阅读说明：本技术 制备可延展的阻挡膜的方法 (Method for producing a ductile barrier film ) 是由 大卫·J·罗韦 克里斯托弗·S·莱昂斯 凯文·W·戈特里克 格雷格·A·安博 于 2019-10-03 设计创作，主要内容包括：本发明提供了一种制备弯曲阻挡膜的方法,该方法包括：将阻挡层沉积在第一有机层与第二有机层之间以形成阻挡膜；以及将该阻挡膜从平坦阻挡膜热成形或真空成形为弯曲阻挡膜；其中该阻挡膜包括具有两个相对主表面的该阻挡层,其中该阻挡层包括屈曲变形部和非屈曲区域；该第一有机层与该阻挡层的该相对主表面中的一个主表面直接接触；并且该第二有机层与该阻挡层的该相对主表面中的另一个主表面直接接触。(The present invention provides a method of preparing a curved barrier film, the method comprising: depositing a barrier layer between the first organic layer and the second organic layer to form a barrier film; and thermoforming or vacuum forming the barrier film from a flat barrier film into a curved barrier film; wherein the barrier film comprises the barrier layer having two opposing major surfaces, wherein the barrier layer comprises a buckling deformation and a non-buckling region; the first organic layer is in direct contact with one of the opposing major surfaces of the barrier layer; and the second organic layer is in direct contact with the other of the opposing major surfaces of the barrier layer.)

1. A method of making a curved barrier film, the method comprising:

(a) depositing a barrier layer between the first organic layer and the second organic layer to form a barrier film; and

(b) thermoforming the barrier film from a flat barrier film into a curved barrier film;

wherein the barrier film comprises:

the barrier layer having two opposing major surfaces, wherein the barrier layer includes a buckling deformation and a non-buckling region;

the first organic layer is in direct contact with one of the opposing major surfaces of the barrier layer; and is

The second organic layer is in direct contact with the other of the opposing major surfaces of the barrier layer.

2. The method of claim 1, further comprising applying heat to the barrier film prior to step (b).

3. The method of claim 2, wherein applying heat to the barrier film comprises applying heat to the barrier film for pre-compression of the barrier film.

4. The method of any one of claims 1 to 3, further comprising depositing the first organic layer or the second organic layer on a substrate.

5. The method of claim 4, wherein the substrate is heat shrinkable.

6. The method of claim 4, wherein the heat-shrinkable substrate shrinks at a predetermined temperature.

7. The method of claim 4, wherein the heat-shrinkable substrate comprises an organic polymer.

8. The method of any one of claims 1 to 7, wherein the barrier layer comprises at least one selected from the group consisting of: metal oxides, metal and mixed metal fluorides, metal and mixed metal nitrides, metal and mixed metal carbides, metal and mixed metal carbonitrides, metal and mixed metal oxynitrides, metal and mixed metal borides, metal and mixed metal oxyborides, metal and mixed metal silicides, and combinations thereof.

9. The method of claim 8, wherein the barrier layer comprises a metal oxide.

10. The method of claim 9, wherein the metal oxide is selected from the group consisting of: silicon oxide, aluminum oxide, titanium oxide, indium oxide, tin oxide, Indium Tin Oxide (ITO), hafnium oxide, tantalum oxide, zirconium oxide, zinc oxide, niobium oxide, and combinations thereof.

11. The method of any one of claims 1 to 10, wherein the first organic layer or the second organic layer comprises an acrylate.

12. The method of any of claims 1-11, wherein the curved barrier film is stretched no less than 1% relative to its unstretched, flat state.

Technical Field

The present disclosure relates to methods of making barrier films.

Background

Many electronic devices are sensitive to ambient gases and liquids and are susceptible to degradation upon permeation of ambient gases and liquids, such as oxygen and water vapor. Inorganic or hybrid inorganic/organic layers have been used in films for electrical, packaging and decorative applications to prevent degradation. For example, a multilayer stack of inorganic or hybrid inorganic/organic layers can be used to prepare a barrier film that is resistant to moisture permeation. Multilayer barrier films have also been developed to protect sensitive materials from water vapor. The water sensitive material may be an electronic component such as organic, inorganic and hybrid organic/inorganic semiconductor devices. While prior art techniques may be available, there is still a need for better barrier films that can be used for encapsulation.

Disclosure of Invention

In one aspect, the present disclosure provides a method of preparing a curved barrier film, the method comprising: (a) depositing a barrier layer between the first organic layer and the second organic layer to form a barrier film; and (b) thermoforming or vacuum forming the barrier film from a flat barrier film into a curved barrier film; wherein the barrier film comprises the barrier layer having two opposing major surfaces, wherein the barrier layer comprises a buckling deformation and a non-buckling region; the first organic layer is in direct contact with one of the opposing major surfaces of the barrier layer; and the second organic layer is in direct contact with the other of the opposing major surfaces of the barrier layer.

Various aspects and advantages of exemplary embodiments of the present disclosure have been summarized. The above summary is not intended to describe each illustrated embodiment or every implementation of the present disclosure. Additional features and advantages are disclosed in the following detailed description. The following drawings and detailed description more particularly exemplify certain embodiments using the principles disclosed herein.

Definition of

For the following defined terms, all definitions shall prevail throughout the specification, including the claims, unless a different definition is provided in the claims or elsewhere in the specification based on a specific reference to a modified form of the term as used in the following definition:

the terms "a", "an" and "the" include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a material comprising "a compound" includes mixtures of two or more compounds.

The term "layer" refers to any material or combination of materials on or covering a substrate.

The term "separated by …," which describes the position of one layer relative to another layer and a layer of a substrate or two other layers, means that the layer is between, but not necessarily contiguous with, the other layers and/or the substrate.

The term "(co) polymer" or "co" polymeric "includes homopolymers and copolymers, as well as homopolymers or copolymers that may be formed, for example, by coextrusion or by reaction, including, for example, transesterification, in compatible blends. The term "copolymer" includes random copolymers, block copolymers, graft copolymers and star copolymers.

Drawings

The disclosure may be more completely understood in consideration of the following detailed description of various embodiments of the disclosure in connection with the accompanying drawings, in which:

fig. 1 is a side view of an exemplary barrier film made according to the present invention.

While the above-identified drawing figures, which may not be drawn to scale, illustrate various embodiments of the disclosure, other embodiments are also contemplated, as noted in the detailed description. In all cases, this disclosure describes the presently disclosed invention by way of representation of exemplary embodiments and not by way of express limitations. It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope and spirit of the principles of this disclosure.

Detailed Description

Before any embodiments of the disclosure are explained in detail, it is to be understood that the invention is not limited in its application to the details of the use, construction and arrangement of components set forth in the following description. The invention is capable of other embodiments and of being practiced or of being carried out in various ways that will become apparent to those skilled in the art upon reading this disclosure. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of "including," "comprising," or "having" and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. It is to be understood that other embodiments may be utilized and structural or logical changes may be made without departing from the scope of the present disclosure.

As used in this specification, the recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5, etc.).

Unless otherwise indicated, all numbers expressing quantities or ingredients, measurement of properties, and so forth used in the specification and embodiments are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached list of embodiments can vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings of the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claimed embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

The inorganic layer of the barrier film is susceptible to strain-induced failure. Typically, when an inorganic oxide is exposed to conditions that induce tensile strain in excess of 0.5%, the inorganic oxide will undergo multiple in-plane fractures, thereby reducing its diffusion characteristics by several orders of magnitude. Potential vapor coatings of interest for thermoforming can be coatings that can be applied to optical lenses. In the case of optical lenses for electrochromic eyewear, coatings such as anti-reflective coatings, barrier coatings, or transparent conductive electrodes are of great interest. Unfortunately, these coatings typically include layers of sufficient thickness that the coatings are brittle and prone to breaking during stretching associated with thermoforming. The present disclosure provides a process for preparing a high performance thermoformed barrier film that is substantially free of cracking.

In some embodiments, the present disclosure provides a method of making a curved barrier film. A barrier layer is deposited between the first organic layer and the second organic layer to form a barrier film. The curved barrier film can then be formed from the flat barrier film by thermoforming the barrier film. The first organic layer and the second organic layer may be cured. The barrier film of the present disclosure can be prepared by heat shrinking. The method of the present disclosure may include applying heat to the barrier film prior to the step of forming the curved barrier film by thermoforming or vacuum forming. Applying heat to the barrier film may include applying heat to the barrier film for pre-compression of the barrier film. A first organic layer or a second organic layer can be deposited on the heat shrinkable substrate and a barrier layer deposited between the first organic layer and the second organic layer to form a layer construction. After heat shrinking the configuration, the bent barrier film formed by the above method may have a buckling deformation portion as shown in fig. 1.

Unless otherwise specified, the barrier layers of various embodiments may be deposited by any suitable method, for example, by any of sputtering, evaporation, chemical vapor deposition, plasma-enhanced chemical vapor deposition, sublimation, electron cyclotron resonance-plasma-enhanced chemical vapor deposition, physical vapor deposition, atomic layer deposition, and combinations thereof.

Both the first organic layer and the second organic layer may be deposited by any suitable method, for example, by applying a layer of a monomer or oligomer to a substrate and crosslinking the layer to form a polymer in situ, for example, by flash evaporation and vapor deposition of a radiation crosslinkable monomer, followed by crosslinking using, for example, an electron beam device, a UV light source, a discharge device, or other suitable means. The coating efficiency can be improved by cooling the carrier. The monomer or oligomer may also be applied to the substrate using conventional coating methods such as roll coating (e.g., gravure roll coating), die coating (slot die coating), spin coating, dip coating, or spray coating (e.g., electrostatic spray coating or ink jet coating), followed by crosslinking as described above. The organic layer may also be formed by applying a layer containing an oligomer or polymer in a solvent and drying the thus-applied layer to remove the solvent. Unless otherwise indicated, the curved barrier films of various embodiments may be formed by any suitable thermoforming process, such as by the process described in U.S. publication No. US 2018/0267222 a1(Ambur et al), which is incorporated by reference in its entirety into the present disclosure. Generally, a formed film is prepared by: the film is pressed against the bending die with high force to produce a film that matches the surface geometry of the die surface. The film may be heated first to allow the film to more easily move and stretch to conform to the mold surface. In thermoforming, gas pressure is the force used to push the film against the mold surface. In the case of vacuum forming, air is vented from one side of the mold and atmospheric pressure is used to push the film against the mold surface. Alternatively, pressurized gas may be used instead of vacuum to push the membrane against the mold surface.

Barrier films of the present disclosure may also be formed by pre-straining a reversibly stretchable film. In some embodiments, the reversibly stretchable film may be formed of a reversibly stretchable material, such as an elastomer. The reversibly stretchable membrane is pre-stretched by a predetermined percentage pre-stretch, represented by X%. The percent draw-down X% may range from about 0.5% to about 500%, from about 0.5% to about 50%, from about 0.5% to about 10%. The strained stretchable film is laminated to a rigid polymeric or metallic substrate and a barrier layer is deposited on the strained stretchable film using the techniques described above. After the first organic layer is deposited on the barrier layer, the reversibly stretchable film is released from the rigid polymeric or metallic substrate and allowed to relax. The buckling deformation formed by this method has a wavy or buckling profile. Optionally, an adhesive may be deposited between the rigid substrate and the reversibly stretchable film.

Referring now to fig. 1, an exemplary curved barrier film 100 made according to the present disclosure is shown. Barrier film 100 includes a barrier layer 120 having a first opposing major surface 126 and a second opposing major surface 128. In the embodiment shown in fig. 1, first organic layer 110 is in direct contact with first opposing major surface 126 of barrier layer 120, and second organic layer 130 is in direct contact with second opposing major surface 128 of barrier layer 120. In other embodiments, a layer that will be described as second organic layer 130 may be in direct contact with first opposing major surface 126 of barrier layer 120, and first organic layer 110 is in direct contact with second opposing major surface 128 of barrier layer 120. The barrier film 100 may further include a substrate 140 in direct contact with the first organic layer 110 or the second organic layer 130. In the embodiment of fig. 1, the substrate 140 is in direct contact with the second organic layer 130. Alternatively, the substrate 140 may be in direct contact with the first organic layer 110. The barrier layer 120 has a buckling deformation 122 and a non-buckling region 124. In some embodiments, the buckling deformation may be irregular. Although one buckling deformation is followed by one non-buckling region as shown in fig. 1, the number of buckling deformations between two adjacent non-buckling regions may be any number, e.g. 1, 2, 3, 4, 5, etc. For example, in some embodiments, a plurality of consecutive flexion deformations may be located between two non-flexion regions. In some embodiments, the plurality of consecutive buckling deformations may be followed by a plurality of consecutive non-buckling regions. In some embodiments, the non-buckling regions may be located at the ends of the barrier layer 120. As shown in fig. 1, the buckling deformation portion 122 has a length L.

In some embodiments, the length L of the flexion deformities 122 may be no more than 400nm, no more than 300nm, no more than 200nm, no more than 100nm, no more than 50nm, no more than 40nm, no more than 30nm, or no more than 20 nm. In some embodiments, the length L of the buckling deformation 122 may be no less than 2nm, no less than 5nm, no less than 10nm, no less than 20 nm. The buckling deformation portion 122 may protrude in the first direction 150, as shown in fig. 1. In some embodiments, the buckling deformations 122 may protrude in a second direction different from the first direction 150. In some embodiments, the buckling deformation 122 may protrude in both the first direction and the second direction. In some embodiments, the first direction and the second direction may be perpendicular to each other. For example, the first direction is along an x-axis of the barrier layer and the second direction is along a y-axis of the barrier layer. However, it should be understood that the first and second directions may also be along other axes of the barrier layer. For example, if the barrier layer 120 is rectangular in shape when viewed from the top, the first direction may be along the length of the rectangular surface and the second direction may be along the width of the rectangular surface.

Barrier layer 120 is characterized by buckling deformations and non-buckling regions. Non-flexed regions, such as regions with substantially straight or substantially sharp edges, may provide technical benefits. For example, it is easy and convenient to prepare a barrier layer having a non-buckling region, thus reducing manufacturing costs. Further, by forming buckling deformations in the barrier layer, a predetermined amount of compressive stress and additional surface area may be introduced into the barrier layer. In practice, the total amount of surface area formed by the barrier layer is greater than the given projected two-dimensional area that is subsequently deployed when the barrier film is subjected to tensile strain. Thus, when the barrier film is stretched, the buckling deformation may relieve stress and help the barrier film to elongate, thereby reducing strain-induced failure. This allows the barrier film of the present disclosure to bend in at least one direction in a plane along the surface of the barrier film to address at least one of thermal stress, mechanical stress, and load caused by deformation of the adjoining substrate or layer, thereby reducing the accumulation of stress or load and preventing the barrier film from cracking or breaking. The stress or load may originate from external forces, including the forces involved in thermoforming. Stress or loading may also occur due to temperature changes and different coefficients of thermal expansion of the barrier layer and the adjacent layer or substrate. Furthermore, stress or load may also be generated by deformation of the adjacent layer or substrate. In addition, stress or loading may result from moisture absorption and resulting expansion of the adjacent layers or substrates.

In some of these embodiments, the curved barrier film may be uniaxially or biaxially stretched relative to its unstretched state by no less than 1%, no less than 2%, no less than 3%, no less than 5%, or no less than 10%, and the curved barrier film is substantially free of cracking or breaking.

Base material

The substrate 140 may be heat shrinkable. The heat-shrinkable substrate may shrink at a predetermined temperature. A suitable substrate 140 may conveniently be an organic polymer layer that is processed to be heat shrinkable by any suitable means. Semicrystalline or amorphous polymers can be made heat shrinkable by orienting them at a temperature above their glass transition temperature Tg and then cooling. Examples of useful semi-crystalline polymer films include polyolefins such as Polyethylene (PE), polypropylene (PP), and syndiotactic polystyrene (sPS); polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyethylene 2, 6-naphthalate; fluoropolymers such as polyvinylidene fluoride and ethylene: tetrafluoroethylene copolymer (ETFE); polyamides such as nylon 6 and nylon 66; polyphenylene oxides and sulfides. Examples of the amorphous polymer film include polymethyl methacrylate (PMMA), Polycarbonate (PC), polyether sulfone (PES), atactic polystyrene (aPS), polyvinyl chloride (PVC), and norbornene-based Cyclic Olefin Polymer (COP) and Cyclic Olefin Copolymer (COC). Some polymeric materials are available in both semi-crystalline and amorphous forms. Semi-crystalline polymers such as those listed above may also be heat-shrunk by heating to a peak crystallization temperature and cooling.

Biaxially or uniaxially oriented polyethylene terephthalate (PET) having a thickness of about 0.002 inches (0.05mm) is considered a convenient choice, as is biaxially oriented polypropylene (BOPP) film. Biaxially oriented polypropylene (BOPP) is commercially available from several suppliers including: exxonmobil Chemical Company of Houston, Tex (Tex.) of Texas; continental Polymers of Swindon, UK; kaiser International Corporation of Taipei City, Taiwan, and PT Indopoly Industry of Yaga, Indonesia (PT Indopoly Swakarsa Industry (ISI) of Jakarta, Indonesia). Other examples of suitable membrane materials are set forth in WO 02/11978 entitled "Cloth-like Polymer membranes" (Jackson et al) (Cloth-like Polymeric Films). In some embodiments, the substrate may be a laminate of two or more polymer layers.

Organic layer

The first organic layer and the second organic layer may be made of the same material or different materials. The organic layer may be made of at least one selected from, but not limited to: organic polymers, polymers comprising inorganic elements, organometallic polymers, hybrid organic/inorganic polymer systems, and combinations thereof. The organic polymer may be at least one selected from, but not limited to: urethanes, polyamides, polyimides, fluoropolymers, polybutenes, isobutylene isoprene, polyolefins, epoxies, thiolenes, parylene, benzocyclobutene, polynorbornenes, polyarylethers, polycarbonates, alkyds, polyanilines, ethylene vinyl acetate, ethylene acrylic acid, and combinations thereof. The inorganic element-containing polymer may be at least one selected from, but not limited to, the following: silicones, polyphosphazenes, polysilazanes, polycarbosilanes, polycarboboranes, carborane siloxanes, polysilanes, phosphazenes, sulfur nitride polymers, siloxanes, polyorganotitanates, polyorganozirconates, and combinations thereof. The organometallic polymer can be at least one organometallic polymer selected from, but not limited to, main group metals, transition metals, and lanthanide/actinide metals, and combinations thereof. The hybrid organic/inorganic polymer system may be at least one selected from the group consisting of, but not limited to, organically modified silicates, ceramic precursor polymers, polyimide-silica hybrids, (meth) acrylate-silica hybrids, polydimethylsiloxane-silica hybrids, and combinations thereof.

In some embodiments, the first organic layer or the second organic layer may comprise an acrylate or an acrylamide. When the organic layer is formed by flash evaporation, vapor deposition of monomers, and then crosslinking, volatilizable acrylate and methacrylate (referred to herein as "(meth) acrylate") or acrylamide or methacrylamide (referred to herein as "(meth) acrylamide") monomers are useful, with volatilizable acrylate monomers being preferred. Suitable (meth) acrylate or (meth) acrylamide monomers have sufficient vapor pressure to evaporate in an evaporator and condense into a liquid or solid coating in a vapor coater.

Examples of suitable monomers include, but are not limited to: hexanediol diacrylate; ethoxyethyl acrylate; cyanoethyl (mono) acrylate; isobornyl (meth) acrylate; octadecyl acrylate; isodecyl acrylate; lauryl acrylate; beta-carboxyethyl acrylate; tetrahydrofurfuryl acrylate; dinitrile acrylates; pentafluorophenyl acrylate; nitrophenyl acrylate; 2-phenoxyethyl (meth) acrylate; 2,2, 2-trifluoromethyl (meth) acrylate; diethylene glycol diacrylate; triethylene glycol di (meth) acrylate; tripropylene glycol diacrylate; tetraethylene glycol diacrylate; neopentyl glycol diacrylate; propoxylated neopentyl glycol diacrylate; polyethylene glycol diacrylate (PEG-diacrylate); tetraethylene glycol diacrylate; bisphenol a epoxy diacrylate; 1, 6-hexanediol dimethacrylate; trimethylolpropane triacrylate; ethoxylated trimethylolpropane triacrylate; propoxylated trimethylolpropane triacrylate; tris (2-hydroxyethyl) -isocyanurate triacrylate; pentaerythritol triacrylate; phenylthioethyl acrylate; naphthyloxy ethyl acrylate; neopentyl glycol diacrylate, MIRAMER M210 (available from milon Specialty Chemical co., ltd., Korea)), KAYARAD R-604 (available from Nippon Kayaku co., ltd., Tokyo, Japan), epoxy acrylate, product number RDX80094 (available from RadCure corporation of felfield, nj, n.j.)); and mixtures thereof. A variety of other curable materials may be included in the polymer layer, such as, for example, vinyl ethers, vinyl naphthalene (vinyl maphalene), acrylonitrile, and mixtures thereof.

In particular, tricyclodecane dimethanol diacrylate is considered suitable. It may conveniently be applied by, for example, a condensed organic coating followed by UV, electron beam or plasma initiated free radical vinyl polymerisation. Thicknesses between about 250nm and 10000nm are considered convenient, and thicknesses approximately between about 750nm and 5000nm are considered particularly suitable. In some embodiments, the organic layer may have a thickness between about 1000nm and 3000 nm.

Barrier layer

The barrier layer 120 may comprise at least one selected from the group consisting of: metal oxides, metal and mixed metal fluorides, metal and mixed metal nitrides, metal and mixed metal carbides, metal and mixed metal carbonitrides, metal and mixed metal oxynitrides, metal and mixed metal borides, metal and mixed metal oxyborides, metal and mixed metal silicides, and combinations thereof.

In some embodiments, the barrier layer 120 may be conveniently formed of metal oxides, metal nitrides, metal oxynitrides, and metal alloys of oxides, nitrides, and oxynitrides. In one aspect, the barrier layer 120 can comprise a metal oxide. In some embodiments, barrier layer 120 may comprise at least one selected from the group consisting of: silicon oxides such as silicon dioxide, aluminum oxides such as aluminum oxide, titanium oxides such as titanium dioxide, indium oxide, tin oxide, Indium Tin Oxide (ITO), hafnium oxide, tantalum oxide, zirconium oxide, zinc oxide, niobium oxide, and combinations thereof. Preferred metal oxides may include alumina, silica alumina, aluminum-silicon nitride and aluminum-silicon-oxynitride, CuO, TiO₂ITO, ZnO, aluminum zinc oxide, ZrO₂And yttria stabilized oxygenAnd (4) zirconium melting. Preferred nitrides may include Si₃N₄And TiN. The barrier layer 120 can generally be prepared by reactive evaporation, reactive sputtering, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition. Preferred methods include vacuum fabrication such as reactive sputtering and plasma enhanced chemical vapor deposition and atomic layer deposition.

The barrier layer is conveniently applied as a thin layer. Barrier layer materials, such as silicon aluminum oxide, can provide good barrier properties, as well as good interfacial adhesion to organic layers. Such layers are conveniently applied by sputtering and a thickness of between about 5nm and 100nm is considered convenient, with a thickness of about 27nm being considered particularly suitable.

The following embodiments are intended to illustrate the disclosure, but not to limit it.

Detailed description of the preferred embodiments

Embodiment 1 is a method of making a curved barrier film, the method comprising: (a) depositing a barrier layer between the first organic layer and the second organic layer to form a barrier film; and (b) thermoforming or vacuum forming the barrier film from a flat barrier film into a curved barrier film; wherein the barrier film comprises the barrier layer having two opposing major surfaces, wherein the barrier layer comprises a buckling deformation and a non-buckling region; the first organic layer is in direct contact with one of the opposing major surfaces of the barrier layer; and the second organic layer is in direct contact with the other of the opposing major surfaces of the barrier layer.

Embodiment 2 is the method of embodiment 1, further comprising applying heat to the barrier film prior to step (b).

Embodiment 3 is the method of embodiment 2, wherein applying heat to the barrier film comprises applying heat to the barrier film for pre-compression of the barrier film.

Embodiment 4 is the method of any one of embodiments 1 to 3, further comprising depositing the first organic layer or the second organic layer on a substrate.

Embodiment 5 is the method of embodiment 4, wherein the substrate is heat shrinkable.

Embodiment 6 is the method of embodiment 4, wherein the heat-shrinkable substrate shrinks at a predetermined temperature.

Embodiment 7 is the method of embodiment 4, wherein the heat-shrinkable substrate comprises an organic polymer.

Embodiment 8 is the method of any one of embodiments 1 to 7, wherein the barrier layer comprises at least one selected from the group consisting of: metal oxides, metal and mixed metal fluorides, metal and mixed metal nitrides, metal and mixed metal carbides, metal and mixed metal carbonitrides, metal and mixed metal oxynitrides, metal and mixed metal borides, metal and mixed metal oxyborides, metal and mixed metal silicides, and combinations thereof.

Embodiment 9 is the method of embodiment 8, wherein the barrier layer comprises a metal oxide.

Embodiment 10 is the method of embodiment 9, wherein the metal oxide is selected from the group consisting of: silicon oxide, aluminum oxide, titanium oxide, indium oxide, tin oxide, Indium Tin Oxide (ITO), hafnium oxide, tantalum oxide, zirconium oxide, zinc oxide, niobium oxide, and combinations thereof.

Embodiment 11 is the method of any one of embodiments 1 to 10, wherein the first organic layer or the second organic layer comprises an acrylate.

Embodiment 12 is the method of any of embodiments 1-11, wherein the curved barrier film is stretched no less than 1% relative to its unstretched flat state.

Examples

Test method

Optical haze measurement

Optical haze measurements were performed using a BYK Hazegard Plus instrument (BYK Gardner USA Company, Columbia, Md.) according to the supplier's instructions. Prior to the measurement process, the instrument was calibrated to 0% haze. The sample was cleaned with compressed air to remove any residual dust or debris prior to measurement.

To measure flat samples (barrier films of comparative example a and comparative example B), 3 inch x 3 inch (7.62cm x 7.62cm) samples were prepared and measurements were made in three different orientations. The average value is reported as "percent haze". For thermoformed samples (barrier films of examples 1-3 and comparative example C), the convex side of the sample was placed on a measuring table and measurements were made in three different orientations to provide an average of the "percent haze".

Examples

The following examples of barrier films were prepared on a vacuum coater similar to the coaters described in U.S. Pat. Nos. 8,658,248(Anderson et al) and 7,018,713(Padiyath et al).

For examples 1 to 3, a substrate roll coater in the form of a heat-shrinkable, biaxially oriented ScotchShield Ultra PET film (commercially available from 3M Corporation, Maplewood, MN) in indefinite length rolls [0.05mm thick, 14 inches (35.6cm) wide ] was utilized. The substrate was advanced at a constant linear speed of 16fpm (4.9 m/min). The substrate was prepared for coating by subjecting it to 20W nitrogen plasma treatment to improve the adhesion of the first organic layer.

For comparative examples B and C, a substrate roll coater in the form of an indefinite length roll [0.05mm thick, 14 inches (35.6cm) wide ] of a thermally stable MELINEX STCH11 PET film commercially available from Dupont Teijin Films, Chester, VA was utilized. The substrate was advanced at a constant linear speed of 16fpm (4.9 m/min). The substrate was prepared for coating by subjecting it to 20W nitrogen plasma treatment to improve the adhesion of the first organic layer.

Example 1

Dicidodecane dimethanol diacrylate (commercially available as SARTOMER SR833S from Sartomer USA of Exxoton, Pa.) was applied by ultrasonic atomization and flash evaporation to form a first organic layer on a ScotchShield Ultra PET substrate to a coating width of 12.5 inches (31.75 cm). The monomer coating was then immediately cured downstream with an electron beam curing gun operating at 7.0kV and 4.0 mA. The flow rate of the liquid monomer into the evaporator was 1.33mL/min, the nitrogen flow rate was 60sccm and the evaporator temperature was set at 260 ℃. The temperature of the processing cylinder was-10 ℃. The thickness of the first organic layer was about 750 nm.

On top of the first organic layer, a barrier layer of silicon aluminum oxide is deposited by AC reactive sputtering. The cathode had a Si (90%)/Al (10%) target from Soleras Advanced Coatings US (Biddeford, ME) from Sorra Advanced Coatings USA. During sputtering, the voltage at the cathode is controlled by a feedback control loop that monitors the voltage and controls the oxygen flow rate so that the voltage remains high without collapse of the target voltage. The system was operated at 16kW and 600V under 3 mtorr argon to deposit a thick layer of approximately 25nm of silicon aluminum oxide onto the organic layer.

A second organic layer is deposited on top of the silicon aluminum oxide layer using a further uniform process. The second organic layer was prepared from the monomer solution by ultrasonic atomization and flash evaporation. The material applied to form the second organic layer was a mixture of 3 wt% of (N- (N-butyl) -3-aminopropyltrimethoxysilane (commercially available under the trade designation DYNASYLAN 1189 from Evonik Industries AG, Essen, Germany) and SARTOMER SR 833S. the mixture flowed into the atomizer at a flow rate of 1.33ml/min, a nitrogen flow rate of 60sccm, and an evaporator temperature of 260. the process drum temperature was-10. once condensed onto the silica alumina layer, the coating mixture was immediately cured using an electron beam curing gun operating at 7.0kV and 10.0 mA. the thickness of the second organic layer was about 750 nm.

A 6 inch x 6 inch (15.24cm x 15.24cm) sheet of the resulting barrier film was laminated with a release film (0.05mm thick PET film with low tack adhesive) applied to each side of the barrier film. The sheet was then fed stepwise into an ACCUFORM IL Series high pressure thermoforming unit (Hy-Tech Forming Systems USA, Phoenix, AZ). The thermoforming tool was equipped with a 75mm diameter pedestal-6 lens curvature forming die. The forming temperature on the heated platen was set at 150-. The laminated barrier film sheet was pressed against the platen at 60psi for six seconds. The sheet was then pressed against the forming die at 500psi for six seconds. The resulting curved film is then removed from the thermoforming unit and allowed to cool to ambient temperature. The release film was removed and the haze of the formed barrier film was evaluated. The results are presented in table 1. When imaged with a Leica DM4000M optical microscope (Leica Microsystems, Buffalo Grove, IL) with 5x, 10x and 20x objective lenses and viewed under bright field conditions, the curved barrier film showed only minor fracture.

Example 2

Dicidol diacrylate (commercially available as SARTOMER SR833S from Saedoma, USA) was applied by ultrasonic atomization and flash evaporation to form a first organic layer on a ScotchShield Ultra PET substrate to a coating width of 12.5 inches (31.75 cm). The monomer coating was then immediately cured downstream with an electron beam curing gun operating at 7.0kV and 4.0 mA. The flow rate of the liquid monomer into the evaporator was 1.33mL/min, the nitrogen flow rate was 60sccm and the evaporator temperature was set at 260 ℃. The temperature of the processing cylinder was-10 ℃. The thickness of the first organic layer was about 750 nm.

On top of the first organic layer, a barrier layer of silicon aluminum oxide is deposited by AC reactive sputtering. The cathode had a Si (90%)/Al (10%) target, available from sorela advanced coatings, usa. During sputtering, the voltage at the cathode is controlled by a feedback control loop that monitors the voltage and controls the oxygen flow rate so that the voltage remains high without collapse of the target voltage. The system was operated at 16kW and 600V under 3 mtorr argon to deposit a thick layer of approximately 25nm of silicon aluminum oxide onto the organic layer.

A second organic layer is deposited on top of the silicon aluminum oxide layer using a further uniform process. The second organic layer was prepared from the monomer solution by ultrasonic atomization and flash evaporation. The material applied to form the second organic layer was a mixture of 3 wt% of (N- (N-butyl) -3-aminopropyltrimethoxysilane (commercially available under the tradename DYNASYLAN 1189) and SARTOMER SR833S the flow rate of this mixture into the atomizer was 1.33ml/min, the nitrogen flow rate was 60sccm, and the evaporator temperature was 260 ℃ the temperature of the process drum was-10 ℃ the coating mixture was cured immediately using an electron beam curing gun operating at 7.0kV and 10.0mA once condensed onto the silica alumina layer the thickness of the second organic layer was about 750 nm.

The resulting barrier film was further processed in 22.5cm x 22.5cm sections using a Karo IV batch orienter (brickner Maschinenbau GmbH & co.kg, Siegsdorf, Germany) with the temperature in the stretching oven set at 165 ℃. The barrier film segments are placed in the loading zone of a Karo orienter by fixing the boundaries of the film segments in one in-plane dimension and allowing the orthogonal in-plane direction to relax 10% relative to its original dimensional dimension when held taut in the orienter. The article is then passed into a stretching oven for 5 minutes where it is heat shrunk along the dimension where it relaxes by 10%. The barrier film segment was removed from the oven and then allowed to cool to ambient temperature.

A 6 inch x 6 inch (15.24cm x 15.24cm) sheet of the resulting barrier film was laminated with a release film (0.05mm thick PET film with low tack adhesive) applied to each side of the barrier film. The sheet was then fed stepwise into an ACCUFORM IL Series high pressure thermoforming unit (supermicro forming systems, usa, phoenix, arizona). The thermoforming tool was equipped with a 75mm diameter pedestal-6 lens curvature forming die. The forming temperature on the heated platen was set at 150-. The laminated barrier film sheet was pressed against the platen at 60psi for six seconds. The sheet was then pressed against the forming die at 500psi for six seconds. The resulting curved film is then removed from the thermoforming unit and allowed to cool to ambient temperature. The release film was removed and the haze of the formed barrier film was evaluated. The results are presented in table 1.

Example 3

Dicidol diacrylate (commercially available as SARTOMER SR833S from Saedoma, USA) was applied by ultrasonic atomization and flash evaporation to form a first organic layer on a ScotchShield Ultra PET substrate to a coating width of 12.5 inches (31.75 cm). The monomer coating was then immediately cured downstream with an electron beam curing gun operating at 7.0kV and 4.0 mA. The flow rate of the liquid monomer into the evaporator was 1.33mL/min, the nitrogen flow rate was 60sccm and the evaporator temperature was set at 260 ℃. The temperature of the processing cylinder was-10 ℃. The thickness of the first organic layer was about 750 nm.

On top of the first organic layer, a barrier layer of silicon aluminum oxide is deposited by AC reactive sputtering. The cathode had a Si (90%)/Al (10%) target available from sonela advanced coatings, inc (bifford, maine, usa). During sputtering, the voltage at the cathode is controlled by a feedback control loop that monitors the voltage and controls the oxygen flow rate so that the voltage remains high without collapse of the target voltage. The system was operated at 16kW and 600V under 3 mtorr argon to deposit a thick layer of approximately 25nm of silicon aluminum oxide onto the organic layer.

A second organic layer is deposited on top of the silicon aluminum oxide layer using a further uniform process. The second organic layer was prepared from the monomer solution by ultrasonic atomization and flash evaporation. The material applied to form the second organic layer was a mixture of 3 wt% of (N- (N-butyl) -3-aminopropyltrimethoxysilane (commercially available under the tradename DYNASYLAN 1189) and SARTOMER SR833S the flow rate of this mixture into the atomizer was 1.33ml/min, the nitrogen flow rate was 60sccm, and the evaporator temperature was 260 ℃ the temperature of the process drum was-10 ℃ the coating mixture was cured immediately using an electron beam curing gun operating at 7.0kV and 10.0mA once condensed onto the silica alumina layer the thickness of the second organic layer was about 750 nm.

The resulting barrier film was further processed in a 22.5cm x 22.5cm section using a Karo IV batch orienter (west gesdorv bruken machines ltd, germany) with the temperature in the stretching oven set at 165 ℃. The barrier film segments are placed in the loading zone of a Karo orienter by fixing the boundaries of the film segments in one in-plane dimension and allowing the orthogonal in-plane direction to relax 10% relative to its original dimensional dimension when held taut in the orienter. The article is then passed into a stretching oven for 5 minutes where it is heat shrunk along the dimension where it relaxes by 10%. The barrier film segment was removed from the oven and then allowed to cool to ambient temperature.

The resulting relaxed barrier film section was reloaded into a Karo IV orienter and heated in an oven at 165 ℃ for 5 minutes, then stretched along the same axis that was previously allowed to relax (5%, at a constant rate of 1%/second). This additional stretching step is included to relieve some of the compressive stress in the film. The stretched barrier film segment is removed from the oven and then allowed to cool to ambient temperature.

A 6 inch x 6 inch (15.24cm x 15.24cm) sheet of the resulting barrier film was laminated with a release film (0.05mm thick PET film with low tack adhesive) applied to each side of the barrier film. The sheet was then fed stepwise into an ACCUFORM IL Series high pressure thermoforming unit (supermicro forming systems, usa, phoenix, arizona). The thermoforming tool was equipped with a 75mm diameter pedestal-6 lens curvature forming die. The forming temperature on the heated platen was set at 150-. The laminated barrier film sheet was pressed against the platen at 60psi for six seconds. The sheet was then pressed against the forming die at 500psi for six seconds. The resulting curved film is then removed from the thermoforming unit and allowed to cool to ambient temperature. The release film was removed and the haze of the formed barrier film was evaluated. The results are presented in table 1. The curved barrier film was substantially free of cracks when imaged with a Leica DM4000M optical microscope with 5x, 10x, and 20x objective lenses and observed under bright field conditions.

Comparative example A

Comparative example a is a flat sheet of the barrier film prepared in example 1, which was not subjected to the final thermoforming step of example 1. Sections of the barrier film were evaluated for haze according to the procedure described above. The results are presented in table 1.

Comparative example B

Dicidol diacrylate (commercially available as SARTOMER SR833S from Saedoma, USA) was applied by ultrasonic atomization and flash evaporation to form a first organic layer on a MELINEX STCH11 PET substrate to a coating width of 12.5 inches (31.75 cm). The monomer coating was then immediately cured downstream with an electron beam curing gun operating at 7.0kV and 4.0 mA. The flow rate of the liquid monomer into the evaporator was 1.33mL/min, the nitrogen flow rate was 60sccm and the evaporator temperature was set at 260 ℃. The temperature of the processing cylinder was-10 ℃. The thickness of the first organic layer was about 750 nm.

On top of the first organic layer, a barrier layer of silicon aluminum oxide is deposited by AC reactive sputtering. The cathode had a Si (90%)/Al (10%) target available from sonela advanced coatings, inc (bifford, maine, usa). During sputtering, the voltage at the cathode is controlled by a feedback control loop that monitors the voltage and controls the oxygen flow rate so that the voltage remains high without collapse of the target voltage. The system was operated at 16kW and 600V under 3 mtorr argon to deposit a thick layer of approximately 25nm of silicon aluminum oxide onto the organic layer.

A second organic layer is deposited on top of the silicon aluminum oxide layer using a further uniform process. The second organic layer was prepared from the monomer solution by ultrasonic atomization and flash evaporation. The material applied to form the second organic layer was a mixture of 3 wt% of (N- (N-butyl) -3-aminopropyltrimethoxysilane (commercially available under the tradename DYNASYLAN 1189) and SARTOMER SR833S the flow rate of this mixture into the atomizer was 1.33ml/min, the nitrogen flow rate was 60sccm, and the evaporator temperature was 260 ℃ the temperature of the process drum was-10 ℃ the coating mixture was cured immediately using an electron beam curing gun operating at 7.0kV and 10.0mA once condensed onto the silica alumina layer the thickness of the second organic layer was about 750 nm.

The haze of the 3 inch x 3 inch sections of the resulting barrier film was evaluated according to the procedure described above. The results are presented in table 1.

Comparative example C

A 6 inch x 6 inch (15.24cm x 15.24cm) sheet of the barrier film of comparative example B was laminated with a release film (0.05mm thick PET film with low tack adhesive) applied to each side of the barrier film. The sheet was then fed stepwise into an ACCUFORM IL Series high pressure thermoforming unit (supermicro forming systems, usa, phoenix, arizona). The thermoforming tool was equipped with a 75mm diameter pedestal-6 lens curvature forming die. The forming temperature on the heated platen was set at 150-. The laminated barrier film sheet was pressed against the platen at 60psi for six seconds. The sheet was then pressed against the forming die at 500psi for six seconds. The resulting curved film is then removed from the thermoforming unit and allowed to cool to ambient temperature. The release film was removed and the haze of the formed barrier film was evaluated. The results are presented in table 1. The curved barrier film showed multiple large fractures when imaged with a Leica DM4000M optical microscope with 5x, 10x and 20x objective lenses and observed under bright field conditions.

Table 1: average percent haze measurement of Barrier films

	Base material	Thermoformed barrier film	Step of precompression	Percent haze average
					Example 1	Heat-shrinkable PET	Is that	Whether or not	3.37
Example 2	Heat-shrinkable PET	Is that	Is that	1.44
					Example 3	Heat-shrinkable PET	Is that	Is that	1.53
Comparative example A	Heat-shrinkable PET	Whether or not	Whether or not	1.55
					Comparative example B	Heat-stable PET	Whether or not	Whether or not	0.71
Comparative example C	Heat-stable PET	Is that	Whether or not	9.40

All references and publications cited herein are expressly incorporated by reference into this disclosure in their entirety. Illustrative embodiments of the invention are discussed herein and reference is made to possible variations within the scope of the invention. For example, features depicted in connection with one exemplary embodiment may be used in connection with other embodiments of the invention. These and other variations and modifications in the invention will be apparent to those skilled in the art without departing from the scope of the invention, and it should be understood that this invention is not limited to the illustrative embodiments set forth herein. Accordingly, the invention is to be limited only by the claims provided below and equivalents thereof.