Coating with a double-layer structure

Abstract

The film comprises a substrate and a coating deposited on the substrate. The coating comprises multiple double layers, each double layer comprising two layers of different materials. Each of the two layers of different materials may contain oxides, metal oxides, alkoxides, metal cones, or oxynitrides. The thickness of each of the two layers of different materials may be between approximately 3 nanometers and approximately 30 nanometers. The thickness of the coating may be between approximately 20 nanometers and approximately 100 nanometers. Films with nanometer-scale coatings can be used for food packaging and other applications.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the priority and benefit of U.S. Provisional Patent Application No. 63 / 457,626, filed on April 6, 2023, which is incorporated herein by reference.

[0002] Field This disclosure relates to coatings and the deposition of coatings onto films, particularly coatings on the nanometer scale.

Background Art

[0003] Background Coatings are used on a wide variety of flexible materials for packaging applications. Examples include, but are not limited to, coatings that protect products (e.g., food products) inside the packaging from external factors, coatings that provide antimicrobial properties (e.g., for the packaging of healthcare products), and coatings that serve other purposes.

[0004] Barrier coatings can be used on flexible packaging materials to protect products from external factors such as, but not limited to, water vapor, water, oxygen, light, odor, grease, and foreign matter. Protection from these external factors is useful for extending the shelf - life of the product and ensuring that the product can be safely used or consumed.

Summary of the Invention

Means for Solving the Problems

[0005] Summary According to an aspect of the present disclosure, a film includes a substrate and a coating deposited on the substrate. The coating includes a plurality of bilayer structures, and each bilayer structure includes two layers with different materials.

[0006] Each of the two layers made of different materials may contain an oxide, metal oxide, alkoxide, metal cone, or oxynitride.

[0007] Each of the double layers may also contain a layer of aluminum oxide and a layer of zinc oxide.

[0008] The double layer adjacent to the substrate may have its aluminum oxide layer in contact with the substrate.

[0009] The thickness of at least two of the multiple bilayers may be uniform.

[0010] At least two of the multiple bilayers may have different thicknesses.

[0011] In at least one of the multiple double layers, the thickness of the two layers made of different materials may be uniform.

[0012] In at least one of the multiple double layers, the thicknesses of the two layers made of different materials may be different.

[0013] The number of multiple bilayers may be between 2 and 12.

[0014] The thickness of each of the two layers made of different materials may be between approximately 3 nanometers and approximately 30 nanometers.

[0015] The coating thickness may be between approximately 20 nanometers and approximately 100 nanometers.

[0016] One layer of the coating in contact with the substrate may be thicker than the other layers of the coating.

[0017] The film may further include a base material, an additional substrate including an ink layer applied on the base material, and an adhesive layer that adheres the additional substrate to the coating.

[0018] The substrate may include a base material and an ink layer, and the coating may be deposited on the ink layer.

[0019] The film may further include an additional substrate and an adhesive layer that adheres the additional substrate to the coating.

[0020] The substrate may include a base material on which the coating is deposited, and the packaging film may further include an ink layer applied on the coating.

[0021] The film may further include an additional substrate and an adhesive layer that adheres the additional substrate to the ink layer.

[0022] The substrate may include a base material and a precoat, and the coating may be deposited on the precoat.

[0023] The film may further include a topcoat applied on the coating.

[0024] The substrate may include polylactic acid.

[0025] The substrate may include paper.

[0026] The film may further include a laminate.

[0027] Two layers with different materials may be formed using a co-reactant or an oxidizing agent.

[0028] The film may be a food packaging film.

[0029] According to another aspect of this disclosure, the film comprises a substrate and a coating deposited on the substrate. The coating comprises a plurality of bilayers, each bilayer comprising two layers of different materials. Each of the two layers of different materials comprises an oxide, metal oxide, alkoxide, metal cone, or oxynitride. The thickness of each of the two layers of different materials is between about 3 nanometers and about 30 nanometers. The thickness of the coating is between about 20 nanometers and about 100 nanometers.

[0030] One layer of the coating in contact with the substrate may be thicker than the other layers of the coating.

[0031] According to another aspect of the present disclosure, a method for producing a film includes alternately depositing two layers of different materials onto a substrate to form a bilayer, the thickness of which is on a nanometer scale. The method further includes forming a coating on the substrate by continuously forming a plurality of bilayers. [Brief explanation of the drawing]

[0032] [Figure 1] Figure 1 is a cross-sectional view of an exemplary film including a barrier coating applied to a substrate, the barrier coating comprising a double layer, each having two layers of different materials.

[0033] [Figure 2] Figure 2 is a cross-sectional view of an exemplary film containing a barrier coating on both sides, along with a base material, an ink layer, and an adhesive layer.

[0034] [Figure 3] Figure 3 is a cross-sectional view of another exemplary film, which includes a barrier coating on both sides, along with a base material, an ink layer, and an adhesive layer.

[0035] [Figure 4]Figure 4 is a cross-sectional view of another exemplary film, which includes a barrier coating on both sides, along with a base material, an ink layer, and an adhesive layer.

[0036] [Figure 5] Figure 5 is a cross-sectional view of an exemplary film including a barrier coating together with a topcoat and a precoat.

[0037] [Figure 6] Figure 6 is a cross-sectional view of another exemplary film including a barrier coating together with a pre-coat.

[0038] [Figure 7] Figure 7 is a cross-sectional view of another exemplary film including a barrier coating together with a topcoat.

[0039] [Figure 8] Figure 8 is a cross-sectional view of an exemplary double-layer configuration of a barrier coating in which the first layer is relatively thicker.

[0040] [Figure 9] Figure 9 is a cross-sectional view of another exemplary double-layer configuration having double layers of different thicknesses.

[0041] [Figure 10] Figure 10 is a cross-sectional view of another exemplary bilayer configuration in which the thickness of the material layers differs within the bilayer.

[0042] [Figure 11] Figure 11 shows the spatial atomic layer deposition (SALD) process for depositing barrier coatings.

[0043] [Figure 12] Figure 12 shows a SALD apparatus for depositing a barrier coating. [Modes for carrying out the invention]

[0044] Detailed explanation This specification discloses films, coatings, and methods for producing them, particularly those having a nanometer scale. The techniques described herein aim to improve coating performance by providing durable and resilient coatings.

[0045] Figure 1 shows an exemplary film 100 on which a coating 102 is applied to a substrate 104. The coating 102 is a barrier coating, and the examples given herein relate to barrier coatings. The techniques described herein are particularly suited to barrier coatings, but are not limited to barrier coatings.

[0046] The film 100 can be used for packaging, such as food packaging (e.g., sealed bags or packages containing food or raw materials, such as snacks, meats, cheeses, etc.), personal care products (e.g., creams, lotions, gels, etc.), pharmaceuticals, sterile medical supplies or medical devices, agricultural products, and similar products that benefit from protection against degradation or contamination and / or require a relatively long shelf life. The substrate provides mechanical strength to the film 100, and the barrier coating 102 provides a barrier against substances (e.g., oxygen, water, gases, particles, contaminants, etc.), without which such substances might penetrate into or through the substrate 104. The barrier coating 102 is deposited on the substrate 104 by spatial atomic layer deposition (SALD).

[0047] While packaging is a suitable application for the technologies described herein, it is not limited to packaging films. Therefore, this disclosure is not limited to packaging films. It should be evident that the teachings and examples provided herein relating to packaging films can be used for other applications or readily adapted to other applications.

[0048] The substrate 104 is flexible and may contain a base material, such as polylactic acid (PLA), paper, paperboard, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polyurethane (PU), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), starch-based polymer, seaweed-based polymer, or similar. The substrate 104 may also contain additional materials or layers thereof, such as an ink layer or precoat (also referred to as a primer). The substrate 104 may be selected to be biodegradable, reusable, or compostable.

[0049] The substrate 104, having a roughness characteristic with peak or valley size of less than approximately 0.2 millimeters, is intended to be usable without unnecessary difficulty.

[0050] If the substrate 104 has pinholes, the nominal width of the pinholes should be less than approximately 10 nanometers so that the barrier coating 102 can reliably close them.

[0051] A useful substrate 104 can have a wide range of surface chemistry. Surface oxygen (O) groups are particularly useful. Precursor chemicals used to form the barrier coating 102 may react with O groups, which facilitates coating deposition. Examples of base materials and primers having such O groups include, for example, PLA, PET, polyvinyl alcohol (PVOH), ethylene vinyl alcohol (EVOH), and acrylics.

[0052] The substrate 104 does not require any specific treatment to increase its surface energy, because it has been found that the barrier coating 102 adheres sufficiently to the substrate 104 even without the above treatment.

[0053] In-line surface treatment can help remove dust and particles to improve surface cleanliness and prevent pinhole formation. Examples of surface treatments (also called pretreatment) include corona treatment, plasma treatment (e.g., argon plasma), and flame treatment. Pretreatment of the surface before applying the barrier coating 102 can help with coating deposition, for example, by smoothing the surface in a way that improves the adhesion of the coating 102. Although surface treatment can be used on the barrier coating 102 because it conformally coats the surface and can encapsulate any dust particles, it is often assumed that it is not necessary.

[0054] Regarding the thermomechanical properties of the substrate 104, in many examples it is useful if the substrate does not expand significantly when heated. The substrate should maintain its shape without deformation at least up to the desired coating temperature. Ideally, the glass transition temperature of the substrate should exceed the coating temperature. Due to the mismatch in CTE between the barrier coating 102 and the substrate 104, a lower coefficient of thermal expansion (CTE) of the substrate tends to reduce the opportunity for thermal stress cracking of the barrier coating 102. In various examples, the material of the substrate 104 is selected to have a CTE that matches or is lower than that of PP, PE, PLA, PVOH, or PU.

[0055] The barrier coating 102 includes a stack of bilayers 106. Any suitable number of bilayers 106 can be used. In various examples, between two and twelve bilayers may be stacked to form the barrier coating 102.

[0056] Each double layer comprises two layers 108, 110 made of different materials. The term "two" and similar terms as used herein refer to open-ended layers unless otherwise specified. In this example, "two layers" means two or more layers, and a double layer may be a triple layer, etc.

[0057] A stack of double layers 106 may be formed by repeating a specific type of double layer 106 to form the barrier coating 102. Repeating double layers 106 provides robustness in that specific layers of materials 108, 110 may crack or develop defects without compromising the overall integrity of the barrier coating 102. Multiple layers of materials 108, 110 may have localized defects, but still provide an overall effective coating.

[0058] In various examples, the thickness of each of the bilayers 106 may be between approximately 3 nanometers and approximately 30 nanometers. More specifically, the thickness of each of the bilayers 106 may be between approximately 4 nanometers and approximately 14 nanometers. In various examples, the total thickness of the barrier coating 102 may be between approximately 20 nanometers and approximately 100 nanometers. More specifically, the total thickness of the barrier coating 102 may be between approximately 30 nanometers and approximately 90 nanometers.

[0059] The double layer 106 typically has identical layers of materials 108 and 110, although the thicknesses of materials 108 and 110 may differ between the double layer 106. For example, the layer of material in contact with the substrate 104 may be thicker than the other layers of material not in contact with the substrate 104. Such a relatively thicker layer of material may help to uniformize the surface roughness of the substrate 104 and enhance the barrier coating effect. A relatively thick first layer may also be used to initiate the formation of a multi-layer coating assumed to follow a few layers, because the first layer penetrates the substrate rather than forming a uniform layer. That is, considering the roughness of the substrate or the unpredictability of the initial deposition on the substrate, a first layer with a relatively thicker nominal thickness than would be required separately by the intended double-layer configuration may be provided. If the first layer is too thin, it may compromise the intended construction of the subsequent layers(s). In this sense, the first layer can be considered a mechanical buffer between the substrate and the coating layers.

[0060] Each layer of material 108, 110 may contain oxides, metal oxides, alkoxides, metal cones (e.g., "alucone" or "zincone"), oxynitrides, or similar materials. For example, each of the bilayers 106 may contain an aluminum oxide layer 108 and a zinc oxide layer 110. The aluminum oxide can act as the primary gas barrier material. The zinc oxide can act as a structural layer and may provide other advantages, such as ultraviolet (UV) light blocking. In various examples, the bilayer 106 may be configured and arranged so that the aluminum oxide layer 108 is in contact with the substrate 104. In other examples, the bilayer 106 may be configured and arranged so that the zinc oxide layer 110 is in contact with the substrate 104, which may improve the barrier performance against moisture. The layer in contact with the substrate (also called the nucleating layer) may be thicker than the other layers. In other examples, other materials such as tin oxide, silicon oxide, and titanium dioxide can be used.

[0061] Figure 2 shows an exemplary film 200, for example, a packaging film using the barrier coating 102 described above.

[0062] The barrier coating 102 is applied to a first substrate, which includes a base material 202, such as paper, PLA, etc. (see above for further examples). The barrier coating 102 can be deposited directly onto the base material 202.

[0063] The film 200 includes a base material 204 and an additional second substrate including an ink layer 206 applied on the base material 204. The base material 204 may be paper, PLA, etc. (see above for further examples). The ink layer 206 may be printed on the base material 204. The ink layer 206 does not have to completely cover the base material 204; that is, ink can be selectively deposited to form images and text while leaving a portion of the base material 204 exposed.

[0064] The film 200 further includes an adhesive layer 208 that adheres a second substrate, formed of a base material 204 and an ink layer 206, to the barrier coating 102. The adhesive layer 208 bonds the first substrate (i.e., the base material 202) having the barrier coating 102 to the second substrate (i.e., the base material 204 and the ink layer 206). The adhesive layer 208 can be applied after the two parts of the film 200 have been completed separately.

[0065] Figure 3 shows an exemplary film 300 (e.g., a packaging film) using the barrier coating 102 described above.

[0066] The film 300 includes a first substrate comprising a base material 302 and an ink layer 304. The base material 302 may be paper, PLA, etc. (see above for further examples). An ink layer 304 may be formed by printing ink onto the base material 302. Depending on the amount of printing, the ink layer 304 does not have to completely cover the base material 302.

[0067] The barrier coating 102 is deposited on the first substrate. More specifically, the barrier coating 102 is deposited on the ink layer 304 and on any portion of the base material 302 that is not covered by the ink layer 304.

[0068] The film 300 includes an additional second substrate, which includes a base material 306, such as paper, PLA, etc. (see above for further examples).

[0069] The adhesive layer 308 adheres the first substrate (i.e., the base material 302 and the ink layer 304) having the barrier coating 102 to the second substrate (i.e., the base material 306). The adhesive layer 308 can be applied after the two parts of the film 300 have been completed separately.

[0070] Figure 4 shows an exemplary film 400 (e.g., a packaging film) that uses the barrier coating 102 described above.

[0071] The film 400 includes a first substrate comprising a base material 402, such as paper, PLA, etc. (see above for further examples). The barrier coating 102 can be deposited directly onto the base material 402.

[0072] The film 400 includes an ink layer 404 applied on the barrier coating 102. The ink layer 404 may be formed by printing ink onto the barrier coating 102. Depending on the amount of printing, the ink layer 404 does not have to completely cover the barrier coating 102.

[0073] The film 400 further includes an additional second substrate, which includes a base material 406, such as paper, PLA, etc. (see above for further examples).

[0074] The adhesive layer 408 adheres the second substrate to the first substrate. That is, the adhesive layer 408 bonds the base material 406 to the ink layer 404 and any portion of the barrier coating 102 that is not covered by the ink layer 404. The adhesive layer 408 can be applied after the two portions of the film 400 have been completed separately.

[0075] Exemplary films 200, 300, and 400 may further include a heat-sealing layer, such as a layer of PE, applied to the exposed surface of the base material to facilitate heat sealing of the closed package, which is particularly useful for food packaging or similar product packaging. Good sealing is important to avoid leakage, infiltration, and contamination that would impair the purpose of the barrier coating.

[0076] Exemplary films 200, 300, and 400 can be considered as two-ply films, in that each base material, together with its accompanying layer, forms a single film. In other examples, any additional suitable multiple-ply similar films (e.g., a single sheet of plastic, aluminum foil, or a functionalized film) may be given to form three-ply or four-ply films that provide similar utility and advantages.

[0077] Figure 5 shows an exemplary film 500 (e.g., a packaging film) that uses the barrier coating 102 described above.

[0078] The film 500 includes a substrate comprising a base material 502 and a pre-coat 504.

[0079] The barrier coating 102 is deposited on a precoat 504, which may also be called a primer. The precoat 504 is useful for filling the pores of the paper-based material, creating a smooth and uniform layer for the barrier coating 102, and providing surface chemistry suitable for the barrier coating (e.g., a primer with oxygen groups if the barrier coating 102 contains a metal oxide). Exemplary materials for the precoat 504 include PVOH, EVOH, acrylic, polyurethane (PU), nanocellulose / microfibrillated cellulose, PLA coating, PE coating, or similar.

[0080] The film 500 further includes a topcoat 506 applied on the barrier coating 102. The topcoat 506 may be useful in protecting the barrier coating 102 from downstream processes, such as conveying. For example, if the barrier coating 102 comes into contact with rollers, it may be damaged (e.g., scratched). A suitable topcoat 506 can protect against such damage. A suitable topcoat 506 may improve the barrier coating 102's resistance to bending defects.

[0081] The topcoat 506 may also provide separation from granular material found in the ink that could damage the barrier coating 102. Therefore, the topcoat 506 may be applied on the barrier coating 102 in this example and in other examples where the barrier coating 102 comes into contact with the ink to protect it from the aforementioned damage (see Figures 2 to 4).

[0082] An exemplary topcoat 506 includes the PE layer for heat sealing and other materials mentioned above that are useful for the precoat 504.

[0083] In various examples, the top coat 506 may be made from the same material as the base material 502, and the base material 502 is made more recyclable.

[0084] The exemplary film 500 can also be considered as a single film. In other examples, any additional suitable multiple layers of similar films (e.g., a single sheet of plastic, aluminum foil, or functionalized film) may be given to form two-layer, three-layer, or four-layer films that provide similar utility and advantages.

[0085] Figure 6 shows an exemplary film 600 (e.g., packaging film) using the barrier coating 102 described above. Further details can be found in the description of film 500 above and will not be repeated here.

[0086] The film 600 includes a substrate comprising a base material 502 with a precoat or primer 504. The barrier coating 102 is deposited on the base material 502, i.e., on the precoat or primer 504.

[0087] Figure 7 shows an exemplary film 700 (e.g., a packaging film) using the barrier coating 102 described above. Further details can be found in the description of film 500 above and will not be repeated here.

[0088] The film 700 includes a substrate containing a base material 502 without a precoat or primer 504. A barrier coating 102 is deposited on the base material 502. A topcoat 506 is deposited on the base barrier coating 102.

[0089] It should be noted that, in addition to the examples given in Figures 2 to 7, other examples derived from these examples are also intended. Furthermore, various known precoat and topcoat materials provide a certain degree of barrier. The barrier coating 102 described herein may be useful in combination with the above materials to further enhance barrier performance.

[0090] Furthermore, the examples given in Figures 2 to 7 may be further enhanced, such as laminates, topcoat sealants, or similar materials. For example, a laminate with a PE layer using an industrial lamination process can be particularly useful for protecting the barrier coating when the barrier coating is exposed, such as in the example in Figure 6. Alternatively, a varnish layer of acrylic or similar material can be applied using flexographic or screen printing. Fabricating the topcoat or laminate layer (see, for example, layer 506 in Figures 5 and 7) from the same material as the base material may offer advantages suitable for reuse purposes.

[0091] Figures 8 to 10 show further details of exemplary double layers having the illustrated exemplary thicknesses. These examples demonstrate that various material thicknesses are possible and may be desired for a given application.

[0092] Figure 8 shows an array 800 in which uniform bilayers 802 having a first material 108 and a second material 110 are repeated. Each layer of the bilayer 802 is deposited to the same nominal thickness (e.g., 5 nm), except for the initial layer 804 of the first material 108, which is relatively thicker to enhance adhesion to the substrate 104.

[0093] Figure 9 shows array 900 with various bilayers 902, 904 having a first material 108 and a second material 110. Each of the bilayers 902, 904 has a material layer 108, 110 of the same nominal thickness (e.g., 4 nm or 5 nm), although this thickness may differ from that of the other bilayers 902, 904.

[0094] Figure 10 shows an array 1000 having a bilayer 1002 of a first material 108 and a second material 110 having different nominal thicknesses (e.g., 3 nm and 5 nm).

[0095] The principles shown in Figures 8 to 10 can be combined to meet the requirements of various applications. In general, the thickness of the double layer may be uniform or varied, and the thickness of the material layers forming each of the double layers may be the same or different among the various double layers.

[0096] Referring to Figure 11, the barrier coating 102 described herein can be deposited on a substrate using SALD. An exemplary SALD process typically involves extruding an active gas (e.g., precursor gas, reactant gas, inert gas, etc.) through one or more slits 1100 and removing an exhaust gas through one or more slits 1102, the slits 1100, 1102 communicating the gas through a network of channels in a structure which may also be called a SALD coater or head. This reduces or eliminates the need for exhaust and purge steps that slow down conventional ALD, and as a result, SALD can be one to two orders of magnitude faster than conventional ALD. SALD can produce ultrathin coatings of compact, conformal, and pinhole-free materials (e.g., metal oxides), and the coating can be deposited at room temperature or low temperatures, under open atmospheric conditions and under pressure, without requiring a vacuum chamber. SALD is mass-producible, compatible with roll-to-roll processes, and has been demonstrated to work on a variety of surfaces, including, but is not limited to, plastics and paper. Further information relating to ALD and SALD can be found in PCT publication WO2021119829, entitled “Apparatus and Method for Thin Film Deposition,” filed on 18 December 2020, which is incorporated herein by reference.

[0097] Figure 12 shows an exemplary space atomic layer deposition apparatus 1200 that can be operated to deposit a barrier coating 102. The apparatus 1200 includes a SALD head 1202, a transport system 1204, and a gas transport system 1206. A heater 1208 may be provided on the SALD head 1202. Using any suitable number of SALD heads 1202, any suitable combination of gases can be transported by the gas transport system 1206, and the barrier coating 102 can be deposited on a flexible substrate that has been transported by the transport system 1204 through the SALD heads 1202. The barrier coating 102 can be constructed by transporting the flexible substrate in one or both directions through one or more SALD heads 1202.

[0098] The conveying system 1204 includes rollers 1210, web guides 1212, nip rollers 1213, idlers 1214, dancers 1216, load cells 1218, and similar components positioned between the unwinder 1220 and the winder 1222, and can convey flexible substrate material 1224, such as thin sheet or membrane material (sometimes referred to as “film” in some cases, particularly in the packaging industry, but not to be confused with a deposited thin film or coating). The conveying system 1204 allows the flexible substrate material 1224 to be unwound from the roll by the unwinder 1220, coated by the SALD head 1202, and wound onto another roll by the winder 1222. The arrangement of rollers can be used to position the flexible material relative to one or more SALD heads 1202 and can be used to control the distance between the surface of the flexible material 1224 and the surface of the SALD head 1202.

[0099] The gas transport system 1206 includes containers 1230, 1232, and 1234 containing an inert gas (e.g., nitrogen), a precursor (e.g., Al(CH3)3, which is trimethylaluminum in the case of aluminum oxide), and a reactant (e.g., an oxidizing agent such as H2O), a mass flow controller 1236, an on / off valve 1238, and gas lines 1240 that fluidly connect these components. Each gas line 1240 can transport the inert gas, precursor, and reactant in pure or mixed form to the SALD head 1202 at a flow rate controlled by the mass flow controller 1236 and the on / off valve 1238, respectively. The configuration and arrangement of the components in Figure 12 are illustrative examples. In other examples, the components may differ in configuration and arrangement.

[0100] Various reactants (also called co-reactants) or oxidizing agents may be provided to react with metals or metal-containing compounds such as aluminum or zinc to form layers of a barrier coating. Examples of co-reactants and oxidizing agents include, among others, water, oxygen, ethanediol, and oxygen plasma. The co-reactants / oxidizing agents may alternate between layers. For example, different co-reactants / oxidizing agents may be used in alternating bilayer materials. Co-reactants / oxidizing agents may be useful in increasing the density of a particular layer.

[0101] The gas line 1240 may be a tube made of a chemically stable or inert material, such as stainless steel or Teflon®, and may be connected between the upstream components of the SALD head 1202. The components may include an inert gas container 1230, chemical containers (e.g., bubblers) 1232, 1234, a mass flow controller 1236, and an on / off valve 1238. This gas transport system 1206 is suitable for transporting one or more precursor gases, one or more reactant gases, and one or more inert gases to the SALD head 1202 in pure form or a suitable mixture. The inert gas container 1230 supplies the inert gas, non-reactive gas to the SALD head 1202 and may also be used to transport the precursor gas from the precursor gas container 1234 and / or the reactant gas from the reactant gas container 1232 to the SALD head 1202. The pressure of the inert gas may be regulated by one or more pressure regulators. Precursor and reactant gases may be produced by techniques such as bubbling a liquid chemical with an inert gas, atomizing a liquid chemical by heating a liquid or solid chemical, direct liquid injection in which a liquid chemical precursor is introduced into a vaporizer that vaporizes the liquid and pushes the gas out of a nozzle, or a combination thereof, but are not limited to the above. The vapor of the chemical may also be supplied in gaseous form from a storage tank, or it may be produced by another device, such as an ozone generator, which may be used to produce the reactant gas. The flow rates of the inert gas, one or more precursor gases, and one or more reactant gases are controlled by a mass flow controller 1236 and on / off valves 1238, such as manual diaphragm valves or pneumatic valves. The flow controller 1236 and valves 1238 may be controlled manually or electronically by a control system.

[0102] As illustrated in Figure 12, one or more SALD heads 1202 transport a precursor, reactant, and inert gas onto a flexible substrate material 1224. The head 1202 includes a plurality of internal gas channels that redirect and distribute the gas onto the flexible material 1224, which is appropriately arranged to produce a SALD, as illustrated in Figure 11. The head 1202 includes any preferred number and configuration of slits 1250 that output the gas to the flexible substrate material 1224. Other components can be integrated into one or more SALD heads 1202 (including, for example, cooling and heating elements and plasma sources, but not limited to these). For example, one or more plasma sources may be built into the head to lower the temperature required for the coating deposition method. According to Figure 12, one or more exhaust pumps 1242 are connected to the head 1202. The discharge pump 1242 removes unreacted precursors and / or reactants, as well as gases such as inert gases, from the space between the operating surface 1244 of the head 1202 and the surface of the flexible material 1224.

[0103] As illustrated in Figure 12, heater 1208 can be used to heat the flexible material 1224 to facilitate chemical reactions on its surface. In the illustrated example, heater 1208 extends along the length of head 1202. Various heaters with different heating outputs, shapes, and sizes (e.g., drum heaters wrapped in the flexible material) may be provided. Furthermore, one or more heaters may be built into head 1202. One or more heaters can also be used to control the position of the flexible material surface relative to one or more SALD heads 1202 based on the mechanical position of the heaters. One or more rollers of the conveying system 1204 may be heated to control the temperature of the flexible material 1224.

[0104] In other examples, one or more sheets of flexible material can be mounted on a translational stage that passes through the head in either one or two directions during the coating process. The translational stage can be heated, and it can also be used to control the distance between the surface of the flexible material and the surface of the SALD head 1202.

[0105] Further information regarding examples of gas transport systems, SALD heads, discharge pumps, heaters, and translational stages can be found in PCT Publication WO2021119829.

[0106] It should be understood that the characteristics and aspects of the various examples shown above can be combined to form further examples similarly included within the scope of this disclosure. Furthermore, the drawings may not be to scale and may be exaggerated in size and shape for illustrative purposes.

Claims

1. Substrate, and Coating deposited on the substrate A film containing, The aforementioned coating is a film comprising multiple double layers, each of which comprises two layers of different materials.

2. Each of the two aforementioned layers, which are made of different materials, oxides, Metal oxides, Alkoxide, Metal cone, or Oxynitride The film according to claim 1, including the film described in claim 1.

3. The film according to claim 1, wherein each of the two layers comprises a layer of aluminum oxide and a layer of zinc oxide.

4. The film according to claim 3, wherein a double layer of aluminum oxide adjacent to the substrate is in contact with the substrate.

5. The film according to claim 1, wherein at least two of the plurality of double layers have a uniform thickness.

6. The film according to claim 1, wherein at least two of the plurality of double layers have different thicknesses.

7. The film according to claim 1, wherein in at least one of the plurality of double layers, the thickness of the two layers made of different materials is uniform.

8. The film according to claim 1, wherein in at least one of the plurality of double layers, the thickness of the two layers made of different materials is different.

9. The film according to claim 1, wherein the number of the plurality of double layers is between two and twelve.

10. The film according to claim 1, wherein the thickness of each of the two layers made of different materials is between approximately 3 nanometers and approximately 30 nanometers.

11. The film according to claim 1, wherein the thickness of the coating is between approximately 20 nanometers and approximately 100 nanometers.

12. The film according to claim 1, wherein one layer of the coating in contact with the substrate is thicker than the other layers of the coating.

13. An additional substrate including a base material and an ink layer applied on the base material, and The adhesive layer that bonds the additional substrate to the coating. The film according to claim 1, further comprising:

14. The substrate comprises a base material and an ink layer. The coating is deposited on the ink layer. The film according to claim 1.

15. Additional substrates, and The adhesive layer that bonds the additional substrate to the coating. The film according to claim 14, further comprising:

16. The substrate includes a base material on which the coating is deposited. The packaging film further includes an ink layer applied on the coating. The film according to claim 1.

17. Additional substrates, and The adhesive layer that adheres the additional substrate to the ink layer The film according to claim 16, further comprising:

18. The substrate comprises a base material and a precoat, The coating is deposited on the precoat. The film according to claim 1.

19. The film according to claim 18, further comprising a top coat applied on the coating.

20. The film according to claim 1, wherein the substrate contains polylactic acid.

21. The film according to claim 1, wherein the substrate includes paper.

22. The film according to claim 1, further comprising a laminate.

23. The film according to claim 1, wherein the two layers made of different materials are formed using a co-reactant or an oxidizing agent.

24. The film according to claim 1, wherein the film is a food packaging film.

25. A film, wherein the film is Substrate and A coating deposited on the substrate, wherein the coating comprises a plurality of double layers, each of which comprises two layers made of different materials, and Includes, Each of the two layers, which are made of different materials, contains an oxide, metal oxide, alkoxide, metal cone, or oxynitride. The thickness of each of the two layers made of different materials is between approximately 3 nanometers and approximately 30 nanometers. The aforementioned coating is a film with a thickness between approximately 20 nanometers and approximately 100 nanometers.

26. The film according to claim 25, wherein one layer of the coating in contact with the substrate is thicker than the other layers of the coating.

27. A method for manufacturing a film, wherein the method is This method involves alternately depositing two layers of different materials onto a substrate to form a double layer, wherein the thickness of the double layer is on a nanometer scale. Forming a coating on the substrate by continuously forming multiple of the double layers. Methods that include...

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