METHOD TO FORM AN ORGANIC FILM SUBSTRATE WITH INORGANIC NANOCOATING LAYER

专利摘要:
Organic Film Prepared by Inorganic Nanocoating The present invention relates to an inorganic nanolayer surface coated polymer film product which is presented with improvements such as improved metallization ability, low cost, low polymer additives and modifiers , better recyclability, and good network properties. further, the method for preparing a flexible film substrate to increase the reactivity or moisture of the substrate for metallization is disclosed. the substrate film is coated with one or more nanolayers of a metal or metal oxide applied by ccvd and/or pecvd in an open atmosphere. the deposited coating acts to increase the surface energy of the film substrate and to reduce the measurement variation of the surface of the substrate or backing film, thereby increasing the wetting ability of the film substrate for metallization and/or to improve the anti-blocking characteristics of the film. deposited coatings can also act as a barrier layer to reduce light and gas permeability and vapor transmission through the substrate.
公开号:BR112014002654B1
申请号:R112014002654-8
申请日:2012-08-06
公开日:2022-01-18
发明作者:Andrew Hunt；Yongdong Jiang；Anthony Robert Knoerzer；Kenneth Scott Laverdure
申请人:Ngimat Co；Pepsico, Inc；
IPC主号:

专利说明:

Background of the InventionTechnical Field
[0001] The present invention relates to an elemental layer over the organic film product and to a method and apparatus for applying the elemental layer. More specifically, the invention described herein relates to an inorganic layer that serves to prevent the polymer film from sticking to itself when rolled or stacked, but can also serve as an interface for future functionalization. This nanolayer can be formed during the original fabrication of the polymer film using a chemical vapor deposition apparatus and is compatible with methods of deposition of high quality antiblock, initiator and/or barrier layers on the surface of a film substrate to improve the characteristics of the film substrate. Description of Related Technique
[0002] Multilayer film structures produced from petroleum based products, polymers, copolymers, biopolymers and paper substrates are often used in flexible films and packaging structures where there is a need for advantageous barrier properties, sealing and graphics capability. The barrier properties in one or more layers comprising the film are important in order to protect the product inside the package from light, oxygen and/or moisture. This need exists, for example, for the protection of foods that may be at risk of losing flavor, hardening, or spoiling if sufficient barrier properties are not present to prevent transmission of light, oxygen, or moisture into the package. Graphical capability may also be required to allow consumers to quickly identify the product they are looking to buy, which also allows food manufacturers to label information such as the nutritional content of the packaged food and present information regarding pricing, such as the barcode on the product.
[0003] In the packaged food industry, protecting food from the effects of moisture and oxygen is important for many reasons, such as health safety and consumer acceptance (ie, preserving product freshness and flavor). Conventional methods for protecting food contents incorporate specialized coatings or layers within or on a surface of the substrate, which act as an impermeable barrier to prevent the migration of light, water, water vapour, liquids and foreign substances into the interior of the substrate. packaging. These coatings may consist of co-extruded polymers (e.g. vinyl acetate alcohol, polyvinyl alcohol and polyvinyl acetate) and/or a thin layer of metal or metal oxide, depending on the level of barrier performance required to preserve the quality of the product stored on the packaging substrate.
[0004] Coatings obtained by chemical vapor deposition are known to provide certain barrier characteristics to the coated substrate. For example, an organic coating such as amorphous carbon can inhibit the transmission of elements such as water, oxygen and carbon dioxide. Therefore, carbon coatings have been applied to substrates, such as polymeric films, to improve the barrier characteristics exhibited by the substrate. Another example of coatings applied to substrates to improve barrier adhesion performance include coatings comprised of inorganic materials, such as inorganic metal oxides. Ethyl vinyl alcohol (EVOH) and other polymer coating layers are widely used to prepare or improve the moisture of the film substrate for the application of a barrier layer (also referred to herein as "metallization initiator"). Aluminum metal, aluminum oxide and silicon oxide are widely used for the direct application of barrier layer(s) directly to substrates (also referred to herein as "metallization"). Aluminum oxides and silicon oxides also offer abrasion resistance due to their glass-like nature.
[0005] The inorganic coatings described above can be deposited onto substrates by various techniques that are known in the art. Such techniques include vapor deposition, or physical vapor deposition (PVD) or chemical vapor deposition (CVD). Examples of PVD include ion beam blasting and thermal evaporation. Examples of CCVD include glow discharge, combustion chemical vapor deposition (CVD) and advanced plasma chemical vapor deposition (PECVD). All these coatings are now produced in a secondary process, after the film has been formed and either rolled or stacked.
[0006] The most commonly known and used method for deposition of barrier layers on packaging film substrates for metallization requires the use of a vacuum chamber to provide the vacuum environment for the deposition of inorganic atoms/ions on the surface. surface of the film substrate. This known technique, as used in the food packaging industry, is formed by rolls of processing packaging film that are less than 1 to 3 meters in width and 500 to 150 thousand meters in length at the operating speed of the food industry. 60 to 300 m/min in a vacuum metallization chamber. This equipment is highly specialized, requires a large amount of electrical energy, and is very expensive. Current vacuum chamber processes for metallizing films are inefficient in many ways, due to the high capital/operating costs and limited operational/production capacity associated with the use of such equipment, and the requirement to use state-of-the-art film to achieve the desired barrier.
[0007] Combustion chemical vapor deposition (CVD) and plasma enhanced chemical vapor deposition (PECVD) apparatus and methods are known in the art, as disclosed in the US Patent. Nos. 5,997,996 and 7,351,449, the disclosures of which are incorporated herein by reference. Typically, a combustion flame or plasma field provides the necessary environment for the deposition of the desired coating through the vapors and gases generated by the combustion or plasma to the substrate. Elemental precursors (eg organometallic compounds) can be vaporized or dissolved in a solvent which can also act as a fuel. The deposition of organic and inorganic oxides can then be carried out under normal and/or open atmospheric pressures and temperatures, without the need for a vacuum chamber, oven and/or pressure chamber.
[0008] As described above, barrier application to food packaging is necessary to protect food and food products from the effects of moisture and oxygen. It is well known in the art that a metallization of petroleum-based polyolefin such as OPP or PET reduces the transmission of moisture and oxygen vapors through the specialty film by about three orders of magnitude. Conventional technology employs a layer of inorganic metal or ceramic material over a special polymer film. The layer of inorganic material may be aluminum, silicon, zinc, or other desired element in the form of a metal or oxide. However, the substrate surface on which the barrier layer will be applied typically needs to be prepared to increase its surface energy so as to be receptive to the deposition of the barrier metal being deposited thereon and/or to " smooth" the surface to be metallized so as to reduce surface caliber variation or surface roughness of the film to be metallized. The term "moisture" is defined herein to include surface energy, adhesion strength, metal bonding strength, and any other associated characteristic that would enhance the surface receptivity of the film layer to the deposition of coatings.
[0009] For example, the use of aluminum metal as a barrier layer in low-energy plastic materials, such as biaxially oriented polypropylene (BOPP) film, requires a metallization initiator to reduce surface measurement variation. of the film substrate and/or to improve adhesion or bonding between the metal and the film substrate. Various chemical methods are used to prepare the surface layer of the substrate to improve the surface of the substrate and/or the bonding of the metal barrier layer to the film substrate. With polymer film substrates, one method of preparing the substrate for metallization is to coextrude a specialized polymer as a skin layer onto the substrate film. These skin layers can comprise vinyl ethyl alcohol (EVOH), polyvinyl alcohol (PVOH), and polyvinyl acetate (PVA), ethyl vinyl acetate (EVA), polyethylene glycol terephthalate (PETG), polyethylene terephthalate amorphous (APET), among other polymers used in the industry. Unfortunately, these materials are expensive and add to the additional cost of making ready-made foils. In addition, having multiple polymer compositions reduces the recyclability of the product.
[00010] Plastic film cores such as OPP, polystyrene (PS) and polyethylene terephthalate (PET) are typically corona discharged or flame treated. This helps to increase the wetting capacity. However, these treatments tend to create adverse and undesirable impacts on film substrate characteristics such as hole formation, chemical surface degradation through intramolecular crosslinking or chain scission which can adversely affect downstream metallization. and heat sealing processes.
[00011] After forming, the film substrates are typically wound around a core for a roll for storage and distribution. Additional additives such as glidants, anti-static and anti-blocking agents as described above are generally incorporated into the substrate films prior to winding and migrate to the surface of the film substrate to prevent or minimize blocking, soldering or "gluing" the film surfaces when the film is wound. The addition of conventional slip and/or anti-block additives interferes with the establishment of an effective metallized barrier layer and tends to degrade the performance of the film substrate, such as anti-block additive particles, along with other particles in the environment, such as as powder, they are transferred from the sealing layer of the film to the surface metallization layer during the winding process. The presence of these particles increases the surface roughness, the surface measure of film variance, and the shape of holes or openings in the metallized layer after it is deposited. Sliding and antistatic agents decrease the surface wetting ability of the film for metallization and further degrade the metal adhesion and barrier potential of the film.
[00012] As such, there is a need for a polymer film product that does not contain such additives, but does not stick to them, and still can be processed on conventional film web handling equipment. To achieve this goal, there is a need in the art for an apparatus and a more efficient and economical method to prepare a substrate for metallization. Likewise, there is a need in the art for an apparatus and an improved method of improving the barrier of a substrate that is less expensive and more energy efficient than traditional metallization, while achieving and maintaining the characteristics of high quality barrier. Furthermore, there is a need in the art for an improved apparatus and method for treating film substrates without the need for the addition of conventional non-sticking or slipping agents to reduce film blockage in an in-line production environment. Summary of the Invention
[00013] Embodiments of the invention described herein include a film substrate with an inorganic nanocoating layer product, an apparatus and method for preparing a film substrate for metallization, an apparatus and method for improving anti-blocking characteristics. of a film substrate, and an apparatus and method for applying a metal barrier to a film substrate. In one embodiment, the apparatus and method described herein utilize the direct combustion of liquids, gases and/or vapors containing chemical precursors or reagents to be deposited on the surface of a film substrate in open environments. Chemical precursors, for example organic solvents, can be sprayed or atomized in an oxidant and combustion, resulting in a vapor and/or gas that is directed to the surface of the substrate forming the respective desired coating. Multiple layers of coating can be deposited onto the substrate by repetitively passing the substrate through the system in a stand-alone or in-line manufacturing environment.
[00014] An embodiment of the present invention comprises a smooth surface of the polymer substrate with an inorganic nanocoating layer less than 50 nm thick that substantially inhibits the bonding of the film substrate to itself. In other embodiments, a thinner layer or layers of nanocoating may be preferred with less than the average thickness of 5 nm, thus providing the desired anti-blocking effect for most applications, while still allowing a film of quality barrier is applied to its surface. Since polymer films are generally rolled or stacked into rolls during the manufacturing process, the inorganic nanocoating layer must be formed during the fabrication of the polymer film or product before the film substrate comes into contact with the polymer film. another polymer. These production lines for polymer films or products move at high speeds in ambient pressures and can be tens of meters wide. In one embodiment, a preferred process that can perform inorganic nanocoating of the polymer film or product in an open environment is chemical combustion vapor deposition (CVD), although any inorganic, thin film process can be used as desired, if it is able to achieve the desired properties.
[00015] The embodiments of the invention described herein can be used in standalone configurations, adapted to existing film production lines, or installed on an in-line film manufacturing substrate and/or processing system. The substrate material to be coated does not need to be heated or treated in an oven or reaction chamber, or positioned under vacuum or non-standard atmospheric conditions to effect deposition of the coating. The heat of combustion provides the necessary conditions for the reaction of chemical precursors. The substrate material to be coated is also heated by the combustion flame, which creates and/or improves the kinetic environment for surface reactions, wetting, diffusion, film nucleation (coating) and film growth ( coating). The chemical precursors used must be properly reactive to form the intended coating. While oxides are the preferred material, other elemental coatings and compounds, for example metals, nitrides, carbides, and carbonates, can also be used as desired.
[00016] Other aspects, embodiments and features of the invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying Figures. The attached figures are schematic and are not intended to be drawn to full scale. For purposes of objectivity, not all components are marked in each Figure, nor do all components of each embodiment of the invention shown where illustration is not necessary enable those skilled in the art to understand the invention. All patent applications and patents incorporated herein by reference are incorporated by reference in their entirety. In case of conflict, this descriptive report, which includes the definitions, will be in control. Brief Description of Figures
[00017] The new features and characteristics of the invention are presented in the attached claims. The invention itself, however, as well as a preferred mode of use, other objects and advantages thereof, will be better understood with reference to the following detailed description of the illustrative embodiments, when read in conjunction with the accompanying Figures, in which: Figure 1 shows a cross-sectional view of a typical prior art food packaging film substrate; Figures 2A to 2D illustrate various embodiments of the apparatus and method used in the present invention described herein; Figures 3A to 3B are representations the apparatus and method as used in on-line substrate film manufacturing and production equipment in accordance with an embodiment of the invention described herein; and Figure 4 is a cross-sectional representation of a film substrate with multiple coating nanolayers in accordance with an embodiment of the invention described herein. Detailed Description
[00018] Figure 1 represents a schematic cross-section of a typical multi-layer packaging or food composite film 10 currently used. The film 10 is constructed of several intermediate polymer layers that work together to provide the film 10 with the required performance characteristics. For example, a graphics layer 14, allows a graphic to be printed or otherwise arranged, and is protected by an outer, transparent base layer 12 which may be comprised of oriented polypropylene (OPP) or polyethylene terephthalate (PET). A layer of glue or laminate 16, which is normally a polyethylene extrusion, acts to bond the outer layers 12 and 14 to the base layer on the inner side of the product 18. A layer of metal may be disposed over the inner base layer 18. through metallization known in the art. Sealing layer 20 is disposed over the OPP or PET of inner base layer 18 to allow an airtight seal to be formed at a temperature lower than the melting temperature of inner base layer 18. Each layer described is formed as a roll. of film which is then unwound and laminated together to form the composite film. Each film to be laminated together produces the composite films, which are composed of multilayer films, as exemplified in Figure 4, when initially extruded or fabricated. The inorganic nanolayer of the present invention may be present on any of the layered surfaces and will result in an inorganic nanolayer interface between the polymer layers.
[00019] Other materials used in the construction of packaging film substrates may include polyesters, polyolefin extrusions, cellulosic polymers, acetate polymers, adhesive laminates, biofilms, such as polylactic acid (PLA) films and polypropylene films. hydroxy-alkanoate (PHA) produced in various combinations resulting in multi-layer composite film structures. The film substrate may be formed by typical coextrusion, lamination or extrusion coating techniques as known in the art. The film substrate may also be composed of polyimide, liquid crystal, polyethylene, or other materials commonly used in electronic, optical, or special or multi-layer packaging applications.
[00020] In both the CCVD and PECVD processes described here, the environment necessary for the coating deposition to occur is provided by the flame, or other means of energy. With CCVD, no oven, auxiliary heating system, or reaction chamber is required for the reaction to take place. In addition, both PECVD and CCVD can be performed under open atmosphere environmental conditions. The plasma or flame provides the energy necessary for the deposition of the coating in the form of the kinetic energy of the species present and radiation. This thermal energy creates the appropriate environment to form reactive species and coincidentally heats the substrate, thus providing the conditions for surface kinetic reactions, diffusion, nucleation and growth to occur. When using fuel solutions, the solvent plays two main roles in CCVD. First, the solvent conveys the coating reagents in close proximity to the substrate, where coating deposition occurs, thus allowing the use of low-cost soluble precursors. Uniform feed rates of any stoichiometry of the reagents can be easily produced simply by varying the concentrations of the reagents in solution and the flow rate of the solution. Second, the combustion of the solvent produces the flame needed for CCVD. Physical vapor deposition (PVD) systems have been made that allow for high vacuum local area to form PVD layers in open atmosphere manufacturing lines otherwise these can be used but are commercially practical. Ambient pressure systems are the preferred modality.
[00021] In general, the CCVD process described herein is carried out under ambient conditions in the open atmosphere to produce a film on an inorganic substrate. The film is preferably amorphous, but may be crystalline, depending on conditions and deposition reagents. The reagent or chemically reactive compound is dissolved or transported in a solvent, typically a liquid organic solvent, such as an alkene, alkyd, or alcohol. The resulting solution is sprayed from a nozzle using oxygen-enriched air as a propellant and ignited. A substrate is positioned at or near the flame end. Flame spray can be avoided by using a hot element, such as a small pilot light. The reactants are burned in the flame and the ions generated from the combustion are deposited on the substrate as a coating.
[00022] The methods and apparatus used for carrying out the methods of the invention described herein provide a less energy-intensive and more efficient method for treating the surfaces of film substrates for a variety of applications. For example, preparing the substrate for metallization is generally necessary to improve the surface moisture of the substrate for the reception of a metallized layer. As discussed above, prior art methods of preparing a substrate for metallization generally require the addition of a skin layer via coextrusion of a coating solution of chemical additives such as EVOH and/or heat treatment. flame or corona discharge before plating. The apparatus and methods herein provide a novel method whereby the surface energy of the film substrate is increased, typically between 1 and 10 dynes, by the addition of the inorganic initiator nanolayer, thereby increasing the substrate surface moisture and , thus improving the adhesion between the deposited metal barrier coating and the substrate.
[00023] In one embodiment, the inorganic surface nanolayer is deposited onto an outer surface of the film substrate and terminates the polymer network of the film substrate so that it will not cross-link when forming multiple layers and is stacked under the roll. or rolled or stacked under material storage conditions. It is also important that the inorganic surface nanolayer allows the future vapor deposition barrier, preparation or adhesive layers applied to the film substrate to bond well and for the heat seal processes to still function as desired. An integral part of the invention includes applying the inorganic nanolayer to the film substrate in order to improve the surface moisture of the final polymer-based film product for future applications.
[00024] By using different inorganic materials, additional properties can be created to increase the use of the film for various applications. For example, elements such as silver can provide antimicrobial/disinfection properties. In other embodiments, inorganic ultraviolet radiation blocking materials, such as zinc oxides and tin oxides, can be used to form a clear nanocoating barrier layer. Other transparent materials, such as silica glasses, can be used to form and/or act as excellent barrier layer(s) of base nanolayer(s).
[00025] An important feature in the economy in the use of polymer-based products is the low cost maintenance. As a result, the inorganic materials used, such as nanolayer coatings, are typically selected from low-cost inorganic elements. In addition, the health aspect of the materials used in forming films for packaging is very important as polymer films are used more frequently in consumer products, which include food and medical packaging. Thus, health safety materials, such as inorganic silica-based materials, are used in a variety of modalities. Silica is the most common oxide of the earth's crust and soil and long term storage in glass containers has a long proven history as a safe and effective storage medium as far as human health requirements are concerned.
[00026] Current surface modifier materials can represent a significant volume and weight fraction of the final product, thus reducing its recyclability. The present invention considerably reduces the material needed to retard or otherwise inhibit adhesion problems, thus reducing the amount of additives in the film, resulting in a more recyclable and/or compostable product. In one embodiment, the inorganic nanolayer is less than 10 nm thick and, more preferably, less than the average thickness of 5 nm. Due to the small thickness of such a layer, the inorganic nanolayer breaks more easily into smaller pieces, resulting in a higher degree of recycled material. In fact, silica is generally used as an additive to improve the strength and durability of polymers. One embodiment of the invention includes an inorganic nanolayer surface layer that alters the bulk physical properties of the film-based polymer, as compared to pure polymer reprocessing, by at least 1%.
[00027] In the case of biodegradable polymers, such as PLA and PHA, a barrier layer applied to them can, in fact, reduce the degradation capacity of the product in packages produced from them. The effective barrier reduces the transmission of moisture or oxygen, which can aid in the degradation process of the film pack. Multiple layers of barrier can form a package that does not degrade due to the core film substrate material (the barrier on both sides), never being exposed to a suitable environment for decomposition. One embodiment of the present invention includes forming an inorganic nanocoating which by itself does not provide an impermeable barrier, but allows a subsequent print, adhesion layers, or quality barrier to be deposited over the inorganic nanocoating in a processing facility. secondary (not in the initial processing line, where the base polymer film and the present nanocoating innovation were formed). The inorganic nanolayer can be deposited on both sides and the film can be used in a variety of ways.
[00028] One of the main uses of the smooth inorganic nanocoating layer is the formation of the subsequent barrier layer on it. Thin film or oxide barrier metallization layers adhere and improve performance on smooth surfaces with few defects. Polymer films easily form these surfaces during manufacture, but the addition of anti-blocking agents, as currently used in the industry, causes increased surface roughness and film defects, with RMS generally greater than 100 no. An important aspect of the results of the present invention is an RMS of less than 30 nm and more preferably, less than 10 nm and, in some cases, an RMS of less than 5 nm.
[00029] Sliding agents are generally used on polymer films to allow for better processing and to ensure that the film does not stick to itself. These materials act as "oil" on a surface to allow for non-adhesive surface characteristics and so that the material does not stick to itself later in storage or on the processing flow roll and winding sets. One embodiment of the present invention provides a film that does not contain glidants. Another modality is the ability to maintain low RMS values while controlling surface wetting properties. The surface tension can be controlled by a combination of surface roughness of the inorganic nanocoating layer and also the enclosing material on the surface. For later adhesion of inorganic barrier layer materials it is desirable for the surface to accept the metal or ionic oxide or a covalent bond. Oxide surfaces provide excellent bonding to both metal and oxide layers, and that with a smooth surface coating. Softness increases the ability to form the barrier. For barrier applications, the surface should have low texture on both the nanometer and micrometer scale.
[00030] A key to the successful application of such interface layers is the fact that they must be formed in-line when the polymer film is formed and before being rolled. The films are produced by a series of processes, which include casting and blowing the films. These processes are typically performed at ambient atmosphere and pressure on large production lines, thus making increasing vacuum deposition from expensive to economically impractical. Thus, a method for in-line film formation with an inorganic nanocoating interface layer at ambient pressure on low temperature polymers is the best way to achieve such an inventive interface nanocoating layer. Aspects of how to do this with a process such as CCVD are set forth in US Patent No. 5,652,021 (Hunt et al.) and US Patent No. 5,863,604 (Hunt et al.), the disclosures of which are incorporated herein. by way of reference.
[00031] In one embodiment, an interface layer created during in-line fabrication is provided as an excellent base layer, on which a barrier layer can subsequently be deposited. The inorganic interface layer also serves to keep the laminated film easy to roll by inhibiting adhesion between adjacent film surfaces on the roll. Once formed, the inorganic interface layer is a dry, tack-free surface that prevents polymers from sticking together. The film can then be further processed successfully since the inorganic interface layer is of such composition that it does not weld or bond to the opposing polymer surface when the film is wound on a roll or stacked. The material of the inorganic nanocoating layer binds strongly to the surface of the initial film substrate as it is preferably deposited by a steam process where the condensation of the coating is bound to the surface of the film substrate with a force that passes through. in tape exfoliation tests. This is indicative of chemical, ionic, or covalent-type bonds as opposed to electrostatic or Vander Waals bonds, which are much weaker. Since the film may proceed through various winding processes before being formed into a package, this bond strength to the substrate is important or the nanocoating layer may peel off, transfer to the surface of the adjacent polymer, or whatever. The barrier film formed over the nanocoating layer can be laminated at a weak interface causing the barrier or laminate to fail. As such, without the application of an interface nanolayer to a surface of the film substrate, the subsequent barrier deposition may not be well formed or able to bond strongly enough directly to the polymer film substrate.
[00032] In one embodiment, the nanocoating interface layer only needs to be applied to an outer surface of the film substrate, but may also be applied to more than one surface of the film substrate to further delay adhesion. In such an embodiment, treating both surfaces of the film with a nanocoating interface layer reduces the need to use additives that cost more than the base polymer and that also degrade the recyclability of the polymer, as described above.
[00033] In one embodiment, the substrate surface of the primary coating film, if subsequent application of a barrier coating is desired, is the smoothest of the outer surfaces of the substrate film. Typically, one side of the film generally has an anti-blocking structured surface, which forms a textured surface, which allows for air deflection as well as reducing contact adhesion between the layers. This textured surface air ventilation can be important in high speed film winding and processing to allow air to enter and exit the film during the winding process and can be very important in subsequent vacuum processing.
[00034] As mentioned above, it is known that in order to form a good barrier layer in subsequent processing operations, it is important that the surface of the film substrate is smooth. While the slippery nature of the nanocoating layer is applied to the roughest or smoothest films, thin film barriers require a smooth surface without the features that can prevent or inhibit thin film material from being deposited over most of the entire surface. . It is preferred that at least 90% of the surface is coated, and even more preferred that more than 99% is accessible to the vapor deposition material without surface roughness, which can cause thin film defects or shadowing.
[00035] It is also important that the layer of inorganic material is very smooth so that it will not impact the continuous uniform and dense growth of the thin film barrier layer on top of it. Columnar growth into the inorganic nanolayer will impair further growth from a vacuum or other thin film barrier layer. The net effect is that a subsequent barrier layer can be grown to produce an Oxygen Transmission Rate (OTR) of less than 10 and a Water Vapor Transmission Rate (WVTR) of less than 2, more preferably, OTR < 2 and WVTR < 1, and even more preferably of OTR < 1 and WVTR < 0.2. In one embodiment, the subsequent barrier layer is transparent to light in the visible spectrum, with less than a 2% change in light transmission compared to the uncoated film being readily achievable. Light transmission can be even higher than uncoated, due to the creation of an intermediate refractive index. In alternative embodiments, the subsequent barrier layer may be translucent or opaque, as appropriate for effective use of the coated film substrate for the flexible packaging or other contemplated end use.
[00036] The present invention has low environmental impact and can produce safer packaging material as a result of reducing the number of organic chemicals mixed within the polymer film substrate. These additives can cause health problems or can reduce the quality of the recyclable material. Silica and the other elements of the present invention are common in the earth's crust, are often used as food additives, and have been safely used in glass containers for many years. As a result, the invention described herein utilizes abundant and safe inorganic materials, with no negative environmental impact as a result of such use.
[00037] Some polymer film substrates are joined in multilayer structures that can decompose or be biodegradable. In one embodiment, the invention described herein forms such a thin layer of inorganic nanocoating, which does not act as a barrier layer alone. Thus, such an inorganic nanocoating layer can be used as a replacement slip layer and not just when future barrier layers are needed in secondary processing. The multilayer package can still be produced with excellent bonding provided by the application of the inorganic nanocoating layer as described herein. In addition, moisture, oxygen and light can pass through the inorganic nanocoating layer, so that the compostable polymer film structures can still be decomposed. In addition, anti-blocking and slipping agents, depending on their chemical nature, may have a degree of environmental toxicity as defined by ASTM D6400 of the family of standards for compostability. Inorganic nano-coating with a proper selection of metal element such as silicon creates a thin layer that will not inhibit the film substrate's compostability and has no proven toxicity to humans with an absolute minimum impact on the environment. environment.
[00038] In an embodiment presented here, a PECVD or CCVD device is used to deposit nanolayers of silica oxides (SiOx) and/or other inorganic oxides on the substrate surface in an open atmosphere atmosphere, thus increasing the energy surface of the substrate and improving the adhesion of the metal barrier layer to the substrate. In one embodiment presented herein, a PECVD or CCVD apparatus is integrated "in-line" with a substrate film manufacturing line for preparing the substrate for metallization and/or treating the film substrate to reduce blockage, before being rolled into a roll.
[00039] Various embodiments of the present invention described herein also comprise an apparatus and methods for applying a barrier layer to the surface of a substrate in open environments. The apparatus and method described herein provide for the direct combustion of liquids and/or vapors containing chemical precursors or reagents to be deposited on the surface of a substrate material in an open atmosphere. Metal oxides, such as aluminum oxides, are formed from the combustion of materials, such as organo-aluminium compounds, with an oxidant, and the resulting burning of a steam and/or gas in an open atmosphere, which is directed towards the substrate surface and results in the deposition of the desired coating.
[00040] The design and function of the CCVD and the equipment have been described in U.S. Patent Nos. 5,652,021, 5,997,956 and 6,132,653, the disclosures of which are incorporated herein by reference. Returning to Figure 2A, a general schematic of the apparatus 40 that is used to carry out the coating deposition process is shown. Chemical precursors 42 may comprise a solvent reagent solution of flammable or non-flammable solvents mixed with the liquid, vapor or gaseous reagents supplied to the nozzle assembly 44 or other flame producing device. The term "nozzle assembly" is used to refer to and generally describe any apparatus that is capable of producing a flame from a fuel supply, including flame-handling devices. Chemical precursors 42 are ignited in the presence of an oxidizing agent 46, resulting in a flame 48. As chemical precursors 42 in the solution or mixture burn, the reactant reacts to form an inorganic vapor and leaves the flame 48, along with other hot gases 50 and the combustion products. The substrate 52 to be coated is located near the flame 48 within the gas region 50.
[00041] In one embodiment, substrate 52 is oriented tangentially to flame 48, or as shown in Figure 2B, substrate 52 is oriented obliquely to flame 48, or at any angle to the final flame 54 of flame 48, so that the hot gases 50 containing the reagent vapor come into contact with the surface of the substrate 56 to be coated. In various embodiments, the substrate 52 may comprise a film or composite film comprising oriented polypropylene (OPP), polyethylene (PE), polylactic acid (PLA), polyhydroxy alkanoate (PHA), terephthalate of polyethylene (PETP), other polyesters, or other known polymer, biopolymer, paper or other cellulosic substrates, alone or in combination, as known in the art.
[00042] Figure 2B is similar to apparatus 40 shown in Figure 2A, but is configured for a non-turbulent flame methodology suitable for chemical precursors comprising gaseous precursors 42 and non-flammable carrier solutions 46. Flame 48 produced by the nozzle assembly 44a normally has the flame characteristics of an inner flame 48a which defines the reduction region, where the majority of the oxidizing gas supplied with the reactant burns, and an outer flame 48b which defines the oxidation region, where the excess fuel oxidizes with any oxidizing gas in the atmosphere. In this exemplary embodiment, the substrate is positioned at an oblique angle to the end flame 54 of the flame 48 so that the hot gases and/or vapors 50 containing the reactant vapor come into contact with the substrate surface 56 of the substrate. 52.
[00043] Again, with reference to Figure 2A, precursor mixture 46 is supplied to nozzle assembly 44. Oxidant 46 is also supplied to nozzle assembly 44 in some form via a separate feed, or is present in the process atmosphere, or the oxidant may be supplied by a separate feed to the process atmosphere or flash point, or the oxidant may be present in the reaction mixture. In the illustrated embodiment, chemical precursor solution 42 is ignited in the presence of oxidant 46 and flame combustion 48, resulting in the generation of heat, gases and/or vapors 50. The generation of heat causes all reactant solutions to liquids present vaporize and increase the temperature of the substrate 52, so as to result in improved surface diffusion of the coating, resulting in a more uniform coating deposited on the surface of the substrate 56.
[00044] In performing CCVD or PECVD, coating deposition on film substrates, certain deposition conditions are preferred. First, the substrate must be located in a zone such that it is heated by the radiant energy of the flame and by the hot gases produced by the flame sufficiently to permit surface diffusion. That temperature zone is present from about the middle of the flame to some distance beyond the edge of the flame. The flame temperature can be controlled to some extent by varying the ratio of oxidant to fuel, as well as by adding non-reactive gases to the feed gas or non-combustible miscible liquids to the feed solution. Second, metal-based precursors need to be vaporized and chemically altered to the desired state. For oxides, this will occur in the flame if enough oxygen is present. Elevated temperatures, radiant energy (infrared, ultraviolet and other radiant energies), and flame plasma also aid in precursor reactivity. Finally, for single-crystal films, the material to be deposited must be in the vapor phase, with the deposition of little or not stable particles. Particle formation can be suppressed by maintaining a low concentration of solutes, and minimizing the distance, and therefore time, between the sites where the reactants react and where the substrate is positioned. The combination of these different factors predicts the best deposition zone to be located in the proximity of the flame tip. If the solution is sprayed, the droplets may attack a substrate located too far away from the flame, possibly resulting in some spray pyrolysis characteristics in the resulting film. In fact, in some configurations, with large droplets or with some reagents, it may be impossible for some spray pyrolysis not to occur.
[00045] In an embodiment of the invention described herein, a plasma torch may also be used in a similar manner to a flame apparatus to obtain similar results. Chemical precursors are pulverized by means of a plasma torch and deposited on the substrate. Reagents and other materials fed into the plasma torch are heated and, in turn, heat the substrate surface in the same manner by the flame modality described herein. In augmented plasma chemical vapor deposition (PECVD), lower plasma temperatures can be utilized, compared to conventional plasma spraying, as less heat is required to cause chemical precursors to react. As a result, precursor chemical reactions occur at lower temperatures, thus allowing substrates with low melting points to take advantage of PECVD. The deposition of the coating on the substrate results from the directing of the plasma gas vapor that contains the charged ions towards the substrate. For example, a chemical precursor gas mixture or solution is introduced into a plasma flame which results in the formation of a chemical vapor. The chemical precursor solution may comprise inorganic metal oxides, such as aluminum oxide or silicon oxide. Once oxidized, the resulting ions in substantially vapor form are directed to the surface of the substrate, resulting in the formation of a solid coating that has formed on the surface of the substrate and that are typically formed at thicknesses in the range of 1 to 50 nanometers.
[00046] In general, as long as the flame is produced, CCVD can occur, in general, regardless of the flame temperature, or the surface temperature of the substrate. The flame temperature depends on the type and amount of reagents, solvent, fuel and oxidant used, and the material and shape of the substrate, and can be determined by one skilled in the art when presented with the particular reagent, solvent, fuel, oxidant and other components and deposition conditions. The flame temperature preferably near the deposition surface of a moving strip line is between about 800°C and 1300°C. Since flames can exist over a wide pressure range, CCVD can be performed at a pressure from about 10 Torr to about thousands of torr, but ambient pressure is preferred to facilitate its use. in the polymer film processing line. Likewise, if the plasma is formed by coating deposition, the temperature of the plasma can range from about 400°C to about 1200°C. The substrate temperature during the CCVD process can also vary depending on the type of coating desired, the substrate material, and flame characteristics. In general, a substrate surface temperature of between about 40°C and 70°C is preferred for temperature sensitive polymer films.
[00047] The deposition rate of the coating on the substrate can vary greatly depending on, among other factors, the coating quality, coating thickness, reagent, substrate material and flame characteristics. For example, longer coating times can result in thicker coatings assuming a relatively constant feed flow rate to the flame, less porous coatings assuming a relatively lower feed flow rate to the flame, or more porous or columnar coatings, assuming a relatively higher flow rate at flame. Likewise, if a higher quality coating is desired, a longer coating time at a lower feed flow rate may be required, while a raw or textured coating can be produced relatively quickly using a higher feed rate. of precursor feed stream. One skilled in the art can determine the feed flow rates and deposition times required to produce a desired coating. Typical deposition rates of the nanocoated product produced using the apparatus and methods disclosed herein range from about 10 nm/min to about 1000 nm/min with the surface of the film typically being coated for 0.1 to 10 seconds.
[00048] As discussed above, the chemical precursor solution in one embodiment is a liquid reagent, dissolved in a liquid solvent. However, solid, liquid, vaporous or gaseous reagents may be used, with a liquid or gaseous solvent, provided that the chemical precursor feed to the flame is normally liquid or gaseous in nature.
[00049] Referring to Figure 2C, an embodiment of the invention described herein, in which a flame redirection source is shown to reduce temperature. The flame redirection technique utilizes an air knife 49 situated at an angle to the flame 48 to redirect gases and/or vapors 50 from the process. The air knife 49 directs a flow of air into the stream of steam 50 from the flame 48. This effectively redirects the flow of steam 50 in the desired direction on the surface of the substrate 56, while at the same time diverting the flow. heat associated with the flame 48 to superheat or melt the substrate 52 to be coated with the steam 50. This method results in heat dissipation directed to the substrate 52 from the heat flux from the flame 48 thus resulting in the deposition of desired coating on the surface of the substrate 56 at lower temperatures. The flame redirection modality also acts to disperse the gas and/or vapor 50 emanating from the flame 48, resulting in a wider deposition stream 50 being directed to the surface of the substrate 56 and area enlargement. coating thereof. In an alternative embodiment, an electromagnetic or "electroredirection" method may be used to redirect the deposition of ions and/or particles from a flame and/or plasma source onto the substrate surface. In this embodiment, the flame and/or plasma source initially directs the ions and/or particle stream and any associated heat in a direction substantially parallel to the substrate of the film to be coated. A field with an electrical potential is generated by means as known in the art, which passes through a portion of the film substrate resulting in redirection and/or acceleration of the ion and/or particle stream emanating from the plasma source or flame on the surface of the film. Chemical bonds within polymer molecules are more easily broken, which results in the rapid formation of free radicals. This results in the deposition of the desired nanocoat to the surface of the film without the associated heat being transferred to the surface of the film thus preventing the potential for melting of the film substrate during the deposition process.
[00050] Referring to Figure 2D, an embodiment of the invention described herein is shown with an array of multiple flame heads 60, which can act in a similar fashion to a flame handler to provide a long flame zone of a given length, which can process the desired width of substrate moving beyond the length of the flame. The longest axis of the flame is equated to the width of the material that undergoes nanocoating. In that embodiment, the multiple flame head assembly 60 includes a flame nozzle assembly 62 which comprises a tube with spaced holes or nozzles therein. Chemical precursors 61, which may also include an oxidant, are fed together from flame nozzle 62 and, when ignited, result in flame bank 64 or linear flame and the generation of hot gases and/or vapors 66. Substrate 52 to be coated is located close to the flame bank 64 within the region of hot gases and/or vapors 66, such that the hot gases and/or vapors 66 containing the reactant vapor will come into contact with the surface of the substrate 56 , resulting in a deposited coating. The flame handler or multiple flame head assembly 60 improves the continuity and thickness of the deposition coating over the entire surface of the substrate 56 as the hot gas and/or steam region 66 is expanded using multiple sources. of flame. The multiple flame head assembly 60 shown in Figure 2D is shown with the flame nozzle assembly 62 aligned with the nozzle holes positioned in a plane, linearly oriented. However, other embodiments are observed in which multiple flame heads or sets of flame nozzles can be conceived of various two-dimensional and three-dimensional geometries, such as square, rhomboid, cylindrical shapes, which can be formed and positioned in relation to the film to be processed. according to the user's need. The industrial flame treater can work well in yielding the desired nanocoating. Therefore, the modality illustrated in Figure 2D should not be interpreted as a limitation to this description.
[00051] Referring to Figure 3A, one embodiment of a CCVD and/or PECVD assembly as described herein is shown "in-line" with a roll winding/lining assembly 70 in a typical production context. In the illustrated embodiment, an unwind unit 76 unwinds film 78 from roll 86 as winding unit 74 winds film 78 onto winding core 84. A flame chamber 72 housing a CCVD coating assembly and/or of PECVD 82 as described here is integrated in line with the unwinding/winding units 76 and 74. The flame chamber 72 constitutes a non-pressurized compartment, in which the CCVD and/or PECVD 82 assembly is housed for the safety of the user and surrounding equipment, and to minimize impurities from external materials. During the unwinding/winding process, a film substrate 78 is drawn from the unwind unit 76 through several rolls and onto a drum 80. After receiving a coating and exiting the nanocoating deposition chamber 72, the film substrate Film 78 is wound around winding core 84. Drum roll 80 rotates and winds and/or draws substrate 78 in close proximity to the hot gases and/or vapors generated by flame assembly 82. In the illustrated embodiment, the roll drum 80 is positioned above the flame assembly 82 so as to maximize the contact surface area between the gases and/or vapors generated by the flame assembly 82, thus resulting in efficient deposition of the coating material carried by the rising hot gases and /or hot vapors on the substrate 78. In various observed embodiments, the drum roll 80 may comprise a temperature control roll, so as to impart a thermal temperature to the substrate. substrate and a differential between the substrate 78 to be coated and the heat generated by the flame assembly 82, which would facilitate the coating of substrates with low melting points without thermal damage to the substrate, in accordance with the method and apparatus of the invention herein presented.
[00052] The metallization initiator process described herein may be performed during ("in-line") or after film fabrication. In-line film surface fabrication is generally pure and free of contaminants, making it ideal for surface preparation because of the challenges of keeping the film surface clean after the fabrication process is complete. For example, dust, antiblock particles, or additives in the polymer film can "pop up" on the surface of the film substrate in a post-production environment. Such conditions can make it difficult to achieve a uniform primer coating during the priming process performed after the film has been manufactured and stored for a period of time. Treatment additives can also migrate through the inorganic nanolayer, as it is not a barrier layer in itself, so it is desired not to have these additives in the film.
[00053] Referring to Figure 3B, an embodiment of the invention described herein is shown, wherein a flame CCVD or PECVD unit is installed in-line with a biaxial film substrate production line 100. In the illustrated embodiment, a biaxial mode film substrate 102 is formed by an extrusion unit 104. The extrusion unit 104 has multiple feed paths so as to produce a film composed of variations in layer composition that are fused together to form a film. of multiple primary layers. The film substrate 102 then passes through a cooling unit 106 and is elongated in the machine (longitudinal) direction in the extension machine of the unit 108 and in the transverse direction in the transverse stretching unit 110. The film substrate, in it then passes through flame assembly 112 where it is coated with the desired inorganic initiator, antiblock nanolayer, and/or barrier coating in accordance with the apparatus and processes described herein. The film-coated substrate is then wound onto a transportable roll in winding unit 114 for further processing or distribution. The resulting coating film includes an inorganic surface nanolayer that terminates the polymer network so that it will not cross-link or block when wound on a multi-layer roll or stacked in a sheet configuration under typical manufacturing storage conditions.
[00054] It should be noted that the embodiments shown in Figures 3A and 3B may utilize plasma-assisted chemical vapor deposition (PECVD) apparatus and methods to carry out the coating process as described herein. As such, the described modalities should not be interpreted as limited to "call" CCVD methods. Plasma can be manipulated by an electromagnetic field in the vicinity of the plasma source in order to direct the ions generated from the plasma reaction onto the surface of the substrate to be coated. Thus, CCVD is not limited to the manufactured product, but is only a method used to make the product described in the original film manufacturing line.
[00055] Figure 4 is a structural diagram depicting one embodiment of a coated substrate 120. In the illustrated embodiment, a film or paper substrate 122 is prepared with a layer of pure or substantially pure silica 124. Substrate 122 with the silica layer 124 is then coated with a supplemental oxide layer 126 and a metal or subsequent oxide layer 128. The oxide layers 126, 128 may be comprised of silica mixed with an additional chemical additive or "contaminant" with the purpose of increasing the reactivity of the prepared surface 124 with the desired additional coatings. In one embodiment, the metal barrier layer deposited by the apparatus and method described herein is between 5 and 50 nm thick, with an optical density greater than 30%. The metallic barrier layer may comprise aluminum, copper, iron, manganese, zinc and/or other metals as indicated by the user's needs. In other embodiments, layer 128 is a layer of oxide deposited through CCVD or layer 128 is a layer of metal deposited by conventional vacuum metallization technology.
[00056] To describe certain embodiments of the apparatus and methods presented herein in the invention, the following examples are provided. Having understood the examples presented herein, one skilled in the art should be able to apply the apparatus and methods presented herein to other chemical deposition methods, and such applications are considered to be within the scope of the invention presented herein. The following examples are for illustrative purposes and should not be construed as limiting the scope of the invention. In the examples, primer coating deposition was performed using CCVD in an atmospheric environment. Covers without sealing and local ventilation to exhaust combustion of residual gas were used in all cases. The chemical precursors consisted of TEOS in an air feed of methane through a film flame treater with a flame temperature of 800°C to 1200°C. Example 1 In-Line Flame Treatment of Oriented Polypropylene Film
[00057] In one example, polypropylene film was extruded and oriented on a film production line. The 70 gauge full thickness film (18 μm thick) was composed of a polypropylene skin layer of Total Petrochemical 8573, a polypropylene core of Total Petrochemical 3371, and an opposing skin layer of polypropylene of Total Petrochemical 3371. Flame treatment was performed on the skin layer 8573 prior to final winding of the oriented extruded film. This film demonstrates the slight improvement in metallization performance than flame treatment alone.
[00058] The flame treatment was carried out with a 2 meter section of an Ensign Ribbon Burner 424-HCW-15/6Ft. The air to the flame was controlled by a King Instruments 7530 rotameter at about 2 cfm. An Alicat Scientific mass flow controller (model MC-10 slpm) measured the flow of methane to the flame. Methane to the flame flowed at the 8.3 slpm setting. The methane stream was mixed with the air stream before entering the burner and then burned.
[00059] The polypropylene film came out of orientation in the transverse direction at a line speed of about 24.40 m/min (80 ft/min) and passed over a cold drum held at 45°C. The burner was placed at the bottom dead center of the drum, oriented above the flame, with a gap of 5 mm between the burner face and the drum surface. Flame gases were expelled through a rectangular channel about 406.4 mm (16 inches) long, 2 meters wide and 25.4 mm (1 inch) high. The channel was placed immediately downstream of the burner and was designed in such a way that the film itself formed on the upper wall of the channel. This allowed for an increase in the contact time between the hot vapors from the flame and the surface of the film.
[00060] Then the film was rolled up for further use, in this case for conventional vacuum metallization. The flame-treated 8573 surface of the film was metallized with aluminum metal to a minimum optical density of 2.3. The oxygen transmission of the metallized film was tested at 23°C with dry oxygen, and resulted in an oxygen transmission rate (OTR) of 1.801 c/(m2^day). Water vapor transmission rates (WVTR) were tested at 38°C and 90% relative humidity, and resulted in a water vapor transmission rate of 6.09 g/(m2^day).
[00061] In comparison, Tock, Richard W., "Permeabilities and Water Vapor Transmission Rates for Commercial Films," Advances In Polymer Technology, Vol. 3, Issue 3, pp. 223 to 231, Fall (1983), lists oriented polypropylene film, with an oxygen transmission rate of 2092 c-mil/(m2 day) [listed as 135 c-mil/(m2 day - atm)], and which is equivalent to 2988 c/(m2 days) for the 70 gauge films used in this example. Tock lists oriented polypropylene film with a water vapor transmission rate of 5.1 g -mil/(m2 day) [listed as 0.33 g -mil/(m2 - day - atmosphere)], which is equivalent to 7.3 g/(m2 days) for the 70 gauge films used in this example. 70 gauge pure oriented polypropylene (OPP) non-flame treated films exhibited OTR > 2000 c/(m2 day), which is beyond the MOCON Oxtran test limits. The same pure OPP films exhibited a WVTR of 8.14 g/(m2 day), which is in agreement with approximate data from Tock. Flame treatment and metallization provide a 40% improvement in oxygen barrier (OTR reduction) based on Tock data and a 25% improvement in barrier moisture (WVTR reduction) compared to film measurements of pure OPP. Example 2 In-line Deposition of SiO2-based Metallization Initiator on Oriented Polypropylene Film
[00062] For comparison purposes, in-line flame deposition of silica (CVD) was performed on skin layer 8573 of the same oriented polypropylene film 8573/3371/3371 as in Example 1 at the same total film thickness of 70 gauge (18 μm thick). The equipment was identical to that described in Example 1, with the only exception of an additional mass flow controller and bubbler that were used to introduce the silica precursor. The silica deposition and flame treatment was applied to the side of the 8573 skin, as in Example 1. Air to the flame was released at 2 cfm. Two Alicat Scientific mass flow controllers, both model MC-10slpm, measured the methane fluxes to the flame. The primary methane for the flame was measured at 6.9 slpm and the gas entering the precursor bubbler had a methane flow setting of 1.4 slpm. The methane gas stream from the bubbler flowed to a heated bubbler that contains tetraethoxysilane (TEOS, 98%, Aldrich), which acts as the silica precursor. The bubbler was heated to 40°C to provide adequate vapor pressure and the bubbler outlet line was heated to 45°C to prevent condensation of the TEOS vapor. Bubbler methane, bypass methane and air gas streams were mixed before the burner and combusted at the burner outlet.
[00063] The polypropylene film left the transverse orientation at a line speed of approximately 24.40 m/min (80 ft/min) and passed through a cold drum held at 45°C. The burner was positioned at dead center at the bottom of the drum, oriented above the flame, with a gap of 5 mm between the burner face and the drum surface. Flame gases escaped through the same rectangular channel as in Example 1.
[00064] The coated film was rolled up and sent to conventional vacuum metallization. The silica coated surface of the film was metallized with aluminum metal to a minimum optical density of 2.3. The oxygen transmission of the metallized film was tested at 23°C with dry oxygen, and resulted in a transmission rate of 63.1 cc/(m2^day). Water vapor transmission was tested at 38°C and 90% relative humidity, and resulted in a water vapor transmission rate of 1.80 g/(m2^day).
[00065] Silica deposition and OPP film metallization produced a 98% improvement in the oxygen barrier (OTR reduction) based on Tock data in Example 1 and a 78% improvement in the moisture barrier (reduction of of WVTR) compared to the pure OPP measurements of Example 1. There is also a significant improvement in barrier over Example 1, which had identical flame conditions in addition to the silica being deposited. Example 3 Metallization Layer on Liquid Fuel Flame Treated PLA Polymer by Roll Coating Machine
[00066] By way of example and for purposes of comparison, a biaxially oriented PLA polymer film substrate was first treated on the inner surface of the roll. The following typical processing conditions were used for the flame originating from the liquid fuel, which atomized the liquid flowing through it into submicron droplets. A fuel solvent containing the toluene or alcohol based solvent at a flow rate of 4 mL/min flowed through an atomizer. Then, the atomized solvent was burned in a flame in the vicinity of the polymer substrate. The polymer film surface was flame treated for 3 turns at a surface flame gas temperature of 550°C, a movement speed of 50.8 m/min (2000 inches/min), and a size of 0.00635 m (0.25 inch) pitch. Then an Al metallization layer was then deposited on top of the flame treated surface by thermal evaporation. The OTR was tested at 23°C and 100% dry oxygen. An OTR of 7.18 cc/m2^day was obtained, which is a significant improvement over the biaxially oriented pure PLA polymer with an OTR of more than 350 cc/m2^day and the oriented pure PLA polymer. metallized biaxially of Al on the inner surface of the roll with an OTR of more than 14.09 cc/m2^day. Example 4SiO2 Metallization Initiator Layer of Liquid CCVD Fed into a Smoke Exhaust in PLA polymer
[00067] As an example to liquid fuel deposition, an initiator nanocoating interface layer based on SiO2 over biaxially oriented PLA polymer substrate for metallization, the following typical processing conditions were used. A CCVD deposition solution containing the fuel solvent and TEOS precursor at a concentration of 9.0 mM flowed at a flow rate of 4 mL/min through the powered atomizer to produce the submicron-sized droplets. The atomized solution was flame burned in front of the polymer film substrate. Then, the SiO2-based nanocoating was deposited for 2 turns at a surface gas temperature of 400°C, a movement speed of 25.4 m/min (1,000 inches/min), and a step size of 0.00635 m (0.25 inch). Prior to SiO2 deposition, the PLA polymer film substrate was flame treated for 1 turn under the same conditions, except that there is no silica precursor. Then, an Al metallization layer was deposited on top of the SiO2 interface layer by thermal evaporation. OTR was tested at 23°C and 100% dry oxygen. An OTR of 2.78 cc/m2^day was obtained, which is a significant improvement over the Al metallized biaxially oriented pure PLA polymer with an OTR of over 350 cc/m2^day, to the Al metallized biaxially oriented PLA on the inner surface of the roll with an OTR of 14.09 cc/m2^day, and the flame-treated biaxially oriented PLA polymer on the inner surface of the roll with an OTR of 7.18 cc/m2^day. Example 5 CCVD SiO2-Based Metallization Initiator Layer on an OPP Polymer Smoke Exhaust
[00068] As an example subsequent to winding the SiO2-based metallization initiator layer onto the OPP polymer produced on the same line as Examples 1 and 2, the following typical deposition conditions were used for the linear flame burner head with a length of 12" and a width of 0.75" in Total Petrochemical's polypropylene smoke extractor. The burner head is manufactured by Flynn Burner Corporation (Model No. T-534). Methane flowed at about 0.67L/min through a bubbler, which contains the TEOS precursor at a temperature of 40°C and a methane bypass line at about 13.8L/min. Then, the methane flowing through the bypass line was mixed with air at a flow rate of about 4.2 slpm ("standard liter per minute"). The mixture of air and methane together with the methane containing TEOS precursor flowed through the linear burner and formed the flame close to the polymer substrate. Then, the SiO2 interface layer was deposited on the polymer surface for 1 turn at a distance of 37 millimeters, with a flame temperature of 1122°C measured close to the burner, and a movement speed of 56.1 m. /min (184 ft/min). The Al metallization layer (70 nm measured by the crystal sensor) was then deposited on top of the SiO2 interface layer by electron beam evaporation. The OTR was tested at 23°C and 100% dry oxygen. An OTR of 43.35 cc/m2^day was obtained (AAT-03D1), which is a significant improvement over the pure OPP polymer with an OTR of over 1000 cc/m2^day. WVTR was also tested at 38°C and 89% relative humidity and a WVTR of 0.35g/m2^day was obtained against pure OPP polymer with a WVTR of 9.3g/m2^day. Example 6Flame Treated Surface with CCVD SiO2-based metallization initiator layer in an OPP Polymer Smoke Exhaust
[00069] As an example for the flame treated polymer substrate, before the SiO2 deposition, the system, substrate and conditions were the same as in Example 5. The difference is that the OPP polymer substrate 9" x12" was first flame treated for 1 turn at a methane flow of 13.8L/min, an air flow of 4.2 slpm, a sample burner distance of 39 mm, a movement speed of 56, 1 m/min (184 ft/min) and a temperature of 1180°C. Then, the flame-treated polymer was deposited by 2 turns of SiO2 at a flame temperature of about 1190°C, a movement speed of 56.1 m/min (184 ft/min) and a sample distance of 39mm burner. The following typical processing conditions were used for SiO2 deposition using a linear flame burner head with a length of 12" and a width of 0.75" in the smoke exhaust. The burner head is manufactured by Flynn Burner Corp (burner model #T-534). Methane flowed at about 0.2 L/min through a bubbler, which contains the TEOS precursor at a temperature of 40°C and a methane bypass line of about 13.8 L/min. Then, the methane flowing through the bypass was mixed with air at a flow rate of about 4.2 slpm. The mixture of air and methane together with the methane containing TEOS flowed through the linear burner and formed the flame close to the polymer substrate. Then, the Al metallization layer was deposited on top of the SiO2 interface layer by electron beam evaporation. The OTR was tested at 23°C and 100% dry oxygen. An OTR of 4.44 cc/m2^days was obtained (AAT06C), which is a significant improvement over the pure OPP polymer with an OTR of over 1000 cc/m^day. WVTR was also tested at 38°C and 89% RH. A WVTR of 0.10g/m2^day was obtained compared to pure OPP polymer with a WVTR of 9.3 g/m2^day. Example 7 Inline Silica Primer Coating and Redirected Flame
[00070] In this example, experiments performed for the deposition of a silica initiator coating by CCVD were conducted in-line on a pilot biaxial oriented film line with a flame redirection configuration, as shown in Figure 3B. A shield was installed to direct the reactive plasma generated by the flame assemblies to maintain the plasma in reactive proximity to the surface of the film substrate. An extended deposition box was located at the end of the shield to expose the film surface to deposition gases for a longer time. Beyond the deposition zone, the gases escaped.
[00071] Both OPP and PLA films were produced and coated with silica in an in-line production context in accordance with the presentation of the invention here. The OPP film comprised a Total 3371 homopolymer polypropylene core layer and Total 8573 random copolymer polypropylene skin layers. The PLA film structure included a Nature Works 4043 metallization surface (~5% crystalline), a core of Nature Works 4032 (~40% crystalline) and a sealing layer of Nature Works 4060 (amorphous PLA) with anti-blocking. The film substrates were then metallized using conventional vacuum metallization techniques. Both OPP and PLA films were metallized to an optical density of 2.3 ± 0.2. This optical density was selected as the minimum barrier performance standard to achieve a functional barrier and to highlight differences in the effectiveness of metallization initiators. As shown in Table 1 below, OPP and PLA films treated with silica using the CCVD method exhibited better metal deposition characteristics, resulting in improved barrier performance. Table 1

[00072] Treatment of the film with a corona discharge before or after the metallization initiator method described herein can also improve coating properties. Conventional flame and corona discharge treatments are normally used to partially oxidize surfaces, especially PE and PP, to allow better adhesion of layers, paints, coatings and to prepare coextruded polymer films for metallization. This can remove surface contaminants such as oils or other species that can disrupt a direct boundary of the inorganic nanolayer of the present invention to the polymer film material. Example 6 shows the potential improved results of surface treatment prior to coating.
[00073] To determine approximate thickness, XRF and XPS were used. XRF sensitive to 10 nanometer thick films. When used to try to detect the silica thickness of the above examples, the thickness was less than the detection limit. Next, XPS was tried, and being very sensitive to the surface, it could detect silica. To correlate silica thickness to known silica thickness in the same polymer, electron beam deposition of silica was performed with a quartz crystal monitor. The Denton Explorer electron beam evaporator was used for the deposition. The process was run at 2*10-6 Torr and 0.3 A/S. The silica was grown at 4, 6 and 8 nm thick, and the corresponding peaks of silica/oxygen XPS in thousands of counts per second (TCPS) were 87/456, 109/494 and 133/614. XPS Si/O peaks for pure OPP were < 1/<1 TCPS. It can be seen that the trend is not linear with ordinate at zero origin, but that it increases with silica. The sample from Example 2 was analyzed by XPS at two different locations on the silica coated section of the film network with Si/S peaks of 14/106 and 7/56 TCPS. Example 6 resulted in a measured result of XPS 1.3/46 of TCPS. The results show that the deposited layer is significantly smaller than 4, 6 and 8 nm electric beam silica and probably much smaller than 2 nm. These are not absolute thicknesses and the XPS results are not linear, but it can be seen that the layer can work very well with a thickness of less than 4 nm and even below 2 nm thickness. In Examples 1 and 2, the flame treatment and silica coated areas were transverse to the center by 0.61 m (2 ft) of a film about 0.92 m (3 m) wide, and the metallization in these central sections was better than the untreated outer section. The sub-2nm silica coating substrate of Example 2 had a greater change in appearance than the untreated than just flame treated in Example 1. This shows that a very thin layer is all that is needed to reinforce the moisture and subsequent processing improvements.
[00074] In attempts at above 8nm average thickness of silica deposited in just one or two CCVD flame treatment steps, the barrier results decreased. This is believed to be due to the growth of a less dense film that has a nanostructured surface. This nano-rough surface can prevent the metallization from being so dense and continuous, which can reduce the barrier. Thus, it is preferred that the layer is less than 8 nm and more preferably that it is less than the average thickness of 4 nm. A layer of a few atoms is theoretically all that should be needed to keep the layer from being welded together, so 2nm or less can provide the desired effects for many applications. No welding of the coated silica rolls took place, and this is true for many rolls without slip or anti-block materials. This small thickness reduces cost and can be formed with high coverage and a smooth texture with just one or a small number of deposition systems in sequence, even on high speed lines.
[00075] Unless otherwise indicated, all numbers expressing ingredient amounts, properties such as molecular weight, reaction conditions, and so on used in the specification and claims are to be understood to be modified in all cases by the term "about". Therefore, unless otherwise indicated, the numerical parameters presented in the following specification and in the appended claims are approximations which may vary depending on the desired properties to be obtained by the present invention. At a minimum, and not in an attempt 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 significant figures reported and by the application of common rounding techniques.
[00076] While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention.

权利要求:
Claims (25)
[0001]
1. Method, comprising: a) forming a substrate (52) of organic film coextruded by a coextrusion process; b) depositing a first layer of inorganic nanocoating directly onto a surface (56) of the film substrate (52) in atmosphere open to increase the wettability of the film substrate (52) for metallization, wherein the first inorganic nanocoating layer is silica, and wherein the inorganic nanocoating layer is deposited on at least one surface (56) of the substrate (52). ) of film before winding and deposited in a process in line with the coextrusion process, where the inorganic nanocoating layer has an average thickness of less than 8nm; and where the surface roughness of the inorganic nanocoating layer is characterized by an RMS value of less than 5nm; and c) depositing a layer of metal directly onto the first inorganic nanocoating layer by a vacuum metallization process to produce a film coated substrate (52), where the metal layer is not a metal oxide layer, where the metal layer is metal is aluminum, and where the metal layer is between 5 and 50 nm thick.
[0002]
2. Method according to claim 1, characterized in that the inorganic nanocoating layer is deposited on at least one surface (56) of the film substrate (52) by the deposition of chemical combustion vapor.
[0003]
3. Method according to claim 1, characterized in that the inorganic nanocoating layer is deposited on at least one surface (56) of the film substrate (52) by plasma-enhanced chemical vapor deposition.
[0004]
4. Method according to claim 1, characterized in that the inorganic nanocoating layer is substantially deposited by redirecting a flame (48, 82, 112).
[0005]
5. Method according to claim 1, characterized in that the inorganic nanocoating layer is substantially deposited by electroredirection of a plasma field.
[0006]
6. Method according to claim 1, characterized in that the film substrate (52) is cast, monoaxially or biaxially oriented cast film.
[0007]
7. Method according to claim 1, characterized in that the film substrate (52) is a blown film.
[0008]
8. Method according to claim 1, characterized in that the film substrate is a biaxial film (102).
[0009]
9. Method according to claim 1, characterized in that the film substrate (52) is a bio-based polymer film.
[0010]
10. Method according to claim 1, characterized in that the film substrate (52) comprises a core polymer layer selected from the group consisting of polyethylene, polypropylene, polystyrene, polylactic acid, polyethylene terephthalate , polyesters and copolymers thereof and mixtures thereof.
[0011]
11. Method according to claim 1, characterized in that the film coated substrate (52) has a water vapor transmission rate of 2.0 g/m2/day or less.
[0012]
12. Method according to claim 1, characterized in that the coated film substrate (52) has an oxygen transmission rate of 10 cc/m2^day or less.
[0013]
13. Method according to claim 1, characterized in that it further comprises depositing an additional inorganic nanocoating layer to form a transparent barrier layer.
[0014]
14. Method according to claim 1, characterized in that between the step of depositing the first inorganic nanocoating layer and the step of depositing the metallic layer, the coated film substrate is rolled.
[0015]
15. Method according to claim 1, characterized in that the step of depositing a first layer of inorganic nanocoating directly onto a surface (56) of the film substrate (52) in an open atmosphere substantially inhibits substrate blocking ( 52) of film.
[0016]
16. Method according to claim 15, characterized in that the inorganic nanocoating layer is deposited on at least one surface (56) of the film substrate (52) by the deposition of chemical combustion vapor.
[0017]
A method according to claim 15, characterized in that the inorganic nanocoating layer is substantially deposited on at least one surface (56) of the film substrate (52) by plasma-enhanced chemical vapor deposition.
[0018]
18. Method according to claim 15, characterized in that the inorganic nanocoating layer is substantially deposited by redirecting a flame (48, 82, 112).
[0019]
The method of claim 15, wherein the inorganic nanocoating layer is substantially deposited by electroredirection of a plasma field.
[0020]
20. Method according to claim 15, characterized in that the inorganic nanocoating layer is substantially deposited on at least one surface (56) of the film substrate (52) before lamination.
[0021]
21. Method according to claim 15, characterized in that the film substrate (52) is cast, monoaxially or biaxially oriented cast film.
[0022]
22. Method according to claim 15, characterized in that the film substrate (52) is a blown film.
[0023]
23. Method according to claim 15, characterized in that the film substrate (52) is a bio-based polymer film.
[0024]
24. Method according to claim 15, characterized in that the film substrate (52) comprises a polymer core layer selected from the group consisting of polyethylene, polypropylene, polystyrene, polylactic acid, polyethylene terephthalate , polyesters, and copolymers thereof and mixtures thereof.
[0025]
25. Method according to claim 15, characterized in that between the step of depositing the first inorganic nanocoating layer and the step of depositing the metallic layer, the coated film substrate is rolled.

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同族专利:

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JP5923606B2|2016-05-24|

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CA2843154C|2015-12-08|

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RU2014104503A|2015-09-20|

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BR112014002654A2|2017-06-13|

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JP2014529516A|2014-11-13|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-16| B15I| Others concerning applications: loss of priority|Free format text: PERDA DA PRIORIDADE US 13/204,483 DE 05/08/2011 REIVINDICADA NO PCT/CA2012/049739 DEVIDO A NAO APRESENTACAO DO CONTEUDO DO DOCUMENTO DE PRIORIDADE JUNTO AO REQUERIMENTO DE ENTRADA NA FASE NACIONAL E O MESMO TAMBEM NAO ESTAR DISPONIVEL NA BIBLIOTECA DIGITAL DA OMPI, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 164O E NO ART. 26 DA RESOLUCAO INPI-PR 77/2013 |

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2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2019-09-17| B12F| Other appeals [chapter 12.6 patent gazette]|

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2021-06-01| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2021-08-10| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-12-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-01-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/08/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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