Metallization processes and products formed therefrom

Abstract

The technology disclosed herein relates to films and products that provide excellent OTR and WVTR properties.

Description

[Technical field]

[0001] The present invention generally contemplates providing metallized surfaces and uses thereof. [Background technology]

[0002] Metallized packaging materials provide excellent barrier properties and are therefore widely used in food packaging applications. Metallized packaging materials are used in a variety of packaging configurations, as enclosures for liquid and solid materials, and as protective enclosures for pharmaceutical and cosmetic compositions. However, despite widespread use, the known barrier properties are not ideal.

[0003] Typically, metallized surfaces are formed by laminating a metal layer or surface. [1] Vapor deposition methods are also known. However, these do not improve the barrier properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] German Patent No. 202018103076.0 Specification Summary of the Invention

[0005] General Description The technical subject matter of the present application is based on the finding that films formed from a special material blend including one or more cellulose nanomaterials, such as nanocrystalline cellulose (CNC), or at least one wax material, and deposited with a thin metal film, exhibit significantly better oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) than metallized or non-metallized surfaces known in the art to have excellent OTR and WVTR properties. A comparison of oxygen barrier properties, OTR at 70% RH and 23°C, and water vapor barrier properties, WVTR at 90% RT and 38°C, is shown for the metallized surface of the present invention, which is approximately 1 ml / m 2 Days or less OTR value, and about 5gr / m 2days or less WVTR value, - Non-metallized surface, - surfaces that do not have cellulosic or waxy materials, such as CNC, in direct contact with the deposited metal, and / or - Metallized surfaces formed by deposition methods other than vapor deposition This is hundreds or thousands of times better than what was measured above.

[0006] Because vapor deposition allows for the formation of specific metal thin films of various thicknesses and porosities or pore densities, metallized films with specific compositions and properties have been developed.

[0007] The inventors therefore provide for metallized material blend films, i.e. films composed or derived from material blends metallized in thin films. As described in more detail herein below, a dry film derived from a material combination or material blend contains the same materials as the material blend from which it is derived. Thus, within the context of the present invention, a film composed of a material blend is a film that includes or consists of the combination of materials specified for the particular blend. Similarly, a film derived from a material blend is a film formed by a particular combination or combination of materials.

[0008] The films of the present invention may comprise a film of a material blend, a thin film of metal, and optionally a substrate. In some configurations, the metallized products of the present invention include: a metallized material blend film comprising a material blend film and at least one metal film disposed on (or in association with, contact with, or on) the material blend film; - a metallized material blend film consisting of a material blend film, a film of at least one metal and a substrate, the film being disposed on (or associated with, or in contact with, or on a surface of) the material blend film and the substrate being disposed on a surface of the material blend film or the at least one metal film; a metallized material blend film comprising a material blend film and at least one metal film disposed on (or in association with, contact with, or on) the material blend film; - a metallized material blend film comprising a material blend film, at least one metal film, and a substrate, the film being disposed on (or associated with, or in contact with, or on a surface of) the material blend film, and the substrate being disposed on a surface of the material blend film or the at least one metal film; and -any other disclosed herein Includes.

[0009] As used herein, the term "material blend" refers to a material component or mixture of components that is comprised of a primary film of a metallized product, optionally formed on a substrate, associated with a metal film by a metallization process that may include or involve vapor deposition. A material blend is a homogenous mixture that includes two or more materials, one of which may be a cellulose material and / or a wax material, and the other material may be an additive with superior OTR and / or WVTR properties that are imparted to the film along with the cellulose material and / or wax when metallized. In some configurations, the material blend does not include or excludes a metal material, where the metal is optionally a zero-valent metal atom. In some configurations, however, the material blend may include a metal material that is comprised of metal nanoparticles, as disclosed herein.

[0010] The films or products of the present invention may generally be structured from two, three or more layers or laminated component regions, films of material blends, metallized surfaces formed from metals, and optionally substrates. Typically, films of material blends are continuous solid films in which the components of the blend are homogeneously distributed. In the metallized products of the present invention, the specific components or materials that make up the blend do not themselves constitute separate material films or layers, nor are they distributed in separate regions of the film made of or formed from the material blend.

[0011] In a first aspect, a metallized material film is provided, the metallized film comprising or consisting of a material blend film, a metal surface, and optionally a substrate, the material blend film comprising at least one cellulose material and / or at least one wax and one or more additional additives.

[0012] In some embodiments, the material blend includes at least one cellulosic material.

[0013] In some embodiments, the material blend includes at least one wax.

[0014] In some embodiments, the material blend includes at least one cellulosic material and at least one waxy material.

[0015] In some embodiments, the metallic surface is a metallic film formed by vapor deposition.

[0016] In some embodiments, the present invention provides a method for producing a method for treating a cancer cell comprising the steps of: - a film of a material blend including a cellulose material, and a vapor-deposited metallized film comprising or consisting of a metal surface; a film of a material blend including a cellulosic material, a vapor deposited metallized film comprising or consisting of a metal surface and a substrate; a deposited metallized film comprising or consisting of a film of a material blend including a wax material and a metal surface; A deposited metallized film comprising or consisting of a film of a material blend including a wax material, a metal surface and a substrate; a deposited metallized film comprising or consisting of a film of a material blend including a cellulosic material and a wax material and a metal surface; a film of a material blend including a cellulosic material and a wax material; a deposited metallized film comprising or consisting of a metal surface and a substrate; Provide one of the following:

[0017] Also provided is a vapor deposited metallized nanocrystalline cellulose (CNC)-based film, the metallized CNC-based film being comprised of a CNC-based film, a metallized surface, and optionally a substrate.

[0018] The present invention also provides surfaces coated with or associated with a metallized film of a material blend, where the metallization can be achieved by vapor deposition.

[0019] Also provided is a metallized film of the material blend, the metallization being by vapor deposition of a thin metal film onto the surface of the film of the material blend.

[0020] In another configuration, a metallized cellulose-based film is provided, the film including a cellulose material, the film laminated with a thin metal film, the thin metal film having a thickness between 500 Å (angstroms) and 100 nm.

[0021] A further configuration is a metallized wax-based film, the film comprising a wax material, the film laminated with a thin metal film, the thin metal film having a thickness of 500 Å (Angstroms) to 100 nm, to provide a metallized wax-based film.

[0022] Yet another configuration is a metallized film comprising a cellulose material and a wax material (i.e., the film comprises at least one cellulose material and at least one wax material), which is laminated with a thin metal film, which has a thickness between 500 Å (angstroms) and 100 nm, to provide the metallized film.

[0023] The metallization may be provided on a substrate, which is either on the surface of the material blend film or on the surface of the metal film. In other words, the metallization may be provided in a "direct configuration" (substrate / blend / metal) where the material blend film is located between the substrate and the metallized surface, or in an "inverse configuration" (blend / metal / substrate) where the substrate is on the metallized surface. In either configuration, the film of the present invention comprises a metal in direct contact with the material blend. As used herein, the term "contact" when referring to the association or interaction between a metal film and a material blend film means that one film layers on a surface area of ​​the other film, typically the complete surface, such that a laminate structure is formed. In some configurations, the contact is an intimate contact (hence direct contact) without any intermediate material or film involved, which allows for a firm, non-peeling association. Without wishing to be bound by theory or mechanism, it is believed that the association is not chemical, but rather an intercalation or penetration or physical anchoring into the pores of the layer of the blend material, typically on the metal layer.

[0024] As described herein, metallization of the material blend film may be achieved by vapor deposition of a metal such as aluminum, or by any known metallization process. When vapor deposition is utilized, it may be direct or indirect. In a direct vapor deposition process, the metal is vapor deposited directly onto the material blend film. In an indirect vapor deposition process, the metal is vapor deposited onto a sacrificial film or substrate and then transferred to the material blend film. "Metalization" thus encompasses metal vapor deposition onto the material blend film. As used herein, metallization is in no way a lamination, flaking, or coating of the material blend film with a metal. Metal vapor deposition consists of vapor deposition, as detailed herein.

[0025] "Vapor deposition" or "physical vapor deposition", PVD, is one of a variety of vacuum deposition methods that can be used to create metallized films or products. Physical vapor deposition is characterized by a process in which metal goes from a condensed phase to a vapor phase and back to the condensed phase in a thin film. The physical vapor deposition process can be sputtering or evaporation. To achieve metallization, the following steps are typically followed: (i) sputtering / evaporation to create a vapor phase, (ii) supersaturating the vapor phase in an inert atmosphere to promote condensation of metal nanoparticles, and (iii) heat treatment under an inert atmosphere to strengthen the nanocomposite.

[0026] In the metallization step, the substrate may be optionally surface treated prior to metallization to improve metal adhesion. Surface pretreatment may be accomplished by any method known in the art, such as plasma, corona discharge, and flame treatment. If present, pretreatment does not include forming an intermediary material layer to separate the substrate and the deposited metal. Typically, such intermediary films are excluded, consisting of starch, PVOH, adhesive materials, and others. Furthermore, if the metal deposition is performed directly on the surface of the material blend film, surface treatment may not be utilized.

[0027] Metallization may be carried out in a conventional metallizer that includes a chamber that is divided into two or more sections, in which the atmosphere is evacuated to a low pressure below atmospheric pressure. A reel or roll of unmetallized film of a blend of materials, for example, cellulosic materials and / or waxes on a substrate, is provided to one of the two sections. The film to be metallized is threaded from the reel to the roll, which moves the film to another section of the metallizer where a metal, such as aluminum, is evaporated and deposited on the surface of the film, usually as it passes around the roll. Typically, the roll is cooled to between -15°C and -35°C. After metallization is complete, the metallized film is returned to the first section of the metallizer, where it is unwound. This process may vary depending, among other things, on the size of the sheet to be coated and the material to be coated.

[0028] A "metal" may be any metallic material or alloy thereof or a combination of two or more metals or metal forms (e.g., two different alloys of the same metal). Metals may be provided in pure metallic form, oxide form, doped form, composite alloy form, or mixtures of metals, oxides, or alloys of such metals. Generally speaking, the metals used are non-toxic, non-leachable metals. Such metals include zinc, aluminum, iron, titanium, tin, and others.

[0029] In some embodiments, the metal is aluminum.

[0030] In some embodiments, the metallic region is comprised of a single metal, while in other embodiments the metal is a mixture or composition of one or more metals or metal oxides or alloys.

[0031] In some embodiments, the material deposited is a metalloid, such as silicone.

[0032] The metal and / or silicone reinforcement on the material blend film surface provides a metallized product in the form of or including a film having an average thickness of 500 Å (angstroms) to 500 nm or 100 nm. The actual thickness of the metallized film may vary. The thickness may be 500 Å to 100 nm, or 500 Å to 95 nm, 500 Å to 90 nm, 500 Å to 85 nm, 500 Å to 80 nm, 500 Å to 75 nm, 500 Å to 70 nm, 500 Å to 65 nm, 500 Å to 60 nm, 500 Å to 55 nm, 500 Å to 50 nm, 500 Å to 45 nm, 500 Å to 40 nm, 500 Å to 35 nm, 500 Å to 30 nm, 500 Å to 25 nm, 500 Å to 25 nm, 500 Å to 35 nm, 500 Å to 30 ... The thickness may be 0 nm, 500 Å to 15 nm, 500 Å to 10 nm, 500 Å to 5 nm, 500 Å to 4 nm, 500 Å to 3 nm, 500 Å to 2 nm, 500 Å to 1 nm, 1 to 100 nm, 5 to 100 nm, 10 to 100 nm, 20 to 100 nm, 30 to 100 nm, 40 to 100 nm, 50 to 100 nm, 60 to 100 nm, 70 to 100 nm, 80 to 100 nm, or 90 to 100 nm.

[0033] In some embodiments, the metallized film is produced by vapor deposition. Thus, a production method that may include vapor-depositing a metal onto the surface of the material blend film may include (i) vapor-depositing a metal onto the surface of a film that is provided on a substrate (direct vapor deposition), or (ii) vapor-depositing a metal onto a substrate to obtain a metallized surface on the substrate and transferring the metal film onto the material blend film (indirect vapor deposition).

[0034] In some embodiments, the method includes obtaining a material blend film on a substrate.

[0035] The film of the material blend may be of various thicknesses, typically the film thickness is between 0.5 and 20 μm. In some embodiments, the thickness is 0.5-19 μm, 0.5-18 μm, 0.5-17 μm, 0.5-16 μm, 0.5-15 μm, 0.5-14 μm, 0.5-13 μm, 0.5-12 μm, 0.5-11 μm, 0.5-10 μm, 0.5-9 μm, 0.5-8 μm, 0.5-7 μm, 0.5-6 μm, 0.5-5 μm, 0.5-4 μm, 0.5-3 μm, 0.5-2 μm, 0.5-1 μm, 5-20 μm, 5-10 μm, 10-20 μm, 15-20 μm, 1-5 μm, 1-10 μm, 1-15 μm, or 1-20 μm.

[0036] In some embodiments, a film of the material blend is formed by applying a material blend or suspension consisting of or including the same onto a substrate using coating techniques such as rod coater, gravure, flexography, blade coater, slot die, etc., and then drying the wet coating to form a dry coated layer on the substrate; a free-standing film of the material blend is formed using methods such as casting and drying, coating and separating a suspension consisting of or including the material blend.

[0037] In some embodiments, the material blend film consists of or comprises a specified material composition. Additives, if present, may be selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others.

[0038] In some embodiments, the additive is at least one carbohydrate, optionally selected from starch, dextrin, cyclodextrin, maltodextrin, pectin, hemicellulose, sorbitol, glycogen, and others.

[0039] In some embodiments, the additive is at least one crosslinker, optionally selected from polyacrylic acid (PAA), polyethyleneimine (PEI), polyurethane, alkenylsuccinic anhydride (ASA), alkylketene dimer (AKD), and others.

[0040] In some embodiments, the additive is at least one polymer selected from any of polyvinyl alcohol (PVOH), polyvinyl acetate (PVAc), ethylene-vinyl alcohol (EVOH), polyvinylpyrrolidone (PVP), ethylene vinyl acetate (EVA), latex, acrylic polymers, thermoplastic polymers, epoxides, polyolefin polymers, and others.

[0041] In some embodiments, the additives are natural additives such as lignin, proteins, chitosan, amino acids, lipids, gelatin, alginic acid, and others.

[0042] In some embodiments, the additive is at least one mineral selected from clay, talc, gypsum, calcite, kaolin, aluminum silicate, illite, vermiculite, smectite, chlorite, halloysite, and others.

[0043] In some embodiments, the additive is at least one surfactant, which is optionally selected from anionic surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants, sulfate surfactants, sulfonic acid surfactants, phosphate surfactants, carboxylate surfactants, antifoaming agents (such as silicone surfactants or organic surfactants), ethoxylate surfactants, fatty acid ester surfactants, glycerol surfactants, sorbitol surfactants, alkyl polyglycosides, and others. In some embodiments, the at least one surfactant may be selected from sodium dodecyl sulfate (SDS), sodium laureth sulfate (SLS), cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), and dimethyldioctadecylammonium bromide (DODAB).

[0044] In some embodiments, the additive is at least one type of nanoparticles, such as SiO2, ZnO, TiO2, Ag, Au, carbon, Al2O3, Fe, and others.

[0045] In some embodiments, the additive is one or more additives selected herein. In some embodiments, the additive is two or more additives, each additive being selected from a different group of additives: carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, and / or nanoparticles.

[0046] In some embodiments, the blend includes at least one additive that is a carbohydrate, or a crosslinker, or a polymer, or a natural additive, or a mineral, or a surfactant, or a nanoparticle type.

[0047] In some embodiments, the blend includes an additive that is a carbohydrate or a polymer or a crosslinker, each independently selected as described above.

[0048] In some embodiments, the additive is at least one carbohydrate, optionally selected from starch, dextrin, cyclodextrin, maltodextrin, pectin, hemicellulose, sorbitol, glycogen, and others.

[0049] In some embodiments, the additive is polyacrylic acid (PAA).

[0050] In some embodiments, the additive is polyethyleneimine (PEI).

[0051] In some embodiments, the additive is a polyurethane.

[0052] In some embodiments, the additive is an alkenyl succinic anhydride (ASA).

[0053] In some embodiments, the additive is an alkyl ketene dimer (AKD).

[0054] In some embodiments, the additive is polyvinyl alcohol (PVOH).

[0055] In some embodiments, the additive is polyvinyl acetate (PVAc).

[0056] In some embodiments, the additive is ethylene-vinyl alcohol (EVOH).

[0057] In some embodiments, the additive is polyvinylpyrrolidone (PVP).

[0058] In some embodiments, the additive is ethylene vinyl acetate (EVA).

[0059] In some embodiments, the additive is a latex.

[0060] In some embodiments, the additive is an acrylic polymer.

[0061] In some embodiments, the additive is a thermoplastic polymer.

[0062] In some embodiments, the additive is an epoxide.

[0063] In some embodiments, the additive is a polyolefin.

[0064] In some embodiments, the additive is polyvinyl alcohol (PVOH), polyvinyl acetate (PVAc), ethylene-vinyl alcohol (EVOH), polyvinylpyrrolidone (PVP), starch, chitosan, polyacrylic acid (PAA), polyethyleneimine (PEI), carbohydrates, ethylene vinyl acetate (EVA), or polyurethane.

[0065] In another aspect, a process for metallizing a material blend film is provided, the process comprising: (i) depositing a metal onto a surface of the material blend film, the film being provided on a substrate (direct deposition); or (ii) depositing a metal onto a substrate to obtain a metallized surface on the substrate and transferring the metallized film onto the material blend film (indirect deposition).

[0066] In some embodiments, the process includes providing a film of the material blend on a substrate. The film of the material blend may be of various thicknesses. Typically, the film has a thickness of 0.5 to 20 μm. In some embodiments, the thickness is 0.5-19 μm, 0.5-18 μm, 0.5-17 μm, 0.5-16 μm, 0.5-15 μm, 0.5-14 μm, 0.5-13 μm, 0.5-12 μm, 0.5-11 μm, 0.5-10 μm, 0.5-9 μm, 0.5-8 μm, 0.5-7 μm, 0.5-6 μm, 0.5-5 μm, 0.5-4 μm, 0.5-3 μm, 0.5-2 μm, 0.5-1 μm, 5-20 μm, 5-10 μm, 10-20 μm, 15-20 μm, 1-5 μm, 1-10 μm, 1-15 μm, or 1-20 μm.

[0067] The metal film may have an average thickness of 500 Å (angstroms) to 500 nm or 100 nm. The average thickness may be 500 Å to 100 nm, or 500 Å to 95 nm, 500 Å to 90 nm, 500 Å to 85 nm, 500 Å to 80 nm, 500 Å to 75 nm, 500 Å to 70 nm, 500 Å to 65 nm, 500 Å to 60 nm, 500 Å to 55 nm, 500 Å to 50 nm, 500 Å to 45 nm, 500 Å to 40 nm, 500 Å to 35 nm, 500 Å to 30 nm, 500 Å to 25 nm, 500 Å to 20 nm, 500 Å to 15 nm, 500 Å to 10 nm, 500 Å to 5 nm, 500 Å to 4 nm, 500 Å to 3 nm, 500 Å to 2 nm, 500 Å to 1 nm, 1 to 100 nm, 5 to 100 nm, 10 to 100 nm, 20 to 100 nm, 30 to 100 nm, 40 to 100 nm, 50 to 100 nm, 60 to 100 nm, 70 to 100 nm, 80 to 100 nm, or 90 to 100 nm.

[0068] The process of depositing a metal such as aluminum onto a material blend surface or a sacrificial surface as disclosed herein may include sputtering / evaporating aluminum metal under conditions suitable to achieve supersaturation of the vapor phase and then depositing the metal onto the surface of the film or sacrificial substrate.

[0069] In some embodiments, the conditions suitable for achieving supersaturation of the vapor phase include: Metal, e.g. aluminum evaporation rate: 3-15g / min Winding speed, 5~15m / sec High vacuum, 0.5~5×10 -4 mbar, and Cooling temperature, -15~-25℃ may include:

[0070] The material blend film on which metallization is accomplished is a film comprising or consisting of a material blend as defined herein.

[0071] The material blends used in the products and processes of the present invention are typically blends of at least one cellulose material, which may be a cellulose nanomaterial or a cellulose micromaterial. Non-limiting examples include crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl methyl cellulose (HPMC), ethyl hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC), or modified or oxidized forms thereof.

[0072] Alternatively, or in addition, the material blend may include at least one wax material. The at least one "wax" used may be any wax material known in the art. In the most general terms, a wax may be a long chain ester or a long chain hydrocarbon.

[0073] In some embodiments, at least one wax is a long chain ester that is the product of a long chain alcohol and a fatty acid. Typically, the wax is derived from an alcohol having at least 12 carbon atoms, and in some cases up to 40 carbon atoms.

[0074] In other embodiments, at least one wax is a paraffin wax obtained by a petroleum dewaxing process. Unlike ester waxes, paraffin waxes are hydrocarbons or mixtures of hydrocarbons containing 20-40 carbon atoms. In some embodiments, paraffin waxes are branched hydrocarbons or mixtures of hydrocarbons of different lengths, including at least one branched hydrocarbon. In some examples, paraffin waxes may also include non-aliphatic materials, such as aromatic materials.

[0075] Non-limiting examples of waxes include naturally derived waxes, synthetic waxes, and semi-synthetic waxes. In some embodiments, at least one wax is selected from among sustainable waxes. Sustainable waxes provide environmental, social, and economic benefits and do not pose environmental or public health risks. Sustainable waxes may be selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and others.

[0076] In some embodiments, the at least one wax is carnauba wax or vegetable wax or beeswax or soy wax or coconut wax or candelilla wax or any other wax known in the art.

[0077] In some embodiments, the at least one wax is a mixture of two or more waxes, any selected from the waxes disclosed herein.

[0078] At least one wax is a modified wax, as defined herein, based on a wax material, but which is chemically modified to associate with at least one functional material. A "modified wax" is thus a composite of wax and functional material. Modified waxes are generally made from unmodified precursors or other precursors to provide modified materials with more desirable properties than known from unmodified wax materials. The properties of the modified may be adjusted compared to the same properties of the unmodified wax, or there may be new properties not present in the unmodified wax, or there may be the same properties that are removed or reduced compared to the unmodified wax. The adjustment of properties may result in an enhancement or reduction of the properties.

[0079] The functional material that complexes with the wax to produce the modified morphology may be any such material that can cause the adjustment of properties. Such functional materials may be selected from carbohydrates, polysaccharides, proteins, amino acids, aliphatic materials, lipids, acrylic polymers, thermoplastic polymers, polyolefin polymers such as PE, PP, and others. In some embodiments, the functional material is a polymer. Non-limiting examples include ethylene vinyl acetate (EVA), polyethylene (PE), polypropylene (PP), polycarbonate (PC), polyethylene oxide (PEO), ethylene acrylic acid (EAA), and others.

[0080] In some embodiments, the functional material is cellulose or a cellulosic material (as defined herein, such as carboxymethyl cellulose (CMC), nanocrystalline cellulose (CNC), microcrystalline cellulose (MCC), and others), starch, rosin, nylon, and others.

[0081] The modified property of the wax may be melting point, solubility, thermal stability, density, viscosity, heat softening, and other mechanical or chemical properties. In some embodiments, the property may be OTR and / or WVTR. In other words, in some embodiments, modified waxes having improved OTR and / or WVTR properties are provided.

[0082] In some embodiments, the modified wax is an EVA modified wax.

[0083] In some embodiments, the modified wax is an EVA modified paraffin wax. EVA modified paraffin is a material prepared by chemical reaction between paraffin wax and EVA. The grade of EVA and the ratio of EVA to paraffin affect the resulting properties such as softening temperature, mechanical properties, etc. The modified wax generally exhibits softening and melting temperatures in the same range as paraffin wax (50-65°C). The mechanical stability of EVA modified wax is significantly higher than that of paraffin wax and increases with higher EVA content. EVA modified wax also exhibits significantly higher adhesive capabilities than paraffin wax. EVA modified wax may be prepared according to procedures known in the art and exemplified herein.

[0084] The latex used in the products of the invention is typically derived from rubber trees as a latex containing 55% water and about 40% rubber material. The chemical composition of latex is a polymer of cis-1,4-polyisoprene having a molecular weight of 100,000 to 1,000,000 Da, with minor amounts of materials such as proteins, fatty acids, resins, and inorganic materials present. The latex used in the products of the invention is in a non-coagulated form (e.g., not a coagulated rubber material, not vulcanized rubber). Alternatively, the latex may be synthetically prepared from petroleum-based chemicals.

[0085] As used herein, a cellulosic material-based film is one that includes, in addition to a cellulosic material, one or more additives that together provide superior OTR and / or WVTR properties.Similarly, a wax-based film is one that includes, in addition to a wax material, one or more additives that together provide superior OTR and / or WVTR properties.

[0086] In some embodiments, the film is comprised of a substrate, a metal film, and a film of a blend of a cellulosic material, a wax material, and other additives.

[0087] The additive or additives used in the cellulosic and / or wax-based films may be selected as detailed herein. In some embodiments, the additive is polyvinyl alcohol (PVOH), polyvinyl acetate (PVAc), ethylene-vinyl alcohol (EVOH), polyvinylpyrrolidone (PVP), starch, chitosan, polyacrylic acid (PAA), polyethyleneimine (PEI), ethylene vinyl acetate (EVA), polyurethane, hydroxypropyl methylcellulose (HPMC), clay, lignin, latex, starch, antifoaming agent, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), nanoparticles (e.g., SiO2, ZnO, and others), proteins, amino acids, aliphatic materials, lipids, acrylic polymers, thermoplastic polymers, preservatives, epoxides, or polyolefins.

[0088] The metallized products of the present invention comprise or consist of cellulosic and / or wax-based films composed of or formed from cellulosic materials and / or waxes and optionally at least one additive. Non-limiting examples of such blends or blend formulations that make up the films of the present invention (numbers in parentheses provided in front of the listed components designate the formulation number): (1) at least one cellulosic material and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others, as defined; (2) at least one wax-based material, as defined above, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (3) at least one cellulosic material, as defined herein, at least one wax-based material, as defined herein, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (4) at least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof, and at least one wax selected from naturally occurring waxes, synthetic waxes, and semi-synthetic waxes, which may further be selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax as defined, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (5) Crystalline nanocellulose (CNC) and at least one wax selected from naturally occurring waxes, synthetic waxes, and semi-synthetic waxes, which may further be selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax as defined, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (6) Nanofibrillated cellulose (NFC) and at least one wax selected from naturally occurring waxes, synthetic waxes, and semi-synthetic waxes, which may further be selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax as defined, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (7) Microfibrillated cellulose (MFC) and at least one wax selected from naturally occurring waxes, synthetic waxes, and semi-synthetic waxes, which may further be selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax as defined, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (8) Microcrystalline cellulose (MCC) and at least one wax selected from naturally occurring waxes, synthetic waxes, and semi-synthetic waxes, which may further be selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax as defined, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (9)-CMC and at least one wax selected from naturally occurring waxes, synthetic waxes, and semi-synthetic waxes, which may further be selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax as defined, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (10)-HPMC and at least one wax selected from naturally occurring waxes, synthetic waxes, and semi-synthetic waxes, which may further be selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax as defined, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (11) Crystalline nanocellulose (CNC) and / or nanofibrillated cellulose (NFC) and / or microfibrillated cellulose (MFC) and / or microcrystalline cellulose (MCC), and / or CMC, and / or HPMC, and at least one wax selected from naturally occurring waxes, synthetic waxes, and semi-synthetic waxes, which may further be selected from carnauba wax, vegetable waxes, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax as defined, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (12)-At least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof, carnauba wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (13) - at least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof, vegetable waxes, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (14) - At least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof, beeswax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (15)-At least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof, at least one modified wax, as defined above, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (16) - at least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof, at least one modified wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, and others; (17)-crystalline nanocellulose (CNC), and / or CMC, and / or HPMC, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; (18)-crystalline nanocellulose (CNC), and / or CMC, and / or HPMC, and at least one additive selected from carbohydrates, crosslinkers and polymers; (19)-crystalline nanocellulose (CNC), and / or CMC, and / or HPMC, and / or MFC, and / or NFC, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; (20)-At least one wax or modified wax and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; (21) - at least one modified wax and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; (22)-At least two waxes or modified wax materials and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; (23)-starch, PVOH, CNC, HPMC and / or CMC, (24)-Clay, PVOH, and CNC, (25)-Starch, PVOH and CNC, (26)-Starch, PVOH, CNC and lignin, (27)-starch, PVOH, MFC and / or NFC, HPMC and / or CMC, (28)-A wax and at least one surfactant, (29)-Wax, latex and at least one surfactant; (30)-Modified wax, latex and at least one surfactant; (31)-Waxes, modified waxes, latexes and at least one surfactant; (32) - Wax, modified wax, at least one surfactant, (33) - starch, PVOH, CNC, HPMC and / or CMC, modified wax, and latex; (34)-starch (4.1-16.5 wt%), PVOH (5-15 wt%), CNC (0.1-5 wt%), HPMC and / or CMC (0.1-0.5 wt%), (35)-Clay (4.2~13% by weight), PVOH (5~12% by weight), CNC (0.1~5% by weight), (36)-Starch (5–14.5 wt%), PVOH (4.5–15.5 wt%), CNC (0.01–5 wt%), (37)-starch (4.5–15 wt%), PVOH (7–14.5 wt%), CNC (0.1–4 wt%), lignin (7.3–13.1 wt%), (38)-starch (5.6 to 14.5% by weight), PVOH (6.5 to 14.2% by weight), MFC and / or NFC (0.1 to 5% by weight), HPMC and / or CMC (0.1 to 0.5% by weight), (39)-Wax (2 to 30% by weight), surfactant (0.1 to 20% by weight), (40)-Wax (2-22% by weight), latex (2-30% by weight), surfactant (0.1-20% by weight), (41)-Modified wax (e.g., EVA modified wax, 1-25% by weight), latex (2-30% by weight), surfactant (0.1-20% by weight), (42)-Wax (1.5-20% by weight), modified wax (e.g., EVA modified wax, 1-20% by weight), latex (2-30% by weight), surfactant (0.1-20% by weight), (43)-wax (1.5 to 22% by weight), modified wax (e.g., EVA modified wax, 1 to 20% by weight), surfactant (0.1 to 20% by weight), and / or (44)—starch (1.5-9.5 wt%), PVOH (1.5-9.2 wt%), CNC (0.1-1.3 wt%), HPMC and / or CMC (0.1-1 wt%), modified wax (e.g., EVA modified wax), and latex (total, 4.5-30.3 wt%) Examples include:

[0089] For each of the above blend formulations, the weight percentages are calculated from the formulation in which the film is ultimately formed. Such formulations are water-based and contain water in addition to the materials and additives shown.

[0090] Films constructed from the above blend formulations include the disclosed materials, and the relative amounts of materials in the dry film may vary (e.g., after evaporation of the medium, water). In some embodiments, the amounts of materials in the dry film may be as follows: (34) - Starch (20-80% dry), PVOH (20-80% dry), CNC (0.5-40% dry), HPMC and / or CMC (0.5-10% dry), (35)-Clay (20-80% dry), PVOH (20-80% dry), CNC (0.5-40% dry), (36)-Starch (20-80% dry), PVOH (20-80% dry), CNC (0.5-40% dry), (37)-starch (20–80% dry), PVOH (20–80% dry), CNC (0.5–40% dry), lignin (30–70% dry); (38) - Starch (20-80% dry), PVOH (20-80% dry), MFC and / or NFC (0.5-40% dry), HPMC and / or CMC (0.5-10% dry), (44)—Starch (5–15% dry), PVOH (5–15% dry), CNC (2–8% dry), HPMC and / or CMC (0.5–2% dry), modified waxes (e.g., EVA modified wax), and latex (50–79% total dry).

[0091] In some embodiments, the aforementioned blend formulations define the film composition of any film defined herein as a "film of a material blend." Additionally, the aforementioned blend formulations define wet formulations (water-based) that form a "film of a material blend." Thus, the aforementioned blend formulations may be considered as wet (suspension) or dry (solid) formulations.

[0092] In some embodiments, each of the films of blend formulations comprising, consisting of, or formed from the above formulations may be provided on a substrate or in an article including a substrate, or may be provided on a metallized film only.

[0093] The present invention further provides a metallized film, the film comprising: (A) at least one cellulose material in an amount of 0.01 to 6 wt. %, wherein the at least one cellulose material is selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof; and / or (B) at least one selected wax in an amount of 1-30% by weight, the at least one wax being optionally selected from naturally occurring waxes, synthetic waxes, and semi-synthetic waxes, the at least one wax optionally being selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax as defined; and (C) at least one additive in an amount of 0.1-20 wt.%, the at least one additive being selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; The present invention provides a metallized film formed from a blend comprising:

[0094] In some embodiments, the at least one additive is a carbohydrate.

[0095] In some embodiments, the at least one additive is a crosslinking agent.

[0096] In some embodiments, at least one additive is a polymer.

[0097] In some embodiments, the at least one additive is a latex.

[0098] In some embodiments, the at least one additive is PEI.

[0099] When more than one member of each material group is present in the blend of the present invention, such as at least two cellulosic materials or at least two wax materials, the weight percent amounts indicated are the amounts of each member of the group or the combined weight percent amounts of all members of the same group. For example, when a blend formulation includes two cellulosic materials, such as CNC and HPMC, the amounts of each of CNC and HPMC may each be 0.01-6 wt.%. Alternatively, the combined amount of both CNC and HPMC may be 0.01-6 wt.%, assuming that the amounts of each of CNC and HPMC are in the ranges indicated. The same principles apply to other combinations of materials in blends to form the metallized films of the present invention.

[0100] In some embodiments, the amount of the at least one cellulosic material is 0.01-6 wt%, 0.05-6 wt%, 0.1-6 wt%, 0.1-5 wt%, 0.1-4 wt%, 0.1-3 wt%, 0.1-2 wt%, 0.1-1 wt%, or 0.1-0.5 wt%, each amount range constituting a separate embodiment and each amount range independently constituting a separate amount of each of the cellulosic materials disclosed herein.

[0101] In some embodiments, the amount of the at least one wax is 1-30%, 1.5-30%, 2-30%, 2.5-30%, 3-30%, 3.5-30%, 4-30%, 4.5-30%, 5-30%, 1-28%, 1-26%, 1-25%, 1-22%, 1-20%, 1-15%, 1-10%, 5-25%, 5-20%, or 5-10% by weight, each amount range constituting a separate embodiment and each amount range independently constituting a separate amount of each of the wax materials disclosed herein.

[0102] In some embodiments, the amount of at least one additive is 0.1-20% by weight, 0.5-20% by weight, 1-20% by weight, 2-20% by weight, 3-20% by weight, 4-20% by weight, 5-20% by weight, 6-20% by weight, 7-20% by weight, 8-20% by weight, 9-20% by weight, 10-20% by weight, 0.1-18% by weight, 0.1-16% by weight, 0.1-15% by weight, 0.1-13% by weight, 0.1-12% by weight, 0.1-10% by weight, 0.1 %. to 9 wt.%, 0.1 to 8 wt.%, 0.1 to 6 wt.%, 0.1 to 4 wt.%, 0.1 to 2 wt.%, 0.1 to 1 wt.%, 4 to 15 wt.%, 5 to 15 wt.%, 1 to 9 wt.%, 0.1 to 10 wt.%, 4 to 16 wt.%, 5 to 12 wt.%, 4 to 13 wt.%, 7 to 13 wt.%, or 7 to 14 wt.%, each of the amount ranges constituting a separate embodiment and each amount range independently constituting a separate amount of each of the additive materials disclosed herein.

[0103] Thus, in some embodiments, a metallized product according to the present invention comprises or consists of a material blend film and a metal film, and optionally a substrate, where the metallization of the material blend film can optionally be achieved by vapor deposition, and the material blend film comprises any of the formulation blends disclosed herein above. In some embodiments, the material blend comprises: starch, PVOH, CNC, HPMC and / or CMC, as defined, or Clay, PVOH, and CNC, as defined; or Starch, PVOH and CNC, as defined; or Starch, PVOH, CNC and lignin, as defined; or starch, PVOH, MFC and / or NFC, HPMC and / or CMC, as defined, or a wax and at least one surfactant, as defined above, or - wax, latex and at least one surfactant, as defined, or - modified wax, latex and at least one surfactant, as defined, or - wax, modified wax, latex and at least one surfactant, as defined above; or a wax, a modified wax, at least one surfactant, as defined above, or - Starch, PVOH, CNC, HPMC and / or CMC, modified waxes and latex It is.

[0104] In some embodiments, the metallized films according to the present invention are configured as films with excellent OTR and / or WVTR. The OTR and WVTR values ​​were achieved by carefully adjusting the composition of the blend film, e.g., the components used, their relative amounts, etc., and the metal used to form the metal film thereon. Excellent results were achieved using any of the following metals: zinc, aluminum, iron, titanium, and tin. Each of the indicated metals was used with a blend formulation disclosed herein to form a metallized product. In some embodiments, the metal is zinc, or aluminum, or iron, or titanium, or tin, and the blend formulation is any of the blend formulations (1)-(44) detailed herein.

[0105] In some embodiments, the metallized film is formed from a metal selected from zinc, aluminum, iron, titanium, and tin, which constitute the metal film, and the blend composition constitutes a blend-based film, and the formulation comprises: (A) at least one cellulose material in an amount of 0.01 to 6 wt. %, wherein the at least one cellulose material is selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof; and / or (B) at least one selected wax in an amount of 1-30% by weight, the at least one wax being optionally selected from naturally occurring waxes, synthetic waxes, and semi-synthetic waxes, the at least one wax being optionally selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax, as defined; and (C) at least one additive in an amount of 0.1 to 20 wt. %, wherein the at least one additive is selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; Includes.

[0106] In some embodiments, the metallized product includes a metal film, e.g., vapor-deposited, onto a film formed from the blend material, and the metal film or product exhibits excellent OTR properties. In some embodiments, the metal is aluminum and the blend material is (17)-crystalline nanocellulose (CNC), and / or CMC, and / or HPMC, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; (18)-crystalline nanocellulose (CNC), and / or CMC, and / or HPMC, and at least one additive selected from carbohydrates, crosslinkers and polymers; (19)-crystalline nanocellulose (CNC), and / or CMC, and / or HPMC, and / or MFC, and / or NFC, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; (23)-starch, PVOH, CNC, HPMC and / or CMC, (24)-Clay, PVOH, and CNC, (25)-Starch, PVOH and CNC, (26)-Starch, PVOH, CNC and lignin, (27)-starch, PVOH, MFC and / or NFC, HPMC and / or CMC, (33) - starch, PVOH, CNC, HPMC and / or CMC, modified waxes and latexes; (34)-starch (4.1-16.5 wt%), PVOH (5-15 wt%), CNC (0.1-5 wt%), HPMC and / or CMC (0.1-0.5 wt%), (35)-Clay (4.2~13% by weight), PVOH (5~12% by weight), CNC (0.1~5% by weight), (36)-Starch (5–14.5 wt%), PVOH (4.5–15.5 wt%), CNC (0.01–5 wt%), (37)-starch (4.5–15 wt%), PVOH (7–14.5 wt%), CNC (0.1–4 wt%), lignin (7.3–13.1 wt%), (38)-starch (5.6 to 14.5% by weight), PVOH (6.5 to 14.2% by weight), MFC and / or NFC (0.1 to 5% by weight), HPMC and / or CMC (0.1 to 0.5% by weight), (44) - starch (1.5-9.5 wt%), PVOH (1.5-9.2 wt%), CNC (0.1-1.3 wt%), HPMC and / or CMC (0.1-1 wt%), modified wax (e.g. EVA modified wax) and latex (total amount 4.5-30.3 wt%), or (34) - Starch (20-80% dry), PVOH (20-80% dry), CNC (0.5-40% dry), HPMC and / or CMC (0.5-10% dry), (35)-Clay (20-80% dry), PVOH (20-80% dry), CNC (0.5-40% dry), (36)-Starch (20-80% dry), PVOH (20-80% dry), CNC (0.5-40% dry), (37)-Starch (20-80% dry), PVOH (20-80% dry), CNC (0.5-40% dry), lignin (30-70% dry), (38) - Starch (20-80% dry), PVOH (20-80% dry), MFC and / or NFC (0.5-40% dry), HPMC and / or CMC (0.5-10% dry), (44) - Starch (5-15% dry), PVOH (5-15% dry), CNC (2-8% dry), HPMC and / or CMC (0.5-2% dry), modified waxes (e.g. EVA modified waxes) and latex (50-79% dry of total volume). is selected from.

[0107] In some embodiments, the metallized product includes a metal film, e.g., vapor-deposited, on a film formed from the blend material, and the metallized product exhibits excellent WVTR properties. In some embodiments, the metal is aluminum and the blend material is (20)-At least one wax or modified wax and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; (21) - at least one modified wax and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; (22)-At least two waxes or modified wax materials and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles and others; (28)-A wax and at least one surfactant, (29)-Wax, latex and at least one surfactant; (30)-Modified wax, latex and at least one surfactant; (31)-Waxes, modified waxes, latexes and at least one surfactant; (32) - Wax, modified wax, at least one surfactant, (39)-Wax (2 to 30% by weight), surfactant (0.1 to 20% by weight), (40)-Wax (2-22% by weight), latex (2-30% by weight), surfactant (0.1-20% by weight), (41)-Modified wax (e.g., EVA modified wax, 1-25% by weight), latex (2-30% by weight), surfactant (0.1-20% by weight), (42)-Wax (1.5-20% by weight), modified wax (e.g., EVA modified wax, 1-20% by weight), latex (2-30% by weight), surfactant (0.1-20% by weight), (43)-Wax (1.5-22% by weight), modified wax (e.g., EVA modified wax, 1-20% by weight), surfactant (0.1-20% by weight), (44) - starch (1.5-9.5 wt%), PVOH (1.5-9.2 wt%), CNC (0.1-1.3 wt%), HPMC and / or CMC (0.1-1 wt%), modified wax (e.g. EVA modified wax) and latex (total amount 4.5-30.3 wt%), or (39)-Wax (70-99% dry), surfactant (1-30% dry), (40) - Wax (30-69% dry), latex (30-69% dry), surfactant (1-40% dry), (41)-Modified wax (e.g., EVA modified wax, 30-69% dry), latex (30-69% dry), surfactant (1-40% dry), (42)-Wax (15-54% dry), modified wax (e.g. EVA modified wax, 15-54% dry), latex (30-69% dry), surfactant (1-40% dry), (43) - wax (30-69% dry), modified wax (e.g. EVA modified wax, 30-69% dry), surfactant (1-40% dry), and / or (44)—starch (5-15% dry), PVOH (5-15% dry), CNC (2-8% dry), HPMC and / or CMC (0.5-2% dry), modified waxes (e.g. EVA modified waxes) and latex (total amount 450-79% dry); is selected from.

[0108] In some embodiments, the metallized film or product includes a metal film, e.g., vapor-deposited, on a film formed from a blended material, and the metallized product exhibits excellent OTR and WVTR properties. In some embodiments, the metal is aluminum, and the blended material includes starch, PVOH, CNC, HPMC and / or CMC, modified wax, and latex. In some embodiments, the blended material includes starch (1.5-9.5 wt%), PVOH (1.5-9.2 wt%), CNC (0.1-1.3 wt%), HPMC and / or CMC (0.1-1 wt%), modified wax (e.g., EVA modified wax), and latex (total amount 4.5-30.3 wt%).

[0109] In some embodiments, the blend formulation from which the film is made is an aqueous formulation (water containing oil) with a viscosity of 3500 cP or less, in some embodiments the viscosity is 100-3500 cP, or 100-1000 cP, or 1000 cP or less, or 500 cP or less, or 150 cP or less.

[0110] While the film of the blended material includes at least one cellulosic material or wax and at least one additive as defined, the additive does not form a separate film of the product of the present invention. In other words, the metallized product of the present invention does not include or exclude polyvinyl alcohol (PVOH), or polyvinyl acetate (PVAc), or ethylene-vinyl alcohol (EVOH), or polyvinylpyrrolidone (PVP), or starch, or chitosan, or polyacrylic acid (PAA), or polyethyleneimine (PEI), or carbohydrates, or ethylene vinyl acetate (EVA), or polyurethane, or hydroxypropyl methylcellulose (HPMC), or clay, or lignin, or latex, or epoxide, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD).

[0111] The material blends used in accordance with the present invention are water-based and may include surfactants (such as fatty acids, spans, Tweens, sucrose ester based surfactants, SDS, and others), salts (organic and inorganic), adhesives, emulsifiers, stabilizers, pH stabilizers, colorants, and other materials, as detailed herein.

[0112] The concentration of the blend in the aqueous formulation may be from 5 to 70% by weight.

[0113] Excluded from the additives that may be used is formaldehyde and any other ingredient that is not approved for food contact or that is environmentally unfriendly or generally toxic.

[0114] In some embodiments, the cellulose material used in the products of the present invention is a cellulose nanomaterial, and in some embodiments, CNC.

[0115] As known in the art, CNC, also known as nanocrystalline cellulose (NCC) or cellulose whiskers, is a fiber made from cellulose, and CNC is typically a single crystal with high purity. CNC constitutes a general class of materials that have mechanical strength equivalent to the bonding strength of adjacent atoms. The resulting highly ordered structure not only results in unusually high strength, but also significant changes in thermal, electrical, optical, magnetic, ferromagnetic, dielectric, conductive, and even superconducting properties. The tensile strength properties of CNC far exceed those of current bulk reinforcement materials, allowing the processing of the highest achievable composite strengths. CNC may be prepared by any method known in the art. For example, CNC may be prepared by the method disclosed in U.S. Pat. No. 9,464,142, which is incorporated herein by reference.

[0116] In some embodiments, the CNC is characterized by having a crystallinity of at least 50%. In some embodiments, the CNC is single crystalline. In some embodiments, the CNC is a high purity single crystalline material.

[0117] In some embodiments, the CNC nanocrystals have a length of at least about 50 nm. In other embodiments, the CNC nanocrystals are at least about 100 nm in length and up to 1,000 nm in length. In other embodiments, the nanocrystals are about 100 nm to 1,000 nm in length, 100 nm to 900 nm in length, 100 nm to 600 nm in length, or 100 nm to 500 nm in length.

[0118] In some embodiments, the nanocrystals are about 10 nm to 100 nm in length, 100 nm to 1,000 nm, 100 nm to 900 nm, 100 nm to 800 nm, 100 nm to 600 nm, 100 nm to 500 nm, 100 nm to 400 nm, 100 nm to 300 nm, or about 100 nm to 200 nm in length.

[0119] The nanocrystals may be selected to have an average aspect ratio (ratio of length to diameter) of greater than or equal to 10. In some embodiments, the average aspect ratio is between 10-100, or between 20-100, or between 30-100, or between 40-100, or between 50-100, or between 60-100, or between 70-100, or between 80-100, or between 90-100, or between 61-100, or between 62-100, or between 63-100, or between 64-100, or between 65-100, or between 66-100, or between 67-100, or between 68-100, or between 69-100.

[0120] In some embodiments, the average aspect ratio is between 67-100.

[0121] The material blend film may be formed on a solid substrate, which may be sacrificial, i.e., a substrate that may be peeled off or decomposed or optionally replaced. Typically, the substrate is a solid substrate on which a film is formed to produce a direct configuration metallized film as disclosed herein. In some embodiments, the substrate may be used to form a material blend film and then peeled off to obtain a free-standing material blend film. Such a free-standing film may be used to produce an inverse configuration metallized film as disclosed herein.

[0122] The substrate may be made of a material selected from a polymeric material, a paper or paper-based material, a polymer-coated paper-based material, a fabric material, a porous material, and a membrane material. In some embodiments, the substrate is a paper or paper-based material, such as cardboard.

[0123] In some embodiments, the substrate is selected from polymeric materials, paper or paper-based materials, polymer-coated paper-based materials such as cardboard, nanocellulose films, nanocellulose / polymer films, fabric materials, porous materials, and membrane materials.

[0124] When used as an independent layer or as a coating layer of a paper-based material or a nanocellulose material, or as an additive to any of the materials that build any of the layers, the "polymeric material" may be a material belonging to any known polymeric material or resin, such as thermoplastic polymers and thermosetting polymers. The polymer may be selected from polymers such as polyethylene, polypropylene, polyvinyl alcohol, ethylene-vinyl alcohol, polyamide, polystyrene, polylactic acid, polyhydroxyalkanoate, polycaprolactone, polyhydroxybutyric acid, polyvinyl acetate, polyacrylonitrile, polybutylene succinate, polyvinylidene chloride, starch, cellulose, polyhydroxyvaleric acid, polyhydroxyhexanoic acid, polyanhydrides, polyethylene terephthalate, polyvinyl chloride, and polycarbonate. In some embodiments, the polymeric material is a polyester (which may be selected from thermosetting plastics and thermoplastics).

[0125] In some embodiments, the polymer is selected from polyethylene, polypropylene, polyester, polyvinyl alcohol, ethylene-vinyl alcohol, polyamide, polystyrene, polylactic acid, polyhydroxyalkanote, polycaprolactone, polyhydroxybutyric acid, polyvinyl acetate, polyacrylonitrile, polybutylene succinate, polyvinylidene chloride, starch, cellulose, polyhydroxyvaleric acid, polyhydroxyhexanoic acid, polyanhydrides, polyethylene terephthalate, polyvinyl chloride, and polycarbonate, or any blend of two or more thereof.

[0126] As used herein, "paper or paper-based material" is a material known in the art. The paper or paper-based material may be used as is, or may be coated with a polymer on one or both sides of the material. In some embodiments, the paper coating material is cardboard. In some embodiments, the paper is kraft paper. As known in the art, kraft paper is paper or cardboard made from chemical pulp produced by the kraft process known in the art. Paper is a highly elastic, tear-resistant, porous paper designed to package products with high strength and durability requirements. Thus, the paper may further be selected from paper-based packaging materials.

[0127] In some embodiments, the paper is selected from bank paper, banana paper, bond paper, book paper, coated paper products, construction paper, sugar paper, cotton paper, fish paper, inkjet paper, kraft paper, glassine paper, kraft paper bags, laid paper, imitation leather paper, mummy paper, oak tag paper, sandpaper, Tyvek paper, wallpaper, Japanese paper, waterproof paper, wax paper, wove paper, Xuan paper, and others.

[0128] As is known in the art, commercially available paper or paper-based products of any of the above types may contain additives, such as clay, calcium carbonate, latex, lignin, starch, titanium dioxide, etc., which are added to the paper during the manufacturing process.

[0129] A "fabric material" is any such material known in the art that is typically a flexible material composed of a network of natural or artificial fibrous materials. The fabric may be any weave, natural fabric, synthetic fabric, knit, woven material, nonwoven material, or mesh of a material selected from cellulose, viscose, fiberglass, carbon fiber, and synthetic fibers. In some embodiments, the fabric may be in the form of a porous material or membrane, selected as indicated.

[0130] A "porous material" or "membrane material" is generally a material that contains pores that can hold or contain solid, liquid, or gaseous materials. In some embodiments, the pores are voids, i.e., are free of any such materials. In some embodiments, the porous material acts as a membrane, a selective barrier, with the degree of selectivity depending on the pore size of the membrane. In some embodiments, the membrane may be fabric- or paper-based.

[0131] The metallized films of the present invention may be used to make barrier materials, such as packaging materials. The packaging may be for holding liquids or solids.

[0132] The film may be formed into sheets or folded or formed sheets of any size and shape. The film may be printed or colored, completely clear or opaque, and may or may not have a surface treatment. The sheet may be cut, folded, or processed into any shape, size, or object, such as a pocket or enclosure or envelope or container formed from the sheet. In some embodiments, the object is for packaging goods, food, liquids, medicines, or any material that needs to be separated or protected from the environment, such as gases, water vapor, exposure, and other harmful agents or conditions that can be protected with the composite material (e.g., by forming an impermeable barrier).

[0133] As is known in the art, packaging materials exhibiting excellent gas barrier properties, such as those of the present invention, are suitable for long-term aseptic packaging of food and beverages, whether in liquid or solid form. Typically, an excellent oxygen barrier is greater than 10 ml / m 2 A good oxygen barrier will have an OTR value of several tens of days. The OTR measured for the metallized film according to the present invention is 1 ml / m 2 days or less, providing exceptionally low barrier properties.

[0134] As the skilled artisan will appreciate, typically OTR measurements are performed at 0% or 50% relative humidity. It is clearly unusual and superior to produce a product with a low OTR at 70% relative humidity. When measured at 70% relative humidity, the metallized films of the present invention have an OTR of about 1 ml / m 2 day or 1ml / m 2 Such films are novel in the art. Thus, the present invention also provides an OTR value of 1 ml / m2 measured at 70% relative humidity and 23° C. 2 Metallized films having an OTR of 10 days or less are also provided.

[0135] In addition, when measured at 90% relative humidity and 38°C, the average yield is 2-10gr / m 2 Metallized films having a WVTR of 100 nm are also provided.

[0136] Further provided is a packaging material in the form of a metallized film according to the invention, and a method of using a metallized film according to the invention for producing packaging materials for liquids and solids.

[0137] The metallized films of the present invention may also be considered composites, since sometimes it may not be possible to distinguish between a metallized film and a film of a material blend. The present invention therefore also provides a composite in the form of a (closely associated) material continuum (substantially free of distinct material regions) comprising a material blend, as defined, and at least one metal, wherein the at least one metal forms a non-peeling interaction with the material blend, and optionally the at least one metal partially interpenetrates (or permeates) the material blend (and / or vice versa), and wherein the composite is provided on (or associated with or bonded to) a surface region of a substrate.

[0138] Further provided is a hybrid material (composite), the material comprising a first region of at least one metal and a second region of a material blend, the first and second regions forming a material continuum of materials of differing composition, the interface of the first and second regions being gradient in at least some amount of the at least one metal and the material blend, and the hybrid material being disposed on (or associated with or bonded to) a surface region of a substrate.

[0139] As described herein, a "composite material" is a hybrid material of metals and material blends that together form a gradient material continuum characterized by regions of different composition. These regions are not distinct, i.e., the boundaries between the metal regions and the material blends are not distinct. In other words, the two regions cannot be peeled from one another without causing damage to the overall composite or to the material components attempting to peel.

[0140] The regions of different composition that define the gradient material continuum are at least a metal region, a material blend region, and a gradient region between two material regions. The gradient region includes an amount of metal and an amount of material blend. This gradient region is typically amorphous in structure and much thinner compared to the metal and blend regions. The gradient of one material into the other may be considered as a mechanical bond that intimately associates or fuses the two material regions into a non-peeling interaction. This mechanical bond is typically physical in nature (i.e., does not substantially involve the formation of chemical bonds between the metal and the blend material), does not involve the use of adhesive materials, and results from the interpenetration of the metal into the blend material region, typically into nano- or micro-sized pores present in the blend material, thereby forming the gradient region. This interpenetration or infiltration of the metal into the blend material and / or the blend material into the metal may be achieved by appropriate processing conditions.

[0141] Interpenetration or intercalation does not involve the use of adhesive materials.

[0142] The degree of interpenetration of one material into the other may vary based on, among other things, the materials used, the composition of the materials, the manufacturing conditions, and others. In some embodiments, the penetration is substantially along the complete area of ​​association of the two regions. In other embodiments, the penetration is along the area of ​​association of the two materials in some regions.

[0143] The amount of each of the materials in the gradient region decreases as you move away from the center of each of the two material regions, or in other words, the amount of metal in the gradient region, for example, decreases as the distance to the material blend region decreases.

[0144] Composites comprised of at least a metal and a blend material may comprise one or more additional materials. In such multi-material composites, the additional material may be present (exclusively or additionally) in gradient regions with the metal in metal regions, with the blend material in blend material regions, or associated with either or both of the metal and / or material blend regions. In some composites, the defined metal / blend composite further comprises an additional material associated with the exposed surface regions of the metal regions and / or blend regions. For example, a composite is provided in which a metal region is associated with the material blend on one end and an additional material is associated with the material blend on the other end. Alternatively or additionally, the material blend comprises a metal region at one end and a different material at the other end.

[0145] In some embodiments, the composite includes a third material region separating the metallic region and the material blend region. In implementations of such techniques, the material of the third material region may interpenetrate the material blend region at one end and permeate the metallic region at the other end.

[0146] The products of the present invention may be formed into any shape and form. As packaging materials, the composite may be formed into a sheet or a three-dimensional object. The composite may be applied to a surface or surface area of ​​a substrate to provide mechanical stability to the composite or to form the composite into a desired shape. The substrate may be any solid material, such as, but not limited to, metal substrates, glass substrates, polymer substrates, biopolymer materials, paper substrates, wood substrates, silicon substrates, heat-sensitive substrates, substantially two-dimensional substrates, three-dimensional substrates, and others.

[0147] In some embodiments, the substrate is a paper material, a polymer, or a biopolymer.

[0148] In some embodiments, the substrate is a polymer selected from polyethylene, polypropylene, polyester, polyvinyl alcohol, ethylene-vinyl alcohol, polyamide, polystyrene, polylactic acid, polyhydroxyalkanote, polycaprolactone, polyhydroxybutyric acid, polyvinyl acetate, polyacrylonitrile, polyvinylidene chloride, cellulose, polyethylene terephthalate, polyvinyl chloride, and polycarbonate.

[0149] In some embodiments, the substrate is cardboard, optionally coated with a polymer selected from polyethylene, polypropylene, polyester, polyvinyl alcohol, ethylene-vinyl alcohol, polyamide, polystyrene, polylactic acid, polyhydroxyalkanote, polycaprolactone, polyhydroxybutyric acid, polyvinyl acetate, polyacrylonitrile, polyvinylidene chloride, cellulose, polyethylene terephthalate, polyvinyl chloride, and polycarbonate.

[0150] In some embodiments, a product is formed into an article of manufacture that includes a metal at least partially infiltrated with CNC, where the metal is inseparable from the CNC, and where the metal and CNC are formed on (or associated with or bonded to) a surface region of a substrate.

[0151] The invention further provides a film of the product of the invention coating a surface of a substrate material. In some embodiments, the substrate forms part of a composite, and the substrate material is associated with either the metal region or the material blend region. In either case, the metal or material blend penetrates or interpenetrates the substrate material, thereby forming a composite with the substrate. Such interpenetration or interpenetration does not allow the metal / blend composite to be peeled off from the substrate. Thus, the invention further provides a metamaterial composite, in which each of the composite materials interpenetrates or interpenetrates at least one other material of the composite, thus providing the material continuum described herein.

[0152] In some embodiments, the substrate is associated with CNC regions, where the CNCs interpenetrate or infiltrate the substrate material.

[0153] In some embodiments, the substrate is a polymer sheet or a sheet of paper material, such as cardboard, that is infiltrated with either a metal or a material blend. In such implementations, the substrate, such as cardboard, is treated with a material blend that interpenetrates and associates with the cardboard sheet. This composite is then treated with a metal to form a substrate / blend / metal composite. This exemplary composite may alternatively be prepared by forming the composite on the surface of a metal sheet or foil.

[0154] Detailed Description of the Preferred Embodiments The processes disclosed herein have been utilized with a variety of blend formulations and metal compositions to obtain metallized films of various compositions. The conditions provided herein are exemplary and may vary based on the formulation, metal, substrate, etc.

[0155] Blended Composition The following exemplary blend formulations were used to form blend films on substrates such as paper, polymer or biopolymer substrates. Formulation 1: starch (4.1-16.5 wt%), PVOH (5-15 wt%), CNC (0.1-5 wt%), HPMC and / or CMC (0.1-0.5 wt%); Formulation 2: kaolin (as clay, 4.2–13 wt%), PVOH (5–12 wt%), CNC (0.1–5 wt%); Formulation 3: starch (5–14.5 wt%), PVOH (4.5–15.5 wt%), CNC (0.01–5 wt%); Formulation 4: starch (4.5–15 wt%), PVOH (7–14.5 wt%), CNC (0.1–4 wt%), lignin (7.3–13.1 wt%); Formulation 5: starch (5.6-14.5 wt%), PVOH (6.5-14.2 wt%), MFC and / or NFC (0.1-5 wt%), HPMC and / or CMC (0.1-0.5 wt%); Formulation 6: soy wax (2-30% by weight), tween20 (0.1-20% by weight); Formulation 7: Paraffin (2-22% by weight), latex (2-30% by weight), span80 (0.1-20% by weight); Formulation 8: EVA modified wax (1-25% by weight), latex (2-30% by weight), tween20 (0.1-20% by weight); Formulation 9: Carnauba wax (1.5-20% by weight), EVA modified wax (1-20% by weight), latex (2-30% by weight), SDS (0.1-20% by weight); Formulation 10: Candelilla wax (1.5-22 wt%), EVA modified wax (1-20 wt%), Tween80 (0.1-20 wt%); Formulation 11: Starch (1.5-9.5% by weight), PVOH (1.5-9.2% by weight), CNC (0.1-1.3% by weight), HPMC and / or CMC (0.1-1% by weight), EVA modified wax and latex (total amount 4.5-30.3% by weight).

[0156] Metallization unit and metallization conditions The metallizer used to accomplish metallization of the film or sacrificial surface of the material blend was a single to multiple chamber metallizer. The film to be metallized was conveyed under reduced pressure to a chamber equipped with a metal vapor source, e.g., a boat heated by Joule effect and fed by a metal wire, such as an aluminum wire, or any other type of suitable source. Sublimation of a metal, such as aluminum, and condensation of the metal onto the surface to be metallized was accomplished using the following conditions: - Metals, e.g. aluminum evaporation rate, 3-15g / min - Winding speed, 5~15m / sec -High vacuum, 0.5~5×10 -4 mbar, and -Cooling temperature, -15~-25℃.

[0157] Other suitable conditions were utilized depending on the metal used, the film or surface over which deposition was to be accomplished, etc.

[0158] A structured metallized film was formed as follows. A Paper / Plastic / Biopolymer Thickness 10-400μm. B blend formulation - thickness 0.5~20μm. C Metallization layer - thickness 0.1-100nm.

[0159] Metal Vapor Deposition Transfer or indirect deposition - High vacuum metallization of plastics for transfer to material blend films A. A high vacuum process was used to metallize the plastic reels. B. The metallized plastic was attached to the paper with an adhesive. C. The product was allowed to cure. D. The plastic and paper were separated and the metal layer was adhered to the material blend only.

[0160] Direct deposition - metallization was performed directly on the material blend film A. The substrate was coated with the material blend prior to metallization to obtain a film thereon. B. The material blend film was metallized by vacuum metallization, where aluminum vapor was allowed to adhere to the surface of the material blend to create a metallic coating.

[0161] Comparison Data Blend compositions were tested that did not contain one or more of the components that make up the formulation of the present invention or contained weight amounts other than those indicated herein. Similar formulations used included:

[0162] Comparative formulation 1: Starch (13%), PVOH (7%), CNC (1.5%) and CMC (1%) provided suspensions with viscosities greater than about 4000 cP, which could not be applied with conventional coating equipment. Films formed from this formulation showed 10 times lower OTR performance compared to the blends of the present invention, which have viscosities below 1000 cP and highly applicable OTR values ​​below 2.

[0163] The failure to apply properly also resulted in insufficient blocking of the paper pores, insufficient smoothing of the surface (10% reduction in roughness compared to 25% reduction in roughness for the blend formulation of the present invention), and poor performance after metallization compared to the paper substrate coated with the metallized blend (Formulation 34).

[0164] Comparative formulation 2: Wax (30%), latex (5%) and surfactant (8%) provided suspensions that were less stable and suffered from phase separation. The suspensions were not homogenous, aggregates formed when applied and the barrier performance was poor (WVTR>50). Metallization onto such films was ineffective and did not improve performance. In contrast, the blend of the present invention (Formulation 40) produced stable homogenous suspensions, smooth homogenous films and good barrier performance (WVTR=8), which was further improved by metallization (WVTR=3).

[0165] Results and Analysis To evaluate the OTR and / or WVTR properties of the inventive structures compared to similar structures that were only face metallized, comparative structures were fabricated and tested.

[0166] 1. In comparing structures formed from metallized films or blended materials derived from the formulations used as described above with structures comprising a metallized substrate without a film of blended material, the following results were obtained: A. Vapor metallization was not possible on porous substrates such as paper, thus the structure did not exhibit barrier properties. B. High surface roughness resulted in less efficient metallization layers and reduced performance. A layer of material blend reduced surface roughness and improved metallization and barrier performance.

[0167] A comparison of OTR (70% RH, 23° C.) and WVTR water (90% RT, 38° C.) performance is shown in Table 1 below.

[0168] TIFF2024526078000001.tif140170

[0169] As shown in Table 1, metallization of bare papers such as glassine, C1S, and even specialty papers did not improve the oxygen barrier performance of the paper. The OTR measured for bare papers was 200 ml / m for glassine and C1S papers. 2 Larger than 6ml / m for special paper 2 The bare paper WVTR was similarly unimpressive.

[0170] However, when metallization was achieved on the material blend film, the oxygen and water vapor barrier performance improved by at least an order of magnitude. 2 The OTR was measured at less than 1 day. The WVTR was also excellent at approximately 5gr / m 2 The values ​​were 0.2 days or less.

[0171] Furthermore, lamination with a polypropylene layer (PP) showed much better and improved OTR and WVTR. The OTR values ​​after lamination with glassine paper and special paper were extremely low (<0.1 ml / m 2 (day), which was at least an order of magnitude better than that of the structure without the material blend layer.

[0172] It is therefore apparent that the material blend used to make the metallized films of the present invention must include a combination of materials that are stable and homogenous in suspension form, form a continuous homogenous film upon drying, have a viscosity of 100-3500 cP, or less than 1000 cP, allowing for application in industrial machinery, and that provide a smooth surface to the substrate and block any pores that may be present.

Claims

1. A metallized film comprising or consisting of a film of a material blend, a metal surface, and optionally a substrate, said material blend film comprising at least one cellulosic material and / or at least one wax and one or more additional additives optionally selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, and nanoparticles.

2. The film of claim 1 , wherein the material blend includes at least one cellulosic material and / or at least one wax.

3. 10. The film of claim 1 which is metallized with a thin metal film, metallization being achieved by vapor deposition of a thin metal film onto a surface of the film of the material blend.

4. 10. The film of claim 1, wherein the film comprises a cellulose and / or wax material laminated with a thin metal film having a thickness between 500 Å (angstroms) and 100 nm.

5. 10. The film of claim 1, wherein the film of the material blend comprises at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, and nanoparticles.

6. The additive is at least one carbohydrate, optionally selected from starch, dextrin, cyclodextrin, maltodextrin, pectin, hemicellulose, sorbitol, and glycogen; or the additive is at least one crosslinking agent, optionally selected from polyacrylic acid (PAA), polyethyleneimine (PEI), polyurethane, alkenylsuccinic anhydride (ASA), and alkylketene dimer (AKD); or the additive is a natural additive, optionally selected from lignin, protein, chitosan, amino acid, lipid, gelatin, and alginic acid; or the additive is at least one natural additive, optionally selected from clay, talc, gypsum, calcite, kaolin, silicic acid.

6. The film of claim 5, wherein the additive is at least one mineral selected from aluminum, illite, vermiculite, smectite, chlorite, and halloysite; or the additive is at least one surfactant selected from anionic surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants, sulfate surfactants, sulfonate surfactants, phosphate surfactants, carboxylate surfactants, antifoaming agents, ethoxylate surfactants, fatty acid ester surfactants, glycerol surfactants, sorbitol surfactants, and alkyl polyglycosides; or the additive is at least one type of nanoparticles.

7. 10. The film of claim 1, wherein the film of the blend material comprises ethylene vinyl acetate (EVA), or latex, or a thermoplastic polymer, or an epoxide.

8. 2. The film of claim 1, wherein the at least one cellulose material is selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl methyl cellulose (HPMC), ethyl hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC), or modified or oxidized forms thereof.

9. The film, base material, said film of a blend material comprising a cellulose material and / or a wax material and at least one additive; and said metal film.

10. The film, base material, A film of a blend material comprising a cellulosic material and a wax material and at least one additive; and said metal film.

11. The film, base material, said film of a wax material and a blend material comprising a wax material and at least one additive; and said metal film.

12. The film, base material, said film of a blend of material comprising a cellulosic material and a wax material and at least one additive; and said metal film.

13. The film of the blend material comprises: (1) at least one cellulosic material and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, and nanoparticles; or (2) at least one wax-based material and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, and nanoparticles; or (3) at least one cellulosic material, at least one wax-based material, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, and nanoparticles; or (4) At least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof, and at least one wax selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (5) Crystalline nanocellulose (CNC), and at least one wax selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (6) Nanofibrillated cellulose (NFC), and at least one wax selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (7) at least one wax selected from microfibrillated cellulose (MFC), carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (8) Microcrystalline cellulose (MCC), and at least one wax selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (9) CMC, and at least one wax selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (10) HPMC, and at least one wax selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (11) Crystalline nanocellulose (CNC) and / or nanofibrillated cellulose (NFC) and / or microfibrillated cellulose (MFC) and / or microcrystalline cellulose (MCC), and / or CMC, and / or HPMC, and at least one wax selected from carnauba wax, vegetable wax, beeswax, soy wax, coconut wax, candelilla wax, and at least one modified wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (12) At least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EEC, MEHEC, or modified or oxidized forms thereof, and carnauba wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (13) At least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof, and at least one additive selected from vegetable waxes, carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (14) At least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof, and beeswax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (15) At least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof, and candelilla wax and at least one modified wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (16) At least one cellulose material selected from crystalline nanocellulose (CNC), nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), or microcrystalline cellulose (MCC), cellulose nitrate, cellulose esters, cellulose acetate, ethyl cellulose, methyl cellulose, HPC, HEC, CMC, HPMC, EHEC, MEHEC, or modified or oxidized forms thereof, and at least one modified wax, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (17) Crystalline nanocellulose (CNC), and / or CMC, and / or HPMC and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (18) crystalline nanocellulose (CNC), and / or CMC, and / or HPMC, and at least one additive selected from carbohydrates, crosslinkers and polymers; or (19) Crystalline nanocellulose (CNC), and / or CMC, and / or HPMC, and / or MFC, and / or NFC, and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (20) At least one wax or modified wax and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (21) At least one modified wax and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (22) At least two waxes or modified wax materials and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or (23) starch, PVOH, CNC, HPMC and / or CMC, or (24) clay, PVOH, and CNC, or (25) Starch, PVOH and CNC, or (26) Starch, PVOH, CNC and lignin, or (27) starch, PVOH, MFC and / or NFC, HPMC and / or CMC, or (28) a wax and at least one surfactant, or (29) A wax, latex and at least one surfactant, or (30) Modified wax, latex and at least one surfactant, or (31) A wax, a modified wax, a latex and at least one surfactant, or (32) A wax, a modified wax, at least one surfactant, or (33) Starch, PVOH, CNC, HPMC and / or CMC, modified wax, and latex, or (34) starch (4.1 to 16.5 wt%), PVOH (5 to 15 wt%), CNC (0.1 to 5 wt%), HPMC and / or CMC (0.1 to 0.5 wt%), or (35) clay (4.2 to 13 wt%), PVOH (5 to 12 wt%), CNC (0.1 to 5 wt%), or (36) starch (5 to 14.5 wt%), PVOH (4.5 to 15.5 wt%), CNC (0.01 to 5 wt%), or (37) starch (4.5 to 15 wt%), PVOH (7 to 14.5 wt%), CNC (0.1 to 4 wt%), lignin (7.3 to 13.1 wt%), or (38) starch (5.6 to 14.5% by weight), PVOH (6.5 to 14.2% by weight), MFC and / or NFC (0.1 to 5% by weight), HPMC and / or CMC (0.1 to 0.5% by weight), or (39) a wax (2 to 30% by weight), a surfactant (0.1 to 20% by weight), or (40) Wax (2 to 22% by weight), latex (2 to 30% by weight), surfactant (0.1 to 20% by weight), or (41) Modified wax (1 to 25% by weight), latex (2 to 30% by weight), surfactant (0.1 to 20% by weight), or (42) Wax (1.5 to 20% by weight), modified wax (1 to 20% by weight), latex (2 to 30% by weight), surfactant (0.1 to 20% by weight), or (43) Wax (1.5 to 22% by weight), modified wax (1 to 20% by weight), surfactant (0.1 to 20% by weight), or (44) Starch (1.5 to 9.5% by weight), PVOH (1.5 to 9.2% by weight), CNC (0.1 to 1.3% by weight), HPMC and / or CMC (0.1 to 1% by weight), modified wax and latex (total, 4.5 to 30.3% by weight) The film of claim 1 comprising or consisting of:

14. A barrier for oxygen or water vapor, said barrier comprising at least one wax or modified wax and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or at least one modified wax and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or at least two modified wax or modified wax materials and at least one additive selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, nanoparticles, or wax and at least one surfactant, or wax, latex and at least one surfactant, or modified wax, latex and at least one surfactant, or wax, modified wax, latex and at least one surfactant, or wax, modified wax, latex and at least one surfactant, or wax, modified wax, at least another surfactant or wax (2-30% by weight), surfactant (0.1-20% by weight) or wax (2-22% by weight), latex (2-30% by weight), surfactant (0.1-20% by weight) or modified wax (1-25% by weight), latex (2-30% by weight), surfactant (0.1-20% by weight) or wax (1.5-20% by weight), modified wax (1-20% by weight), latex (2-30% by weight), surfactant (0.1-20 wt%), or a metallized film derived from a formulation comprising wax (1.5-22 wt%), modified wax (1-20 wt%), surfactant (0.1-20 wt%), starch (1.5-9.5 wt%), PVOH (1.5-9.2 wt%), CNC (0.1-1.3 wt%), HPMC and / or CMC (0.1-1 wt%), modified wax and latex (total amount 4.5-30.3 wt%).

15. A metallized film comprising a material blend film and a metal surface, the material blend film comprising at least one cellulosic material and / or at least one wax and one or more additional additives selected from carbohydrates, crosslinkers, polymers, natural additives, minerals, surfactants, and nanoparticles.