Product packaging with self-sterilizing components

Abstract

A package comprising: a sterile barrier packaging film; a self-sterilizing component comprising: a plurality of chlorite ions and water, wherein the self-sterilizing components are substantially free of energy-activated catalysts and acid-releasing compounds; a package interior formed by hermetically sealing the sterile barrier packaging film; and a headspace within the package interior comprising carbon dioxide present in an amount greater than or equal to 5% by volume of the headspace. When the package is exposed to ultraviolet (UV) light having a wavelength of 254 nm, the chlorite ions react with water to produce chlorine dioxide (ClO2), which is released into the headspace. In the absence of any UV light, chlorine dioxide (ClO2) is not produced.

Description

Technical Field

[0001] The present disclosure generally relates to sterilizing gas generating packaging for various products. In particular, these packaging are self-sterilizing by providing a controlled release of chlorine dioxide (ClO2) gas for sterilizing various products, including food, medical devices and medical supplies. Background Art

[0002] Chlorine dioxide (ClO2) is a powerful oxidant and disinfectant. Packaging that produces ClO2 and is self-sterilizing can be a cheaper, safer, and faster alternative to other sterilization methods, such as exposing the product to ethylene oxide (EtO) gas. However, the timing and amount of ClO2 gas release in the package can be difficult to control.

[0003] Some technologies rely on reactions based on chlorate in the presence of a co-reactant. In U.S. Application Publication No. 2018 / 272019 A1, chlorite or chlorate is used with a co-reactant (which is an oxidant and / or an acid). Some technologies rely on different chemical reactions involving chlorite ions, water and ultraviolet light, which do not utilize energy-activated catalysts or acid-releasing compounds. In WO 2017 / 031349 A1, the layer that produces chlorine dioxide comprises a polymer composition and a plurality of chlorite ions. The layer that produces chlorine dioxide is substantially free of energy-activated catalysts and substantially free of acid-releasing compounds. However, when exposed to UV light and moisture, the membrane is able to produce chlorine dioxide.

[0004] There is a need to release ClO2 gas in a controlled and efficient manner for deodorizing, disinfecting and / or sterilizing packaging. Summary of the invention

[0005] Provided is a package that releases ClO2 gas for deodorization, disinfection and / or sterilization in a controlled and efficient manner from the reaction of a self-sterilizing component.

[0006] One aspect is a package comprising: a sterile barrier packaging film; a self-sterilizing component comprising: a plurality of chlorite ions and water, wherein the self-sterilizing components are substantially free of energy-activated catalysts and acid-releasing compounds; a package interior formed by hermetically sealing the sterile barrier packaging film; and a headspace within the package interior comprising carbon dioxide present in an amount greater than or equal to 5% by volume of the headspace. When the package is exposed to ultraviolet (UV) light having a wavelength of 254 nm, the chlorite ions react with the water to produce chlorine dioxide (ClO2), which is released into the headspace. In the absence of any UV light, chlorine dioxide (ClO2) is not produced. The water in the package is in proximity to the plurality of chlorite ions.

[0007] In one or more embodiments, the relative humidity inside the package at 72.5°F is in the range of greater than or equal to 20% to less than or equal to 100%.

[0008] In one or more embodiments, a salt comprising sodium chlorite, potassium chlorite, calcium chlorite, magnesium chlorite, lithium chlorite, ammonium chlorite, or mixtures thereof provides a plurality of chlorite ions.

[0009] In one or more embodiments, the sterile barrier packaging film is substantially transparent to ultraviolet (UV) light.

[0010] In one or more embodiments, the sterile barrier packaging film comprises a main layer and a patch fixed to the main layer, wherein the patch provides a plurality of chlorite ions. In an embodiment, the patch comprises: a patch support that is permeable to chlorine dioxide and defines a first major surface of the patch; and a patch sealing layer that comprises a plurality of chlorite ions dispersed in a polymer composition, wherein the patch sealing layer contacts the patch support and defines a second major surface of the patch, and wherein the patch sealing layer is fixed to the main layer.

[0011] In one or more embodiments, a plurality of chlorite ions are present in a layer of the self-sterilizing packaging film, and the salt combined with the polymer composition provides the plurality of chlorite ions.

[0012] In an embodiment, the polymer composition comprises at least one of: polyethylene, polypropylene, polyacrylate, or a copolymer of any of these.

[0013] Another aspect is a packaged product comprising: a packaging film; a plurality of chlorite ions; water; a package interior formed by hermetically sealing the packaging film; a product inside the package; and a head space inside the package comprising carbon dioxide present in an amount greater than or equal to 5% by volume of the head space; wherein the self-sterilizing components comprise: water and a plurality of chlorite ions, and these components are substantially free of energy-activated catalysts and substantially free of acid-releasing compounds.

[0014] In an embodiment, when the film is exposed to ultraviolet (UV) light having a wavelength of 254 nm, the reaction of these chlorite ions with water produces chlorine dioxide (ClO2), which is released into the headspace and effectively sterilizes the product inside the package.

[0015] In an embodiment, the packaging film comprises a main layer and a patch fixed to the main layer, wherein the patch provides a plurality of chlorite ions. In an embodiment, the patch comprises: a patch support permeable to chlorine dioxide; and a patch sealing layer comprising a plurality of chlorite ions dispersed in a polymer composition, wherein the patch sealing layer is in contact with the patch support, and wherein the patch sealing layer is fixed to the main layer. In an embodiment, the polymer composition comprises at least one of the following: polyethylene, polypropylene, polyacrylate, or a copolymer of any of these.

[0016] The product inside the package can be a medical device or a medical product. The product inside the package can be a food.

[0017] Another aspect is a method of sterilizing a packaged product, comprising: providing an unsealed package comprising: a sterile barrier packaging film comprising a primary layer and a plurality of chlorite ions; and a package interior; and introducing water into the package interior; introducing a product to be sterilized into the package interior, introducing a gas comprising carbon dioxide into the package interior of the package; after introducing the gas comprising carbon dioxide, hermetically sealing an open end of the unsealed package to form a self-sterilizing package containing the packaged product and a headspace, wherein the headspace comprises carbon dioxide in an amount greater than or equal to 5% by volume of the headspace; and exposing the self-sterilizing package to UV radiation; wherein the self-sterilizing components comprise: water and a plurality of chlorite ions, and the components are substantially free of energy-activated catalysts and acid-releasing compounds. Water is proximate to the plurality of chlorite ions.

[0018] In one or more embodiments, an amount of at least 1.39 μg / mL of chlorine dioxide is generated within the package within a period of 5 minutes.

[0019] In one or more embodiments, the UV radiation comprises a 254 nm wavelength.

[0020] These and other aspects of the invention are described in the following detailed description.In any case, the above summary of the invention should not be interpreted as limiting the claimed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The present disclosure may be more fully understood by considering the following detailed description of various embodiments of the present disclosure in conjunction with the accompanying drawings, in which:

[0022] Figure 1 is a schematic side view of a sterile barrier packaging film according to an embodiment;

[0023] Figure 2 is a schematic side view of a sterile barrier packaging film according to an embodiment;

[0024] Figure 3is a schematic plan view of a package according to an embodiment; and

[0025] Figure 4 is a schematic cross-sectional view of a package according to an embodiment.

[0026] These drawings are not necessarily drawn to scale. The same reference numerals used in the drawings refer to the same components. However, it should be understood that the use of a reference numeral to refer to a component in a given drawing is not intended to limit the component labeled with the same reference numeral in another drawing. DETAILED DESCRIPTION

[0027] The package of the present disclosure comprises a sterile barrier packaging film; comprises the following self-sterilizing components: a plurality of chlorite ions and water, wherein the self-sterilizing components are substantially free of energy-activated catalysts and acid-releasing compounds; a package interior formed by hermetically sealing the sterile barrier packaging film; and a head space inside the package, which comprises carbon dioxide (CO2) present in an amount greater than or equal to 5% by volume of the head space. When the package is exposed to ultraviolet (UV) light having a wavelength of 254 nm, the chlorite ions react with the water to produce chlorine dioxide (ClO2), which is released into the head space. In the absence of any UV light, chlorine dioxide (ClO2) is not produced. The water in the package is in proximity to the chlorite ions.

[0028] Some currently available production ClO2 and are self-sterilizing packaging bring these problems: ClO2 in packaging The time and amount of gas release may be difficult to control. The packaging and method herein provide a solution for such problems, which is by releasing ClO2 in a controlled and efficient manner Gas is used for deodorization, disinfection and / or sterilization. This is achieved by including CO2 gas in the head space of the packaging. A way to achieve efficiency is due to the head space without the CO2 gas added, for any given chlorite ion concentration and delivery form, the ClO2 gas yield increases. A way to achieve control is to use a reaction scheme that depends on UV light, discussed below about reaction (1). CO2 is included in the head space of the packaging Gas is produced by the mechanism of UV activation The combination of gas advantageously leads to providing a self-sterilizing packaging, and its efficacy is improved by head space management. For both medical devices and food packaging, the present disclosure provides a low-cost solution with minimal changes for existing packaging lines and procedures, so as to achieve the benefits in terms of control and / or efficiency.

[0029] It is shown herein to significantly improve ClO2 yield by using CO2 gas at concentrations on the order of about 1.5 times and higher relative to air alone in the headspace of the package according to the following reaction:

[0030]

[0031] Without intending to be bound by theory, it is understood that CO2 dissolves in the water added to the package containing chlorite ions in the humidification step. Dissolution results in the formation of carbonic acid. Weak acid counteracts the base (i.e., hydroxyl, OH-), helping to drive the reaction according to (1) to the right. Ultimately, carbonic acid reduces the pH to a level sufficient to significantly increase the yield of the reaction according to (1) in the presence of UV light. It should be noted that (1) does not include the presence of energy-activated catalysts and acid-releasing compounds. However, the presence of CO2 and the formation of carbonic acid (HCO3) do not create a sufficiently acidic environment to induce spontaneous generation of ClO2 gas by the chlorite ions present. Therefore, the generation of ClO2 gas is still controlled by UV light activation (hv). The packaging described herein releases ClO2 gas on demand when exposed to ultraviolet (UV) light, and the addition of CO2 to the packaging has the effect of increasing the ClO2 gas generation achieved compared to the headspace without CO2.

[0032] When exposed to ultraviolet (UV) light with a wavelength of 254nm, the amount of chlorite ions present in the packaging is effective for deodorizing, disinfecting and / or sterilizing the product arranged inside the packaging. For example, the concentration of chlorite ions in the coating on the layer of the packaging or the patch fixed to the layer of the packaging can be changed in quantity to deliver the desired amount of ClO2 gas. Moreover, the concentration of chlorite ions can be changed according to the thickness of the layer or coating or patch, the surface area (length x width) and / or pattern of the layer or coating or patch, the volume inside the packaging and the desired effect (such as deodorizing, disinfecting or sterilizing). Any suitable amount of chlorite ions can be included to deodorize, disinfect or sterilize the inside of the packaging, and the content of the packaging can vary depending on the volume inside the packaging. Advantageously, by including CO2 gas in the head space of the packaging herein, compared with the head space without CO2 gas, for any given chlorite ion concentration and delivery form, the ClO2 gas yield is improved. In this way, chlorite ions are used more efficiently. For example, when CO2 gas is present, a smaller amount of chlorite ions will be required to obtain the same amount of ClO2 gas than when no CO2 gas is present in the headspace.

[0033] Reference to "substantially transparent to ultraviolet radiation" means that the transmission of UV light through the layer or film is at least sufficient to allow the reaction of (1) to occur. In one or more embodiments, at least 10% of the ultraviolet light can be transmitted through the layer or film.

[0034] As used herein, water "in proximity" to chlorite ions means close enough to dissociate the salt that provides these ions. In one or more embodiments, the water is in contact with the chlorite ions.

[0035] In one or more embodiments, the ClO2 gas concentration in the headspace is measured by extracting a gas sample of the headspace and dissolving the ClO2 in water, which is then tested by conventional techniques for measuring ClO2 concentration in water. The exemplary technique is performed on an apparatus called ChlordioX Plus provided by Palintest.

[0036] In one or more embodiments, the CO2 gas concentration in the headspace is measured by a conventional gas detector suitable for detecting CO2. Exemplary technology is provided by Mocon and is called or a device called PAC CHECK provided by Mocon.

[0037] Packaging

[0038] Materials suitable for making hermetically sealed packaging are used herein. The hermetically sealed packaging herein allows ClO2 to be effectively retained for a period of time, promoting one or more of deodorization, disinfection and sterilization in the packaging. The packaging comprises a sterile barrier packaging film, which comprises a main layer and a self-sterilizing component.

[0039] Any suitable packaging may include a layer or coating that includes chlorite ions.

[0040] Any suitable packaging may contain a patch comprising a patch support permeable to chlorine dioxide and a sealing layer comprising chlorite ions.

[0041] At least a portion of the package is substantially transparent to ultraviolet light.The package may be in the form of a bag, pouch, or other suitable container.

[0042] In one or more embodiments, the packaging herein complies with ISO 11607-1 (2006), "Packaging for terminally sterilized medical devices."

[0043] Preferably, packaging as herein described and corresponding self-sterilizing component release a certain amount of chlorine dioxide with sufficient amount to deodorize or disinfect or sterilize the product in the packaging. Chlorine dioxide gas is contained in the packaging and lasts for a sufficiently long time to deodorize or disinfect or sterilize the product in the packaging. Chlorine dioxide gas is usually produced in the time period of UV light exposure, and this time period may be relatively short, such as the magnitude of about a few seconds or a few minutes. Subsequent deodorization or disinfection or sterilization occurs while containing gas, and this may be a relatively long time, such as the magnitude of about a few hours or a few days. In one or more embodiments, the packaging of this paper is effective to disinfect and / or sterilize medical devices. In one or more embodiments, the packaging of this paper is effective to deodorize and / or sterilize food products.

[0044] Suitable products include, but are not limited to, medical devices, medical supplies, and food.

[0045] References to "medical devices" include, but are not limited to, diagnostic tools, implants, surgical tools, and medical instruments. References to "medical supplies" include, but are not limited to, bandages, gauze, tubing, catheters, and syringes.

[0046] As used herein, "deodorization" means removing or hiding an unpleasant smell. In many cases, an unpleasant smell may be caused by bacteria that produce peculiar smells, and killing bacteria can have a deodorizing effect. Packages as described herein and corresponding self-sterilizing components can release any suitable amount of ClO2 gas to deodorize the articles (such as food products, which can be, for example, agricultural products) stored in the package. For example, at least 2 parts per million (ppm) of ClO2 gas can be released into the package inside. Typically, release at least 10ppm of ClO2 gas is enough to deodorize agricultural products. If the package is sealed, because additional chlorine dioxide is released, the concentration of chlorine dioxide can increase over time. The ClO2 required for effective deodorization of the articles stored in the package is carried out The amount of gas will depend in part on the property of the article. In addition, the article is exposed to ClO2 The time of gas will affect the ability of ClO2 gas to deodorize the article. In certain embodiments, release a certain amount of ClO2 gas continuously enough to expose the article to at least 2ppm-hours of ClO2 gas to deodorize the article. For example, chlorine dioxide may be released in an amount that produces at least 10 ppm-hour of ClO 2 gas, or at least 20 ppm-hour of ClO 2 gas, to deodorize items.

[0047] As used herein, "disinfection" means reducing the number of surviving bacteria. In order to determine whether a product is disinfected, a product that has undergone a disinfection treatment such as exposure to ClO2 gas can be compared with a control product that has not undergone a disinfection treatment to determine whether the bacterial load has been reduced; and, if it has been reduced, the product will be considered to have been disinfected. Alternatively, the bacterial load of the product can be compared before and after the treatment to determine whether the product has been disinfected. The packaging described herein and the corresponding self-sterilizing component can release any suitable amount of ClO2 gas to disinfect the medical device arranged in the packaging. For example, at least 10 parts per million (ppm) or more of ClO2 gas can be released into the interior of the packaging. Typically, the self-sterilizing component can release 50ppm or more of ClO2 gas to disinfect the medical device. If the packaging is sealed, the concentration of chlorine dioxide can increase over time because additional chlorine dioxide is released. The amount of ClO2 gas required for effective disinfection of the medical device will depend in part on the properties of the device. In addition, the time of exposing the medical device to ClO2 gas will affect the ability of ClO2 gas to disinfect the medical device. In some embodiments, the self-sterilizing component releases an amount of ClO2 gas for a time sufficient to expose the medical device to 100 ppm-hour or more of ClO2 gas to sterilize the product, including 150 ppm-hour or more of ClO2 gas, or 200 ppm-hour or more of ClO2 gas to sterilize the medical device.

[0048] As used herein, "sterilization" means making without bacteria or other living organisms.Packaging as described herein and correspondingly self-sterilizing component can release any suitable amount of ClO gas to sterilize the medical device arranged in the packaging.For example, at least 200 parts per million (ppm) or more of ClO gas can be released into packaging inside.Typically, self-sterilizing component can release 500ppm or more of ClO gas to sterilize medical device.ClO required for effective sterilization of medical device The amount of gas will depend in part on the property of the device.In addition, medical device is exposed to ClO The time of gas will affect the ability of ClO gas to sterilize the device.In certain embodiments, self-sterilizing component releases a certain amount of ClO gas to continue to be enough to expose medical device to 1000ppm-hour or higher ClO gas to sterilize the device time, including 1500ppm-hour or more ClO gas or 2000ppm-hour or more ClO gas to sterilize medical device.

[0049] Self-sterilizing components

[0050] The self-sterilizing components include water and a plurality of chlorite ions, wherein the self-sterilizing components are substantially free of energy-activated catalysts and acid-releasing compounds. Reference to "self-sterilizing components" means those compounds that participate in the reaction that generates ClO2 gas.

[0051] In one or more embodiments, the self-sterilizing component consists essentially of water and a plurality of chlorite ions, and does not contain an energy-activated catalyst and an acid-releasing compound. As used herein, an "acid-releasing compound" is a compound that can produce an acid and a hydronium ion in the presence of moisture, and the hydronium ion can react with the chlorite ion to form ClO2 gas. U.S. Patent No. 6,605,304 lists many acid-releasing compounds for gas generation, including carboxylic acids, esters, anhydrides, acyl halides, phosphoric acid, phosphate esters, trialkylsilyl phosphates, dialkyl phosphates, sulfonic acids, sulfonic acid esters, sulfonyl chlorides, phosphosilicates, phosphosilicate anhydrides, carboxylic acid esters of poly-alpha-hydroxy alcohols (such as sorbitan monostearate or sorbitol monostearate), phosphosiloxanes, and acid-releasing waxes (such as propylene glycol monostearate releasing wax). U.S. Pat. No. 6,605,304 also lists inorganic acid releasers as acid-releasing compounds, such as polyphosphates, including tetraalkylammonium polyphosphates, potassium dihydrogen phosphate, potassium polymetaphosphate, sodium metaphosphate, borophosphates, aluminum phosphates, silicophosphates, sodium polyphosphates such as sodium tripolyphosphate, potassium tripolyphosphate, sodium potassium phosphate, and salts containing hydrolyzable metal cations such as zinc. In some embodiments described herein, the chlorine dioxide-generating layer or film described herein for generating ClO2 gas is substantially free of such compounds. In one or more embodiments, the self-sterilizing component does not contain carbonic acid.

[0052] Any suitable source of chlorite ions may be used. Typically, the source of chlorite ions is chlorite. As used herein, "chlorite" is not limited to embodiments in which the anion and cation form solid crystals, but includes virtually any form in which such salts are known to exist, contained in an aqueous or other solution or dispersed within a polymer matrix. In some embodiments, the cation in the chlorite is an organic cation, and in some embodiments, the cation in the chlorite is inorganic. In some such embodiments, the chlorite is sodium chlorite, potassium chlorite, calcium chlorite, magnesium chlorite, lithium chlorite, or ammonium chlorite. In some embodiments, the chlorite is sodium chlorite.

[0053] As used herein, an "energy-activated catalyst" is a catalyst compound that can catalyze the conversion of ClO after being activated by electromagnetic energy (such as visible light). - Compounds that oxidize to ClO2 gas.

[0054] As used herein, "substantially free of energy-activated catalysts" means that the self-sterilizing component does not contain an energy-activated catalyst, or contains an amount of energy-activated catalyst that does not significantly promote the generation of ClO2 gas. In some embodiments, the ratio of energy-activated catalyst to chlorite ion source (such as chlorite ion salt) in the chlorine dioxide generating layer (by weight) is less than or equal to 1:2. For example, the ratio of energy-activated catalyst to chlorite ion source can be less than or equal to 1:5, such as less than or equal to 1:10, or less than or equal to 1:20.

[0055] As used herein, an "acid-releasing compound" is a compound that can generate an acid and hydronium ions in the presence of moisture and the absence of UV light, and the hydronium ions can react with chlorite ions to form ClO2 gas. Herein, although CO2 is present and can generate carbonic acid when dissolved in water, carbonic acid does not participate in the reaction according to (1) and therefore the self-sterilizing component does not contain carbonic acid.

[0056] As used herein, "substantially free of acid-releasing compounds" means that the self-sterilizing component does not contain acid-releasing compounds, or contains an amount of acid-releasing compounds that does not significantly promote the generation of ClO2 gas. In some embodiments, the ratio of acid-releasing compounds to chlorite ion sources (such as chlorite ion salts) in the chlorine dioxide generating layer (by weight) is less than or equal to 1:10. For example, the ratio of acid-releasing compounds to chlorite ion sources can be less than or equal to 1:20, such as less than or equal to 1:50, or less than or equal to 1:100.

[0057] Water is present to participate in the reaction according to (1). In one or more embodiments, the relative humidity in the package at 72.5°F is greater than or equal to 20% to less than or equal to 100% and all values ​​and subranges therebetween, including but not limited to greater than or equal to 40% to less than or equal to 100%, or preferably greater than or equal to 60% to less than or equal to 100%.

[0058] In one or more embodiments, a plurality of chlorite ions may be provided in a layer of the self-sterilizing packaging film via a salt combined with the polymer composition.

[0059] In one or more embodiments, the patch provides a plurality of chlorite ions.

[0060] Aseptic barrier packaging film

[0061] The sterile barrier packaging film is an effective barrier to prevent the spread of microorganisms. In one or more embodiments, the sterile barrier packaging film comprises a main layer and a self-sterilizing component. At least a portion of the sterile barrier packaging film is substantially transparent to ultraviolet (UV) light. For example, one side wall of the package may be transparent and the other may be opaque. When the package is hermetically sealed, the transparency is sufficient to transmit UV light through the package and allow the UV light to contact the self-sterilizing component.

[0062] The sterile barrier packaging film may comprise a monolayer film or a multilayer film. The sterile barrier packaging film may be flexible or rigid depending on the type of package being formed. The sterile barrier packaging film may be, for example, one side of a bag, pouch or container, or may be a lid of a container, such as a thermoformed tray.

[0063] In one or more embodiments, the sterile barrier packaging film comprises a main layer. In an embodiment, the sterile barrier packaging film comprises a main layer and a patch fixed to the main layer, wherein the patch provides a plurality of chlorite ions. In an embodiment, the main layer of the sterile barrier packaging film comprises a plurality of chlorite ions and a polymer composition.

[0064] In another embodiment, a plurality of chlorite ions are present in a coating on the self-sterilizing packaging film. The coating comprises chlorite in combination with a polymer composition. Any suitable coating composition may be used to coat the self-sterilizing packaging film. For example, the coating composition may comprise one or more chlorites, one or more other suitable coating components, and one or more suitable solvents or diluents. In some embodiments, one or more coating components are water-soluble or water-dispersible.

[0065] Suitable coating components may include materials that retain chlorite ions on the self-sterilizing packaging film. In some embodiments, the coating composition comprises a polymer or resin that is compatible with the self-sterilizing packaging film to be coated. After the coating is dried or cured, the coating preferably adheres to the self-sterilizing packaging film.

[0066] The coating composition can include any suitable polymer. In some embodiments, the coating composition includes one or more of polyethylene, ethylene vinyl acetate, ethylene-alpha olefin, or polypropylene.

[0067] The coating composition can include any suitable amount of chlorite ions, such as the amounts discussed above. In some embodiments, the chlorite ions are present in a salt, and the salt is present in an amount ranging from 0.1 wt % to 30 wt % relative to the total weight of the coating. For example, the salt can be present in an amount ranging from 10 wt % to 20 wt % relative to the total weight of the coating.

[0068] The coating composition can be applied in any suitable manner. For example, the surface to be coated can be immersed in the coating composition, or the coating composition can be sprayed, rolled, printed or otherwise deposited on the surface of the film. In some embodiments, the coating is pattern-coated to coat certain portions of the surface of the self-sterilizing packaging film and leave certain portions of the self-sterilizing packaging film uncoated.

[0069] In another embodiment, a plurality of chlorite ions are present in the layers of the self-sterilizing packaging film. That is, chlorite is incorporated into one of the layers of the self-sterilizing packaging film.

[0070] In one or more embodiments, the main layer of the sterile barrier packaging film is a sealing layer, which is sealed to form an airtight seal. That is, the sealing layer is included in a thermoplastic polymer or polymer mixture that softens when exposed to heat and recovers its initial state when cooled to room temperature. The sealing layer can be used to combine the sterile barrier packaging film with a base material, usually by heat sealing, to form a peripheral seal. The base material can be a rigid or flexible thermoformed tray. The base material can be a film of the same type or different types as the sterile barrier packaging film. Typically, the sealing layer can include any suitable polymer composition or thermoplastic material, including but not limited to synthetic polymers, such as polyester, polyamide, polyolefin, polystyrene, etc. Thermoplastic materials can also be included in any synthetic polymer cross-linked by radiation or chemical reaction during manufacturing or post-manufacturing process operations. Exemplary polyolefins include polyethylene (PE) and polypropylene (PP).

[0071] In one or more embodiments, the primary layer and / or one or more additional layers provide barrier functionality, including a gas barrier and / or a moisture barrier.

[0072] The gas barrier layer is preferably an oxygen barrier layer and is preferably a core layer located between and protected by the surface layers. For example, the oxygen barrier layer may be in contact with the first surface layer and the adhesive layer, or may be sandwiched between two adhesive layers, between two surface layers, or between an adhesive layer and a surface layer.

[0073] The gas barrier (such as a chlorine dioxide barrier or an oxygen barrier) is preferably selected to provide a sufficiently reduced gas permeability to protect the product arranged in the sealed package from undesirable degradation or, for example, oxidation processes. For example, the film may comprise an oxygen barrier having an oxygen permeability that is sufficiently low to prevent or slow oxidation of the product to be packaged in the film. In some embodiments, the packaging film has a gas permeability of less than 150 cm at 1 atmosphere and 23°C. 3 / m 2 / 24h, if less than 10cm at 1 atmosphere and 23℃ 3 / m 2In order to protect oxygen-sensitive items from degradation caused by oxygen contact over time, the film can have an oxygen transmission rate (O2TR) of less than 1, such as less than 0.1, less than 0.01, or less than 0.001 cm at 1 atmosphere and 23°C. 3 / m 2 / 24h O2TR.

[0074] The moisture barrier is preferably selected to provide a sufficiently reduced moisture permeability to protect the items disposed in the sealed package from undesirable degradation. For example, the film may include a water barrier having a moisture permeability that is sufficiently low to prevent harmful effects on the packaged items (such as medical devices). According to various embodiments, the preferred film will have a moisture permeability of less than 15 g / m at 38°C and 90% RH. 2 In some embodiments, the film has a water vapor transmission rate (WVTR) of less than 1, less than 0.1, or less than 0.01 g / m at 38°C and 90% RH. 2 / 24h WVTR.

[0075] The barrier layer may comprise any suitable material and may be of any suitable thickness. Gas barrier layers may include polyvinyl alcohol (PVOH), ethylene vinyl alcohol (EVOH), polyvinylidene chloride (PVDC), polyamides, polyesters, polyalkylene carbonates, polyacrylonitrile, nanocomposites, metallized films such as aluminum vapor phases deposited on polyolefins, and the like, as known to those skilled in the art. Suitable moisture barrier layers include aluminum foil, PVDC, fluoropolymers like polychlorotrifluoroethylene (PCTFE), polyolefins such as HDPE, LLDPE, and cyclic olefin copolymers (COC), and metallized films such as aluminum vapor phases deposited on polyolefins, and the like, as known to those skilled in the art. It is desirable to select the thickness of the barrier layer to provide the desired combination of performance properties sought (e.g., with respect to oxygen permeability, water vapor permeability, resistance to delamination, etc.).

[0076] If the film includes a moisture barrier, care may need to be taken to ensure that the chlorite ions of the film (e.g., a sealing layer or coating layer containing chlorite ions) are exposed to sufficient moisture to release ClO2 gas. In some embodiments, the atmosphere of the packaging manufacturing line can be controlled to ensure that the chlorite-containing layer is exposed to sufficient moisture. In some embodiments, the package can be in the form of a three-sided sealed bag, wherein the items (e.g., food products, pharmaceuticals, medical devices, or other products) are arranged in the bag before the fourth side is finally sealed to seal the product in the bag. When the product is in the three-sided sealed bag, a humidified gas such as a steam stream containing nitrogen or a heated water stream can be used to flush the bag and provide sufficient moisture for the generation of ClO2 gas before the final sealing. In some embodiments, the packaging film can be stored in a high moisture environment before packaging on the line.

[0077] Aseptic barrier packaging film optionally further comprises the sublayer of the outer layer that can serve as packaging.The outer layer is seen by the user / consumer, and is usually exposed to the environment around the packaging.In both single-layer and multilayer embodiments, the outer surface of film can have desired appearance characteristics and can have high gloss.And it preferably withstands contact with sharp objects and provides wear resistance, and for these reasons, the outer layer is often referred to as a damage-resistant layer.This outer damage-resistant layer can be used as or can also not be used as a heat-sealable layer, and therefore can comprise one or more suitable heat-seal polymers, such as polyethylene or polypropylene.As the outer surface layer of film, this layer is also the outer layer of any packaging, bag, pouch or other container made by this film under the most common situation, and therefore is subjected to for example following processing and destruction: equipment during packaging, and during transportation and storage with the friction of other packaging and shipping containers and storage shelves.

[0078] The outer surface layer should be easy to machine (i.e., easy to feed into and operate through a machine, such as for conveying, packaging, printing, or as part of a film or bag manufacturing process). Suitable rigidity, flexibility, flex crack resistance, modulus, tensile strength, coefficient of friction, printability, and optical properties are also often designed into the outer layer by appropriately selecting materials. The layer may also be selected to have characteristics suitable for producing a desired heat seal portion that may be resistant to burn-through (e.g., burned through by an impulse sealer) or may be used as a heat seal surface in certain packaging embodiments (e.g., using an overlap seal).

[0079] The oriented film of this layer or any other layer can be uniaxially oriented or biaxially oriented. The thickness of this outer layer is typically 0.5 to 2.0 mils. Thinner layers may not work well in promoting the damage resistance, but thicker layers, although more expensive, can still be advantageously used to produce films with unique highly desired puncture resistance and / or damage resistance.

[0080] In some embodiments, the outer layer is transparent to UV light.

[0081] The sterile barrier packaging film optionally further comprises other layers including, but not limited to, a body layer, an intermediate layer, an adhesive layer and a reflective layer.

[0082] The body layer may be provided to provide additional functionality such as rigidity or heat sealability, or to improve machinability, cost, flexibility, barrier properties, etc. The body layer may be of any suitable thickness or may even be omitted in certain applications.

[0083] Films as described herein may include one or more adhesive layers (also referred to in the art as "tiing layers"), which may be selected to promote adhesion of adjacent layers in a multilayer film to each other and prevent undesired delamination.

[0084] The films herein may comprise any suitable number of tie layers or adhesive layers of any suitable composition. Depending on the composition of the layer in contact with the tie layer, each adhesive layer is formulated and positioned to provide a desired level of adhesion between specific layers of the film.

[0085] The inner layer, outer layer, intermediate layer or bonding layer can be formed from any suitable thermoplastic material, such as polyamide, polystyrene, styrene copolymers such as styrene-butadiene copolymers, polyolefins, and in particular members of the polyethylene family (such as LLDPE, VLDPE, HDPE, LDPE, COC, ethylene vinyl ester copolymers or ethylene alkyl acrylate copolymers), polypropylene, ethylene-propylene copolymers, ionomers, polybutene, α-olefin polymers, polyesters, polyurethanes, polyacrylamides, anhydride-modified polymers, acrylate-modified polymers, polylactic acid polymers, or different blends of two or more of these materials.

[0086] Various additives can be included in the polymer used in one or more of the main layer, sublayer, base layer, coating, external layer, internal layer and intermediate layer or bonding layer of the packaging comprising the main layer, sublayer, base layer, coating, external layer, internal layer and intermediate layer or bonding layer. For example, the layer can be coated with anti-blocking powder. Moreover, conventional antioxidants, anti-blocking additives, polymer plasticizers, acids, moisture or gas (such as oxygen) scavengers, slip agents, colorants, dyes, pigments, sensory agents can be added to one or more film layers of the film, or the film can be free of such added ingredients.

[0087] The packaging film may include one or more layers reflecting UV light. Examples of suitable materials for such layers include metal foil or deposits, such as vacuum metallized layers or sputtered layers. A reflective layer may be used as a coating and applied, wherein reflective particles such as metal flakes are dispersed in a polymer binder. The film may be configured so that when the film is exposed to UV radiation, the self-sterilizing component is positioned between the reflective layer and the UV source. In some such embodiments, one or more reflective layers contact the layer of the film. By increasing the UV exposure of the chlorite dispersed in the film (e.g., dispersed in a sealing layer or arranged in a coating on the sealing layer), the reflective layer may be optically designed to maximize productivity.

[0088] Aseptic barrier packaging films described herein can have any suitable thickness. In certain embodiments, the packaging film has a total thickness of less than about 50 mils, and more preferably the film has a total thickness of from about 1.0 to 10 mils (25-250 microns (μ)), such as from about 1 to 5 mils or from about 2 to 3.5 mils. For example, any monolayer of the entire multilayer film or multilayer film can have any suitable thickness, including 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 50 mils, or any value of 0.1 or 0.01 mils in increments between these values.

[0089] In some embodiments, these packaging films are 50 mils (1270 microns) thick or thicker, or 1 mil (25.4 microns) thin or thinner. In various embodiments, these packaging films have a thickness between about 2-4 mils (51-102 microns).

[0090] Patch

[0091] The patch comprises a patch support permeable to chlorine dioxide and a patch sealing layer. The patch support defines a first major surface, and the patch sealing layer defines a second major surface of the patch. In one or more embodiments, the patch is granted to a common assignee according to WO2019 / 132934 A1, the disclosure of which is incorporated herein by reference in its entirety.

[0092] The patch may be secured to the inner surface of the sterile barrier packaging film.

[0093] The membrane forming the patch or sheet may comprise, consist essentially of, or consist of a patch support and a sealing layer comprising chlorite ions. The patch support may comprise one or more layers, provided that chlorine dioxide is permeable through each layer.

[0094] The film may be in the form of a sheet from which one or more patches may be formed. For example, the sheet may be punched or cut to form the patches. As used herein, a "sheet" includes a roll of film.

[0095] The patch support may be formed of a material that is permeable to chlorine dioxide or that can be modified to be permeable to chlorine dioxide. For example, any support that is initially impermeable to chlorine dioxide may be made permeable by perforating to form a patch support. Thus, a wide variety of materials may be used to form a patch support.

[0096] Oxygen permeability can serve as a proxy for chlorine dioxide permeability. In some embodiments, the patch support will have a permeability of at least 100 cm at 1 atmosphere and 23°C. 3 / m 2 / 24h, at least 250cm at 1 atmosphere and 23°C 3 / m2 / 24h oxygen transmission rate (O2TR). The oxygen transmission rate (O2TR) can be measured by any suitable method. For example, the oxygen transmission rate can be measured according to ASTM D398S.

[0097] The patch support may be formed of fibers or any other suitable form of material. In some embodiments, the patch support comprises a nonwoven material. In some embodiments, the nonwoven material comprises spun polyolefin fibers, polyester fibers, polyamide fibers, etc. In some embodiments, the patch support comprises polyethylene fibers. In some embodiments, the polyethylene fibers are high-density polyethylene fibers. In some embodiments, the high-density polyethylene fibers are flash-spun high-density polyethylene fibers. A suitable example of flash-spun high-density polypropylene fibers is Dupont's Thin sheet material.

[0098] In some embodiments, the patch support is paper or cloth. In some embodiments, the patch support is a polymer membrane that is permeable to chlorine dioxide or is perforated or otherwise modified to be permeable to chlorine dioxide.

[0099] Preferably, the patch support is opaque to ultraviolet radiation, particularly ultraviolet light having a wavelength in the range of from about 200 nm to about 390 nm. For example, the patch support blocks more than 90% or more of the transmission of ultraviolet light. In some embodiments, the patch support blocks 95% or more of the transmission of ultraviolet light. A patch support having ultraviolet light opacity can be helpful in a method for accelerating the decomposition of chlorine dioxide to reduce the amount of time from activation of chlorite ions to safe opening of a package containing a patch having a sealing layer containing chlorite ions.

[0100] Examples of materials that may be UV opaque and may be used to form the patch support include polymers having aromatic moieties that absorb UV 254 nm light, such as polyesters, aromatic polyamides, polystyrene, etc. Flash spun high density polyethylene fibers such as DuPont's May be UV opaque.

[0101] The patch or the sheet used to form the patch may include any suitable patch sealing layer, which includes chlorite ions. As used herein, a "patch sealing layer" is a layer comprising a composition, which is configured to fix the patch to another structure (such as the surface of a packaging material or packaging film) via melt bonding or chemical bonding (such as adhesion). The patch sealing layer can be a single layer or multiple layers. For example, a single layer patch sealing layer may include chlorite ions mixed with a heat-sealable polymer composition. A multilayer patch sealing layer may include a first layer containing chlorite ions and a second separate layer having a sealing function. For example, the second separate layer of the patch sealing layer having a sealing function may include a heat-sealable polymer composition, a cold seal adhesive, or a pressure-sensitive adhesive. The patch may be adhered to the packaging film on the entire sealing layer surface, or only a portion of the sealing layer surface (i.e., point bonding or bonding at the edge of the patch).

[0102] The patch sealing layer can be applied on any suitable support, to form a patch or a thin sheet for forming a patch. It should be understood that a patch or a thin sheet for forming a patch is a "film". As used herein, a "film" is a thin structure with a length and width significantly larger than its depth or thickness. Typically, the length and width of the film are at least 100 times greater than the thickness of the film, such as at least 1000 times greater than the thickness of the film. Thus, the term "film" can include paper, cloth, nonwoven material, and polymer film.

[0103] Typically, the patch sealing layer contains at least about 0.1% chlorite by weight so that a sufficient amount of chlorine dioxide can be generated. The patch sealing layer can contain any suitable amount of chlorite. The amount of chlorite can be varied to help control the amount of ClO2 gas generated. In a non-limiting example, the weight percentage of chlorite is, for example, 0.1%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70% of the weight of the patch sealing layer, or any amount therebetween. In some embodiments, the lower weight range of chlorite may be, for example, 0.1%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, or 65% of the weight of the patch sealing layer composition, while the upper weight range of chlorite may be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70% of the weight of the patch sealing layer composition. The present disclosure includes all weight percentage ranges defined by any combination of these lower and upper limits.

[0104] The composition of the patch sealant layer is designed to incorporate sufficient sodium chlorite for the desired ClO2 release level while maintaining a stable dispersion. An example of a coating formulation that meets this purpose includes a sodium chlorite solution; deionized water, a base for the coating formulation (e.g., a polyolefin copolymer dispersion), a viscosity modifier (e.g., xanthan gum), and a defoaming agent (e.g., a nonionic-ionic surfactant).

[0105] No matter the composition or type of patch sealing layer and the method for applying patch sealing layer, the patch sealing layer can have any suitable thickness.In certain embodiments, the patch sealing layer produced or the thin sheet for forming patch has the thickness from about 0.1 mil to about 1 mil, such as from about 0.25 mil to about 0.75 mil.When coating is applied on for example nonwoven material, coating can be applied with any suitable weight.For example, dry coating weight can be from about 1 to about 15 pounds / reams (lb / rm), such as from about 3 to about 11lb / rm.

[0106] Preferably, the patch sealing layer is substantially transparent to ultraviolet radiation. The patch sealing layer can be applied to the patch support in any suitable manner. For example, the patch sealing layer and the patch support can be coextruded to form a film, which can form a patch or a thin sheet for forming a patch. The patch sealing layer can be coated, sprayed, rolled, printed, adhered or otherwise applied to the patch support. The patch sealing layer can be arranged throughout the entire surface of the patch support or throughout one or more parts of the surface of the patch support. In certain embodiments, the patch sealing layer is applied to the entire surface of the patch support using a gravure or air knife coating process.

[0107] The patch sealing layer may comprise more than one layer, provided that chlorite ions are present in at least one layer. The layer containing chlorite ions and any layers between the layer containing chlorite ions and the sealing layer surface are substantially transparent to ultraviolet radiation.

[0108] Methods of manufacture and use, including gas generation

[0109] Generally speaking, the packages disclosed herein are manufactured by providing an unsealed package and a self-sterilizing component, introducing a gas comprising carbon dioxide into the unsealed package, and hermetically sealing the product within the interior of the self-sterilizing package. Thereafter, the self-sterilizing package is exposed to ultraviolet radiation, whereupon chlorine dioxide gas is generated, allowing for deodorization, disinfection, and / or sterilization.

[0110] The films described herein may be manufactured in any suitable manner, such as by conventional processes. Processes for producing flexible films may include, for example, cast film or blown film extrusion processes, or lamination processes.

[0111] The packaging material can be formed by film in any suitable manner. In certain embodiments, the packaging material is formed by heat-sealing the film itself or another suitable film. In certain embodiments, the packaging material is thermoformed such as a tray. In certain embodiments, the film is heat-sealed across the opening of the container or the base material.

[0112] In some embodiments, the interior of the package is exposed to humidified gas to introduce water. The humidified gas can have any suitable relative humidity. For example, the relative humidity of the humidified gas can be in the range of about 20% to 100%. In some such embodiments, the relative humidity of the humidified gas is in the range of about 20% to 100%. In some such embodiments, the relative humidity of the humidified gas is in the range of about greater than or equal to 60% to less than or equal to 100%.

[0113] In some embodiments, gas flushing is used to provide carbon dioxide to the interior of the package. Just before sealing the package, the package headspace is flushed with a gas containing carbon dioxide. The gas flushing can be done with a gas of 100% carbon dioxide or a gas mixture containing less than 100% carbon dioxide. In this way, CO2 is injected into the headspace of the package and then the package is sealed, thereby effectively increasing the carbon dioxide content of the headspace to at least 5%.

[0114] Can be exposed to UV radiation by any suitable mode with packaging material as herein described, so that chlorine dioxide is produced by a plurality of chlorite ions.The packaging material is designed to contain water inside.For example, the packaging material inside can be exposed to water vapor or humidified gas.When exposed to UV light, release ClO2 gas.For example, due to the manufacturing process or environmental conditions for producing aseptic barrier packaging film, sufficient moisture can be present in the packaging material, so that only film or this packaging material need be exposed to UV light to produce ClO2.In certain embodiments, there can be an intermediate storage time between producing self-sterilizing packaging material and being exposed to ultraviolet light.In some such embodiments, the intermediate storage time is in the range of about one minute to about two days.In some such embodiments, the storage time is in the range of about one hour to about one day.

[0115] The amount of ClO2 gas generated by the self-sterilizing components described herein can be adjusted by, for example, varying the wavelength of the UV light and exposure time, the amount of water vapor (moisture) present, the concentration of chlorite in the composition, or the length of the storage period. According to embodiments herein, when CO2 gas is present, for a given set of UV exposure, water, chlorite concentration, and packaging configuration, the amount of ClO2 gas generated is increased compared to the absence of added CO2 gas.

[0116] In some embodiments, the UV light has a wavelength in the range of about 200 nm to 400 nm. In some such embodiments, the UV light has a wavelength in the range of about 230 nm to 320 nm. In some such embodiments, the UV light has a wavelength in the range of about 240 nm to 280 nm. Preferably, the UV light comprises light having a wavelength of about 254 nm.

[0117] In some embodiments, the package is exposed to UV light for a period of time greater than 10 milliseconds. In some embodiments, the package is exposed to UV light for a period of time greater than 10 seconds. In some embodiments, the package is exposed to UV light for a period of time greater than ten minutes.

[0118] In some embodiments, the step of exposing the package to ultraviolet light may be repeated one or more times.

[0119] In some embodiments, the method further comprises the step of heating the package.

[0120] In some embodiments, the method for generating ClO2 gas comprises the following steps: (a) providing a self-sterilizing composition of water and chlorite ions in an atmosphere of greater than or equal to 5% carbon dioxide in the interior of a package, and (b) exposing the package to ultraviolet (UV) light. Optionally, step (b) can be repeated one or more times to generate additional amounts of ClO2 gas.

[0121] A method of sterilizing a packaged product herein includes: providing an unsealed package comprising: a sterile barrier packaging film comprising a main layer and a plurality of chlorite ions; and a package interior; and introducing water into the package interior; introducing a product to be sterilized into the package interior, and introducing a gas comprising carbon dioxide into the package interior of the package; after introducing the gas comprising carbon dioxide, hermetically sealing an open end of the unsealed package to form a self-sterilizing package containing the packaged product and a head space, wherein the head space comprises carbon dioxide in an amount greater than or equal to 5% by volume of the head space; and exposing the self-sterilizing package to UV radiation; wherein the self-sterilizing components comprise: water and a plurality of chlorite ions, and these components are substantially free of energy-activated catalysts and acid-releasing compounds. Water is proximate to the plurality of chlorite ions.

[0122] Before describing several exemplary embodiments of the present invention, it should be understood that the present invention is not limited to the details of construction or process steps set forth in the following description. The present invention is capable of other embodiments and of being practiced or carried out in various ways.

[0123] Turning to the attached figure, Figure 1 is a schematic side view of a sterile barrier packaging film according to an embodiment. Figure 1In the present invention, the sterile barrier packaging film 10 includes a main layer 12 and a coating 16, which includes chlorite ions. The main layer 12 can be a sealing layer having a polymer composition as described herein. The coating can cover the entire inner surface 14 of the main layer 12, or the coating 16 can cover less than the entire inner surface 14. In one or more embodiments, the coating covers a surface area of ​​the inner surface 14 of greater than or equal to 10% to less than or equal to 100%, and all values ​​and sub-ranges therebetween, including greater than or equal to 20%, greater than or equal to 30%, greater than or equal to 40%, greater than or equal to 50%, greater than or equal to 60%, greater than or equal to 70%, greater than or equal to 80%, greater than or equal to 90%, greater than or equal to 95%.

[0124] exist Figure 2 , a schematic side view of a sterile barrier packaging film according to an embodiment is provided, the sterile barrier packaging film 20 comprising a main layer 26 and an optional sublayer 22. The main layer 26 comprises chlorite ions and a sealing polymer or a polymer-based formulation. When present, the optional sublayer 22 can be an outer layer. The main layer 26 can be applied to the sublayer 22 in any suitable manner to form a film. Preferably, due to the thermal sensitivity of the chlorite ions, the method for applying the main layer 26 to the sublayer 22 is carried out at a temperature significantly lower than the temperature typically associated with extrusion. Preferably, the main layer 26 is applied to the sublayer 22 at room temperature.

[0125] Figure 3 Schematic plan views of packages according to embodiments are provided. Figure 3 The package 50 of the embodiment comprises two films sealed together as side walls, including a first side wall 60 and a second side wall (not shown). In this embodiment, the side walls are sealed together at a first side seam or heat seal 52, a second side seam or heat seal 54, a third side seam or heat seal 56, and a fourth side seam or heat seal 58, and the volume in these seams or seals at least partially defines the interior of the package. The first side wall 60 comprises a packaging film according to an embodiment of the present invention, including but not limited to Figure 1 and Figure 2 The other side wall (not shown) may or may not comprise a multilayer packaging film having a chlorine dioxide generating layer.

[0126] Figure 4It is a schematic cross-sectional view of the package according to an embodiment.Package 300 is formed by the first packaging film 200 and the second packaging film 299, and this first packaging film and this second packaging film can be made of the same or different material.Patch 100 is fixed on the surface 202 of the first packaging film 200, and this first packaging film limits at least a portion of the inside 302 of the package with internal volume.Patch 100 comprises patch support 120 and the patch sealing layer 110 that comprises chlorite ion.Patch 100 is fixed on the surface 202 of the first packaging film 200 via patch sealing layer 110.Patch support 120 is permeable to chlorine dioxide and is preferably opaque to ultraviolet light.The patch sealing layer 110 that comprises chlorite ion faces the outside of the package, so that when UV light is applied to the package, chlorite ion is easy to be used for producing ClO2 gas.Additional benefit is that the sealing layer that contains chlorite does not directly contact the product in the package.

[0127] The first packaging film 200 and the second packaging film 299 are substantially transparent to ultraviolet light and substantially impermeable to chlorine dioxide. The first packaging film 200 defines a first side 307 of the package 300 , and the second packaging film 299 defines a second side 309 of the package 300 .

[0128] An article or product 400 is disposed in the package interior 302. Ultraviolet light may be applied to the package 300 through the first side 307 to generate chlorine dioxide gas from the chlorite ions in the patch sealing layer 110. The generated chlorine dioxide may deodorize, disinfect, or sterilize the article or product 400.

[0129] Examples

[0130] Patch. The patch used in the examples was made as follows: The patch comprised a chlorine dioxide permeable patch support and a sealing layer. The patch support was TYVEK 1073B coated with the coating formulation of Table 1, which formed the sealing layer.

[0131] Table 1.

[0132]

[0133] Each patch had a coating weight of approximately 7 pounds per ream (lb / rm).

[0134] In these examples, when the pouch with the patch was exposed to ultraviolet light having a wavelength of 254 nm (UV254) for 60 seconds, UV254 exposure was performed using an XL-1500 UV Crosslinker Unit (containing six 16W UV254 bulbs) at a distance of 2" from the UV bulb.

[0135] Improved Palintest. In these examples, when analyzing the ClO2 gas concentration of the extracted gas, a Palintest suitable for packaging headspace analysis purposes (referred to herein as "Improved Palintest") was used, which was tested as follows for each pouch with headspace. Measurements were made in a fume hood, and each pouch was stirred before testing to ensure uniform concentration. A syringe was used to pierce one side of the pouch to extract 20 mL of headspace gas. The syringe needle was immediately placed in 40 mL of cooled deionized water (38 ° F) in a beaker (to prevent leakage) to draw 5 mL of cooling water. The syringe was then shaken vigorously to dissolve the ClO2 gas in the water. Then 5 mL of water containing the dissolved ClO2 gas was drained into the beaker. Another flushing of the syringe was performed by drawing 5 mL of the beaker contents into the syringe, shaking the syringe, and then draining the syringe contents into the beaker. The beaker contents with ClO2 dissolved in water were then analyzed by the Palintest ChlordioX Plus to determine the ClO2 content (mg). To calculate the ClO2 concentration, multiply the ClO2 content (mg) by 0.04L water and divide by 0.02L headspace to convert the units from mgClO2 / L water to mgClO2 / L headspace based on a standard of 40mL of cooled deionized water and 20mL of headspace gas. A quick calculation based on this standard can be made by simply multiplying the Palintest contents by 2 to get the headspace concentration.

[0136] Comparative Example 1

[0137] Example 2

[0138] Comparative Example 3

[0139] Pouch with patch. In Examples 1-3, a pouch with patch for delivering chlorite ions was made as follows. A sterile barrier packaging film was obtained, which included a layer of biaxially oriented polyamide (BOPA) and a multilayer film containing a polyethylene (PE)-based layer. The PE-based layer served as a heat seal layer for forming a pouch. The patch made as described above was applied to the PE-based layer.

[0140] Two sheets of sterile barrier packaging film were cut to 8" x 10" size (BOPA / PE) and 1 patch (4 inch (10.16 cm) diameter) was sealed to one of the PE-based layers with the patch seal layer facing the outside of the PE-based layers. The two sheets of sterile barrier packaging film were then heat sealed together so that the PE-based layers faced each other and the patch sealed to one of the films was now between the films. Three sides of the film were sealed to form a seam, resulting in an unsealed pouch with the fourth side open.

[0141] The unsealed pouches were then exposed to a humidification step by storing them in a room having a temperature of 35°C and 80% relative humidity (RH) for 2 hours.

[0142] The unsealed pouches were then exposed to vacuum and sealed on the fourth side. A test gas of air or carbon dioxide was then injected into each pouch with a gas flush to create a headspace and then resealed by heat sealing.

[0143] The first set of comparative pouches (Samples 1.1-1.3) according to Comparative Example 1 received 40 mL of air in the headspace. The second set of inventive pouches (Samples 2.1-2.3) according to Example 2 received 40 mL of CO2. The third set of comparative pouches (Samples 3.1-3.3) according to Comparative Example 3 received 40 mL of CO2.

[0144] Comparative Example 1 and Example 2 were exposed to ultraviolet light (UV254) having a wavelength of 254 nm for 60 seconds. Comparative Example 3 was not exposed to UV254.

[0145] Comparative Example 1, Example 2 and Comparative Example 3 were all placed in a completely dark drawer without ambient light for 5 minutes. A completely dark drawer was used to avoid degradation of ClO2 gas by ambient light. Thereafter, in a fume hood, 20 mL of the headspace gas was extracted and dissolved in 40 mL of cooled deionized water. The ClO2 concentration of the extracted gas was analyzed using a modified Palintest.

[0146] Table 2 summarizes these samples and the ClO2 concentration measurements.

[0147] Table 2.

[0148]

[0149]

[0150] *The measured value of <0.02 mg / L is the lowest possible measured value on the test device.

[0151] From Table 2, it can be concluded that the chlorite-containing patch exposed to UV254 for 60 seconds in a headspace with 100% CO2 by volume produced about twice as much ClO2 as the headspace with air. In the absence of exposure to UV254 and a headspace with 100% CO2 by volume, no ClO2 was detected, indicating that carbonic acid did not react spontaneously with sodium chlorite.

[0152] Example 4

[0153] Comparative Example 5

[0154] Pouch with patch. In Examples 4-5, a pouch with patch for delivering chlorite ions was made as follows. A sterile barrier packaging film was obtained, which included a layer of biaxially oriented polyamide (BOPA) and a multilayer film containing a polyethylene (PE)-based layer. The PE-based layer served as a heat seal layer for forming a pouch. The patch made as described above was applied to the PE-based layer, with the patch seal layer facing the outside of the package.

[0155] Two sheets of sterile barrier packaging film were cut to 8" x 10" size (BOPA / PE) and 1 patch (4 inch (10.16 cm) diameter) was sealed to one of the PE-based layers with the patch seal layer facing the outside of the PE-based layers. The two sheets of sterile barrier packaging film were then heat sealed together so that the PE-based layers faced each other and the patch sealed to one of the films was now between the films. Three sides of the film were sealed to form a seam, resulting in an unsealed pouch with the fourth side open.

[0156] The unsealed pouch was then exposed to a humidification step by exposure to a hand-held steamer for 10 seconds at approximately 5 inches from the open fourth side.

[0157] The unsealed pouches were then exposed to vacuum and sealed on the fourth side. A volume of 100 mL of test gas was then injected into each of the pouches to create a headspace. The composition of the test gas differed in CO2 content.

[0158] The first set of pouches according to Example 4 (Samples 4.1-4.5) received CO2-containing gas varying from 20% by volume to 100% by volume. The comparative pouch according to Comparative Example 5 (Sample 5.1) received 100% air.

[0159] Example 4 and Comparative Example 5 were exposed to ultraviolet light (UV254) having a wavelength of 254 nm for 60 seconds.

[0160] Example 4 and Comparative Example 5 were placed in a completely dark drawer without ambient light for 5 minutes. A completely dark drawer was used to avoid degradation of ClO2 gas by ambient light. Thereafter, in a fume hood, 20 mL of the headspace gas was extracted and dissolved in 40 mL of cooled deionized water. The ClO2 concentration of the extracted gas was analyzed using a modified Palintest.

[0161] Table 3 summarizes these samples and the ClO2 concentration measurements.

[0162] Table 3.

[0163]

[0164] From Table 3, it can be concluded that the chlorite-containing patch exposed to UV254 in a headspace with 100% CO2 by volume produced about twice as much ClO2 as a headspace with 100% air. The increase in ClO2 was also shown for a change in CO2 content from 20% by volume to 80% by volume relative to a headspace with 100% air.

[0165] Example 6

[0166] Comparative Example 7

[0167] In Examples 6-7, a pouch with a patch for delivering chlorite ions was made according to Examples 4-5.

[0168] The first set of pouches according to Example 6 (Samples 6.1-4.4) received CO2-containing gas varying from 5% by volume to 100% by volume. The comparative pouch according to Comparative Example 7 (Sample 7.1) received 100% air.

[0169] Example 6 and Comparative Example 7 were exposed to ultraviolet light (UV254) having a wavelength of 254 nm for 60 seconds.

[0170] Example 6 and Comparative Example 7 were placed in a completely dark drawer without ambient light for 5 minutes. A completely dark drawer was used to avoid degradation of ClO2 gas by ambient light. Thereafter, in a fume hood, 20 mL of the headspace gas was extracted and dissolved in 40 mL of cooled deionized water. The ClO2 concentration of the extracted gas was analyzed using a modified Palintest.

[0171] Table 4 summarizes these samples and the ClO2 concentration measurements.

[0172] Table 4.

[0173]

[0174] From Table 4, it can be concluded that the chlorite-containing patch exposed to UV254 in a headspace with as little as 5% CO2 by volume produced about 1.5 times more ClO2 than a headspace with 100% air. CO2 levels of 10% by volume, 15% by volume, and 100% by volume also showed increased ClO2 relative to a headspace with 100% air.

[0175] Example 8

[0176] Comparative Examples 9-12

[0177] Pouches with Chlorite Ions. In Examples 8-12, pouches for delivering chlorite ions were made as follows.

[0178] A 3-side sealed pouch measuring 5" x 10.5" was made on a production packaging machine. A 4" diameter Tyvek patch coated with the coating in Table 1 was sealed to the inside.

[0179] The pouch with the unsealed fourth side was then exposed to a humidification step by storing in a room having a temperature of 35° C. and 80% relative humidity (RH) for 2 hours.

[0180] The unsealed pouches were then exposed to vacuum and sealed on the fourth side. The test gas was then injected into each of the pouches by gas flushing to create a headspace. The various test gases were analyzed.

[0181] As shown in Table 5, each set of pouches received 40 mL of test gas in the headspace.

[0182] All samples of Examples 8-12 were exposed to ultraviolet light (UV254) with a wavelength of 254 nm for 60 seconds, and then placed in a completely dark drawer without ambient light for 5 minutes. A completely dark drawer was used to avoid ClO2 gas being degraded by ambient light. Thereafter, in a fume hood, 20 mL of headspace gas was extracted and dissolved in 40 mL of cooling deionized water. The ClO2 concentration of the extracted gas was analyzed using a modified Palintest.

[0183] Table 5 summarizes these samples and the ClO2 concentration measurements.

[0184] Table 5.

[0185]

[0186]

[0187] It can be concluded from Table 5 that the presence of CO2 in the headspace has the greatest effect on increasing ClO2 concentration relative to the other gases tested: air, N2, O2, and He.

[0188] Example 13

[0189] Comparative Example 14

[0190] Pouches with Chlorite Ions. In Examples 13-14, pouches for delivering chlorite ions were made as follows.

[0191] Two sheets of nylon laminate film were cut to 5" x 11". The two sheets were then heat sealed on three sides to form an unsealed pouch with an open fourth side.

[0192] Obtain a 32% by weight sodium chlorite stock solution. For each pouch, add 3 drops of chlorite solution to the open fourth side using a pipette. Because the sodium chlorite solution contains water, no additional humidification is required.

[0193] The unsealed pouch was sealed on the fourth side and the air was evacuated from the headspace using a septum. A separate pouch filled with 100% CO2 from a pressurized cylinder was then used as a reservoir to fill the headspace of the sample pouch.

[0194] As shown in Table 6, each pouch received 40 mL of headspace gas.

[0195] All samples of Example 13-14 are exposed to ultraviolet light (UV254) with a wavelength of 254nm for 75 seconds, and then placed in a completely dark drawer without ambient light for 5 minutes. A completely dark drawer is used to avoid ClO2 gas being degraded by ambient light. Thereafter in a fume hood, 20mL of headspace gas is extracted and dissolved in 40mL of cooling deionized water. The ClO2 concentration of the extracted gas is analyzed using an improved Palintest.

[0196] Table 6 summarizes these samples and the ClO2 concentration measurements.

[0197] Table 6.

[0198]

[0199] From Table 6 it can be concluded that exposing chlorite ions to UV254 for 75 seconds in a headspace with 100% CO2 by volume produces more than 5 times more ClO2 than a headspace with air.

[0200] Example 15

[0201] Comparative Example 16

[0202] Pouch with patch. In Examples 13-14, a pouch with patch for delivering chlorite ions was made as follows. A sterile barrier packaging film comprising a nylon layer and a peelable sealant layer was obtained. The peelable sealant layer served as a heat seal layer for forming a pouch. A patch made as described above was applied to the peelable sealant layer, with the patch sealant layer facing outward.

[0203] Two sheets of sterile barrier packaging film were cut to a size of 8"x8" (20.32 cm x 20.32 cm), and 1 patch (6 inches (15.24 cm) x 6 inches (15.24 cm)) was sealed to one layer of the peelable sealant layer. The two sheets of sterile barrier packaging were then heat sealed on three sides to form an unsealed pouch with an open fourth side.

[0204] The unsealed pouch was then exposed to a humidification step by exposure to a hand-held steamer for 10 seconds at approximately 5 inches from the open fourth side.

[0205] The unsealed pouches were then exposed to vacuum and sealed on the fourth side. A test gas of either air or carbon dioxide was then injected into each of the pouches to create a headspace.

[0206] As shown in Table 7, each pouch received 60 mL of headspace gas.

[0207] Example 15-16 is exposed to ultraviolet light (UV254) with a wavelength of 254nm for 60 seconds, and then placed in a completely dark drawer without ambient light for 5 minutes. A completely dark drawer is used to avoid ClO2 gas being degraded by ambient light. Thereafter in a fume hood, 20mL of the headspace gas is extracted and dissolved in 40mL of cooling deionized water. The ClO2 concentration of the extracted gas is analyzed using a modified Palintest.

[0208] Table 7 summarizes these samples and the ClO2 concentration measurements.

[0209] Table 7.

[0210]

[0211] From Table 7, it can be concluded that a patch containing chlorite exposed to UV254 for 60 seconds in a headspace with 100% CO2 by volume produces about 2.8 times more ClO2 than a headspace with air. It should be noted that the larger surface area (26 in in this example) 2 Compared to 12.56in in the previous example 2 ) patches produce more ClO2.

[0212] Unless otherwise indicated, all numerical values ​​used in the specification and claims expressing the quantity of ingredients, properties such as molecular weight, reaction conditions, etc. should be understood as being modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that can vary depending on the desired properties sought to be obtained by the present disclosure. At the very least, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of reported significant digits and by applying customary rounding techniques.

[0213] Throughout this specification, references to "one embodiment," "certain embodiments," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic described in conjunction with that embodiment is included in at least one embodiment of the present invention. Thus, phrases such as "in one or more embodiments," "in certain embodiments," "in one embodiment," or "in an embodiment" appearing in various places throughout this specification do not necessarily refer to the same embodiment of the present invention. Furthermore, in one or more embodiments, particular features, structures, materials, or characteristics may be combined in any suitable manner.

[0214] Although the present invention has been described herein with reference to specific embodiments, it should be understood that these embodiments are merely illustrations of the principles and applications of the present invention. It is clear to those skilled in the art that various modifications and variations may be made to the method and apparatus of the present invention without departing from the spirit and scope of the present invention. Therefore, the present invention is intended to include modifications and variations within the scope of the appended claims and their equivalents.

[0215] Example

[0216] Embodiment A: A packaging material comprising:

[0217] Sterile barrier packaging films;

[0218] A self-sterilizing component comprising: a plurality of chlorite ions and water, wherein the self-sterilizing components are substantially free of an energy-activated catalyst and an acid-releasing compound;

[0219] The interior of the package is formed by hermetically sealing the sterile barrier packaging film; and

[0220] A headspace within the package comprises carbon dioxide present in an amount greater than or equal to 5% by volume of the headspace.

[0221] Embodiment B: A package as described in any of Embodiments A or CL, wherein when the package is exposed to ultraviolet (UV) light having a wavelength of 254 nm, the reaction of the chlorite ions with water produces chlorine dioxide (ClO2), which is released into the head space.

[0222] Embodiment C: The package of any one of embodiments AB or DL, wherein in the absence of any UV light, chlorine dioxide (ClO2) is not generated.

[0223] Embodiment D. The package of any one of Embodiments AC or EL, wherein water is in proximity to the plurality of chlorite ions.

[0224] Embodiment E: The package of any of Embodiments AD or FL having a relative humidity within the interior of the package in a range of greater than or equal to 20% to less than or equal to 100% at 72.5°F.

[0225] Embodiment F: The package of any of Embodiments AE or GL, wherein the plurality of chlorite ions is provided by a salt comprising sodium chlorite, potassium chlorite, calcium chlorite, magnesium chlorite, lithium chlorite, ammonium chlorite, or a mixture thereof.

[0226] Embodiment G: The package of any one of Embodiments AF or HL, wherein the sterile barrier packaging film is substantially transparent to ultraviolet (UV) light.

[0227] Embodiment H: The package of any one of Embodiments AG, wherein the sterile barrier packaging film comprises a main layer and a patch fixed to the main layer, wherein the patch provides the plurality of chlorite ions.

[0228] Embodiment I: The packaging material as described in Embodiment H, wherein the patch comprises:

[0229] a patch support permeable to chlorine dioxide and defining a first major surface of the patch; and

[0230] A patch sealing layer comprising the plurality of chlorite ions dispersed in a polymer composition, wherein the patch sealing layer contacts the patch support and defines a second major surface of the patch, and wherein the patch sealing layer is secured to the main layer.

[0231] Embodiment J: The packaging material of Embodiment I, wherein the polymer composition comprises at least one of polyethylene, polypropylene, polyacrylate, or a copolymer of any of these.

[0232] Embodiment K: The package of any of Embodiments AG, wherein the plurality of chlorite ions are present in a coating on the self-sterilizing packaging film, and the coating comprises chlorite in combination with a polymer composition.

[0233] Embodiment L. The packaging of Embodiment K, wherein the polymer composition comprises at least one of polyethylene, polypropylene, polyacrylate, or a copolymer of any of these.

[0234] Embodiment M: A packaged product comprising:

[0235] Packaging film;

[0236] multiple chlorite ions;

[0237] water;

[0238] The interior of the package formed by hermetically sealing the packaging film;

[0239] the product inside the packaging; and

[0240] a headspace inside the package comprising carbon dioxide present in an amount greater than or equal to 5% by volume of the headspace;

[0241] The self-sterilizing components include water and a plurality of chlorite ions, and these components are substantially free of energy-activated catalysts and substantially free of acid-releasing compounds.

[0242] Embodiment N: A packaged product as described in any of Embodiments M or OS, wherein when the packaging film is exposed to ultraviolet (UV) light having a wavelength of 254 nm, the reaction of the chlorite ions with water produces chlorine dioxide (ClO2), which is released into the head space and effectively sterilizes the product inside the package.

[0243] Embodiment O: The packaged product of any one of Embodiments M, N, R or S, wherein the packaging film comprises a main layer and a patch secured to the main layer, wherein the patch provides the plurality of chlorite ions.

[0244] Embodiment P: The packaged product of Embodiment O, wherein the patch comprises:

[0245] a patch support that is permeable to chlorine dioxide; and

[0246] A patch sealing layer comprising the plurality of chlorite ions dispersed in a polymer composition, wherein the patch sealing layer is in contact with the patch support, and wherein the patch sealing layer is secured to the primary layer.

[0247] Embodiment Q: The packaged product of Embodiment P, wherein the polymer composition comprises at least one of polyethylene, polypropylene, polyacrylate, or a copolymer of any of these.

[0248] Embodiment R: A packaged product as described in any one of embodiments MQ or S, wherein the product inside the package is a medical device or a medical supply.

[0249] Embodiment S: A packaged product as described in any of embodiments MR, wherein the product inside the package is a food.

[0250] Embodiment T: A method for sterilizing a packaged product, comprising:

[0251] Supplied in unsealed packaging containing:

[0252] a sterile barrier packaging film comprising a primary layer and a plurality of chlorite ions; and

[0253] Inside the packaging; and

[0254] introducing water into the interior of the packaging;

[0255] The product to be sterilized is introduced into the packaging.

[0256] introducing a gas comprising carbon dioxide into the interior of the package;

[0257] After introducing the gas comprising carbon dioxide, hermetically sealing the open end of the unsealed package to form a self-sterilizing package containing the packaged product and a head space, wherein the head space comprises carbon dioxide in an amount greater than or equal to 5% by volume of the head space; and

[0258] exposing the self-sterilizing package to UV radiation;

[0259] The self-sterilizing components include water and a plurality of chlorite ions, and these components are substantially free of energy-activated catalysts and acid-releasing compounds.

[0260] Embodiment U. The method of any one of Embodiments T, V or W, wherein water is in proximity to the plurality of chlorite ions.

[0261] Embodiment V: The method of any one of Embodiments T, U or W, wherein at least 1.39 μg / mL of chlorine dioxide is generated within the package within 5 minutes.

[0262] Embodiment W. The method of any one of Embodiments T, U or V, wherein the UV radiation comprises a wavelength of 254 nm.

Claims

1. A packaging material, comprising: Sterile barrier packaging films; A self-sterilizing component comprising: a plurality of chlorite ions and water, wherein the self-sterilizing components are substantially free of an energy-activated catalyst and an acid-releasing compound; The interior of the package is formed by hermetically sealing the sterile barrier packaging film; and a headspace inside the package comprising carbon dioxide in an amount greater than or equal to 5% by volume of the headspace, in, When the package is exposed to ultraviolet (UV) light having a wavelength of 254 nm, the reaction of the chlorite ions with water produces chlorine dioxide (ClO2), which is released into the headspace.

2. The package according to claim 1, wherein: In the absence of any UV light, no chlorine dioxide (ClO2) is produced.

3. The package according to claim 1, wherein: Water is in proximity to the plurality of chlorite ions.

4. The package of claim 1 having a relative humidity within the interior of the package in a range of greater than or equal to 20% to less than or equal to 100% at 72.5°F.

5. The package according to claim 1, wherein: A salt comprising sodium chlorite, potassium chlorite, calcium chlorite, magnesium chlorite, lithium chlorite, ammonium chlorite, or a mixture thereof provides the plurality of chlorite ions.

6. The package according to claim 1, wherein: The sterile barrier packaging film is substantially transparent to ultraviolet (UV) light.

7. The package according to claim 1, wherein: The sterile barrier packaging film comprises a main layer and a patch fixed to the main layer, wherein the patch provides the plurality of chlorite ions.

8. The package according to claim 7, wherein: The patch contains: a patch support permeable to chlorine dioxide and defining a first major surface of the patch; and A patch sealing layer comprising the plurality of chlorite ions dispersed in a polymer composition, wherein the patch sealing layer contacts the patch support and defines a second major surface of the patch, and wherein the patch sealing layer is secured to the main layer.

9. The package according to claim 8, wherein: The polymer composition comprises at least one of polyethylene, polypropylene, polyacrylate, or a copolymer of any of these.

10. The package according to claim 1, wherein: The plurality of chlorite ions are present in a coating on the sterile barrier packaging film, and the coating comprises chlorite in combination with a polymer composition.

11. The package according to claim 10, wherein: The polymer composition comprises at least one of polyethylene, polypropylene, polyacrylate, or a copolymer of any of these.

12. A packaged product comprising: Packaging film; multiple chlorite ions; water; The interior of the package is formed by hermetically sealing the packaging film; The product inside the packaging; as well as a headspace inside the package comprising carbon dioxide present in an amount greater than or equal to 5% by volume of the headspace; wherein the self-sterilizing components comprise: water and the plurality of chlorite ions, and these components are substantially free of energy-activated catalysts and substantially free of acid-releasing compounds, Among them, when the packaging film is exposed to ultraviolet (UV) light having a wavelength of 254nm, the reaction of the chlorite ions with water produces chlorine dioxide (ClO2), which is released into the head space and effectively sterilizes the product inside the package.

13. The packaged product of claim 12, wherein: The packaging film comprises a main layer and a patch fixed to the main layer, wherein the patch provides the plurality of chlorite ions.

14. The packaged product of claim 13, wherein: The patch contains: a patch support that is permeable to chlorine dioxide; and A patch sealing layer comprising the plurality of chlorite ions dispersed in a polymer composition, wherein the patch sealing layer is in contact with the patch support, and wherein the patch sealing layer is secured to the primary layer.

15. The packaged product of claim 14, wherein: The polymer composition comprises at least one of polyethylene, polypropylene, polyacrylate, or a copolymer of any of these.

16. The packaged product of claim 12, wherein: The product inside the package is a medical device or a medical supply.

17. The packaged product of claim 12, wherein: The product inside the packaging is a food.

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