A COATING COMPOSITION COMPRISING INTEGRATED FUNCTIONALITY

Abstract

A coating composition for applying a very thin film coating to a substrate such as a polymeric film comprises a copolymer such as a block copolymer (BCP) that is compatible with the substrate, an alcohol solvent or solvents capable of dissolving the copolymer, a hydrolysed metal alkoxide precursor, a carboxylic acid stabiliser, and an active agent in an ionic, molecular, or small nanoparticle form. The active agent is configured to provide a functionality to the coating composition, selected from antimicrobial, antifungal, barrier, therapeutic, electrical, electronic, magnetic and optical. The composition is a sol comprising a continuous non-sedimentable/stable suspension of very small sized (of nano order) amorphous inorganic polymers in their oligomeric or polymeric state, and comprising the active agent dispersed in a hydrolysed metal alkoxide-BCP matrix. Substrates coated with very thin coatings are also provided, including coated LDPE which is activated before coating by UV/ozone, plasma or corona treatment prior to deposition of a wetting layer.

Claims

1.-43. (canceled)

44. A method of forming a coated substrate comprising the steps of: dissolving a block copolymer (BCP) in a solvent to provide a BCP solution; mixing the BCP solution with a hydrolysed metal alkoxide and an active agent to provide a coating composition as a colloidal dispersion comprising the active agent dispersed in a hydrolysed metal alkoxide-BCP matrix; depositing the coating composition onto a surface of a substrate; and curing the coating on the substrate, wherein: the substrate is a polymer packaging material provided as a sheet or film; the coating composition comprises less than 0.5% BCP by weight and 0.5 to 5% hydrolysed metal alkoxide by weight; the coating composition is deposited on the surface of the substrate at a thickness of less than 250 nm; and the BCP and solvent are compatible with the substrate.

45. The method according to claim 44 in which the method includes the steps of activating a surface of the substrate by UV/ozone, plasma or corona treatment, and depositing an alcohol-based wetting layer on to the activated surface, prior to deposition of the coating composition.

46. The method according to claim 44, in which the solvent is selected from ethyl acetate/IPA, ethyl acetate/tert-butanol, and ethyl acetate/ethanol.

47. The method according to claim 44, in which the BCP is selected from polystyrene-b-poly(X), where X is selected from ethylene oxide, 4-vinylpyridine, methyl methacrylate, acrylic acid and lactic acid.

48. The method according to claim 44, in which the polymer packaging material is a laminate material and optionally a paper-polymer laminate.

49. The method according to claim 44, in which the substrate is a plastic film for packaging of foods, medical devices, pharmaceuticals or horticulture products.

50. The method according to claim 44, in which the active agent is an antimicrobial agent.

51. A method according to claim 44, in which the active agent is configured to induce gas or water vapour barrier properties to the substrate.

52. A coated substrate comprising a substrate that is continuously and homogenously spray, dip or slot die assisted coated with a coating composition at a thickness of less than 250 nm and then cured, wherein the coating composition is a sol comprising: a block copolymer is compatible with the substrate; alcohol solvent capable of dissolving the block-copolymer and compatible with the substrate; a hydrolysed metal alkoxide precursor; a carboxylic acid stabiliser; and an active agent selected from an ion, molecule, compound or nanoparticle, wherein the substrate is a polymer packaging material provided as a sheet or film, and the composition is a polymeric sol comprising the active agent dispersed in a hydrolysed metal alkoxide-block-copolymer matrix, and wherein the coating composition comprises less than 0.5% block copolymer by weight.

53. A coated substrate according to claim 52, in which the substrate is a polymer packaging material provided as a sheet or film.

54. A coated substrate according to claim 52, in which the polymer packaging material provided as a sheet or film is a laminate material and optionally a paper-polymer laminate.

55. A coated substrate according to claim 52, in which the polymer packaging material provided as a sheet or a film is a polyolefin and the and the BCP is polyolefin-compatible.

56. A coated substrate according to claim 52, in which the polymer packaging material provided as a sheet or a film is selected from HDPE and LDPE.

57. A coated substrate according to claim 52, in which the active agent is an antimicrobial agent.

58. A coated substrate according to claim 52, in which the active agent is configured to induce gas or water vapour barrier properties to the substrate.

59. A coated substrate according to claim 52, in which the coating composition comprises 0.5 to 5% hydrolysed metal alkoxide by weight;

Description

DETAILED DESCRIPTION OF THE INVENTION

[0059] All publications, patents, patent applications and other references mentioned herein are hereby incorporated by reference in their entireties for all purposes as if each individual publication, patent or patent application were specifically and individually indicated to be incorporated by reference and the content thereof recited in full.

Definitions and General Preferences

[0060] Where used herein and unless specifically indicated otherwise, the following terms are intended to have the following meanings in addition to any broader (or narrower) meanings the terms might enjoy in the art:

[0061] Unless otherwise required by context, the use herein of the singular is to be read to include the plural and vice versa. The term “a” or “an” used in relation to an entity is to be read to refer to one or more of that entity. As such, the terms “a” (or “an”), “one or more,” and “at least one” are used interchangeably herein.

[0062] As used herein, the term “comprise,” or variations thereof such as “comprises” or “comprising,” are to be read to indicate the inclusion of any recited integer (e.g. a feature, element, material, characteristic, property, method/process step or limitation) or group of integers (e.g. features, elements, materials, characteristics, properties, method/process steps or limitations) but not the exclusion of any other integer or group of integers. Thus, as used herein the term “comprising” is inclusive or open-ended and does not exclude additional, unrecited integers or method/process steps.

[0063] The process presented here enables the deposition of one or a combination of the surface of substrates such as polymers, ceramics, silicon, metals, metal alloys and glass. The integratable functionalities can be in the form of ions, molecules, compounds or nanoparticles having applications such as antimicrobial, antifungal, barrier, therapeutic, electrical, electronic, magnetic and optical. This generic deposition process involves the formulation of a coating solution containing a selected copolymer, preferably a BCP, a selected metalorganic precursor, such as titanium alkoxide, zirconium alkoxide or silicon alkoxide, where the alkoxide can be tert-butoxide or lower chain length alkoxide such as isobutoxide, isopropoxide, ethoxide or methoxide, a stabilizer and a selected required functionality all homogeneously dispersed in a suitable solvent or solvent mixture. The solvent and stabilizer/homogenizer can be selected/changed based on the substrate (for chemical compatibility), on which the coating is to be made, and the functionality to be integrated. The solvent is selected from a list of alcohols and the stabilizer is selected from a list of carboxylic acids. In case of polymer coatings, especially polyolefins, due to their chemically inert nature, the polymer needs to be activated before the deposition process. All other substrates are merely cleaned for removal of dirt, grease and other environmental contaminants prior to the coating process. The film can be deposited by either a dip, spray or slot die assisted coating process. The film is generally deposited as a very thin film. The invention presented here enables a continuous/homogeneous deposition of active (antimicrobial, barrier, magnetic, optical, electrical and electronic) functionalities on the surface of plastic films that will have applications in packaging of foods, medical devices, pharmaceuticals and horticulture products, medical device coatings as well as in flexible electronics, UV blocking films and antireflective surfaces. The invention will enable, in general, the functionalisation of substrates such as polymer, ceramics, metals, metal alloys, silicon and glass which will present innumerable opportunities in various fields for researchers skilled in the art.

[0064] The coating composition of the present invention is provided as a colloidal dispersion (sol). The sol is a continuous non-sedimentable/stable suspension of small nanosized (i.e. less than 50 nm, preferably less than 10 nm) amorphous inorganic polymers in their oligomeric or polymeric state. The functional (active) materials added will also be incorporated as ionic species (Ag, Zn, Cu, Ga etc.) or as molecular components (chitosan, carvacrol, thymine etc.) or as very tiny solids (nanoparticles) of less than 5 nm as opposed to the case of prior arts. The very small size of the amorphous inorganic polymers present in the sol allows it to be stabilized by Brownian motion as opposed to the referenced prior art's dispersions which is stabilized by acid/base, surfactants and/or dispersing agents such as high molecular weight polyethylene oxide groups. This Brownian motion induced stability clearly demonstrates that the sol is not consisted of large particles as opposed to the discussed prior arts (EP 3138880 A1, WO 2015/166858 and WO/2006/049368) which use dispersions of electrostatically or sterically stabilized solid particles to make thick coatings.

[0065] As used herein the term “active agent” refers to a component such as an ion, compound, molecule, particle or nanoparticle. In one embodiment, the active agent is configured to provide a functionality to the coating composition, selected from antimicrobial, antifungal, moisture or gas barrier, therapeutic, electrical, electronic, magnetic and optical. Thus, the active agent may be an antimicrobial agent (i.e. a silver ion, or a nanoparticle), a metal, an electrically conducting material, a magnetic material, a therapeutic material or an optically active agent. Examples of antimicrobial agents include ions of silver, zinc, magnesium or gallium, or their nanoparticles, or any of the available natural antimicrobials (e. g. carvacrol, thymine etc.), or a polysaccharide such as chitosan. Similarly suitable electronic, magnetic, optical or therapeutic functionality can also be incorporated. Active agents having optical functionalities include rare earth metals (Neodymium, Yttrium, Scandium, Cerium, Terbium and Lanthanides, group IV elements such as carbon and silicon and metamaterials consisting of gold or any other suitable metal nanoparticles. Active agents with magnetic properties include metals such as iron, cobalt or nickel. Any element or their alternative form or phase that have electrical or electronic properties including graphite. Any other inorganic or organic elements or compounds with UV-absorption, reflective or antireflective properties such as MgZnO, MgF2, aluminium etc. that are compatible with the process and materials in question can be employed as active agents. Any organic or inorganic elements or compounds that have therapeutic or antiinfection functionalities such as silver, magnesium, zirconium, zinc, plant derived alkaloids, chitosan etc. In one embodiment, the coating composition comprises 0.001 to 5% of active agent, for example 0.1 to 3% (wt/vol). In one embodiment, the active agent (for example an active agent salt) is mixed with the metal alkoxide to provide an active agent-metal alkoxide complex, which is mixed with the BCP solution. The ratio of active agent to metal alkoxide may be 1:50 to 1:2 (wt/wt).

[0066] As used herein, the term “solvent” refers to a solvent that is capable of dissolving the copolymer, and in particular a block copolymer (BCP). Solvents useful for dissolving BCPs are known to the skilled person, and include alcohols such as isobutyl alcohol, tert-butyl alcohol, isopropyl alcohol, ethyl alcohol, ethyl acetate, methyl ethyl ketone etc. In one embodiment, the solvent is substrate-compatible (i.e. does not degrade the polymer surface). In one embodiment, the solvent or mixture of solvents used need to completely wet the substrate surface. In one embodiment, the solvent is an alcohol. In one embodiment, the solvent comprises a combination of alcohols. For example, when the substrate is a polyolefin, the solvent is typically selected from ethyl acetate/IPA, ethyl acetate/tert-butanol, and ethyl acetate/ethanol, in which the components of the solvent may be present in a ratio selected from 1/99 to 15/85 A ratio of up to 50% distilled or deionised water may also be used as one part in the solvent mixture depending on the substrate used. Thus, in one embodiment, the solvent is selected from ethyl acetate/IPA/distilled water, ethyl acetate/tert-butanol//distilled water, and ethyl acetate/ethanol/distilled water.

[0067] As used herein, the term “copolymer” refers to any macromolecule comprising two species of monomeric units in a polymerised form. The copolymer may be linear or branched, and may be an alternating, periodic, statistical, block, stereoblock, or gradient copolymer. Examples of copolymer include Polystyrene-polymethylmethacrylate, Polystyrene-polyisoprene, Polymethylmethacrylate-polymethyl disilane, Polyisoprene-polybutadiene, Polyethylene-polystyrene. In a preferred embodiment, the copolymer is a block copolymer (BCP).

[0068] As used herein, the terms “block-copolymer” or “BCP” refers to a linear copolymer consisting of a single chain and comprising two or more homopolymer subunits linked by covalent bonds. In one embodiment, the BCP comprises a first polymer and a second polymer. In one embodiment, the first polymer is selected from polystyrene, polybutadiene, polymethyl methacrylate, polyisoprene, polyethylene or any polyolefin. In one embodiment, the first polymer is PS. In one embodiment, the first polymer is PE. In one embodiment, the second polymer is selected from the group ethylene oxide, 4-vinylpyridine, methyl methacrylate, acrylic acid or lactic acid. In a preferred embodiment, the BCP is polystyrene-b-poly(X), where X is selected from ethylene oxide, 4-vinylpyridine, methyl methacrylate, acrylic acid and lactic acid. In another preferred embodiment, the BCP is PE-b-poly(X), where X is selected from ethylene oxide, 4-vinylpyridine, methyl methacrylate, acrylic acid and lactic acid. Other block copolymers suitable for the invention include any cationic, anionic or amphiphilic block-copolymer system and suitable examples are polystyrene-b-polylactide, polystyrene-b-polybutylene oxide, polymethyl methacrylate-b-polyacrylic acid, polybutadiene-b-polyethylene oxide. In one embodiment, the coating composition comprises 0.01 to 3% BCP, for example 0.1 to 3%, 0.1 to 2%, 0.1 to 1%, 1 to 2%, 2 to 3%, 1 to 3% (wt/v). In a preferred embodiment, the BCP employed is compatible with the substrate.

[0069] As used herein, the term “hydrolysed metal alkoxide precursor” or “hydrolysed metal alkoxide” refers to a hydrolysis product of a metal alkoxide such as tert-butoxide, isobutoxide, isopropoxide or ethoxide. These hydrolysis products may have terminal groups such as R—O—O—H, R—OH etc., where R is the oligomer of the inorganic functionality. In presence of the carboxylic acid stabilizer, the metal alkoxide may form extensive linked structures (oligomers) upon hydrolysis both by covalent bonding and chelation by the stabilizer. In one embodiment, the metal alkoxide precursor is selected from a titanium alkoxide, zirconium alkoxide or silicon alkoxide precursor. In one embodiment, the coating composition comprises 0.1 to 10% hydrolysed metal alkoxide precursor, for example 0.1 to 3%, 0.5 to 5%, 1 to 10%, 5 to 10% (wt/vol).

[0070] As used herein, the term “carboxylic acid stabiliser” refers to one of the long chain or short chain carboxylic acids containing the R—COOH group, where R refers to the rest of the molecule. Examples of carboxylic acids that can be used are acetic acid, propionic acid, oxalic acid, lauric acid, or any of the amino acids. In one embodiment, the coating composition comprises 0.5 to 10% carboxylic acid stabiliser, for example 0.5 to 5%, 1 to 10%, 5 to 10% (wt/vol).

[0071] As used herein, the term “substrate” typically refers to a polymer, ceramic, metal, metal alloy, silicon or glass substrate, or a combination thereof. The substrate may be rigid, semi-rigid, or a flexible. In one embodiment, the substrate is planar, for example a film or sheet. In one embodiment, the substrate is a polymer. In one embodiment, the polymer is a polyolefin, for example a thermoplastic polyolefin. In one embodiment, the substrate is polyolefin film for example a polyethylene film. In one embodiment, the substrate is a laminate comprising a polymer layer, for example a paper-polymer laminate film. The polymer may be a polyolefin such as a thermoplastic polyolefin, for example PE, polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), or a polyolefin elastomers (POE), for example polyisobutylene (PIB), ethylene propylene rubber (EPR), ethylene propylene diene monomer (M-class) rubber (EPDM rubber). In one embodiment, the substrate is polyethylene, such as HDPE or LDPE.

[0072] As used herein, the term “activated” as applied to the surface of the substrate refers to a treatment of the surface to make it reactive, so that it can react with the coating composition. This is used when the substrate is a non-reactive substrate, such as a polyolefin. In one embodiment, the surface of the polyolefin is activated by UV/ozone, plasma or corona treatment. In one embodiment, an alcohol-based wetting layer is deposited on to the activated polyolefin surface, prior to deposition of the coating composition. When the substrate is a polyolefin, a polyolefin compatible solvent must be used to dissolve the BCP. In one embodiment, the solvent is selected from ethyl acetate/IPA, ethyl acetate/tert-butanol, or ethyl acetate/ethanol or a single solvent from this list. When the substrate is another polymer, for example a plastic, a single solvent may be employed.

[0073] As used herein, the term “cured” (or “annealed”) as applied to the coated substrate refers to a heating process in which the coated substrate is heated to a certain temperature (for example 50-100° C.) for a period of time (generally less than 10 minutes) and then cooled at room temperature. The purpose of the curing process is to remove the solvents from the coated substrate.

[0074] As used herein, the term “very thin film” or “very thin coating” means a film or coating having a thickness of less than 250 nm, and preferably less than 200 nm or 150 nm.

Exemplification

[0075] The invention will now be described with reference to specific Examples. These are merely exemplary and for illustrative purposes only: they are not intended to be limiting in any way to the scope of the monopoly claimed or to the invention described. These examples constitute the best mode currently contemplated for practicing the invention.

Example 1

[0076] In one experiment, a 0.5% (wt/vol) PS-b-PEO BCP is dissolved in a 1:10 (vol ratio) ethyl acetate: IPA solvent mixture and kept stirring at a slightly elevated temperature (30-60° C.). A complex containing a hydrolysed titanium isopropoxide-silver nitrate is prepared separately by combining 2.5 g TTIP (titanium tetraisopropoxide), 2.7 g acetic acid, 1.6 g distilled water and 0.2 g silver nitrate. In the final step the BCP solution and titania-silver complex solution is combined and the sol is then topped up to the required dilution with an IPA-distilled water mix, in this experiment, to make a solution with solid content of 1-10%, as required, for example 3.2%. This sol is then stirred for a minimum of 5 hrs to homogenize.

[0077] LDPE films were treated under UV/ozone, plasma or corona for 2 seconds to 3 mins and subsequently wetted with the alcohol, for example IPA, to form an interlayer and the coating composition was then deposited by a simple dip/spray/slot die coating procedure. The coated substrates were then cured at 40-100° C. for a short time period (<10 min) to remove the solvents.

[0078] The films were then characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM) etc. for visualizing film formation and successful samples were then analyzed for their antimicrobial activity against gram negative and gram positive bacteria or for their other relevant properties.

Example 2

[0079] In one experiment, a 0.3% (wt/vol) PE-b-PEO BCP is dissolved in a 1:10 (vol ratio) ethyl acetate: ethanol solvent mixture and kept stirring at a slightly elevated temperature (30-60° C.). A complex containing a hydrolysed titanium isopropoxide-silver nitrate is prepared separately by combining 2 g TTIP (titanium tetraisopropoxide), 0.8 g acetic acid, 1.3 g distilled water and 0.7 g silver nitrate. In the final step the BCP solution and titania-silver complex solution is combined and the sol is then topped up to the required dilution with an ethanol-distilled water mix, in this experiment, to make a solution with solid content of 1-10%, as required. This sol is then stirred for a minimum of 5 hrs to homogenize. LDPE films were treated under UV/ozone, plasma or corona discharge for 2 seconds to 3 mins and subsequently wetted with the alcohol, for example IPA, to form an interlayer and the coating composition was then deposited by a simple dip/spray/slot die coating procedure. The coated substrates were then cured at 40-100° C. for a short time period (<10 min) to remove the solvents.

[0080] The films were then characterized for their relevant properties.

Example 3

[0081] In one experiment, a 0.7% (wt/vol) PE-b-PEO BCP is dissolved in a 1:10 (vol ratio) ethyl acetate/tert-butanol solvent mixture and kept stirring at a slightly elevated temperature (30-60° C.). A complex containing a hydrolysed titanium isopropoxide-silver nitrate is prepared separately by combining 2.5 g TTIP (titanium tetraisopropoxide), 1.6 g acetic acid, 1.6 g distilled water and 1.4 g silver nitrate. In the final step the BCP solution and titania-silver complex solution is combined and the sol is then topped up to the required dilution with an ethanol-distilled water mix, in this experiment, to make a solution with solid content of 1-10%, as required. This sol is then stirred for a minimum of 5 hrs to homogenize.

[0082] LDPE films were treated under UV/ozone, plasma or corona discharge for 2 seconds to 3 mins and subsequently wetted with the alcohol, for example IPA, to form an interlayer and the coating composition was then deposited by a simple dip/spray/slot die coating procedure. The coated substrates were then annealed at 40-100° C. for a short time period (<10 min) to remove the solvents.

[0083] The films were then characterized for their relevant properties.

Equivalents

[0084] The foregoing description details presently preferred embodiments of the present invention. Numerous modifications and variations in practice thereof are expected to occur to those skilled in the art upon consideration of these descriptions. Those modifications and variations are intended to be encompassed within the claims appended hereto.