Antibacterial packaging materials

Abstract

An antimicrobial package comprising a substrate and a coating, the coating comprising a first polymer component selected from the group consisting of polyacrylic resins, polyvinyl butyral polyurethanes, polyesters, polyvinyl alcohols, cellulosic polymers and mixtures thereof; - low adhesion, slip or release agents selected from the group consisting of polysiloxanes, carnauba wax, lecithin, fatty acids, fatty acid amides, fatty acid esters, magnesium stearate, vegetable oils, and mixtures thereof; -Antibacterial and Optionally, - Defoamer -Fusion aid -Wetting agent -Crosslinking agent - and mixtures thereof and wherein the coating comprises one or more functional agents selected from the group consisting of: - 50 to 99.49 wt. % of said first polymer component; - 0.5 to 35% by weight of said low adhesion, slip or release agent, and 0.01 to 15% by weight of an antibacterial agent, -0-10% by weight of functional agent - Weight percentages are based on 100 parts by weight of dry coating.

Description

[Technical field]

[0001] The present invention relates to packaging materials having antimicrobial, especially antiviral, properties.

[0002] In particular, the present invention relates to packaging materials for use in packaging food products. [Background technology]

[0003] Packaging acts as a barrier since it is designed to contain and protect its contents from the external environment. In addition, it plays an important role as a communication aspect to the customer. Therefore, packaging needs to be considered as both a barrier and a communication aspect, and both aspects are relevant from a safety perspective.

[0004] When surfaces are exposed to the environment outside of a controlled manufacturing process, debris accumulates that may contain disease-causing microorganisms. This can include droplets containing microorganisms, more specifically viruses, that fall onto packaging surfaces and remain for some time. Surface disinfection practices can prevent the risk of disease transmission through microbial inactivation, but this is not always possible outside the production facility or in the supply chain to markets and homes. For this reason, active surfaces that can combat microbial contamination are attractive to customers and add value.

[0005] Because packaging surfaces are exposed to the environment throughout the distribution chain and are difficult to sanitize once they leave the production facility, antimicrobially active packaging surfaces are desirable to reduce the risk of person-to-surface and surface-to-person disease transmission, thereby protecting the supply chain and end customers. Sustained and robust antimicrobial activity of packaging surfaces throughout the life of the package is essential to ensure protection along the supply chain, through warehouses and store shelves, and into the customer's home.

[0006] Furthermore, to maintain the antimicrobial effect and activity against diseases that may be transmitted by contact with the packaging surface, it is desirable to eliminate or minimize the migration of antimicrobial agents to the external environment, and therefore specific formulations must be implemented to ensure that the packaging remains active from the date of manufacture until the expiration date. Summary of the Invention

[0007] It is an object of the present invention to provide packaging and / or packaging materials with improved antimicrobial properties suitable for reducing the risk of disease transmission through contact with the packaging surface.

[0008] In particular, the object of the present invention is to provide a packaging that is non-sticky, low-adhesive or slippery, which prevents or reduces the adhesion of microorganisms and viruses to the packaging surface, even if debris, droplets or any carrier adheres to said surface, and at the same time inhibits microbial infection by inactivating the remaining attached microorganisms (antibacterial properties). The present invention also applies to packaging that is intended to be distributed through the cold chain, since storage under refrigerated conditions can prolong the activity of pathogenic bacteria in some cases.

[0009] An object of the present invention is therefore a package as defined in the appended claims, which are considered to be included in this disclosure.

[0010] The subject of the present invention is a packaging comprising a substrate and a coating, as defined in the appended claims, having antibacterial, antiviral properties and also the ability to cause droplets and debris to slide off or resist adhesion, said coating being antibacterial and low-stick, the low-stick, slip or release properties of the coating acting to reduce the accumulation of contamination on the packaging surface, and the antibacterial behavior acting to inactivate microorganisms present in residual contamination.

[0011] As used herein, the term "packaging(s)" applies to packaging sheets or films having a flexible substrate, as well as to packages having a rigid or self-supporting substrate, such as containers.

[0012] The present invention provides a wide field of active coating surfaces that can be applied to any kind of packaging, such as packaging obtained by extrusion and injection molding, such as protective trays, boxes, and anything with a semi-rigid or rigid consistency and appearance. Moreover, the present invention can provide heat sealability to packaging film surfaces and also to materials after thermoforming, as a result of further discovered specific properties of the formulated coating. This opens the possibility of producing composite packaging and boxes with a flexible element sealed in a rigid part, providing a wider field of active surfaces for sales offers and customers.

[0013] In some embodiments of the invention relating to heat-sealable coatings, sealing via the coating can occur at temperatures between 70 and 150° C. for times between 25 milliseconds and 20 seconds, depending on the substrate, and preferably around 100° C. for 0.5 seconds. The coating, when applicable, can reduce the sealing temperature of the plastic substrate, allowing sealing at lower temperatures or allowing a reduction in the time required for complete sealing.

[0014] The coating is a first polymer component selected from the group consisting of polyacrylic resins, polyvinyl butyrals, polyurethanes, polyvinyl alcohols (fully hydrolyzed (DH>98) or partially hydrolyzed), cellulosic polymers, polyesters, preferably selected from the group consisting of polyhydroxyalkanoates, polybutylene succinates and polylactic acids and mixtures thereof; - a low adhesion, slip or release agent selected from the group consisting of polysiloxanes, polyethylene glycols, polyethylene, carnauba wax, lecithin, polyamides, fatty acid amides, fatty acids, fatty acid esters, magnesium stearate, vegetable oils, paraffin waxes and mixtures thereof; and -Antibacterial agents Includes.

[0015] The formulation may further optionally include one or more of the following functional agents: - Defoamer -Fusion aid -Wetting agent -Crosslinking agent - and mixtures thereof

[0016] In the coating composition, the first polymeric component is generally the majority component by weight and, alone or in combination with a low adhesion, slip or release agent, forms a continuous phase or matrix within which the antimicrobial agent is dispersed or dissolved.

[0017] The polyacrylic acid resins for use as the first polymer component include polyacrylic acid, polyacrylates and polymethacrylates.

[0018] Polyester resins for use as the first polymer component include polyethylene terephthalate, polyhydroxyalkanoate, polycaprolactone, polybutylene succinate, polylactic acid, or mixtures thereof.

[0019] Preferred polyhydroxyalkanoates include lactic acid polyesters, polyhydroxybutyrate, polyhydroxybutyrate-valerate, polyhydroxybutyrate-propanoate, polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxybutyrate-hexadecanoate, polyhydroxybutyrate-octadecanoate, poly-3-hydroxybutyrate-4-hydroxybutyrate, poly-3-hydroxybutyrate-co-3-hydroxyhexanoate, or mixtures thereof.

[0020] Cellulosic polymers include cellulose, nitrocellulose, chitosan, cellulose acetate, carboxymethylcellulose, methoxycellulose, hydroxymethylcellulose, cellulose acetate butyrate, cellulose acetate propionate, cellulose-2-hydroxyethyl methyl ether, cellulose-hexadecyl 2-hydroxyethyl ether, cellulose acetate butanoate, or mixtures thereof.

[0021] The first polymer component is hydrophobic or hydrophilic, whereas the low adhesion, slip or release agent is generally a hydrophobic or superhydrophobic material or substance, or an amphiphilic-like material or substance.

[0022] The terms "hydrophobic" and "superhydrophobic" as used herein refer to water repellency and have their usual meaning in the chemical and polymer arts. In particular, when used herein with respect to a material, the term "hydrophobic" means that the material has a contact angle with water of at least 90 degrees. The term "superhydrophobic" means that the material has a contact angle of 150 degrees or greater.

[0023] The term amphiphilic, as used herein, means a material having both hydrophobic and hydrophilic parts and has its usual meaning in the chemical and polymer arts.

[0024] Preferred polysiloxanes include dimethylpolysiloxane, silicone vinyl polymers, silicone emulsions and silicone oils and alkylated siloxane polymers (or silicone waxes) and mixtures thereof. Particularly preferred are dimethylpolysiloxane and silicone waxes and mixtures thereof.

[0025] Preferred vegetable oils include soybean oil, castor oil, rapeseed oil, palm oil, sunflower oil, and coconut oil and mixtures thereof.

[0026] Antimicrobial agents suitable for use according to the invention include metals (e.g. titanium, silver, gold, copper, platinum, zinc, etc.), alloys, oxides or salts of said metals, glasses or clays containing said metal oxides or salts. The metals may be in the form of nanoparticles or may be supported on nano-, micro- or macro-silica or silicone-based or clay-based carriers. Antimicrobial agents also include antimicrobial peptides, silicone-based antimicrobial agents and quaternary ammonia cations (Qua Ts).

[0027] Additionally, the antimicrobial agent may take the form of a germicide, optionally encapsulated within a heat, moisture or temperature sensitive polymer, which may include peroxide, propylene glycol, triethylene glycol, dodecanoic acid, formaldehyde, glutaraldehyde, thymol, clove oil, cinnamon oil, grapefruit extract, eucalyptus extract, antimicrobial plant extracts, chlorine or iodine in a solvent such as water, ethanol, isopropanol, or mixtures thereof.

[0028] Preferred antimicrobial agents include silver ion materials such as silver chloride, titanates, silver phosphate, zinc oxide, silicone tethered quaternary amines, thymol, clove oil, cinnamon oil, grapefruit seed extract, eucalyptus extract, or mixtures of the foregoing.

[0029] In all embodiments, silver ions are the preferred antimicrobial agent.

[0030] The coating is formulated as a solution, dispersion, suspension, or melt containing the first polymer component, the low adhesion component, the antimicrobial agent, and, where appropriate, a solvent. Suitable solvents include water, ethyl acetate, ethanol, isopropanol, methanol, hexadecane, dodecane, and mixtures thereof.

[0031] The coating solution, dispersion or slurry may have a dry content of 0.5-70% by weight, with a dry content of 10-25% by weight being preferred, more preferably about 15% by weight.

[0032] The loading of the antimicrobial component in the coating solution or dispersion may be from 0.001% to 60% by weight, preferably from 0.01 to 15% by weight of the dry content of the final formulation.

[0033] After the coating and drying process, the solvent retention of the residual coating should preferably be less than 15 g / m2, regardless of the solvent and substrate combination used.

[0034] Suitable coating methods for the present invention include rotogravure printing, flexographic printing, offset printing, digital printing, and extrusion coating. The first polymer component, antimicrobial agent, low adhesion, slip or release component may also be extruded and / or injected in combination.

[0035] For rotogravure printing, the cylinder should be engraved to achieve the following ranges of coat weight (dry basis weight): 0.1-20 grams per square meter.

[0036] Rotogravure cylinders can be engraved with all kinds of techniques, such as helioengraving, electroengraving, laser etc.

[0037] In the case of flexographic printing, anilox engraving is utilized to allow for a continuous engagement technique to prevent discontinuities during flexographic printing.

[0038] The coating that provides the antimicrobial properties can be applied in one pass or in several passes.

[0039] The coatings of the present invention may be applied directly to the surface of the packaging substrate or over or in combination with inks, moisture or oxidation resistant barrier coatings, sealing lacquers, release lacquers, low adhesion or food contact lacquers, allowing a combination of properties and various packaging stratifications.

[0040] In a preferred embodiment, the packaging includes one or more adhesion-promoting layers disposed between the substrate and the antimicrobial coating. The adhesion-promoting layers prepare the surface to receive the coating, resulting in improved functionality. These adhesion-promoting layers act by improving the adhesion of the coating to the substrate, retaining the coating on the surface and preventing it from being removed by delamination, abrasion, or absorption into the substrate. The effect of retaining the coating on the surface is that the coating properties are maintained for a longer time along the packaging supply chain, leading to improved functionality. Furthermore, less coating is required to achieve the same performance, since more coating is available on the surface of the packaging.

[0041] The adhesion-promoting layer may be a printing layer printed with a printing ink, a clay coating, a barrier coating, a primer layer or coating.

[0042] Inks and primers can modify the surface energy of a substrate, improving coating adhesion. Clays and other barrier coatings can also modify the surface energy of a substrate, further reducing the porosity of the substrate, improving the availability of the coating on the surface of the packaging without increasing the application volume.

[0043] During the printing process, one layer is often not completely dry and / or cured before the next layer is laid down; that is, once the structure is fully assembled, further drying / curing occurs along with various chemical and physical interactions between the layers of this structure. This curing can be considered a temporary state, being completed within 24-72 hours depending on the primer, ink and varnish used. This curing and the above mentioned interactions have been found to further increase the activity of the coating layers once the system is assembled, in addition to the improved adhesion mentioned above.

[0044] Suitable primers include acrylic varnishes, preferably with the addition of isocyanates, optionally in combination with a layer printed with printing ink.

[0045] In the coating composition, the weight amounts of the first polymer component, the low adhesion, slip or release agent and the antimicrobial agent are preferably such that after curing and / or drying, the hydrophobic surface is obtained. If the first polymer component itself is not hydrophobic, the low adhesion, slip or release agent must be present at a sufficiently high concentration at the surface of the coating to provide a hydrophobic surface. Typically, this is achieved by the low adhesion, slip or release agent migrating to the surface of the coating during drying or curing, thus increasing the concentration of this material compared to the coating bulk, resulting in a hydrophobic surface. Thus, a minor amount of the low adhesion, slip or release agent is sufficient to provide a hydrophobic surface.

[0046] In general, the coating upon drying, curing and conversion process - 50 to 99.49% by weight of the first polymer component, preferably 70 to 99.49% by weight 0.5 to 35% by weight of a low adhesion, slip or release component, preferably 1% to 10%; and - 0.01 to 15% by weight of an antibacterial agent, preferably 0.01 to 10% by weight, more preferably 0.01 to 2% by weight These weight percentages are based on 100 parts by weight of dry coating and the percentages add up to 100%.

[0047] Suitable substrate materials include paper, cardboard, glass, metal and in particular plastic materials such as polypropylene (PP), polyethylene (PE), polyethylene-polypropylene copolymers, polystyrene (PS), polyethylene terephthalate (PET), bioplastics such as polyhydroxyalkanoates (PHA), polybutylene succinate (PBS) or polylactic acid (PLA).

[0048] In one embodiment, the substrate includes a film or sheet made of or including the above materials, the film or sheet having a metal coating. Packaging substrates also include multi-layer laminates of the above films and sheets, as well as laminates including polymer layers laminated or coated on paper. The film or sheet may or may not be compostable and / or biodegradable in multiple environments.

[0049] Substrates in the form of a film or sheet may have a heat-sealable coating. In the case of flexible substrates having a heat-sealable coating, the coated substrate may be sealed to another surface such as a tray or box, or may be folded, for example, into a tube, to obtain a package having an antimicrobial coating on its exterior or interior. The substrate, in the form of a film or sheet, may be thermoformable and an antimicrobial coating may be applied to the substrate prior to thermoforming to obtain the formed packaging structure.

[0050] As previously mentioned, the term "packaging" as used herein also includes packaging in which the substrate is a shaped structure such as a rigid or semi-rigid container, box or carton of glass, metal, plastic, paper or cardboard. Such materials may be formed by injection molding, thermoforming, folding, or other suitable forming techniques.

[0051] For thermoformed and folded rigid or semi-rigid substrates, the coating can be printed or sprayed onto the substrate while flat. The antimicrobial activity of the coating is then maintained during or activated by the folding or thermoforming process, thus imparting antimicrobial activity to the rigid or semi-rigid structure. Substrates suitable for this process include paper and cardboard, polypropylene, polyethylene, polyethylene-polypropylene copolymers, ABS, polyethylene terephthalate, polystyrene, polylactic acid, polybutyl succinate, polyhydroxyalkanoates.

[0052] As described below, the coating composition comprising the first polymer component, the antimicrobial agent, and the low adhesion, slip or release component can also be extruded, coextruded, and injected to provide rigid or semi-rigid antimicrobial packaging that maintains its antimicrobial properties after heat treatment.

[0053] Suitable polymers for injection molding in combination with the coating composition comprising the first polymer component, the antimicrobial component and the low adhesion, slip or release agent include polypropylene, polyethylene, polyethylene-polypropylene copolymer, ABS, polyethylene terephthalate, polystyrene, polylactic acid, polybutyl succinate, polyhydroxyalkanoate.

[0054] According to one embodiment of the invention, the packaging comprises: The substrate is an injection molded or extruded packaging structure obtained by injection molding or extrusion molding a polymer blend comprising a polymer selected from the group consisting of polypropylene, polyethylene, polyethylene-polypropylene copolymer, ABS, polystyrene, polyethylene terephthalate and bioplastics, preferably polyhydroxyalkanoates, polybutylene succinate or polylactic acid, and mixtures thereof, and an antimicrobial agent and a low adhesion, slip or release agent as defined above, and optionally the components of a coating composition comprising said first polymer component as defined above.

[0055] The components of the coating composition, including the antimicrobial agent, low adhesion, slip or release agent, and optionally said first polymer component, can be mixed and extruded or injected directly with a suitable polymer for injection molding as mentioned in the previous paragraph, or they can be mixed with a carrier resin to form a masterbatch which is later injected or extruded with said suitable polymer.

[0056] In a preferred embodiment, the masterbatch should be added at 0.1-10% by weight into the injection molded polymer, and includes: - 45 to 97% by weight of carrier polymer (injection molding resin); preferably 80 to 97% 1 to 30% by weight of a first polymer component 1 to 5% by weight of a low adhesion, slip or release agent, preferably 1 to 3%; and - 1-20% by weight of antibacterial agent, preferably 1-10%

[0057] The compound further comprises -Nucleating agent and -Surfactants and stabilizers may include.

[0058] When the materials are mixed together without the use of a masterbatch, the following is one preferred embodiment: - 73% to 99.399% by weight of injection molded polymer; - 0.5% by weight to 20% by weight of said first polymer component, - 0.1% to 2% by weight of a low adhesion, slip or release agent, preferably less than 1.5% by weight; and - 0.001% to 5% by weight of an antibacterial agent, preferably 0.1% to 1%.

[0059] Depending on the choice of substrate, as previously discussed, the coating can be applied directly to an untreated packaging surface or to a surface that has been previously treated, for example, with corona treatment, primer, ink, etc. After application of the coating, curing must occur to remove solvent from the coating, if present, and to allow physical or chemical crosslinking. Long periods of time and elevated temperature curing may be required to stabilize the behavior of the coating.

[0060] In accordance with the present invention, the use of a coating containing the low-stick, slip or release components described above results in a packaging surface that is less susceptible to adhesion of water droplets and other debris, which in turn reduces microbial build-up and residence time. This works in conjunction with the antimicrobial properties of the coating, leading to improved antimicrobial properties and reduced antimicrobial loading. The combined benefits of antimicrobial and release or slip properties allow for easier unwinding of coated reels. [Brief description of the drawings]

[0061] [Figure 1] The accompanying drawings show, by way of example, a preferred layer structure of the packaging of the present invention. [Diagram 2] The accompanying drawings show, by way of example, a preferred layer structure of the packaging of the present invention. [Diagram 3] The accompanying drawings show, by way of example, a preferred layer structure of the packaging of the present invention. [Figure 4] The accompanying drawings show, by way of example, a preferred layer structure of the packaging of the present invention. [Diagram 5] The accompanying drawings show, by way of example, a preferred layer structure of the packaging of the present invention. [Figure 6] The accompanying drawings show, by way of example, a preferred layer structure of the packaging of the present invention.

[0062] The active coating layer 2 is applied onto a substrate 4 as the outermost layer of the packaging structure, optionally with an ink or print layer 6, or a barrier coating layer 8 therebetween. A sealant or lacquer layer 10 suitable for providing heat sealability may be applied to the other side of the packaging opposite the active coating layer. However, in some embodiments, the active coating layer may be heat sealable. A metallized layer 12 may be applied to the outer surface of the packaging opposite the active coating layer. The packaging may include one or more substrate layers 4A and 4B. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0063] The disclosure of coating layer components provided above is to be construed as a disclosure of the specific combination of each of the recited polymeric components with each of the recited slip or release agents and / or each of the recited antimicrobial agents.

[0064] In a preferred embodiment, which provides a coating layer suitable for rotogravure printing and then heat sealing the coated surface, the polymer component is preferably an acrylic, polyurethane or cellulosic polymer.

[0065] In this embodiment, the preferred low adhesion, slip or release agent is selected from the group consisting of polysiloxanes such as silicone vinyl polymers, silicone emulsions, dimethylpolysiloxanes, silicone oils and alkylated silicone polymers (or silicone waxes), polyethylene glycols, polyethylene, carnauba wax, lecithin, polyamides, fatty acids, fatty acid esters, magnesium stearate, vegetable oils such as soybean oil, rapeseed oil, palm oil, sunflower oil, coconut oil and castor oil, paraffin waxes, and mixtures thereof.

[0066] Any of the antimicrobial agents mentioned hereinabove may be combined with each of the polymeric components and / or the slip or release agents, however, the antimicrobial agent is preferably selected from silver chloride, titanate, silver phosphate, silicone tethered quaternary amines, zinc oxide, antimicrobial plant extracts or mixtures thereof. In these embodiments, the coating composition is preferably formulated in an aqueous solvent.

[0067] The weight ranges of the components of the coating compositions disclosed above also apply to the components of the preferred embodiments which follow.

[0068] A preferred embodiment is also the following packaging with a coating: A) The first polymer component is an acrylic polymer or polyvinyl butyral, and the slip or release agent is selected from the following: paraffin wax, silicone-containing polymer, carnauba wax, or vegetable-derived oil. The antimicrobial agent is silver ion, preferably formulated in an aqueous solvent. B) The first polymer component is an acrylic or polyurethane polymer, the slip or release agent is selected from paraffin wax, silicone-containing polymers, carnauba wax or vegetable oil, the antimicrobial agent is a silver phosphate glass, and the coating is preferably formulated in an aqueous solvent. C) The first polymer component is an acrylic or polyurethane polymer, the slip or release agent is selected from paraffin wax or a silicone containing polymer, and the antimicrobial agent is a silver phosphate ceramic, preferably formulated in an aqueous solvent. D) The first polymer component is a cellulosic polymer, the slip or release agent is selected from paraffin wax or a silicone containing polymer, coconut oil, carnauba wax or a vegetable oil, preferably coconut oil, and the antimicrobial agent is a silver phosphate ceramic, preferably formulated in an aqueous solvent. E) The first polymer component is a cellulosic polymer, the slip or release agent is selected from paraffin wax or a silicone-containing polymer, carnauba wax, a vegetable oil, preferably coconut oil, and the antimicrobial agent is thymol, cinnamon oil, clove oil or mixtures thereof, preferably formulated in an aqueous solvent.

[0069] Further preferred embodiments in which the coating layer is suitable for printing by rotogravure but not for heat sealing due to the presence of chemical crosslinks are packagings in which the first polymer component of the coating is a polyester, polyvinyl butyral, polyurethane or cellulosic polymer, in particular packagings in which the coating is: F) the first polymer component is a polyester, polyvinyl butyral, polyurethane, or a cellulosic polymer; the slip or release agent is selected from paraffin wax, silicone-containing polymers, carnauba wax, polyamides and mixtures thereof; The antimicrobial agent is selected from silver chloride, titanate, silver phosphate, silicone tethered quaternary amines or mixtures thereof, and the coating composition preferably includes a crosslinker based on an isocyanate or aldehyde derivative. These coatings are preferably formulated with ethyl acetate as the solvent. G) the first polymer component is a polyester, polyvinyl butyral, polyurethane, or a cellulosic polymer; the slip or release agent is selected from paraffin wax, carnauba wax, coconut oil, polyamides and mixtures thereof; The antimicrobial agent is a silicone tethered quaternary amine or a mixture of silver chloride, titanate, silver phosphate, silicone tethered quaternary amine, and an antimicrobial plant extract, and the coating composition preferably includes a crosslinker based on an isocyanate or aldehyde derivative. These coatings are preferably formulated with ethyl acetate as the solvent. EXAMPLES

[0070] In the following examples, percentages are by weight unless otherwise specified.

[0071] [Example 1] A coating was prepared containing: Nitrocellulose-based polymer (85% on dry matter basis) Silicone-containing polymer (7% based on dry matter) Silver ions (1% on a dry matter basis) Functional agents (7% based on dry matter) Ethyl acetate (85% based on the total of the above dry ingredients) is used. The coatings were applied by rotogravure printing to polypropylene or polyethylene-based films. Coating weights ranged from 0.5 to 3 g / m2 at a line speed of 250 m / min, followed by a 24-hour cure at ambient temperature. Tested according to ISO 21702:2019 against influenza A virus and NL63 human coronavirus with a 24-hour contact time, the coatings showed virucidal activity with an R value of >1.

[0072] [Example 2] A coating was prepared comprising: Polyester (91% on a dry matter basis) Polydimethylsiloxane 7%, Silicone-tethered quaternary amine 0.02%-2% (dry content) Uses isocyanate-based crosslinking agents Ethyl acetate (40% based on the total of the above dry components) was used as the solvent. The coatings were applied by rotogravure printing technique to polypropylene or polyethylene based films. Coating weights ranged from 0.5 to 2.5 g / m2 and line speeds were 200 m / min. After isocyanate crosslinking, the coatings were cured for 72 h at ambient temperature. Tested against NL63 human coronavirus with a 24-h contact time according to ISO21702:2019, the coatings showed virucidal activity with an R value of >1.

[0073] [Example 3] A coating was prepared comprising: Polyurethane (92% on a dry matter basis) Carnauba wax 7% Silver ion 1% Use an aqueous solvent (85% based on the total of the above dry ingredients). The coating was applied by rotogravure printing to polypropylene film at coating weights of 1–3 g / m2 and showed virucidal activity with an R value of >2 when tested against feline calicivirus according to ISO 21702:2019 with a contact time of 24 h.

[0074] [Example 4] A coating was prepared comprising: Acrylic polymer (90-92.9% on a dry matter basis) Vegetable oil (7% on a dry matter basis) Silver ions (0.1-3% on a dry matter basis) Use an aqueous solvent (85% based on the total of the above dry ingredients). The coating was applied to polypropylene film using a gravure printing technique at a coating weight of 1-2 g / m2. It was tested against E. coli and S. aureus according to ISO 22196 with a contact time of 24 hours and showed a reduction of more than 3 logs.

[0075] [Example 5] A coating was prepared comprising: Chitosan (90-92.9% based on dry matter) Coconut oil (7% on a dry matter basis) Mixture of clove, cinnamon and thymol oil (0.1-3% on a dry matter basis) Use an aqueous solvent (85% based on the total of the above dry ingredients). The coating was applied by hand to polypropylene film at coating weights of 1-4 g / m2 and retarded mold growth.

[0076] [Example 6] Paper base material (weight 60g / m 2 ) was applied with a clay coating, which was then printed in 1-9 colors by continuous rotogravure printing, after which the following antimicrobial coating was applied over the printed layer: Acrylic polymer (90% on a dry matter basis) Polysiloxane (4% on dry matter basis) Silver ions on an inorganic carrier (1.4% based on dry matter) Functional agents (4.6% on a dry matter basis) Use an aqueous solvent (70% based on the total of the above dry components). This coating is applied by rotary gravure printing at a rate of 1.4 to 2 g / m 2 and showed greater than 2 log bacterial reduction when tested against E. coli and Staphylococcus aureus according to ISO 22196 with a 24 hour contact time.

[0077] [Example 6a] The procedure of Example 6 was repeated using polypropylene film as the substrate, and essentially the same results were obtained in terms of antimicrobial activity according to ISO 22196.

[0078] [Example 7] A substrate consisting of an aluminum film was rotogravure printed in seven colors and the following antimicrobial coatings were applied: Polyvinyl butyral (92% on a dry matter basis) Polysiloxane (4% on dry matter basis) Silver ions on an inorganic carrier (0.8% based on dry matter) Functional agents (3.2% on a dry matter basis) Using ethyl acetate solvent (75% based on the sum of the dry ingredients above) and crosslinker (15% based on the coating formulation above). This coating is applied by rotary gravure printing at a rate of 1.4 to 2 g / m 2 When applied at 180 m / min and tested against E. coli and S. aureus at a 24 hour contact time per ISO 22196, it showed a >4 log reduction in bacteria, and at a 24 hour contact time per ISO 21702, it showed a >1 log reduction in viral titers.

[0079] [Example 8] A primer layer of acrylic varnish containing isocyanate is applied to a substrate made of polypropylene film at a rate of 0.2 to 1.5 g / m 2 and a printing layer containing the printing ink was applied over the primer layer according to the needs of the figure. Then the following antibacterial coating was applied over the printing layer: Acrylic polymer (90% on a dry matter basis) Fatty acids (4% on dry matter basis) Silver ions on a solid carrier (1% based on dry matter) Functional agents (5% based on dry matter) Use an aqueous solvent (70% based on the total of the above dry ingredients). It has been found that curing the coating applied over the primer layer and ink acts to enhance the antimicrobial activity of the coating itself.

[0080] [Example 9] A coating was prepared comprising: Acrylate polymer (90% based on dry matter) Polysiloxane / Silicone Wax (4% on dry matter basis) Silver ions on an inorganic carrier (1.4% based on dry matter) Functional agents (4.6% on a dry matter basis) Use an aqueous solvent (70% based on the total of the above dry components).

[0081] [Example 10] A coating was prepared comprising: Polyvinyl butyral (92% on a dry matter basis) Polysiloxane / Silicone Wax (4% on dry matter basis) Silver ions on an inorganic carrier (0.8% based on dry matter) Functional agents (3.2% on a dry matter basis) Using ethyl acetate solvent (75% based on the total of the dry ingredients above) and crosslinker (15% based on the total of the coating formulation above).

Claims

1. An antimicrobial package comprising a substrate and a coating, the coating comprising a first polymer component selected from the group consisting of polyacrylic resins, polyvinyl butyrals, polyurethanes, polyvinyl alcohols, cellulosic polymers and polyesters, preferably selected from the group consisting of polyhydroxyalkanoates, polybutylene succinates and polylactic acids and mixtures thereof; - low adhesion, slip or release agents selected from the group consisting of polysiloxanes, carnauba wax, lecithin, fatty acids, fatty acid amides, fatty acid esters, magnesium stearate, vegetable oils, and mixtures thereof; -Antibacterial agents, and Optionally, - Defoaming agent - Fusion aid - Wetting agent - Crosslinking agent - and mixtures thereof and wherein the coating comprises one or more functional agents selected from the group consisting of - 50 to 99.49 wt. % of said first polymer component; - 0.5 to 35% by weight of said low adhesion, slip or release agent, and - 0.01 to 15% by weight of an antibacterial agent, - 0 to 10% by weight of functional agent - weight percentages are based on 100 parts by weight of dry coating; Including packaging.

2. 2. The package of claim 1, wherein the first polymeric component is a polyacrylic resin and the low adhesion, slip or release agent is a polysiloxane, preferably a mixture of dimethylpolysiloxane and a silicone wax.

3. 2. The package of claim 1, wherein the first polymer component is polyvinyl butyral and the low adhesion, slip or release agent is a polysiloxane, preferably a mixture of dimethylpolysiloxane and a silicone wax.

4. 2. The package of claim 1, wherein the polyacrylic resin is selected from polyacrylic acid, polyacrylates and polymethacrylates.

5. 2. The package of claim 1, wherein the polysiloxane is selected from the group consisting of dimethylpolysiloxane, silicone vinyl polymer, silicone emulsion and silicone oil, silicone wax and mixtures thereof.

6. 2. The package of claim 1, wherein the polyester is selected from the group consisting of polyhydroxyalkanoates, polyethylene terephthalates, polycaprolactones, polybutylene succinates, polyvinyl succinates, polylactic acids, and mixtures thereof.

7. 2. The package of claim 1, wherein the vegetable oil is selected from the group consisting of soybean oil, castor oil, rapeseed oil, palm oil, sunflower oil, and coconut oil, and mixtures thereof.

8. the antimicrobial agent is a metal selected from the group consisting of titanium, silver, gold, copper, platinum, and zinc, an oxide or salt of said metal, an alloy, a glass or clay containing said metal oxide; 2. The package of claim 1, wherein the metal may be in the form of nanoparticles or may be supported on a nano-, micro-, or macro-silica, silicone, or clay carrier.

9. 10. The package of claim 1, wherein the antimicrobial agent is selected from the group consisting of antimicrobial peptides, silicone-based antimicrobial agents and quaternary ammonium cations (Qua Ts).

10. 10. The package of claim 1, wherein the antimicrobial agent is a germicide selected from the group consisting of peroxide, propylene glycol, triethylene glycol, dodecanoic acid, formaldehyde, glutaraldehyde, thymol, clove oil, cinnamon oil, grapefruit seed extract, eucalyptus extract, antimicrobial plant extracts, a solution of chlorine or iodine in a solvent such as water, ethanol, isopropanol or mixtures thereof, the germicide optionally being encapsulated within a heat, moisture or temperature sensitive polymeric material.

11. 10. The package of claim 1, wherein the coating is obtained from a solution or dispersion comprising the first polymeric component, the slip or release agent, and the antimicrobial agent, and a solvent selected from the group consisting of water, ethyl acetate, ethanol, isopropanol, methanol, hexadecane, dodecane, and mixtures thereof.

12. In the coating, the first polymer component is a polyester; the slip or release agent is selected from polysiloxanes, carnauba wax, fatty acids, fatty acid amides, and mixtures thereof; 10. The package of claim 1, wherein the antimicrobial agent is selected from silver chloride, titanate, silver phosphate, silicone tethered quaternary amine, thymol, grapefruit seed extract, clove oil, cinnamon oil, or mixtures thereof, and the coating optionally further comprises an isocyanate based crosslinker.

13. 2. The packaging of claim 1, wherein the substrate is made of or comprises a material selected from the group consisting of paper, cardboard, glass, metal or a polymeric material selected from the group consisting of polypropylene, polyethylene, polyethylene-polypropylene copolymer, polystyrene, polyethylene terephthalate and bioplastics, preferably polyhydroxyalkanoates, polybutylene succinate or polylactic acid, and mixtures of said polymeric materials.

14. 10. The package of claim 1, wherein the coating is applied to provide a coating basis weight of 0.01 to 20 g / m2 based on dry coating.

15. 2. The packaging of claim 1, wherein the substrate comprises a monolayer or multilayer film or sheet comprising or consisting of paper, cardboard, polypropylene, polyethylene, polyethylene-polypropylene copolymers, polystyrene, polyethylene terephthalate and bioplastics, preferably polyhydroxyalkanoates, polybutylene succinate or polylactic acid, as well as mixtures of said polymeric materials, and optionally comprising a metallized layer.

16. 10. The packaging of claim 1, wherein the coating layer is applied to a flexible substrate and the coating is heat sealable to allow sealing of the substrate to itself or to another surface such as a tray or box.

17. 17. The package of claim 16, wherein the package is sealed in a tubular form and the coating is inside the tubular form.

18. 10. The package of claim 1, wherein the coating is applied to a paper, cardboard, or plastic substrate prior to the substrate being subsequently thermoformed.

19. 10. The package of claim 1, wherein the coating is applied to a paper, cardboard or plastic substrate before the substrate is folded into a rigid or semi-rigid form.

20. 10. The packaging of claim 1, wherein the substrate is an injection molded or extruded packaging structure obtained by injection molding or extrusion of a polymer blend comprising: Polymers selected from the group consisting of polypropylene, polyethylene, polyethylene-polypropylene copolymers, ABS, polystyrene, polyethylene terephthalate and bioplastics, preferably polyhydroxyalkanoates, polybutylene succinates or polylactic acids and mixtures thereof, an antimicrobial agent selected from the group consisting of titanium, silver, gold, copper, platinum, zinc, oxides or salts of said metals, alloys, glasses or clays containing said metal oxides, antimicrobial peptides, silicone-based antimicrobial agents, quaternary ammonia cations (Qua Ts), peroxides, propylene glycol, triethylene glycol, dodecanoic acid, formaldehyde, glutaraldehyde, thymol, clove oil, cinnamon oil, grapefruit seed extract, eucalyptus extract, antimicrobial plant extracts, solutions of chlorine or iodine in a solvent, said antimicrobial agent being optionally encapsulated within a heat, moisture, or temperature sensitive polymeric material; and A low adhesion, slip or release agent selected from the group consisting of silicone vinyl polymers, silicone emulsions, dimethylpolysiloxanes, silicone oils, silicone waxes, carnauba wax, lecithin, fatty acids, fatty acid esters, magnesium stearate, vegetable oils, preferably soybean oil, rapeseed oil, palm oil, sunflower oil, coconut oil, castor oil, and mixtures thereof.

21. 21. The packaging of claim 20, wherein the substrate is an injection molded or extruded packaging structure obtained by injection molding or extrusion of a polymer blend comprising a polymer selected from the group consisting of polypropylene, polyethylene, polyethylene-polypropylene copolymer, ABS, polystyrene, polyethylene terephthalate, and bioplastics, preferably polyhydroxyalkanoates, polybutylene succinate or polylactic acid, and mixtures thereof, together with a masterbatch comprising: a polymer component selected from the group consisting of polyurethanes, polyacrylic resins, polyethylene terephthalates, polyvinyl alcohols, polyhydroxyalkanoates, polylactic acids, cellulosic polymers and mixtures thereof; - low adhesion, slip or release agents selected from the group consisting of silicone vinyl polymers, silicone emulsions, dimethylpolysiloxanes, silicone oils, carnauba wax, lecithin, fatty acids, fatty acid esters, magnesium stearate, vegetable oils, preferably soybean oil, rapeseed oil, palm oil, sunflower oil, coconut oil, castor oil, and mixtures thereof; - a germicide selected from the group consisting of titanium, silver, gold, copper, platinum, zinc, oxides or salts of said metals, alloys, glasses or clays containing said metal oxides, antimicrobial peptides, silicone based antimicrobials, quaternary ammonia cations (Qua Ts), peroxides, propylene glycol, triethylene glycol, dodecanoic acid, formaldehyde, glutaraldehyde, thymol, clove oil, cinnamon oil, grapefruit seed extract, eucalyptus extract, antimicrobial plant extracts, solutions of chlorine or iodine in a solvent, said germicide being optionally encapsulated within a heat, moisture or temperature sensitive polymeric material.

22. 22. The packaging of claim 20 or 21, wherein the substrate is an extruded packaging structure and the coating is co-extruded with the substrate.

23. 10. The package of claim 1, wherein the coating is applied to a rigid or semi-rigid packaging structure after the packaging structure is formed to impart antimicrobial properties.

24. 10. The package of claim 1, further comprising an adhesion enhancing layer disposed between the substrate and the antimicrobial coating, the adhesion enhancing layer being selected from the group consisting of a clay coating, a printing layer printed with a printing ink, a barrier coating, and an acrylic primer.

25. a first polymer component selected from the group consisting of polyacrylic resins, polyvinyl butyral and mixtures thereof; - a low adhesion, slip or release agent selected from the group consisting of polysiloxanes, preferably silicone vinyl polymers, silicone emulsions, dimethylpolysiloxane silicone oils and silicone waxes, and mixtures thereof; and -Antibacterial agents A composition comprising:

26. 26. The composition of claim 25, wherein the antimicrobial agent is selected from the group consisting of germicides selected from the group consisting of titanium, silver, gold, copper, platinum, zinc, oxides or salts of said metals, alloys, glasses or clays containing said metal oxides, antimicrobial peptides, silicone-based antimicrobials, quaternary ammonia cations (Qua Ts), peroxides, propylene glycol, triethylene glycol, dodecanoic acid, formaldehyde, glutaraldehyde, thymol, clove oil, cinnamon oil, grapefruit seed extract, eucalyptus extract, antimicrobial plant extracts, solutions of chlorine or iodine in a solvent, wherein the germicide is optionally encapsulated within a heat, moisture, or temperature sensitive polymeric material.

27. 27. A method for producing antimicrobial packaging comprising the step of applying the composition of claim 25 or 26 to a flexible or rigid packaging substrate.

28. 27. A method of making a packaging having antimicrobial properties comprising blending the composition of claim 25 or 26 with a thermoplastic polymeric material and molding or thermoforming the blend to provide the packaging.

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