.

[0112] In one embodiment of the present invention, the cured composition is present as a coating on a substrate in a thickness range of 5 to 250 μm, such as 5 to 225 μm, such as 5 to 200 μm, such as 5 to 175 μm, such as 5 to 150 μm, either alone or as a component in a coating composition.

[0113] In one embodiment of the present invention, the cured composition is a clearcoat coating on the surface of a substrate.

[0114] Halogenation step The method of the present invention includes a step of treating the cured composition defined above with a halogenating agent to halogenate the HALS present in the cured composition.

[0115] Halogenation of HALS results in the formation of N-halo-hindered amines (haloamines) in the cured composition. The presence of haloamines in the cured composition can advantageously impart antibacterial properties to the cured composition.

[0116] To prepare haloamines from HALS, two approaches: halogenating the HALS before incorporation into the curable composition, or halogenating the HALS present in the cured composition (in other words, the HALS is present in the curable composition before curing) can typically be used.

[0117] In the method of the present invention, the HALS is present in the cured composition, and the halogenation can be carried out by any suitable means, for example, spraying, dipping, or wiping the surface of the cured composition with a halogenating agent in a diluted form, optionally as desired. In the method of the present invention, it is preferred that the HALS is not halogenated before being incorporated into the curable composition.

[0118] Suitable halogenating agents include hypochlorites (e.g., calcium hypochlorite, lithium hypochlorite, and sodium hypochlorite), chlorinating agents such as trichloroisocyanuric acid and dichloroisocyanurates (e.g., potassium dichloroisocyanurate and sodium dichloroisocyanurate), and iodinating agents such as povidone iodine (Betadine®), but are not limited thereto. In one embodiment, the halogenating agent is used in a stoichiometric excess as measured by the amount of HALS present in the curable composition, for example, at least 10% molar excess, at least 30% molar excess, at least 50% molar excess, at least 100% molar excess, or at least 200% molar excess.

[0119] In one embodiment of the present invention, the halogenating agent may be a chlorinating agent, particularly sodium hypochlorite, more specifically an aqueous solution of sodium hypochlorite (commonly also called bleach), and even more specifically a commercially available 5.25 - 8.25% w / w aqueous solution of sodium hypochlorite from Chlorox®.

[0120] In one embodiment of the present invention, sodium hypochlorite is further diluted from its original commercial form, such as by adding water. In one embodiment, sodium hypochlorite is present as a household bleach (5.25 - 8.25% w / w sodium hypochlorite in water) diluted with at least 10% water, such as at least 20% water, such as at least 30% water, such as at least 40% water, such as at least 50% water.

[0121] In another embodiment, the halogenating agent is an iodinating agent such as Betadine® (povidone iodine).

[0122] In an exemplary embodiment, after treating the composition with a halogenating agent, the method may include an optional step of removing the residual halogenating agent. For example, the cured composition can be contacted with water in an amount sufficient to remove the residual halogenating agent, either directly (e.g., spraying) or indirectly (e.g., by wiping with a wet cloth or sponge).

[0123] In an exemplary embodiment, the presence of haloamines in the cured composition after treating the composition with a halogenating agent was detected using a zinc iodide (ZnI) / starch indicator. In an exemplary embodiment, a cotton swab was saturated with the ZnI / starch indicator and rubbed on the treated surface. The solution on the swab changed from clear to dark blue / violet in the presence of chlorine. Other methods of detecting haloamines known in the art, such as detection by titration techniques, are also suitable.

[0124] A wide variety of hindered amines can be evaluated for antibacterial activity along with the concentration required to promote such activity. Log 10 Data is used to characterize the antibacterial properties of the haloamine-containing cured composition and to identify which compositions may be suitable for antibacterial applications. In an exemplary embodiment, JIS Z 2801:2010 is used for Log of gram-positive and gram-negative bacteria. 10The reduction was quantified. In one embodiment, at least a 1,000-fold reduction (i.e., a 3 log-10 reduction) was observed in the number of at least one of Staphylococcus aureus and Escherichia coli.

[0125] In one embodiment of the present invention, in order to restore and / or enhance the antibacterial activity of the surface where the cured composition is present, depending on the application (e.g., once or multiple times a day, or once a week, or once a month or once every two months, etc.), the substrate surface is periodically treated with a halogenating agent as needed.

[0126] In one embodiment of the present invention, the surface of the substrate containing the cured composition exhibits substantially improved antibacterial properties as compared to the surface of a substrate coated with the same curable composition without HALS.

[0127] In one embodiment of the present invention, after the step of treating the surface of the substrate with a halogenating agent, the surface retains more than 50% of its antibacterial properties for up to 3 weeks or up to 4 weeks or up to 5 weeks or up to 6 weeks (based on the concentration of halogen remaining in the coating present as halogenated HALS).

[0128] Other methods, compositions and uses The present invention also relates to a method of treating a cured composition with a halogenating agent to halogenate HALS present in the cured composition, wherein the cured composition comprises a cured product of a curable composition comprising HALS and a (meth)acrylate functionalized compound. The curable composition can be as defined above.

[0129] The present invention also relates to a cured composition comprising an N-halo-hindered amine, obtained by (a) curing the curable composition as defined above; and (b) then converting the HALS to an N-halo-hindered amine by treating the HALS with a halogenating agent.

[0130] The present invention also relates to the use of at least one HALS, at least one (meth)acrylate functionalized compound and at least one halogenating agent for obtaining an antibacterial coating on the surface of a substrate. The antibacterial properties of the coating can be determined according to JIS Z 2801:2010 as described above. For example, the antibacterial coating can show at least a 1,000-fold reduction (i.e., a 3 log-10 reduction) in the number of at least one of Staphylococcus aureus and Escherichia coli compared to a coating that does not contain any HALS or haloamine.

[0131] Aspects of the present invention Exemplary non-limiting embodiments of the present invention can be summarized as follows:

[0132] Aspect 1: A method for protecting the surface of a substrate, comprising: - applying a curable composition comprising a (meth)acrylate functionalized compound and a hindered amine light stabilizer (HALS) to the surface of the substrate; - curing the curable composition to provide a cured composition; - treating the cured composition with a halogenating agent to halogenate the HALS present in the cured composition; and - optionally, removing the residual halogenating agent. A method comprising.

[0133] Aspect 2: The method of Aspect 1, wherein the cured composition treated with a halogenating agent provides a protective coating on the surface of the substrate.

[0134] Aspect 3: The method of Aspect 2, wherein the protective coating exhibits one or more (or two or more, or three or more, or four or more) of the following properties: microbial resistance, light resistance, heat resistance, impact resistance, scratch resistance and chemical resistance; preferably, the protective coating is a microbial resistance (or antibacterial) protective coating.

[0135] Aspect 4: The method of Aspect 2 or 3, wherein the protective coating is a clear coat coating.

[0136] Aspect 5: The method of any one of Aspects 2 to 4, wherein the protective coating has a thickness in the range of 5 to 250 μm, such as 5 to 225 μm, such as 5 to 200 μm, such as 5 to 175 μm, such as 5 to 150 μm.

[0137] Aspect 6: The method of any one of Aspects 1 to 5, wherein the curing includes one of the following: (1) exposing the curable composition to UV energy and / or visible light; (2) exposing the curable composition to an electron beam; (3) initiating polymerization using a redox-generated radical; or (4) initiating polymerization by using a heat-generated radical.

[0138] Aspect 7: The method of any one of Aspects 1 to 6, wherein the curable composition is cured by exposing the curable composition to UV energy.

[0139] Aspect 8: The method of any one of Aspects 1 to 7, wherein the curable composition is cured by exposing the curable composition to visible light.

[0140] Aspect 9: The method of any one of Aspects 1 to 6, wherein the curable composition is cured by exposing the curable composition to an electron beam.

[0141] Aspect 10: The method of any one of Aspects 1 to 6, wherein the curable composition is cured by initiating polymerization using a redox-generated radical.

[0142] Aspect 11: The method of any one of Aspects 1 to 6, wherein the curable composition is cured by initiating polymerization using a heat-generated radical.

[0143] Aspect 12: The method of any one of Aspects 1 to 10, wherein the curable composition is not cured by initiating polymerization using a heat-generated radical.

[0144] Aspect 13: A method according to any one of Aspects 1 to 12, wherein the halogenating agent is selected from chlorinating agents such as hypochlorites (e.g., calcium hypochlorite, lithium hypochlorite, and sodium hypochlorite), trichloroisocyanuric acid, and dichloroisocyanurates (e.g., potassium dichloroisocyanurate and sodium dichloroisocyanurate), and iodinating agents such as povidone iodine (Betadine (registered trademark)).

[0145] Aspect 14: A method according to any one of Aspects 1 to 13, wherein the halogenating agent is a chlorinating agent, particularly sodium hypochlorite, and more specifically a sodium hypochlorite solution.

[0146] Aspect 15: A method according to any one of Aspects 1 to 14, wherein the HALS has at least one nitrogen atom bonded to one hydrogen atom and two carbon atoms, and the carbon atom does not have a hydrogen atom directly bonded thereto.

[0147] Aspect 16: A method according to any one of Aspects 1 to 15, wherein the HALS has at least one nitrogen atom bonded to one hydrogen atom and two carbon atoms, and the carbon atom is not a carbonyl carbon.

[0148] Aspect 17: A method according to any one of Aspects 1 to 16, wherein the curable composition contains a HALS that can crosslink within the cured composition.

[0149] Aspect 18: A method according to any one of Aspects 1 to 16, wherein the curable composition contains a HALS that can form a covalent bond within the curable composition, preferably without crosslinking within the cured composition.

[0150] Aspect 19: The method of Aspect 18, wherein the HALS is an ethylenically unsaturated HALS, particularly 2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate.

[0151] Aspect 20: A method according to any one of Aspects 1 to 16, wherein the curable composition contains a HALS that cannot form a covalent bond within the curable composition.

[0152] Aspect 21: The method of Aspect 20, wherein the HALS is a non-ethylenically unsaturated HALS, particularly bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

[0153] Aspect 22: The total amount of HALS in the curable composition is at least 3% by weight, particularly 3 - 30% by weight, especially 3 - 25% by weight, 3 - 20% by weight, 3 - 15% by weight, 3 - 10% by weight, 4 - 30% by weight, 4 - 25% by weight, 4 - 20% by weight, 4 - 15% by weight, 4 - 10% by weight, 5 - 30% by weight, 5 - 25% by weight, 5 - 20% by weight, 5 - 15% by weight, 5 - 10% by weight, 6 - 30% by weight, 6 - 25% by weight, 6 - 20% by weight, 6 - 15% by weight, 6 - 10% by weight, 7 - 30% by weight, 7 - 25% by weight, 7 - 20% by weight, 7 - 15% by weight or 7 - 10% by weight, based on the total weight of the composition, of any of the methods of Aspects 1 - 21.

[0154] Aspect 23: The curable composition contains HALS that can form covalent bonds within the cured composition, and the total amount of HALS in the curable composition is 10 - 30% by weight, particularly 12.5 - 30% by weight, 15 - 30% by weight, or 20 - 30% by weight, based on the total weight of the curable composition, of any one of the methods of Aspects 1 - 16.

[0155] Aspect 24: The curable composition contains HALS that cannot form covalent bonds within the cured composition, and the total amount of HALS in the curable composition is 3 - 15% by weight, particularly 3 - 12% by weight, 3 - 10% by weight, or 4 - 10% by weight, based on the total weight of the curable composition, of any one of the methods of Aspects 1 - 16.

[0156] Aspect 25: The curable composition contains HALS that cannot form covalent bonds within the cured composition, and the total amount of HALS in the curable composition is 6 - 15% by weight, particularly 6 - 12% by weight, or 6 - 10% by weight, based on the total weight of the curable composition, of any one of the methods of Aspects 1 - 16.

[0157] Aspect 26: A method according to any one of Aspects 1 to 25, wherein the curable composition comprises a (meth)acrylate-functionalized monomer.

[0158] Aspect 27: A method according to Aspect 26, wherein the (meth)acrylate-functionalized monomer has 1 to 6 (meth)acrylate groups, particularly 1 to 3 (meth)acrylate groups.

[0159] Aspect 28: A method according to any one of Aspects 1 to 27, wherein the curable composition comprises a mono(meth)acrylate-functionalized monomer.

[0160] Aspect 29: A method according to any one of Aspects 1 to 28, wherein the curable composition comprises a (meth)acrylate-functionalized monomer containing two or more (meth)acrylate functional groups per molecule.

[0161] Aspect 30: A method according to any one of Aspects 1 to 29, wherein the curable composition comprises a (meth)acrylate-functionalized oligomer.

[0162] Aspect 31: A method according to Aspect 30, wherein the (meth)acrylate-functionalized oligomer has 1 to 18 (meth)acrylate groups, particularly 2 to 6 (meth)acrylate groups.

[0163] Aspect 32: A method according to any one of Aspects 1 to 31, wherein the curable composition comprises a (meth)acrylate-functionalized oligomer selected from the group consisting of a (meth)acrylate-functionalized urethane oligomer, a (meth)acrylate-functionalized epoxy oligomer, a (meth)acrylate-functionalized polyether oligomer, a (meth)acrylate-functionalized polydiene oligomer, a (meth)acrylate-functionalized polycarbonate oligomer, a (meth)acrylate-functionalized polyester oligomer, a (meth)acrylate-functionalized (meth)acrylic oligomer, and mixtures thereof.

[0164] Aspect 33: The (meth)acrylate-functionalized compound of the curable composition is optionally combined with one or more (meth)acrylate-functionalized oligomers containing two or more (meth)acrylate groups per molecule, selected from the group consisting of (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyether oligomers, (meth)acrylate-functionalized polyester oligomers, and mixtures thereof, and one or more (meth)acrylate-functionalized monomers having 1 to 6 (meth)acrylate groups per molecule, according to any of the methods of Aspects 1 to 32.

[0165] Aspect 34: The total amount of the (meth)acrylate-functionalized compound in the curable composition is 0.1 to 97% by weight, particularly 1 to 95% by weight, 5 to 93% by weight, 10 to 90% by weight, 15 to 85% by weight, 20 to 80% by weight, or 25 to 75% by weight based on the weight of the curable composition, according to any of the methods of Aspects 1 to 33.

[0166] Aspect 35: The curable composition further comprises one or more of various additives including, but not limited to, photoinitiators, antioxidants, UV absorbers, light stabilizers, anti-foaming agents, solvents, flow or leveling agents, colorants, pigments, dispersants (wetting agents), slip additives, fillers, thixotropic agents, matting agents, thermoplastic resins such as acrylic resins not containing free radical polymerizable functional groups, waxes, or other various additives conventionally used in coating, sealing, adhesive, molding, or ink technologies.

[0167] Aspect 36: The substrate on which the curable composition is applied comprises one or more of metals, paper, cardboard, thick paper, glass, plastics (e.g., thermoplastic resins such as polyolefins, polycarbonates, acrylonitrile-butadiene-styrene (ABS) and blends thereof), composite materials, wood, leather, carbon fiber glass, non-woven fabrics, ceramics (e.g., granite, marble), pigment coatings, concrete, and combinations thereof, according to any of the methods of Aspects 1 to 35.

[0168] Aspect 37: A method according to any one of Aspects 1 to 36, wherein the substrate surface is periodically treated with a halogenating agent to restore and / or enhance the antibacterial resistance of the surface where the cured composition is present.

[0169] Aspect 38: A method according to any one of Aspects 1 to 37, wherein the coating, curing and treatment steps are repeated such that the substrate contains two or more layers of the cured composition.

[0170] Aspect 39: A method according to any one of Aspects 1 to 38, wherein the surface of the substrate containing the cured composition exhibits substantially improved antibacterial properties as compared to a cured composition not containing HALS.

[0171] Aspect 40: A method according to any one of Aspects 1 to 39, wherein after the step of treating the surface of the substrate with a chlorinating agent, the surface retains more than 50% of its antibacterial properties for up to 3 weeks or up to 4 weeks or up to 5 weeks or up to 6 weeks (based on the concentration of halogen remaining in the coating present as halogenated HALS).

[0172] Aspect 41: A method according to any one of Aspects 1 to 39, wherein the antibacterial properties of the surface of the substrate are reactivated or enhanced by periodically contacting the surface with a halogenating agent such as sodium hypochlorite or povidone iodine.

[0173] Aspect 42: A method of treating a cured composition with a halogenating agent to halogenate HALS present in the cured composition, wherein the cured composition comprises a cured product of a curable composition comprising HALS and a (meth)acrylate functionalized compound.

[0174] Aspect 43: The method of Aspect 42, wherein the halogenating agent is sodium hypochlorite or Betadine® (povidone iodine).

[0175] Aspect 44: A curable composition comprising a (meth)acrylate-functionalized compound and a HALS, wherein the total amount of HALS in the composition is at least 3% by weight, preferably at least 6% by weight, based on the weight of the composition.

[0176] Aspect 45: The curable composition according to aspect 44, wherein the HALS is a hindered amine compound having a hydrogen atom bonded to a nitrogen atom of an amine group.

[0177] Aspect 46: The curable composition according to aspect 44 or 45, wherein the carbon atom adjacent to the nitrogen atom of the HALS is not a carbonyl carbon.

[0178] Aspect 47: The curable composition according to any one of aspects 44 to 46, wherein the curable composition contains a HALS that can crosslink within the cured composition.

[0179] Aspect 48: The curable composition according to any one of aspects 44 to 46, wherein the curable composition preferably contains a HALS that can form a covalent bond within the cured composition without crosslinking within the cured composition.

[0180] Aspect 49: The curable composition according to aspect 48, wherein the HALS is an ethylenically unsaturated HALS, particularly 2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate.

[0181] Aspect 50: The curable composition according to any one of aspects 44 to 46, wherein the curable composition contains a HALS that cannot form a covalent bond within the cured composition.

[0182] Aspect 51: The curable composition according to aspect 50, wherein the HALS is a non-ethylenically unsaturated HALS, particularly bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

[0183] Aspect 52: A curable composition according to any one of Aspects 44 to 51, wherein the total amount of HALS in the curable composition is at least 3% by weight, particularly 3 to 30% by weight, particularly 3 to 25% by weight, 3 to 20% by weight, 3 to 15% by weight, 3 to 10% by weight, 4 to 30% by weight, 4 to 25% by weight, 4 to 20% by weight, 4 to 15% by weight, 4 to 10% by weight, 5 to 30% by weight, 5 to 25% by weight, 5 to 20% by weight, 5 to 15% by weight, 5 to 10% by weight, 6 to 30% by weight, 6 to 25% by weight, 6 to 20% by weight, 6 to 15% by weight, 6 to 10% by weight, 7 to 30% by weight, 7 to 25% by weight, 7 to 20% by weight, 7 to 15% by weight or 7 to 10% by weight based on the total weight of the composition.

[0184] Aspect 53: A curable composition according to any one of Aspects 44 to 46, wherein the curable composition contains HALS capable of forming covalent bonds within the cured composition, and the total amount of HALS in the curable composition is 10 to 30% by weight, particularly 12.5 to 30% by weight, 15 to 30% by weight, or 20 to 30% by weight based on the total weight of the curable composition.

[0185] Aspect 54: A curable composition according to any one of Aspects 44 to 46, wherein the curable composition contains HALS incapable of forming covalent bonds within the cured composition, and the total amount of HALS in the curable composition is 3 to 15% by weight, particularly 3 to 12% by weight, 3 to 10% by weight, or 4 to 10% by weight based on the total weight of the curable composition.

[0186] Aspect 55: A curable composition according to any one of Aspects 44 to 46, wherein the curable composition contains HALS incapable of forming covalent bonds within the cured composition, and the total amount of HALS in the curable composition is 6 to 15% by weight, particularly 6 to 12% by weight, or 6 to 10% by weight based on the total weight of the curable composition.

[0187] Aspect 56: A curable composition according to any one of Aspects 44 to 55, wherein the curable composition contains a (meth)acrylate-functionalized monomer.

[0188] Aspect 57: The curable composition of Aspect 56, wherein the (meth)acrylate-functionalized monomer has 1 to 6 (meth)acrylate groups, particularly 1 to 3 (meth)acrylate groups.

[0189] Aspect 58: The curable composition according to any one of Aspects 44 to 57, wherein the curable composition contains a mono(meth)acrylate-functionalized monomer.

[0190] Aspect 59: The curable composition according to any one of Aspects 44 to 58, wherein the curable composition contains a (meth)acrylate-functionalized monomer having two or more (meth)acrylate functional groups per molecule.

[0191] Aspect 60: The curable composition according to any one of Aspects 44 to 59, wherein the curable composition contains a (meth)acrylate-functionalized oligomer.

[0192] Aspect 61: The curable composition of Aspect 60, wherein the (meth)acrylate-functionalized oligomer has 1 to 18 (meth)acrylate groups, particularly 2 to 6 (meth)acrylate groups.

[0193] Aspect 62: The curable composition according to any one of Aspects 44 to 61, wherein the curable composition contains a (meth)acrylate-functionalized oligomer selected from the group consisting of a (meth)acrylate-functionalized urethane oligomer, a (meth)acrylate-functionalized epoxy oligomer, a (meth)acrylate-functionalized polyether oligomer, a (meth)acrylate-functionalized polydiene oligomer, a (meth)acrylate-functionalized polycarbonate oligomer, a (meth)acrylate-functionalized polyester oligomer, a (meth)acrylate-functionalized (meth)acrylic oligomer, and mixtures thereof.

[0194] Aspect 63: The (meth)acrylate-functionalized compound of the curable composition is one or more (meth)acrylate-functionalized oligomers containing two or more (meth)acrylate groups per molecule, selected from the group consisting of (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyether oligomers, (meth)acrylate-functionalized polyester oligomers, and mixtures thereof, optionally combined with one or more (meth)acrylate-functionalized monomers having 1 to 6 (meth)acrylate groups per molecule, of any one of Aspects 44 to 62.

[0195] Aspect 64: The total amount of the (meth)acrylate-functionalized compound in the curable composition is 0.1 to 97% by weight, particularly 1 to 95% by weight, 5 to 93% by weight, 10 to 90% by weight, 15 to 85% by weight, 20 to 80% by weight, or 25 to 75% by weight based on the weight of the curable composition, of any one of Aspects 44 to 63.

[0196] Aspect 65: The curable composition further comprises one or more of various additives including, but not limited to, photoinitiators, antioxidants, UV absorbers, light stabilizers, anti-foaming agents, solvents, flow or leveling agents, colorants, pigments, dispersants (wetting agents), slip additives, fillers, thixotropic agents, matting agents, thermoplastic resins such as acrylic resins not containing free radical polymerizable functional groups, waxes, or other various additives conventionally used in coating, sealing, adhesive, molding, or ink technologies.

[0197] Aspect 66: A cured composition containing N-halo hindered amine, obtained by (a) curing the curable composition according to any one of Aspects 44 to 65; and (b) then treating the cured composition with a halogenating agent to convert HALS to N-halo hindered amine.

[0198] Aspect 67: The curable composition of Aspect 66, wherein the halogenating agent is a chlorinating agent, particularly sodium hypochlorite.

[0199] Aspect 68: The curable composition of Aspect 66 or 67, wherein the curing includes one of (1) exposing the curable composition to UV energy and / or visible light; (2) exposing the curable composition to an electron beam; (3) initiating polymerization using a redox-generated radical; or (4) initiating polymerization by using a heat-generated radical.

[0200] Aspect 69: Use of at least one HALS, at least one (meth)acrylate-functionalized compound, and at least one halogenating agent to obtain an antibacterial coating on the surface of a substrate.

[0201] In this specification, the embodiments have been described in a way that enables a clear and concise specification, but it is intended that the embodiments can be variously combined or separated without departing from the present invention, as will be understood. For example, it will be understood that all the preferred features described herein are applicable to all aspects of the invention described herein.

[0202] In some embodiments, the invention of this specification can be construed to exclude any element or process step that does not substantially affect the basic and novel characteristics of the compositions and methods described herein. Further, in some embodiments, the invention can be construed to exclude any element or process step not specified herein.

[0203] The present invention is illustrated and described herein with reference to specific embodiments, but the present invention is not intended to be limited to the details shown. Rather, various modifications can be made in detail within the scope and range of equivalents of the claims without departing from the present invention.

Examples

[0204] Preparation of a cured acrylate composition The curable composition was applied to an aluminum test panel at a thickness of 1 mil and cured with a medium-pressure mercury arc lamp having UVA energy of 500 mJ / cm 2 . The cured sample was then conditioned at 72°F / 50%RH for 24 hours.

[0205] Chlorination process The test panel coated with the cured acrylate resin was immersed in a 50 / 50 bleach / DI aqueous solution for 1.5 minutes. The panel was then rinsed with DI water for 1.5 minutes (twice) to remove residual bleach and dried for 24 hours. The presence of haloamine was confirmed by using a ZnI / starch solution (Sigma-Aldrich) as an indicator of the "active" surface. A cotton swab was saturated with the solution and rubbed multiple times on the treated surface. The color change of the saturated cotton swab from transparent to purple is an indicator of the presence of haloamine.

[0206] Testing of the cured resin coating for antibacterial activity Example 1. Seven coated samples (1A - 1H) specified in the following table were tested using the method described in JIS Z 2801:2010 (or ISO 22196:2011). The coating formulation contains PRO14589, which is a blend of a polyfunctional urethane acrylate oligomer and an acrylate monomer having a series of functions that provide a good balance of flexibility and hardness. The % of HALS shown is based on the weight of HALS compared to the total weight of the uncured formulation. TIFF2025519422000003.tif64170

[0207] The samples were tested against Staphylococcus aureus and Escherichia coli, and the contact time was 24 hours. The following table shows the results of the test. TIFF2025519422000004.tif80170

[0208] Regardless of whether the sample was chlorinated (Samples 1A and 1B), it was observed that no reduction in the level of Staphylococcus aureus or E. coli was detected when no HALS was present in the sample. In contrast, Sample 1C containing 2% Tinuvin® 770 as HALS showed a significant reduction in the levels of these two microorganisms, while Samples 1D, 1E and 1F containing 5%, 7.5% and 10% of Tinuvin® 770 as HALS, respectively, showed an almost complete reduction. In comparison, Sample G containing 7.5% TEMPO methacrylate as HALS showed a slightly lower reduction of Staphylococcus aureus (compared to Sample 1E) and a significantly lower reduction of E. coli (compared to Sample 1E).

Claims

1. A method for protecting the surface of a substrate, comprising: - applying a curable composition comprising a (meth)acrylate-functionalized compound and a hindered amine light stabilizer (HALS) to the surface of the substrate; - curing the curable composition to provide a cured composition; - treating the cured composition with a halogenating agent to halogenate the HALS present in the cured composition; and - optionally, removing the residual halogenating agent A method comprising the steps of:

2. The method according to claim 1, wherein the curing is carried out by free radical, cationic and / or anionic polymerization, preferably by free radical polymerization.

3. The curing comprises one of (1) exposing the curable composition to UV energy and / or visible light; (2) exposing the curable composition to an electron beam; (3) initiating polymerization by using a redox-generated radical; or (4) initiating polymerization by using a heat-generated radical. Preferably, the curing comprises one of (1) exposing the curable composition to UV energy and / or visible light; or (2) exposing the curable composition to an electron beam. The method according to claim 1.

4. The method according to any one of claims 1 to 3, wherein the halogenating agent is a chlorinating agent, particularly sodium hypochlorite, more specifically a sodium hypochlorite solution.

5. The method according to any one of claims 1 to 4, wherein the HALS has at least one nitrogen atom bonded to one hydrogen atom and two carbon atoms, and the carbon atoms do not have a hydrogen atom directly bonded thereto.

6. The method according to any one of claims 1 to 5, wherein the HALS has at least one nitrogen atom bonded to one hydrogen atom and two carbon atoms, and the carbon atoms are not carbonyl carbons.

7. The method according to any one of claims 1 to 6, wherein the HALS can form a covalent bond within the cured composition, preferably without being crosslinked to the cured composition.

8. The method according to claim 7, wherein the HALS is 2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate.

9. The method according to any one of claims 1 to 6, wherein the HALS cannot form a covalent bond within the cured composition.

10. The method according to claim 9, wherein the HALS is bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.

11. The method according to any one of claims 1 to 10, wherein the total amount of HALS in the curable composition is at least 3% by weight, in particular 3 to 30% by weight, 3 to 25% by weight, 3 to 20% by weight, 3 to 15% by weight, 3 to 10% by weight, 4 to 30% by weight, 4 to 25% by weight, 4 to 20% by weight, 4 to 15% by weight, 4 to 10% by weight, 5 to 30% by weight, 5 to 25% by weight, 5 to 20% by weight, 5 to 15% by weight, 5 to 10% by weight, 6 to 30% by weight, 6 to 25% by weight, 6 to 20% by weight, 6 to 15% by weight, 6 to 10% by weight, 7 to 30% by weight, 7 to 25% by weight, 7 to 20% by weight, 7 to 15% by weight or 7 to 10% by weight, based on the total weight of the composition.

12. The method according to any one of claims 1 to 11, wherein the (meth)acrylate-functionalized compound of the curable composition comprises one or more (meth)acrylate-functionalized oligomers containing two or more (meth)acrylate groups per molecule, selected from the group consisting of (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyether oligomers, (meth)acrylate-functionalized polyester oligomers, and mixtures thereof, optionally combined with one or more (meth)acrylate-functionalized monomers having 1 to 6 (meth)acrylate groups per molecule.

13. The method according to any one of claims 1 to 12, wherein the total amount of the (meth)acrylate-functionalized compound in the curable composition is 0.1 to 97% by weight, in particular 1 to 95% by weight, 5 to 93% by weight, 10 to 90% by weight, 15 to 85% by weight, 20 to 80% by weight or 25 to 75% by weight, based on the weight of the curable composition.

14. The method according to any one of claims 1 to 13, wherein the substrate comprises one or more of metal, paper, cardboard, thick paper, glass, plastic, composite material, wood, leather, carbon fiber glass, non-woven fabric, ceramic (e.g., granite, marble), pigment coating, concrete, and combinations thereof, preferably one or more of metal, paper, cardboard, thick paper, glass, plastic, composite material, wood, leather, carbon fiber glass, ceramic (e.g., granite, marble), pigment coating, concrete, and combinations thereof, more preferably a non-cellulose substrate.

15. A method of treating a cured composition with a halogenating agent to halogenate HALS present in the cured composition, wherein the cured composition comprises a cured product of a curable composition comprising HALS and a (meth)acrylate functionalized compound.

16. A curable composition comprising a (meth)acrylate functionalized compound and HALS, wherein the total amount of HALS in the composition is at least 3% by weight, preferably at least 6% by weight, based on the weight of the composition.

17. A cured composition comprising N-halo-hindered amine, obtained by (a) curing the curable composition defined in claim 16; and (b) then converting HALS to N-halo-hindered amine by treating HALS with a halogenating agent.

18. Use of at least one HALS, at least one (meth)acrylate functionalized compound and at least one halogenating agent for obtaining an antibacterial coating on the surface of a substrate.

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