WO2021152412A1 - Film multicouche avec couche de nanocomposite et couche de polyuréthane - Google Patents

Film multicouche avec couche de nanocomposite et couche de polyuréthane Download PDF

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Publication number
WO2021152412A1
WO2021152412A1 PCT/IB2021/050265 IB2021050265W WO2021152412A1 WO 2021152412 A1 WO2021152412 A1 WO 2021152412A1 IB 2021050265 W IB2021050265 W IB 2021050265W WO 2021152412 A1 WO2021152412 A1 WO 2021152412A1
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WIPO (PCT)
Prior art keywords
layer
polymer
multilayer film
film
nanocomposite
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PCT/IB2021/050265
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English (en)
Inventor
Peter D. Condo
David Scott Thompson
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3M Innovative Properties Company
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Publication date
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Publication of WO2021152412A1 publication Critical patent/WO2021152412A1/fr

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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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Definitions

  • Displays and electronic devices have evolved to be curved, bent, or folded and provide new user experiences.
  • These device architectures may include flexible organic light emitting diodes (OLEDs), plastic liquid crystal displays (LCDs) and the like, for example.
  • OLEDs organic light emitting diodes
  • LCDs plastic liquid crystal displays
  • the present disclosure relates to multilayer films including an ionomeric or nanocomposite layer and a polyurethane.
  • the multilayer film can be a display film that can protect a display window and survive folding tests intact.
  • the protective display film may maintain optical properties of a display film while providing scratch resistance to the display.
  • a multilayer film in some aspects, includes an aliphatic cross-linked polyurethane layer and a nanocomposite layer fixed to the aliphatic cross-linked polyurethane layer.
  • the nanocomposite layer includes at least one polymer and metal oxide nanoparticles dispersed in the at least one polymer.
  • the at least one polymer includes a first polymer including (meth)acrylic acid monomer units (acrylic acid monomer units, methacrylic acid monomer units, or both acrylic acid and methacrylic acid monomer units).
  • the metal oxide nanoparticles are surface modified with a surface modifying agent comprising a carboxylic acid silane of formula 1 :
  • R1 is a Ci to Cio alkoxy group
  • R2 and R3 are independently selected from the group consisting of Ci to Cio alkyl and Ci to Cio alkoxy groups
  • A is a linker group selected from the group consisting of Ci to Cio alkylene or arylene groups, Ci to Cio aralkylene groups, C2 to Ci 6 heteroalkylene or heteroarylene groups, and C2 to Ci 6 amide containing groups.
  • the multilayer film may include additional layers.
  • an additional nanocomposite layer may be fixed to the polyurethane layer on the side opposite the nanocomposite layer.
  • the additional nanocomposite layer may be as described for the nanocomposite layer.
  • the additional nanocomposite layer may optionally be replaced with a layer of the at least one polymer without the metal oxide nanoparticles.
  • FIGS. 1-4 are schematic diagram side elevation views of illustrative multilayer films
  • FIG. 5 is a schematic illustration of an illustrative stress-strain curve
  • FIGS. 6-10 are schematic diagram perspective views of illustrative display articles including illustrative multilayer films.
  • Displays and electronic devices have evolved to be curved, bent, or folded and provide new user experiences.
  • These device architectures may include flexible organic light emitting diodes (OLEDs), plastic liquid crystal displays (LCDs) and the like, for example.
  • OLEDs organic light emitting diodes
  • LCDs plastic liquid crystal displays
  • a flexible cover sheet or flexible window film replaces a conventional glass cover sheet.
  • This flexible cover sheet has a number of design parameters such as; high visible light transmission, low haze, excellent scratch resistance and puncture resistance, in order to protect the elements included in the display devices.
  • the flexible cover sheet may also need to withstand thousands of folding events around a tight bend radius (about 5 mm or less) without showing visible damage.
  • the flexible cover sheet must be able to unfold without leaving a crease after being bent at elevated temperature and humidity.
  • a variety of hard coated plastic substrates have been explored. More exotic materials like hard coated colorless transparent polyimide films have also been shown to have high hardness and good scratch resistance. However, many hard coated films fail to withstand folding events around a tight bend radius without showing visible damage.
  • Conventional ionic elastomers possess some of desired properties such as high visible transmission and low haze, chemical resistance, and flexibility.
  • conventional ionic elastomeric polymers lack the desired mechanical features or abrasion resistance, impact resistance, tensile modulus, for example, desired for a protective layer in a display film.
  • Particulate fillers have been incorporated into polymers to improve mechanical properties.
  • the vast majority of commercially available filled polymers are opaque and thus are unsuitable for use in optical articles. Additionally, rigid particulate fillers can adversely affect the flexibility properties of the polymers with which they are combined.
  • One technique for providing modified properties is to blend polymeric materials.
  • This approach can be problematic as the preparation of blends to improve one property, such as flexibility, can adversely affect other properties, such as optical properties. This is especially true for optical properties, since the vast majority of polymer blends have at least some degree of immiscibility. A lack of miscibility can dramatically affect optical properties such as visible light transmission, haze and clarity. Even polymers that have the same or similar monomeric composition can be immiscible, if, for example, the polymers have differing degrees of branching. Thus, modification of a polymeric composition by blending the polymeric composition with another polymer, even a seemingly similar polymer, is not a trivial undertaking, especially when the blended composition has desired optical properties. It has been unexpectedly found that blends of different polymers including similar content of (meth)acrylic acid monomer units provide improved mechanical properties while maintaining desired optical properties (e.g., high optical transparency and/or low optical haze).
  • the multilayer films of the present disclosure achieve the contradictory goals of flexibility, optical transparency and improved mechanical properties, according to some preferred embodiments.
  • the nanocomposite layers of the multilayer film typically include a polymeric matrix and a surface-modified nanoparticle filler.
  • the polymeric matrix which may also be referred to as a polymeric phase, includes at least one polymer (e.g., a polymer or a blend of polymers).
  • the nanocomposite layers of the present disclosure utilize metal oxide nanoparticles, which are particles with an average diameter that is in the nanometer range. These particles give improved mechanical properties to the nanocomposites, and because of their small size, according to some embodiments, the nanoparticles do not appreciably scatter visible light.
  • the nanoparticles can be surface modified to achieve compatibility with the at least one polymer to avoid agglomeration or aggregation of the nanoparticles in the nanocomposite which would lead to inferior optical properties.
  • the surface modifying agent is typically a carboxylic acid-functional silane.
  • the acid-functional groups on the surface modifying agent improve the compatibility of the particles with the acid-functional (meth)acrylic polymer(s) of the at least one polymer. Some of the acid-functional groups on the surface-modified nanoparticles may also be neutralized like at least some of the acid-functional groups on the (meth)acrylic polymer(s). Acid-functional groups in the surface modifying agent are preferred for dispersibility of the nanoparticles in water.
  • the acid groups of the acid silane when added to the basic surface unmodified nanoparticle solution (for example, NACLO 2327), are at least partially neutralized which renders the silane soluble in the aqueous phase such that the surface of the silica can be modified readily. Furthermore, it has been found that in the coating and melt processing of the ionic elastomer nanocomposite materials that the acid silane on the surface of the particles can allow for interaction of the nanoparticles with the ionic groups of the elastic ionomer polymers leading to excellent compatibility of the nanoparticles in the host polymer matrix.
  • the basic surface unmodified nanoparticle solution for example, NACLO 2327
  • the present disclosure relates to multilayer display film with glass that protects a display and may survive flexing, folding or impact tests.
  • the protective display film maintains optical properties of a display film while providing impact and scratch resistance to the display.
  • the display film can include a transparent anti-shatter layer disposed on a shape memory polyurethane layer.
  • display film “protective film”, and “protective display film” are herein used interchangeably.
  • Transparent substrate or “transparent layer” refers to a substrate or layer that has a high light transmission (typically greater than 85% or 90%) over at least a portion of the surface of the substrate over at least a portion of the light spectrum with wavelengths of about 350 to about 1600 nanometers, including the visible light spectrum (wavelengths of about 380 to about 750 nanometers).
  • the term may include “polyurethane-ureas” in which both urethane linkages and urea linkages are present.
  • Polyurethane acrylate refers to a polymer that includes primarily urethane and acrylate moieties or segments.
  • glass transition temperature refers herein to the “on-set” glass transition temperature by DSC and is measured according to ASTM E1256-082014.
  • miscible or “miscibility” refer to at least two polymers that are compatible with each other such that blends of the at least two polymers do not phase separate so as to form phase separated microdomains that are large enough to produce significant scattering of visible light (wavelengths of about 400 to about 700 nm).
  • immiscible or “immiscibility” refer to at least two polymers that are incompatible with each other such that blends of the at least two polymers phase separate so as to form phase separated microdomains that are large enough to produce significant scattering of visible light (wavelengths of about 400 to about 700 nm) resulting in unacceptable haze.
  • the term “protective layer” may also be referred to as an abrasion resistant or anti-shatter layer.
  • the protective layer may also be referred to as an “elastic ionomer nanocomposite layer”.
  • the present disclosure relates to multilayer films with a nanocomposite layer (e.g., elastic ionomer nanocomposite layer) fixed to an aliphatic cross-linked polyurethane layer that can protect a display or display window and may survive flexing, folding or impact tests.
  • the protective film maintains optical properties of a display film while providing durability to the display.
  • the aliphatic cross-linked polyurethane layer can provide energy dissipation.
  • the polyurethane can deform (e.g., under impact) and then recover its original shape. In some cases, this process dissipates energy.
  • the nanocomposite layer preferably can deform with the polyurethane layer and recover its original shape as well.
  • the nanocomposite layer typically provides different surface properties than the polyurethane layer.
  • the protective display film generally includes a nanocomposite layer (e.g., a transparent elastic ionomer nanocomposite layer) directly fixed to an (e.g., transparent) aliphatic crosslinked polyurethane layer.
  • the nanocomposite layer provides a non-tacky surface to the surface of a display regardless of the properties of the underlying polyurethane layer, which are often tacky when the glass transition temperatures of the materials are below room temperature.
  • this multilayer film enables displays to survive impact events and recover from bending.
  • the protective display film typically includes at least one layer of an elastic ionomer nanocomposite fixed to a transparent aliphatic crosslinked polyurethane layer.
  • the transparent aliphatic crosslinked polyurethane layer may have an average thickness (unweighted mean thickness over an area of the layer) less than 500 micrometers, or less than 250 micrometers, or less than 200 micrometers, or less than 100 micrometers, or less than 50 micrometers.
  • the nanocomposite layer may be positioned to be the outer surface of the display. The thickness of the nanocomposite layer can be in the range from 5 to 125 micrometers, from 5 to 70 micrometers, or from 5 to 30 micrometers.
  • the protective display film can include a layered structure including other layers disposed on the side opposite the nanocomposite layer. These additional layers may include additional layers of (e.g., elastic ionomer) nanocomposite, elastic ionomer containing layers, and transparent substrate layers.
  • additional layers may include additional layers of (e.g., elastic ionomer) nanocomposite, elastic ionomer containing layers, and transparent substrate layers.
  • the aliphatic cross-linked polyurethane layers may be a cross-linked polymer such as a cross-linked polyurethane material or a cross-linked polyurethane acrylate material. These polyurethane layers may be beneficial in energy dissipation and may have an onset glass transition temperature as measured by differential scanning calorimetry (DSC) of less than 27 degrees Celsius, or less than 20 degrees Celsius, or less than 10 degrees Celsius, or less than 5 degrees Celsius.
  • DSC differential scanning calorimetry
  • the multilayer film may protect flexible optical displays even under conditions of dynamic folding.
  • the polyurethane layer may have a low onset glass transition temperature as measured by DSC, such as 5 degrees Celsius or less, or zero degrees Celsius or less, or -5 degrees Celsius or less, or -10 degrees Celsius or less or in a range from -40 to 5 degrees Celsius, or in a range from -30 to 5 degrees Celsius, or in a range from -20 to 5 degrees Celsius, or in a range from -15 to 5 degrees Celsius.
  • the transparent aliphatic cross-linked polyurethane layer may have a Tan Delta peak value of 0.5 or greater, or 0.8 or greater, or 1.0 or greater, or 1.2 or greater.
  • the polyurethane layer or layers may have a Young’s Modulus (E') greater than 0.9MPa over the temperature range of -40 degrees Celsius to 70 degrees Celsius.
  • FIG. 1 is a schematic diagram side elevation view of an illustrative multilayer film 100 which may be a protective display film.
  • the terms “display film”, “cover film”, “protective film”, “protective cover film” or “protective display film” are used interchangeable herein.
  • the multilayer film 100 includes a (e.g., transparent elastic ionomer) nanocomposite layer 110 disposed on a (e.g., transparent) aliphatic cross-linked polyurethane layer 120.
  • the nanocomposite layer 110 is directly fixed to the aliphatic cross-linked polyurethane layer 120. By directly fixed, it is meant that the nanocomposite layer is in direct contact to the polyurethane.
  • the surface of the polyurethane may be treated to enhance adhesion of the nanocomposite layer, but such treatment should not provide any significant change in thickness to the polyurethane.
  • Examples of such treatment may include activation of the surface via corona treatment or atmospheric plasma.
  • the surface is lightly etched to increase the surface area of the polyurethane surface and provide reactive groups to interact with the ionomer nanocomposite.
  • the thickness of any surface treatments should not exceed 100 nm in thickness.
  • the thickness of the nanocomposite layer 110 can be in the range of 5 to 125 microns, 5 to 100 microns, 5 to 70 microns, or 5-50 microns. In some exemplary cases, the thickness is in the range of 5 to 30 microns.
  • the surface of the nanocomposite layer 110 may be optionally provided with a low surface energy coating 105 to enhance abrasion resistance and provide improved tactile feel of the surface as described further elsewhere herein.
  • the low surface energy coating 105 can result in a high static contact angle.
  • a static water contact angle Q which may be at least 100 degrees or at least 110 degrees is schematically illustrated in FIG. 1.
  • FIG. 2 is a schematic diagram side elevation view of an illustrative multilayer fdm 200 that includes an additional (e.g., elastic ionomer) layer 115 on the aliphatic cross-linked polyurethane layer 120 on the side opposite the nanocomposite layer 110 such that the aliphatic cross-linked polyurethane layer 120 separates the nanocomposite layer 110 and the additional layer 115.
  • the fdm 200 includes an aliphatic cross-linked polyurethane 120 and a nanocomposite layer 110 disposed on the aliphatic cross-linked polyurethane layer 120.
  • the nanocomposite layer 110 and the additional layer 115 are both directly fixed to the aliphatic cross-linked polyurethane layer 120.
  • the surface of the polyurethane may be treated to enhance adhesion of the nanocomposite layer.
  • the surface of the nanocomposite 110 may be optionally provided with a low surface energy coating 105 to enhance abrasion resistance and provide improved tactile feel of the surface.
  • the additional layer 115 can be an elastic ionomer nanocomposite as described further elsewhere herein.
  • FIG. 3 is a schematic diagram side elevation view of an illustrative multilayer film 300.
  • the film 300 includes a (e.g., transparent) aliphatic cross-linked polyurethane layer 120 and a (e.g., transparent elastic ionomer) nanocomposite layer 110 disposed on the aliphatic cross-linked polyurethane layer 120.
  • the nanocomposite layer 110 is directly fixed to the aliphatic cross-linked polyurethane layer 120.
  • a transparent substrate 130 may be directly fixed or coupled to the aliphatic cross-linked polyurethane layer 120 on the side opposite the nanocomposite layer 110, such that the nanocomposite layer 110 is separated from the transparent substrate 130 by the aliphatic cross-linked polyurethane layer 120.
  • the transparent substrate 130 preferably has high transmission and low haze and a thickness of less than 100 micrometers, or in a range from 12.5 to 100 micrometers.
  • the surface of the elastomeric ionomer nanocomposite 110 may be optionally provided with a low surface energy and/or low coefficient of friction coating 105 to provide improved tactile feel of the surface as described further elsewhere herein.
  • FIG. 4 is a schematic diagram side elevation view of an illustrative multilayer film 400 that includes a nanocomposite layer 110 and an additional (e.g., elastic ionomer) layer 115 fixed on opposing sides of the aliphatic cross-linked polyurethane layer 120, such that the aliphatic cross-linked polyurethane layer 120 separates the nanocomposite layer 110 and the additional layer 115.
  • a transparent substrate 130 is directly fixed to additional layer 115, such that the additional layer 115 separates the polyurethane layer 120 and the substrate 130.
  • the surface of the elastomeric ionomer nanocomposite 110 may be optionally provided with a low surface energy and/or low coefficient of friction coating 105 to provide improved tactile feel of the surface as described further elsewhere herein.
  • the nanocomposite layer 110 may be bonded directly to, and substantially coextensive with, the polyurethane layer 120.
  • any other two layers illustrated as being immediately adjacent one another may be bonded directly to, and substantially coextensive with, each other.
  • Two layers described as substantially coextensive means that the two layers extend over a common area being at least 70 percent of an area of the larger (by area) of the two layers, unless the context clearly indicates differently. In some cases, the common area is at least 80 percent or at least 90 percent of the area of the larger of the two layers.
  • a further multilayer fdm embodiment includes an elastic ionomer nanocomposite layer disposed on a liner fdm, for example an unprimed polyester (PET) fdm layer where a premask fdm has been applied to the opposite surface of the elastic ionomer nanocomposite layer, wherein the elastic ionomer layer separates the liner fdm and the premask fdm.
  • PET unprimed polyester
  • a further multilayer fdm embodiment includes an elastic ionomer layer disposed on a liner fdm, for example an unprimed polyester (PET) fdm layer where a premask fdm has been applied to the opposite surface of the elastic ionomer layer, wherein the elastic ionomer layer separates the liner fdm and the premask fdm.
  • a further multilayer fdm embodiment includes a transparent aliphatic cross-linked polyurethane layer separating two release liners.
  • a further multilayer fdm embodiment includes an transparent aliphatic cross-linked polyurethane layer separating a release liner from an adhesive layer, and a second release liner is disposed on the adhesive layer.
  • the adhesive layer may be an optically clear adhesive layer, as described herein or a pressure sensitive adhesive layer, or any adhesive or coupling layer described herein.
  • the illustrative multilayerl fdm constructions may include an ink border that defines a viewing window.
  • the ink border may be a continuous frame element printed, for example, onto the transparent aliphatic cross-linked polyurethane layer, for example.
  • the multilayer fdm may include one or more additional layers. Additional layers may include conductive layers for touch sensitive display elements or barrier layers.
  • One or more additional transparent polymeric substrate layers may be disposed in the display fdm of any useful polymeric material that provides desired mechanical properties (such as dimensional stability) and optical properties (such as light transmission and clarity) to the display fdm. Examples of materials suitable for use in the polymeric substrate layer include polymethylmethacrylate, polycarbonate, polyamides, polyimide, polyesters (PET, PEN), polycyclic olefin polymers, and thermoplastic polyurethanes.
  • the optional one or more barrier layers may include a transparent barrier layer.
  • the transparent barrier layer may be disposed on the nanocomposite layer.
  • the transparent barrier layer can mitigate or slow ingress of oxygen or water through the display film.
  • Transparent barrier layers may include for example, thin alternating layers of silica, alumina or zirconia together with an organic resin. Exemplary transparent barrier layers are described in US7,980,910 and W02003/094256.
  • Optional additional layers may include a microstructure layer, an anti-glare layer, anti- reflective layer, or an anti-fingerprint layer. Additional optional layers may be disposed in the interior of the display film.
  • One useful additional layer disposed within the display film is a sparkle reduction layer as described in WO2015/191949.
  • the sparkle reduction layer may be particularly useful with high definition displays that include anti -glare coatings.
  • the overall thickness of the display film described herein may have any useful value depending on the application.
  • the thickness of the display film is a balance between being thick enough to provide the desired display protection and thin enough to provide the level of flexibility desired for the device application and reduced thickness to meet desired design parameters.
  • the level of flexibility desired is a display film having a bend radius of 40mm or less, 20mm or less, 10mm or less, 7mm, or less, 5 mm or less, or 4 mm or less, or 3 mm or less or in a range from 1 to 20 mm, a range from 1 to 10mm, a range from 1 to 7mm, or a range of from 1 to 5mm.
  • the overall thickness of the multilayer film may be in a range from 30 to 300 micrometers, or from 40 to 200 micrometers, or from 40 to 150 micrometers.
  • the display film folds upon itself it may have a total thickness in a range from 30 to 200 micrometers or from 40 to 150 micrometers.
  • the display film moderately flexes it may have total thickness in a range from 300 to 500 micrometers.
  • the display film is curved but does not appreciably flex, it may have total thickness in a range from 500 to 1000 micrometers.
  • the multilayer films described herein may have a haze value of 4% or less, 3% or less, 2% or less, or 1.5% or less, or 1% or less, or 0.5% or less. In some embodiments, the multilayer film may have a haze value of 5% or less.
  • the multilayer film may have a clarity of 95% or greater, 97% or greater, 98% or greater, or 99% or greater.
  • the multilayer film may have a visible light transmission of 85% or greater, or 90% or greater, or 93% or greater.
  • the multilayer film may have a yellow index or b* value of 5 or less, or 4 or less, or 3 or less, or 2 or less, or 1 or less. In some embodiments, the multilayer film may have a yellow index or b* value of 2 or less.
  • the nanocomposite layer 110 includes at least one polymer and metal oxide nanoparticles dispersed in the at least one polymer. This layer may have an average thickness in a range of 5- 125 microns, 5-70 microns, or 5-50 microns. In some exemplary cases, the thickness is in the range of 5-30 microns.
  • the nanocomposite layer may be capable of stretching within an elastic range, so that permanent deformation does not occur.
  • the proportional limit for a material is defined as the maximum stress at which the stress is proportional to strain (Hooke's law).
  • the elastic limit is the minimum stress at which permanent deformation can be measured.
  • the nanocomposite layer may have a strain at the elastic limit that is 10% greater than the strain at the proportional limit, 20% greater than the strain at the proportional limit, 50% greater than the strain at the proportional limit, or 100% greater than the strain at the proportional limit.
  • the graph shown in FIG. 5 illustrates this concept.
  • compositions suitable for use in the nanocomposite layer 110 are nanocomposites that include at least one (meth)acrylic polymer (e.g., one (meth)acrylic polymer or two or more miscible (meth)acrylic polymers) and surface-modified metal oxide nanoparticles, where the surface-modified metal oxide nanoparticles are surface modified with an acid-functional silane surface modifying agent, and where the (meth)acrylic polymer(s) are at least partially neutralized.
  • the nanocomposites may be melt processable into films that are optically transparent. By melt processable it is meant that the nanocomposites are able to be melt processed, that is to say that the nanocomposites can be heated and made to flow without causing degradation.
  • Nanocomposite does not mean that the nanocomposite has been melt processed and in no way indicates a processing step.
  • the nanocomposites may also be made by coating processes from aqueous dispersions on to a substrate such that the film can be removed from the substrate or transferred to another layer like polyurethane layer 120
  • the (meth)acrylic polymer(s) include (meth)acrylic acid monomers units (i.e., acrylic acid monomer units, methacrylic acid monomer units, or both acrylic acid monomer units and methacrylic acid monomer units).
  • the (meth)acrylic polymers are homopolymers of acrylic acid or methacrylic acid.
  • the (meth)acrylic polymers are copolymers of at least one (meth)acrylic monomer unit that is acid-functional and at least one monomer that is a (meth)acrylate that is not acid-functional.
  • the (meth)acrylic polymers can contain other non-(meth)acrylate monomers that are co-polymerizable with the (meth)acrylic and (meth)acrylate monomers.
  • the copolymers can be formed by the polymerization or copolymerization using free radical polymerization techniques.
  • the at least one (meth)acrylic polymer includes a copolymer containing (meth)acrylic acid and at least one co-monomer.
  • co-monomers include ethylene, propylene, alkyl(meth)acrylates, aryl(meth)acrylates, alkaryl(meth)acrylates, acrylonitrile, and carbon monoxide.
  • a nanocomposite includes at least one polymer and metal oxide nanoparticles dispersed in the at least one polymer of the nanocomposite.
  • Each polymer can have a number average molecular weight of at least 10000 grams/mole.
  • the at least one polymer of the nanocomposite includes a first polymer including (meth)acrylic acid monomer units (monomer units selected from the group consisting of methacrylic acid monomer units and acrylic acid monomer units).
  • the metal oxide nanoparticles are surface modified with a surface modifying agent including a carboxylic acid silane of Formula 1 described elsewhere herein.
  • the first polymer has a number average molecular weight of at least 12000 grams/mole or at least 15000 grams/mole.
  • each polymer of the at least one polymer has a number average molecular weight of at least 12000 grams/mole or at least 15000 grams/mole.
  • the at least one polymer can be a blend of first and second polymers, and each of the first and second polymers can have a number average molecular weight of at least 12000 grams/mole or at least 15000 grams/mole.
  • the number average molecular mass of a polymer can be determined by gel permeation chromatography (GPC). Polymer characterization by GPC systems is well known.
  • the Viscotek TDAmax (Malvern Panalytical, a part of Spectris pic). This system is equipped with multiple detectors for determination of molecular weight. Absolute molecular weight of small polymers can be measured using a right angle light scattering detector, direct output of absolute molecular weight of polymers without extrapolation can be obtained using low angle light scattering. Additional detectors can be used to assess information concerning polymer structure, for example branching using intrinsic viscosity detector and information concerning copolymer composition can be investigated using a photodiode array UV detector when UV absorbing components are present. Further details of this instrument can be found from the supplier. In some embodiments, the first polymer, or each polymer of the at least one polymer, has a number average molecular weight less than 100,000 grams/mole.
  • the first polymer further includes at least one monomer unit (e.g., a second type of monomer unit when the (meth)acrylic acid monomer units are a first type of monomer unit) selected from the group consisting of ethylene, propylene, alkyl(meth)acrylates, aryl(meth)acrylates, alkaryl(meth)acrylates, acrylonitrile, and carbon monoxide.
  • the first polymer includes at least one monomer unit (e.g., a second type of monomer unit) selected from the group consisting of ethylene and propylene.
  • the first polymer further includes at least one monomer unit (e.g., a third type of monomer unit) selected from the group consisting of n-butyl acrylate, isobutyl acrylate, isopropyl acrylate, n-propyl acrylate, ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, iso-octyl acrylate and methyl methacrylate.
  • the first polymer can be aterpolymer, for example.
  • the first polymer includes (meth)acrylic acid monomer units; ethylene monomer units, propylene monomer units, or a combination of ethylene and propylene monomer units; and at least one alkyl (meth)acrylate monomer unit.
  • the at least one polymer can be a blend of two or more (meth)acrylic polymers.
  • a wide range of blends of (meth)acrylic polymers are suitable.
  • suitable blends include blends of acrylic acid or methacrylic acid homopolymers with copolymers of acrylic acid or methacrylic acid and at least one additional monomer (e.g., selected from the group consisting of ethylene, propylene, alkyl(meth)acrylates, aryl(meth)acrylates, alkaryl(meth)acrylates, acrylonitrile, and carbon monoxide).
  • blends of acrylic acid or methacrylic acid homopolymers with copolymers of acrylic acid or methacrylic acid and at least two additional monomers include blends of acrylic acid or methacrylic acid homopolymers with copolymers of acrylic acid or methacrylic acid and at least two additional monomers (e.g., the copolymer can be aterpolymer).
  • the blends include a copolymer of acrylic acid or methacrylic acid and at least one additional monomer with a different copolymer of acrylic acid or methacrylic acid and at least one additional monomer.
  • blends of a copolymer of acrylic acid or methacrylic acid and at least one additional monomer with a copolymer of acrylic acid or methacrylic acid and at least two additional monomers can also include different copolymers of acrylic acid or methacrylic acid and at least two additional monomers.
  • the at least one polymer includes a second polymer different from the first polymer.
  • the first and second polymers can be different by virtue of having different molecular weights, different acid content, different neutralization percent, different amounts of the same monomer units, and/or by being compositionally distinct, for example.
  • the second polymer is compositionally distinct from the first polymer. Compositionally distinct in this context can be understood to mean that at least one of the first and second polymers has a least one type of monomer unit not present in the other of the first and second polymers.
  • the first polymer can include two different monomer units (e.g., (meth)acrylic acid and either ethylene or propylene) and the second polymer can include a different third monomer unit (e.g., n-butyl acrylate or isobutyl acrylate) in addition to the two monomer units of the first polymer.
  • Compositionally distinct includes different acid types (e.g., methacrylic acid monomer units versus acrylic acid monomer units) and different ion types (an ion at least partially neutralizing an ionomer can be considered to be part of the ionomer), for example.
  • the second polymer can have a number average molecular weight of at least 10000 grams/mole, or at least 12000 grams/mole, or at least 15000 grams/mole.
  • the second polymer includes (meth)acrylic acid monomer units.
  • the second polymer includes at least one monomer unit selected from the group consisting of ethylene, propylene, alkyl(meth)acrylates, aryl(meth)acrylates, alkaryl(meth)acrylates, acrylonitrile, and carbon monoxide.
  • the second polymer includes at least one monomer unit selected from the group consisting of ethylene and propylene.
  • the second polymer further includes at least one monomer unit selected from the group consisting of n-butyl acrylate, isobutyl acrylate, isopropyl acrylate, n- propyl acrylate, ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, iso-octyl acrylate and methyl methacrylate.
  • the second polymer includes (meth)acrylic acid monomer units; ethylene monomer units, propylene monomer units, or a combination of ethylene and propylene monomer units; and at least one alkyl (meth)acrylate monomer unit.
  • the content of (meth)acrylic acid monomer units in the first polymer, and optionally in the second polymer is greater than 12 weight percent. This has been found to help in dispersing the first polymer, and optionally the second polymer, in water. In some embodiments, the content of (meth)acrylic acid monomer units in the first and the second polymers is similar. This has been found to help the compatibility of the polymers and to improve optical properties, for example.
  • the first polymer includes (meth)acrylic acid monomer units at a first weight percent wl
  • the second polymer includes (meth)acrylic monomer units at a second weight percent w2.
  • At least one of wl and w2 is greater than 12 weight percent, or greater than 13 weight percent, or greater than 14 weight percent, or greater than 15 weight percent. In some embodiments, at least one of wl and w2 is less than 50 weight percent, or less than 30 weight percent, or less than 25 weight percent. In some such embodiments, or in other embodiments,
  • the nanocomposite is formed from an aqueous dispersion including the first and second polymers as described further elsewhere herein.
  • each of wl and w2 is greater than 12 weight percent, or greater than 13 weight percent, or greater than 14 weight percent, or greater than 15 weight percent.
  • is less than 10 weight percent, or less than 9 weight percent, or less than 8 weight percent, or less than 7 weight percent, or less than 6 weight percent.
  • is in a range of 0 to 10 weight percent or in a range of 0 to about 9 weight percent (e.g., 8.8 or 9 or 9.2 weight percent can be considered to be about 9 weight percent).
  • each of the two polymers in dispersion includes two monomer units (e.g., a (meth)acrylic acid monomer unit and a second monomer unit such as ethylene or propylene)
  • the acid content of either the first polymer (wl) or second polymer (w2) may be in a range greater than 27 weight percent, for example.
  • may be up to 15 weight percent, for example.
  • a first nanocomposite, or a first concentrated aqueous dispersion, that includes the first polymer is melt processed with the second polymer (also referred to as an additional polymer) to form a nanocomposite (e.g., a second nanocomposite) that includes both the first and second polymers.
  • the second polymer is not dispersible in water with or without a neutralizing agent.
  • w2 can be less than 12 weight percent and/or
  • wl is greater than 12 weight percent, or greater than 13 weight percent, or greater than 14 weight percent, or greater than 15 weight percent; or in a range of 13 to 50 weight percent, or 13 to 35 weight percent, or 13 to 27 weight percent, or 14 to 22 weight percent, or 15 to 21.5 weight percent, or 15 to 21 weight percent, or 15 to 20.5 weight percent.
  • w2 is at least 10 weight percent; or in a range of 10 weight percent to 25 weight percent, or to 21.5 weight percent, to 21 weight percent, or to 20.5 weight percent; or w2 can be in any range described for wl .
  • wl is in a range of 15 to 20.5 weight percent and w2 is in a range of 10 to 20.5 weight percent or 15 to 20.5 weight percent. In some embodiments, at least one of wl and w2 is in a range of 14 to 22 weight percent or in a range of 15 to 21.5 weight percent.
  • the first polymer includes (meth)acrylic acid monomer units at a weight percent wl and further includes ethylene monomer units
  • the second polymer includes (meth)acrylic acid monomer units at a weight percent wl and further includes ethylene monomer units.
  • wl is greater than 15 weight percent
  • is less than 10 weight percent.
  • the first polymer includes (meth)acrylic acid monomer units at a weight percent wl and further includes ethylene monomer units
  • the second polymer includes (meth)acrylic acid monomer units at a weight percent wl, and further includes ethylene monomer units, and further includes at least one monomer unit selected from the group consisting of n-butyl acrylate, isobutyl acrylate, isopropyl acrylate, n-propyl acrylate, ethyl acrylate, methyl acrylate, 2- ethylhexyl acrylate, iso-octyl acrylate and methyl methacrylate.
  • wl is greater than 15 weight percent
  • is less than 15 weight percent, or less than 13 weight percent, or less than 12 weight percent.
  • the first polymer is at least partially neutralized.
  • the first polymer includes a carboxylic acid group where the proton of the carboxylic acid group is replaced by a cation, such as a metal cation.
  • a cation such as a metal cation.
  • Monovalent, divalent, and higher valency cations are suitable.
  • the first polymer is at least partially neutralized with metal cations, alkylammonium cations, or a combination thereof.
  • the first polymer is at least partially neutralized with sodium cations, calcium cations, potassium cations, zinc cations, lithium cations, magnesium cations, aluminum cations, or a combination thereof.
  • the first polymer is at least partially neutralized with nonmetallic cations.
  • the first polymer can be at least partially neutralized with alkylammonium cations.
  • the nanocomposite is formed from an aqueous dispersion as described further elsewhere herein.
  • the first polymer in the aqueous dispersion, is at least partially neutralized with at least one nonvolatile neutralizing agent, or at least one volatile neutralizing agent, or a combination of volatile and nonvolatile neutralizing agents.
  • the first polymer in the aqueous dispersion, is at least partially neutralized with nonvolatile amine cations, volatile amine cations (e.g., cations of dimethylethanolamine or ammonium cations), or a combination of volatile and nonvolatile amine cations.
  • volatile amine cations e.g., cations of dimethylethanolamine or ammonium cations
  • the first polymer can be at least partially neutralized with a combination of different types of cations (e.g., metallic and nonmetallic cations or any combinations of cations describe herein).
  • the first polymer can be an at least partially neutralized ionomer prior to being dispersed in the aqueous dispersion.
  • the ionomer is sufficiently neutralized that no additional neutralizing agents need to be added to the aqueous dispersion. In other embodiments, the ionomer is further at least partially neutralized by additional neutralizing agents added to the aqueous dispersion as described further elsewhere herein.
  • the second polymer is at least partially neutralized.
  • each polymer of the at least one polymer, or each polymer including (meth)acrylic acid monomer units is at least partially neutralized.
  • the second polymer, or other polymers of the at least one polymer can be at least partially neutralized with any cation or combination of cations described for the first polymer.
  • Suitable ethylene (meth)acrylic acid copolymers can be obtained from commercial sources such as PRIMACOR 5980i from SK Global Chemical Co. Ltd. (Seoul, South Korea) , NUCREL 925 and 960 from Dow Chemical Co. (Midland, MI), ESCOR 5200 from Exxon-Mobil (Irving, TX), and AC-5180 from Honeywell (Morris Plains, NJ), for example.
  • Suitable partially neutralized ethylene (meth)acrylic acid copolymers can be obtained from commercial sources such as, for example, SURLYN 1601, 1706, 1707, 7940, 9020, 9120, 8150 and PC-350, and HPF 1000 from Dow Chemical Co. (Midland, MI), for example.
  • metal oxide nanoparticles are suitable.
  • suitable metal oxide nanoparticles include metal oxides of silicon (silicon is considered to be a metalloid and thus is included in the list of metal oxides), titanium, aluminum, hafnium, zinc, tin, cerium, yttrium, indium, antimony or mixed metal oxides thereof.
  • the more desirable metal oxide nanoparticles are those of silicon.
  • the metal oxide nanoparticles can be silica (S1O2) nanoparticles or SiOx (0 ⁇ x ⁇ 2) nanoparticles.
  • the size of such particles can be chosen to avoid significant visible light scattering.
  • the surface-modified metal oxide nanoparticles can be particles having a (e.g. unassociated) primary particle size or associated particle size of greater than 1 nm (nanometers) and less than 200 nm. In some embodiments, the particle size is greater than 4 nm, greater than 5 nm, greater than 10 nm, or greater than 20 nm. In some embodiments, the particle size is less than 190 nm, less than 150 nm, less than 100 nm, less than 75 nm, or less than 50 nm.
  • the nanoparticles have a size ranging from 4-190 nm, 4-100 nm, 4-75 nm, 10-50 nm, or 20-50 nm. In embodiments where a low optical haze is desired, a particle size of less than 100 nm, less than 75 nm, or less than 50 nm is typically preferred. It is typically desirable that the nanoparticles are unassociated. Particle size can be measured in a wide variety of ways such as by transmission electron microscopy (TEM). Typically, commercially obtained metal oxide nanoparticles are supplied with a listed particle size or particle size range.
  • TEM transmission electron microscopy
  • the nanoparticles are surface modified to improve compatibility with the polymer matrix material and to keep the nanoparticles non-associated, non-agglomerated, non-aggregated, or a combination thereof.
  • the surface modification used to generate the surface-modified nanoparticles includes at least one acid-functional silane surface modifying agent.
  • the acid- fimctional silane surface modifying agent can have the general Formula 1 :
  • R1 is a Ci to C 10 alkoxy group
  • R2 and R3 are independently selected from the group consisting of Ci to C 10 alkyl and Ci to C 10 alkoxy groups.
  • the group A is a linker group selected from the group consisting of Ci to C 10 alkylene or arylene groups, Ci to C 10 aralkylene groups, C2 to Ci 6 heteroalkylene or heteroarylene groups, and C2 to Ci 6 amide containing groups.
  • A is an alkylene group with 1-3 carbon atoms.
  • acid-functional silanes may be commercially available
  • one aspect of the current disclosure includes the synthesis of the carboxylic acid-functional silanes of Formula 1.
  • an anhydride -functional silane such as (3- triethoxysilyl)propylsuccinic anhydride, which can be obtained from commercial sources such as Gelest, Inc. (Morrisville, PA), could be used to prepare the acid-functional silane surface modification agent.
  • a solution is prepared of an organic acid anhydride dissolved in a first organic solvent.
  • a second solution is prepared of an aminosilane in a second organic solvent. The two solutions are combined. The combined solution is stirred continuously at a suitable temperature and duration to synthesize a carboxylic acid-functional silane of Formula 1.
  • a solution is prepared of an organic acid anhydride dissolved in an organic solvent.
  • An aminosilane is dissolved in the organic acid anhydride solution.
  • the solution containing the organic acid anhydride and aminosilane is stirred continuously at a suitable temperature and duration to synthesize a carboxylic acid silane of Formula 1.
  • the first and second organic solvents may be the same or different. In the case where the first and second organic solvent are different, then the first and second organic solvents are miscible. Both first and second organic solvents are miscible with water.
  • Suitable organic acid anhydrides include succinic anhydride (3,4-dihdrofuran-2,5-dione), tetrahydrofuran-2,5-dione, 3-alkyltetrahydrofuran-2,5-diones such as 3-methyltetrahydrofuran-2,5- dione and 3-ethyltetrahydrofuran-2,5-dione, tetrahydropyran-2,6-dione, 3-alkyltetrahydropyran- 2,6-diones such as 3-methyltetrahydropyran-2,6-dione and 3-ethyltetrahydropyran-2,6-dione 4- alkyltetrahydropyran-2,6-diones such as 4-methyltetrahydropyran-2,6-dione, 4- ethyltetrahydropyran-2,6-dione, and 4,4’-methyltetrahydropyran-2,
  • Suitable aminosilanes include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, N- phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, n- butylaminopropyltrimethoxysilane, n-butylaminopropyltriethoxysilane, 3-(N- allylamino)propyltrimethoxysilane, (N,N-diethyl-3-aminopropyl)trimethoxysilane, and (N,N- diethyl-3 -aminopropyltriethoxysilane.
  • Suitable aminosilanes can be obtained from commercial sources such as Gelest, Inc. (Morrisville, PA), Alfa Aesar (Ward Hill, MA), Millipore Sigma (Burlington, MA), and Momentive Performance Materials (Waterford, NY).
  • a particularly suitable aminosilane is aminopropyltrimethoxysilane.
  • organic solvents can be used. Suitable organic solvents include N,N- dimethylformamide (DMF) which can be obtained from commercial sources such as OmniSolv (Billerica, MA).
  • DMF N,N- dimethylformamide
  • the surface -modified metal oxide nanoparticles are prepared by combining an aqueous nanodispersion of surface unmodified metal oxide nanoparticles of basic pH and a carboxylic acid-functional silane surface modifying agent, reacting the carboxylic acid- functional silane surface agent with the metal oxide nanoparticle surface resulting in an aqueous nanodispersion of surface-modified metal oxide nanoparticles where the nanoparticles are surface modified with a carboxylic acid.
  • an aqueous nanodispersion of surface unmodified metal oxide nanoparticles is combined with a solution of a carboxylic acid silane of Formula 1 in an organic solvent.
  • an aqueous nanodispersion of surface unmodified metal oxide nanoparticles is combined with a base and a solution of a carboxylic acid silane of Formula 1 in an organic solvent.
  • an aqueous nanodispersion of surface unmodified metal oxide nanoparticles is combined with a carboxylic acid silane of Formula 1.
  • the carboxylic acid silane of Formula 1 is added at a concentration sufficient to modify 10 to 100% of the total metal oxide nanoparticle surface area in the nanodispersion.
  • the metal oxide nanoparticles may have a variety of sizes. Typically, the average particle size is greater than 1 nm and less than 200 nm.
  • the particle size is greater than 4 nm, greater than 5 nm, greater than 10 nm, or greater than 20 nm. In some embodiments, the particle size is less than 190 nm, less than 150 nm, less than 100 nm, less than 75 nm, or less than 50 nm. Typically, the nanoparticles have a size ranging from 4-190 nm, 4-100 nm, 4-75 nm, 10-50 nm, or 20-50 nm.
  • typical preferred ranges are from 4-100 nm, 4-75 nm, or 4-50 nm.
  • a base may be added to the aqueous nanodispersion of surface unmodified metal oxide nanoparticles to maintain the pH in the desired range since the addition of the carboxylic acid silane solution of Formula 1 will tend to lower pH.
  • the organic solvent is removed from of the solution of carboxylic acid silane in organic solvent prior to combining the carboxylic acid silane and aqueous nanodispersion of surface unmodified metal oxide nanoparticles.
  • Aqueous nanodispersions of unmodified metal oxide nanoparticles may be prepared or, in some embodiments, aqueous nanodispersions of unmodified metal oxide nanoparticles may be obtained commercially.
  • Suitable surface unmodified metal oxide nanoparticles include aqueous nanodispersions commercially available from Nalco Chemical Company (Naperville, IL) under the trade designation “Nalco Colloidal Silicas” such as products NALCO 2326, 1130, DVSZN002, 1142, 2327, 1050, DVSZN004, 1060, and 2329K; from Nissan Chemical America Corporation (Houston, TX) under the tradename SNOWTEX such as products ST-NXS, ST-XS, ST-S, ST-30, ST-40, ST-N40, ST-50, ST-XL, and ST-YL; from Nyacol Nano Technologies, Inc.
  • the surface unmodified metal oxide nanoparticles may be dispersed in an aqueous solution with a pH in the range 8-12.
  • Suitable bases include ammonium hydroxide which can be obtained from commercial sources such as Millipore Sigma (Burlington, MA).
  • the surface-modified metal oxide nanoparticles are used as a nanodispersion, and the particles are not isolated.
  • Another aspect of the present disclosure involves the preparation of nanodispersions of surface-modified metal oxide nanoparticles without precipitation, gelation, agglomeration, or aggregation, where the metal oxide nanoparticles are surface modified with a carboxylic acid silane of Formula 1.
  • an aqueous nanodispersion of surface unmodified metal oxide nanoparticles and solution of a carboxylic acid silane of Formula 1 in an organic solvent are combined in a reactor and heated at a suitable temperature and duration to react the carboxylic acid silane of Formula 1 with the surface of the metal oxide nanoparticles.
  • an aqueous nanodispersion of surface-unmodified metal oxide nanoparticles, base, and a solution of carboxylic acid silane of Formula 1 in an organic solvent are combined in a reactor and heated at a suitable temperature and duration to react the carboxylic acid silane of Formula 1 with the surface of the metal oxide nanoparticles.
  • a solvent exchange is performed on the aqueous nanodispersion of surface-modified metal oxide nanoparticles and organic solvent to remove the organic solvent.
  • the reactor is open, under reflux conditions, and in other embodiments the reactor is closed and under pressure.
  • the reactor is glass and in some embodiments the reactor is stainless steel.
  • the nanocomposite includes at least 1% by weight of surface-modified metal oxide nanoparticles and no more than 70% by weight of surface -modified metal oxide nanoparticles.
  • the surface -modified metal oxide nanoparticle concentration is from 5-60% by weight, or from 10-50% by weight.
  • Additional additives may include flame retardants, thermal stabilizers, anti-slip agents, neutralizing agents, UV absorbers, light stabilizers, antioxidants, crosslinking agents, mold release agents, catalysts, colorants, anti-stat agents, defoamers, plasticizers, and other processing aids, for example.
  • An aqueous dispersion can be used in forming the nanocomposite or ionomer layers without nanoparticles.
  • an aqueous dispersion includes water; at least one polymer dispersed in the water; and metal oxide nanoparticles dispersed in the water.
  • the at least one polymer includes a first polymer including (meth)acrylic acid monomer units and optionally having a number average molecular weight of at least 10000 grams/mole.
  • the first polymer is at least partially neutralized.
  • the metal oxide nanoparticles are surface modified with a carboxylic acid silane surface modifying agent.
  • the carboxylic acid silane surface modifying agent can be or include a carboxylic acid silane of Formula 1, described elsewhere herein.
  • the metal oxide nanoparticles can optionally be omitted when an ionomer layer not including nanoparticles is desired.
  • the additional layer 115 can be an elastic ionomer of one polymer, an elastic ionomer blend of two or more polymer or an elastic ionomer nanocomposite including metal oxide nanoparticles in one elastic ionomer polymer or two or more elastic ionomer polymers layer.
  • the layer 115 may include a multilayer structure (not shown in figures) with different elastic ionomer and/or elastic ionomer nanocomposite layers.
  • the layer 115 may have a thickness in a range of 5-125 microns, 5-70 microns, 5-50 microns, or 5-30 microns.
  • the additional layer 115 is preferably capable of stretching within an elastic range, so that permanent deformation does not occur.
  • the proportional limit for a material is defined as the maximum stress at which the stress is proportional to strain (Hooke's law).
  • the elastic limit is the minimum stress at which permanent deformation can be measured.
  • the additional layer 115 may have a strain at the elastic limit that is 10% greater than the strain at the proportional limit, 20% greater than the strain at the proportional limit, 50% greater than the strain at the proportional limit, or 100% greater than the strain at the proportional limit. Again, the graph shown in FIG. 5 illustrates this concept.
  • compositions suitable for use in additional layer 115 include those that include at least one (meth)acrylic polymer (e.g., one (meth)acrylic polymer or two or more miscible (meth)acrylic polymers) and may optionally include surface-modified metal oxide nanoparticles, where the surface-modified metal oxide nanoparticles are surface modified with an acid-functional silane surface modifying agent, and where the (meth)acrylic polymer(s) are at least partially neutralized.
  • the elastic ionomers may be melt processable into films that are optically transparent. By melt processable it is meant that the elastic ionomers are able to be melt processed, that is to say that the polymer or polymer nanocomposite can be heated and made to flow without causing degradation.
  • the elastic ionomers may also be made by coating processes from aqueous dispersions on to a substrate such that the fdm can be removed from the substrate or transferred to another layer like polyurethane layer 120.
  • the (meth)acrylic polymer(s) include (meth)acrylic acid monomers units (i.e., acrylic acid monomer units, methacrylic acid monomer units, or both acrylic acid monomer units and methacrylic acid monomer units).
  • the (meth)acrylic polymers are homopolymers of acrylic acid or methacrylic acid.
  • the (meth)acrylic polymers are copolymers of at least one (meth)acrylic monomer unit that is acid-functional and at least one monomer that is a (meth)acrylate that is not acid-functional.
  • the (meth)acrylic polymers can contain other non-(meth)acrylate monomers that are co-polymerizable with the (meth)acrylic and (meth)acrylate monomers.
  • the copolymers can be formed by the polymerization or copolymerization using free radical polymerization techniques.
  • the at least one (meth)acrylic polymer includes a copolymer containing (meth)acrylic acid and at least one co monomer.
  • co-monomers are suitable. Suitable co-monomers include ethylene, propylene, alkyl(meth)acrylates, aryl(meth)acrylates, alkaryl(meth)acrylates, acrylonitrile, and carbon monoxide.
  • suitable compositions for layer 115 are detailed in the description of layer 110, and further supported by the experimental examples.
  • the aliphatic cross-linked polyurethane layer 120 may have a glass transition temperature of 27 degrees Celsius or less, or less than 20 degrees Celsius, or less than 10 degrees Celsius, or less than 5 degrees Celsius.
  • the polyurethane layer may have a low glass transition temperature, such as 5 degrees Celsius less, or zero degrees Celsius or less, or -5 degrees Celsius or less, or -10 degrees Celsius or less, or in a range from -80 to 5 degrees Celsius, or in a range from -40 to 5 degrees Celsius, or in a range from -30 to 5 degrees Celsius, or in a range from -20 to 5 degrees Celsius, or in a range from -15 to 5 degrees Celsius, or in a range from -10 to 5 degrees Celsius, or in a range from -5 to 5 degrees Celsius.
  • the aliphatic cross-linked polyurethane layer may have a Tan Delta peak value of 0.5 or greater, or 0.8 or greater, or 1.0 or greater, or 1.2 or greater, or 1.4 or greater, or from 0.5 to 2.5, or from 1 to 2.5, or from 1 to 2.
  • the polyurethane layer or layers have a Young’s Modulus (E') greater than 0.9MPa over the temperature range -40 degrees Celsius to 70 degrees Celsius.
  • the polyurethane layer would not be referred to as a pressure sensitive adhesive.
  • the aliphatic cross-linked polyurethane layer may be formed of a plurality of layers, and at least two of these layers having a different glass transition temperature value. These layers may have a different glass transition temperature value by at least 2 degrees Celsius, or at least 5 degrees Celsius, or at least 10 degrees Celsius, for example. In some cases, each polyurethane layer peak Tan Delta values may occur at different frequencies at a specified temperature.
  • the aliphatic cross-linked polyurethane layer may have a thickness of at least 20 micrometers, or at least 30 micrometers, or at least 50 micrometers.
  • the aliphatic cross-linked polyurethane layer may have a thickness in a range from 20 to 200 micrometers, or 50 to 150 micrometers, or from 75 to 150 micrometers.
  • the thickness of the polyurethane layer may be a balance between being thick enough to provide the desired protection to the display and thin enough to provide the dynamic performance requirements and/or reduced thickness for industrial design considerations.
  • the aliphatic cross-linked polyurethane layer may be a cross-linked polymer layer formed of a cross-linked polyurethane material or a cross-linked polyurethane acrylate material.
  • the polyurethane layer may be designed to have beneficial properties with respect to impact resistance and the ability to survive dynamic folding at low temperature conditions, for example.
  • a cross-linked polyurethane layer preferably includes chemically or covalently crosslinked materials derived from step growth polymerization of isocyanate and polyol oligomers. Selection of reactant isocyanates and polyols may modify the glass transition temperature of the resulting cured polyurethane.
  • the cross-linked polyurethane layer may be coated onto the transparent polymeric or glass substrate layer (that may be primed) and then be cured or cross-linked to form a thermoset polyurethane layer.
  • the cross-linked polyurethane layer could be produced as a film that is then laminated to the transparent glass layer in a subsequent process step. Such lamination could be assisted with heat, vacuum, or through the use of an adhesive or combination thereof.
  • Polyurethane is a polymer composed of organic units joined by carbamate (urethane) links.
  • the polyurethanes described herein are thermosetting polymers that do not melt when heated.
  • Polyurethane polymers may be formed by reacting a di- or polyisocyanate with a polyol. Both the isocyanates and polyols used to make polyurethanes contain on average two or more functional groups per molecule.
  • the polyurethanes described herein may be derived from components that have functionality greater than 2.4 or 2.5.
  • the isocyanate and polyol components can be mixed just prior to application of the material to the substrate used for making the display film.
  • the average functionality of the isocyanates used to make the transparent aliphatic cross-linked polyurethane layer is less than 3.5 (i.e. an average of 3.5 isocyanate functional groups per molecule) or 3 or less.
  • the ideal cured material exhibits stable material properties with respect to the display film use in application.
  • the polyurethane layer preferably does not exhibit appreciable flow but is stable enough to provide durability in physical testing in folding devices, for example low temperature dynamic folding performance.
  • the aliphatic cross-linked polyurethane layer may also contain inorganic nanoparticles, either functional that are chemically reacted to the matrix or non-functional that are not reacted to the polyurethane matrix resin.
  • the incorporation of nanoparticles may provide beneficial properties related to impact resistance and energy dissipation from impact events.
  • polyisocyanates may be used to from the cross-linked polyurethane layer.
  • the term polyisocyanate includes isocyanate-functional materials that generally include at least 2 terminal isocyanate groups.
  • Polyisocyanates include diisocyanates (materials with 2 terminal isocyanate groups) and higher polyisocyanates such as triisocyanates (materials with 3 terminal isocyanate groups), tetraisocyanates (materials with 4 terminal isocyanate groups), and the like.
  • the reaction mixture contains at least one higher isocyanate if a difunctional polyol is used. Higher isocyanates are particularly useful for forming crosslinked polyurethane polymers.
  • Diisocyanates may be generally described by the structure OCN — Z — NCO, where the Z group may be an aliphatic group, an aromatic group, or a group containing a combination of aromatic and aliphatic groups.
  • an aliphatic isocyanate such as isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4’-diisocyanate (H12MDI), dimeryl diisocyanate (DDI), pentamethylenediisocyanate (PDI), hexamethylenedisocyanate (HDI), and oligomers, derivatives, or combinations of these isocyanates.
  • IPDI isophorone diisocyanate
  • H12MDI dicyclohexylmethane-4,4’-diisocyanate
  • DDI dimeryl diisocyanate
  • PDI pentamethylenediisocyanate
  • HDI hexamethylenedisocyanate
  • Triisocyanates include, but are not limited to, polyfunctional isocyanates, such as those produced from isocyanurates, biurets, allophanates, uretdiones, iminooxadiazinediones, carbodiimides, uretoneimines adducts, and the like.
  • polyfunctional isocyanates such as those produced from isocyanurates, biurets, allophanates, uretdiones, iminooxadiazinediones, carbodiimides, uretoneimines adducts, and the like.
  • Some commercially available polyisocyanates include portions of the DESMODUR and MONDUR series from Bayer Corporation, Pittsburgh, Pa., and the PAPI series from Dow Plastics, a business group of the Dow Chemical Company, Midland, Mich.
  • isocyanates based on HDI are preferred to provide a glass transition temperature below 10 °C.
  • Monomeric HDI can be used, but in some embodiments, it is preferred to use oligomers of HDI. Oligomeric HDI can reduce the vapor pressure of the isocyanate to allow safer handling and may provide functionalities greater than 2.0 to provide chemical crosslinking of the polyurethane layer material.
  • the HDI oligomers can contain functional groups including isocyanurates, biurets, allophanates, uretdiones, iminooxadiazinediones, carbodiimides, or uretoneimines.
  • prepolymers derived from HDI and polyols can be used.
  • HDI oligomers containing uretdione functionality and isocyanurate functionality are preferred.
  • Particularly useful higher isocyanates include those available from Bayer Corporation under the trade designations DESMODURN3300A, Desmodur N3400, and MONDUR 489.
  • An oligomer containing both uretdione and isocyanurate groups can be obtained under the trade name DESMODUR N3400, and an oligomer containing isocyanurate groups can be obtained under the tradename DESMODUR N3300.
  • DESMODUR N3300A is particularly suitable aliphatic polyisocyanate.
  • polyols may be used to form the cross-linked polyurethane layer.
  • the term polyol includes hydroxyl-functional materials that generally include at least 2 terminal hydroxyl groups.
  • Polyols include diols (materials with 2 terminal hydroxyl groups) and higher polyols such as triols (materials with 3 terminal hydroxyl groups), tetraols (materials with 4 terminal hydroxyl groups), and the like.
  • the reaction mixture contains at least some diol and may also contain higher polyols. Higher polyols are particularly useful for forming crosslinked polyurethane polymers.
  • Diols may be generally described by the structure HO — B — OH, where the B group may be an aliphatic group, an aromatic group, or a group containing a combination of aromatic and aliphatic groups, and the B group may contain a variety of linkages or functional groups, including additional terminal hydroxyl groups.
  • the polyol is an oligomeric polyether such as polyethylene glycol, polypropylene glycol, or polytetramethylene ether glycol.
  • aliphatic polyester polyols are particularly useful.
  • Useful polyester polyols are linear and non-linear polyester polyols including, for example, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polycyclohexanedimethyl adipate, polydiethylene glycol adipate, polybutylene succinate, polyhexamethylene sebacate, polyhexamethylene dodecanedioate, and poly e-caprolactone and copolymers of these polyesters.
  • polyester polyols available from King Industries, Norwalk, Conn., under the trade name “K-FLEX” such as K-FLEX 188 or K- FLEX A308.
  • the polyester polyol can include polyesters derived from cyclohexanedimethanol and aliphatic diacids.
  • polyester polyols that are liquids at room temperature to facilitate mixing and coating at ambient temperature.
  • polyester polyols that produce a sharp tan delta signal in DMA testing, such as polyesters based on cyclohexanedimethanol and neopentyl glycol.
  • the polyurethane layer may be derived from an oligomeric polyol.
  • the polyol component may include a chain extender with a molecular weight of less than 200 g/mol.
  • the polyol component comprises only oligomeric polyol and is substantially free of chain extenders.
  • To produce a polyurethane layer with a glass transition temperature below 10 °C it can be preferable to limit the amount of the isocyanate component. In some embodiments using HDI- derived isocyanates, it can be preferable to use less than 40 wt% isocyanate component based on the total core layer composition, or less than 38 wt%, or less than 35 wt%.
  • an isocyanate component containing uretdione groups it is preferable to use an isocyanate component containing uretdione groups.
  • uretdione groups When uretdione groups are included, it can be preferable to use an excess of hydroxyl functional groups relative to isocyanate groups. The excess hydroxyl groups can react with the uretdione groups to form allophanate groups to provide cure and chemical crosslinking.
  • the cross-linked polyurethane layer is preferably prepared such that the combined average functionality of the polyol component and the isocyanate component is greater than 2.4 or 2.5.
  • both the polyol and isocyanate each have an average functionality greater than 2.4 or 2.5.
  • only the isocyanate has an average functionality greater than 2.4 or 2.5, and the polyol component has an average functionality of about 2.0.
  • only the polyol has an average functionality greater than 2.4 or 2.5, and the isocyanate component has an average functionality of about 2.0.
  • the isocyanate index is defined as the molar content of isocyanate functional groups divided by the hydroxyl functional groups.
  • the crosslinked polyurethane is preferably prepared with an isocyanate index between 0.6 and 1.2 or between 0.7 and 1.1 or between 0.75 and 1.05.
  • the isocyanate component can contain uretdione functionality. Under appropriate conditions, excess hydroxyl groups can react with the uretdione functional groups for form an allophanate group that further enhances crosslinking.
  • an alternative index can be calculated by dividing the sum of the moles of isocyanate functional groups and uretdione functional groups by the moles hydroxyl functional groups. In some embodiments, it is preferable that this alternative index be between 0.8 and 1.2 or between 0.85 and 1.1 or between 0.90 and 1.0.
  • the degree of crosslinking of the polyurethane layer can be related to the amount of gel content in the urethane.
  • the gel content can be measured by submerging a sample of urethane in a solvent, such as refluxing THF, to extract the non-gel component. The gel content can then be measured gravimetrically by dividing the remaining dried weight after extraction by the weight of sample before extraction.
  • the core layer can have a gel content of greater than 80%, or greater than 90%, or greater than 95%.
  • the reactive mixture used to form the cross-linked polyurethane layer also contains a catalyst. The catalyst facilitates the step-growth reaction between the polyol and the polyisocyanate.
  • catalysts generally recognized for use in the polymerization of urethanes may be suitable for use with the present disclosure.
  • aluminum -based, bismuth-based, tin-based, vanadium-based, zinc-based, or zirconium-based catalysts may be used.
  • Tin-based catalysts are particularly useful. Tin-based catalysts have been found to significantly reduce the amount of outgassing present in the polyurethane.
  • dibutyltin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin dimercaptide, dibutyltin dioctoate, dibutyltin dimaleate, dibutyltin acetonylacetonate, and dibutyltin oxide.
  • dibutyltin dilaurate catalyst DABCO T-12 commercially available from Air Products and Chemicals, Inc., Allentown, Pa. is particularly suitable.
  • the catalyst is generally included at levels of at least 200 ppm or even 300 ppm or greater.
  • the glass transition temperature of the cross- linked polyurethane layer (or core layer) be 10 degrees Celsius or less, or 5 degrees Celsius or less, or 0 degrees Celsius or less, or -5 degrees Celsius or less, or -10 degrees Celsius or less, or in a range from -40 to 5 degrees Celsius, or in a range from -30 to 5 degrees Celsius, or in a range from -20 to 5 degrees Celsius, or in a range from -15 to 5 degrees Celsius.
  • the crosslinked material have a high Tan Delta (>0.5, >0.8, >1.0 or greater than 1.2).
  • the transparent cross-linked polyurethane layer may have a cross-link density in a range from 0.1 to 1.0 mol/kg or from 0.2 to 0.9 mol/kg or from 0.37 to 0.74 mol/kg.
  • the crosslink density of the cured polyurethane coatings is calculated using the method described in Macromolecules, Vol. 9, No. 2, pages 206-211 (1976). To implement this model, integral values for chemical functionality are required. DESMODURN3300 is reported to have an average functionality of 3.5 and an isocyanate equivalent weight of 193 g/equiv.
  • This material was represented in the mathematical model as a mixture of 47.5 wt% HDI trimer (168.2 g/equiv.), 25.0 wt% HDI tetramer (210.2 g/equiv.), and 27.5 wt% of HDI pentamer (235.5 g/equiv.).
  • This mixture yields an average equivalent weight of 193 g/equiv. and an average functionality of 3.5.
  • Desmodur N3400 is reported to have an average functionality 2.5 and an equivalent weight of 193, and it is reported to be blend of the HDI isocyanurate trimer and HDI uretdione dimer.
  • This material was represented in the mathematical model as a mixture of 19 wt% HDI isocyanurate trimer, 33 wt% HDI uretdione dimer, and 10 wt% of HDI uretdione trimer and 38 wt% of HDI tetramer having one isocyanurate group and one uretdione group.
  • the functionality was determined by the sum the isocyanate groups and the uretdione groups in the cases where there was an excess of hydroxyl groups relative to the sum of the isocyanate and uretdione groups.
  • An transparent aliphatic cross-linked polyurethane containing layer or layers may be formed by free radical polymerization of multifunctional urethane acrylate oligomers.
  • the urethane acrylate oligomer may be mixed with other low molecular weight monofunctional and/or multifunctional acrylates to modify the pre-cured viscosity of the resin for the purposes of processing.
  • the average functionality of the multifunctional acrylate used in the polyurethane layer prior to cure is less than 3 (i.e. 3 functional acrylate functional groups per molecule) or can be 2 or less.
  • the cured (or crosslinked) material may exhibit stable material properties with respect to the display fdm use in application, that is, the polyurethane acrylate layer may not exhibit appreciable flow.
  • the transparent polyurethane acrylate material may be coated onto the transparent polymeric or glass substrate layer (that may be primed) and then be cured or cross-linked to form a thermoset or cross-linked polyurethane acrylate layer.
  • the polyurethane acrylates described herein are thermosetting polymers that may not melt when heated.
  • Urethane acrylate oligomers can be comprised of a wide variety of urethane materials with acrylate or methacrylate reactive groups. Urethane acrylate oligomers are commercially available from vendors such as, for example, Sartomer of Exton, Pennsylvania (a subsidiary of Arkema) and Allnex (Ebecryl Brand name).
  • Examples of commercially available aliphatic urethane oligomers include but are not limited to CN9002, CN9004 and CN3211 available from Sartomer Company and those sold under the Ebecryl brand name.
  • the transparent substrate 130 may have any useful thickness.
  • the transparent substrate layer 130 has a thickness in a range from 10 to 100 micrometers or from 20 to 80 micrometers.
  • the transparent substrate 130 may be formed of any useful polymeric material that provides the desired mechanical properties (such as dimensional stability) and optical properties (such as light transmission and clarity) to the multilayer fdms 300 and 400 of FIG. 3 and FIG. 4.
  • polymeric materials suitable for use as the substrate 130 include polymethylmethacrylate, polycarbonate, polyamides, polyimide, polyesters (PET, PEN), polycyclic olefin polymers, and thermoplastic polyurethanes.
  • One useful polymeric material for forming the transparent substrate 130 is polyimide.
  • the polyimide substrate layer is colorless.
  • Colorless polyimide can be formed via chemistry or via nanoparticle incorporation. Some exemplary colorless polyimides formed via chemistry are described in WO 2014/092422. Some exemplary colorless polyimides formed via nanoparticle incorporation are described in Journal of Industrial and Engineering Chemistry 28 (2015) 16-27.
  • Useful colorless polyimide films may have glass transition temperatures greater 220 degrees Celsius or greater than 250 degrees Celsius or even greater than 300 degrees Celsius and tensile moduli greater than 6GPa, or greater than 6.5GPa or even Greater than 7GPa. These high modulus polymers exhibit excellent resistance to plastic deformation
  • Polymeric transparent substrate layers 130 may have any useful tensile modulus or offset yield stress value.
  • the polymeric transparent substrate 130 may have an offset yield stress value that is greater than 50MPa or greater than 75MPa.
  • the polymeric transparent substrate layer 130 may be referred to as a “high yield” substrate and may have an offset yield stress value that is greater than 110 MPa, or greater than 130 MPa, or greater than 150 MPa, or greater than 180 MPa, or greater than 200 MPa.
  • yield stress or “offset yield stress” refers herein to “0.2% offset yield strength” as defined in ASTM D638-14.
  • ASTM D638 -14 section A2.6 defines the test method for “offset yield strength” which is defined as the stress at which the strain exceeds by a specified amount (the offset) an extension of the initial proportional portion of the stress-strain curve. It is expressed in force per unit area, usually megapascals (or poundsforce per square inch, for example).
  • the transparent substrate layer may be formed of any useful glass material.
  • the glass layer may be treated to provide beneficial properties.
  • the transparent glass layer may be ion implanted, chemically strengthened or tempered, and the like.
  • the transparent glass layer may have a thickness that is appropriate for a given bend radius or radius of curvature.
  • the transparent glass layer may have a thickness of from 25 to 100 micrometers or from 25 to 50 micrometers.
  • Suppliers of thin transparent glass include Coming, Nippon Electric Glass, Schott and Asahi Glass.
  • a low surface energy coating 105 may be applied to the surface of the nanocomposite layer 110
  • Such layers can provide a low coefficient of friction coating 105 to provide improved lubricity and tactile feel of the surface. They also can impart water and oil repellency, easy to clean properties to the surface because of the highly fluorinated surface.
  • Such coating layers can be created for example by application of fluorosilane coatings to the surface. The coatings can be applied from solution in coating processes, spray processes, or by physical vapor deposition processes. The layers typically have thicknesses in the range of 1-50 nm and result in no negative change in optical properties.
  • fluorosilane coatings examples include OPTOOL DSX-E and OPTOOL DAC-HP available for Daiken Chemical Europe GmbH (Dusseldorf, Germany) and NOVEC Electronic grade coatings available from 3M Company (St. Paul, MN) one particular solution being NOVEC 2202.
  • the surface of the layers may be treated prior to coating to improve adhesion. Some examples of treatment can be plasma cleaning of the surface, atmospheric plasma activation of the surfaces, or plasma etching of the surface and deposition of a thin glass like layer designed to have chemical bonding to the fluorosilane. Examples of plasma etching processes may be found in U.S. Pat. Appl. Pub. No. 2010/0165276 (David et al.).
  • a layer (e.g., the coating 105) layer having a surface energy less than 35 mN/m, or less than 30 mN/m, or less than 25 mN/m is disposed on the nanocomposite layer 110 opposite the aliphatic cross-linked polyurethane layer 120.
  • a layer (e.g., the coating 105) layer having a static water contact angle of at least 100 degrees, or at least 110 degrees is disposed on the nanocomposite layer 110 opposite the aliphatic cross-linked polyurethane layer 120.
  • a static water contact angle Q is schematically illustrated in FIG. 1.
  • FIG. 6 is a schematic diagram side elevation view of an illustrative multilayer fdm 100 on an optical display 160 forming an article 600.
  • a coupling layer 140 fixes the multilayer film 100 to the optical display 160.
  • FIG. 7 is a schematic diagram side elevation view of an illustrative multilayer film 200 on an optical display 160 forming an article 700.
  • a coupling layer 140 fixes the multilayer film 200 to the optical display 160.
  • FIG. 8 is a schematic diagram side elevation view of an illustrative multilayer film 300 on an optical display 160 forming an article 800.
  • a coupling layer 140 fixes the multilayer film 300 to the optical display 160.
  • FIG. 9 is a schematic diagram side elevation view of an illustrative multilayer film 400 on an optical display 160 forming an article 900.
  • a coupling layer 140 fixes the multilayer film 300 to the optical display 160.
  • the multilayer films 100, 200, 300, and 400 in FIGS. 6-9 may include additional elements and layers that are not shown.
  • the coupling layer 140 For the purposes of the following description of the coupling layer 140, multilayer film 100 will be used, but the coupling layer may be disposed on any of the multilayer film constructions described herein.
  • a coupling layer 140 adheres the multilayer film 100 to the optical display 160.
  • the coupling layer 140 may be a pressure sensitive adhesive.
  • the coupling layer 140 permanently fixes the multilayer film 100 to the optical display 160.
  • the multilayer film and coupling layer 140 can be removed/debonded/repositioned, relative to the optical element 160, with the application of heat or mechanical force such that the multilayer film is replaceable or repositionable by the consumer.
  • the coupling layer may be comprised of acrylate, silicone, silicone polyoxamide, silicone polyurea, polyolefin, polyester, polyurethane or polyisobutylene or mixtures thereof as long as the coupling layer has suitable optical properties in terms of low haze, high transmission and low yellow index.
  • the coupling layer may be an optically clear adhesive or pressure sensitive adhesives
  • the coupling layer 140 may have a shear modulus (G’) of 300 kPa or less, or 200 kPa or less, or 100 kPa or less or 50 kPa or less over a temperature range for example -40°C to 70°C, or from -40°C to 50°C, or from -30°C to 50°C, or from -20°C to 50°C.
  • G shear modulus
  • the rheological properties of the material can be measured using a parallel plate rheometer to probe the shear modulus as a function of temperature as well as to determine the glass transition temperature (Tg) of the material.
  • This test can be done by using an 8 mm diameter by about 1 mm thick disk of the coupling layer material and placing it between the probes of a DHR parallel plate rheometer (TA Instruments, New Castle, DE).
  • a temperature scan can be performed, for example, by ramping from -45°C to 50°C at 3°C/min. During this ramp, the sample is oscillated at a frequency of 1 Hz and a strain of approximately 0.4%.
  • the shear moduli (G' and G") are recorded at selected key temperatures.
  • the Tg of the material can be determined as the peak in the tan delta vs. temperature profde.
  • the shear storage modulus (G') below about 2 MPa over the entire temperature range from about -20°C to about 40°C when measured using the test described above
  • a release liner or premask layer may be disposed on the coupling layer 140.
  • the release liner may be easily removed for application to an optical display or to reveal the multilayer film, before placement onto an optical display 160.
  • the removable or release liner (or premask layer) may provide transport protection to the underlying multilayer film and optional coupling layer 140.
  • the removable liner may be layer or film that has a low surface energy to allow clean removal of the liner from the multilayer film 100 and optional coupling layer 140.
  • the removable liner may be a layer of polyester coated with a silicone, for example.
  • the removable liner may provide temporary structure to the optional coupling layer 140.
  • WO2014/197194 and WO2014/197368 describe removable liners that emboss a coupling layer where the coupling layer loses its structures slowly once the removable liner is stripped away from the optical adhesive layer. This allows for ease of application where the temporary structure can allow for air bleed in lamination which then disappears in the laminated construction.
  • FIG. 10 is a schematic diagram perspective view of an illustrative folding article 1000 including an illustrative multilayer fdm 200.
  • the multilayer fdm 200 may be any of the multilayer fdm constructions described herein disposed on an optical element such as an optical display 340.
  • the display device may not be a folding article and may only flex within a certain range, or may be a static curved display device.
  • An optical display 340 may form at least a portion of display device.
  • the display device 1000 may include a display window 320.
  • the display device 1000 can be any useful article such as a phone or smartphone, electronic tablet, electronic notebook, computer, and the like.
  • the optical display may include an organic light emitting diode (OLED) display panel.
  • the optical display may include a liquid crystal display (LCD) panel or a reflective display. Examples of reflective displays include electrophoretic displays, electrofluidic displays (such as an electrowetting display), interferometric displays or electronic paper display panels, and are described in US 2015/0330597. In some cases, the optical display could be a static graphic film.
  • the multilayer film 100 and the optical display 340 may be foldable so that the optical display 340 faces itself and at least a portion of multilayer film 100 contacts or directly faces another portion of the film 100, as illustrated in FIG. 10.
  • the multilayer film 100 and the optical display 340 may be flexible or bendable or foldable so that a portion of the multilayer film 100 and the optical display 340 can articulate relative to another portion of the multilayer film 100 and the optical display 340.
  • the multilayer film 100 and the optical display 340 may be flexible or bendable or foldable so that a portion of the multilayer film 100 and the optical display 340 can articulate at least 90 degrees or at least 170 degrees relative to another portion of the multilayer film 100 and the optical display 340.
  • the multilayer film 100 and the optical display 340 may be flexible or bendable or foldable so that a portion of the multilayer film 100 and the optical display 340 can articulate relative to another portion of the multilayer film 100 and optical display 340 to form a bend radius of 5 mm or less in the multilayer film 100 at the bend or fold line.
  • the multilayer film 100 and the optical display 340 may be flexible or bendable or foldable so that a portion of the multilayer film 100 and optical display 340 can articulate relative to another portion of the multilayer film 100 and the optical display 340 to form a bend radius such that the multilayer film 100 overlaps itself and is separated from each other by a distance on 10 mm or less, or 6 mm or less or 3 mm or less or 1 mm or less.
  • an optical device (e.g., corresponding to article 600, 700, 800, 900, or 1000), includes an optical display 160 or 340 and any of the multilayer film described herein bonded to the optical display.
  • the multilayer film is bonded to, and substantially coextensive with, a light output surface (display window 320) of the optical display.
  • the multilayer films described herein may have a haze value of 5% or less, 4% or less, 3% or less, 2% or less, or 1.5% or less, or 1% or less. In some embodiments the multilayer film may have a haze value of greater than 5% if the surface is structured to provide an antiglare function.
  • the multilayer film may have a clarity of 95% or greater, 97% or greater, 98% or greater, or 99% or greater.
  • the multilayer film may have a visible light transmission of 85% or greater, or 90% or greater, or 93% or greater.
  • the multilayer film may have a yellow index or b* value of 5 or less, or 4 or less, or 3 or less, or 2 or less, or 1 or less. In many embodiments, the multilayer film may have a yellow index or b* value of 1 or less.
  • aqueous colloidal silica dispersion (NALCO 2327) was placed in a 75.71 liter stainless steel reactor. Agitation was initiated. 15.58 kg of carboxylic acid silane solution (Preparation Example 1) was added to the reactor. The contents of the reactor were heated to 80°C. Upon reaching 80°C, the reactor was sealed, and the contents of the reactor maintained at 80°C with continuous agitation for 24 hours. After 24 hours, the contents of the reactor were cooled and filtered with a 50 pm filter and transferred to two 18.93 liter plastic lined metal drums. The pH of the nanoparticle dispersion was 5.5 and the nanoparticle concentration was calculated to be 31.3 wt%.
  • SURLYN 9120 is a partially neutralized poly(ethylene-co- methacrylic acid) ionomer with a melt flow index (MFI) of 1.3, acid content of 19 weight percent, with 38% neutralization with Zn 2+ ions.
  • MFI melt flow index
  • 1.21 kilograms of the 28 weight percent sodium hydroxide (NaOH) aqueous solution from Preparatory Example 4 was added to the reactor. The agitation was increased to 120rpm.
  • the mixture was heated to 150°C and held for 2.5 hours with continuous agitation in the closed (pressurized) reactor.
  • the ionomer dispersed to form a milky white aqueous solution with -15% by weight neutralized SURLYN 9120.
  • PRIMACOR 5980i is a poly(ethylene-co-acrylic acid) Copolymer with a MFI of 300, acid content of 20.5 weight percent, and it is not neutralized.
  • SURLYN 9120 is a partially neutralized poly(ethylene- co-methacrylic acid) ionomer with a melt flow index (MFI) of 1.3, acid content of 19 weight percent, with 38% neutralization with Zn 2+ ions.
  • SURLYN 8150 1275 grams of deionized water was placed in a two liter cylindrical glass reactor (Ace Glass, Vineland, NJ). 225 grams of SURLYN 8150 ionomer was added to the reactor and agitation initiated at 120 rpm. SURLYN 8150 is a partially neutralized poly(ethylene-co- methacrylic acid) ionomer with a MFI of 4.5, acid content of 19 weight percent, and 45 percent neutralization with Na + ions. No additional base was added to the reactor. The mixture was heated to 100°C and held for 2.5 hours with continuous agitation in the open (atmospheric pressure) reactor. The ionomer dispersed to form a hazy aqueous dispersion.
  • SURLYN 7940 is a partially neutralized poly(ethylene-co- methacrylic acid) ionomer with a MFI of 2.6, acid content of 15 weight percent, and 40 percent neutralization with Li + ions.
  • DMEA was added to the reactor. The mixture was heated to 100°C and held for 2.5 hours with continuous agitation in the open (atmospheric pressure) reactor. The ionomer dispersed to form an opaque white aqueous dispersion.
  • NUCREL 960 is a poly(ethylene-co-methacrylic acid) copolymer with a MFI of 60, acid content of 15 weight percent, and 0 percent neutralization. 0.95 kilograms of the 28 weight percent sodium hydroxide solution from Preparatory Example 4 was added to the reactor. The agitation was increased to 120rpm. The mixture was heated to 150°C and held for 2.5 hours with continuous agitation in the closed (pressurized) reactor. The ionomer dispersed to form a hazy aqueous dispersion of partially neutralized ionomer.
  • a film was made by coating the 15wt% SURLYN 9120 aqueous dispersion from Preparatory Example 5 on to the unprimed side of a 75 pm polyester substrate (PET).
  • the dispersion was applied to the PET substrate in a roll to roll process where the solution was metered through a slot die onto the moving web. Thickness was controlled by the use of a metering pump and a mass flow meter and solution was filtered through a Roki HT-40 filter (ROKI TECHNO Co., Ltd., Tokyo, Japan).
  • the volatile components of the dispersion were removed by drying in a three-zone air flotation zoned oven (ovens temperatures set to 66°C, 93°C and 135°C).
  • the dried coating had a thickness of ⁇ 10 pm and the film was wound into a roll.
  • the coating on PET had a Transmission of 93.0%, Haze of 0.82%, and Clarity of 99.9%.
  • the 75 pm PET substrate for all coating examples had a Transmission of 91.5%, Haze of 0.65%, and Clarity of 99.9%.
  • a coating solution was made by mixing 668 grams of the 15wt% dispersion of SURLYN 9120 from Preparatory Example 5 and 82 grams of carboxylic acid modified S1O2 nanodispersion from Preparatory Example 3.
  • a film was made by coating the ionic elastomer nanocomposite dispersion onto the unprimed side of a 75 pm polyester substrate (PET). The dispersion was applied to the PET substrate in a roll to roll process where the solution was metered through a slot die onto the moving web. Thickness was controlled by the use of a metering pump and a mass flow meter and solution was filtered through a Roki HT-40 filter (ROKI TECHNO Co., Ltd., Tokyo, Japan).
  • the volatile components of the dispersion were removed by drying in a three- zone air flotation zoned oven (ovens temperatures set to 66°C, 93 °C and 135°C).
  • the dried coating had a thickness of ⁇ 10pm and the film was wound into a roll.
  • the dried film had 20wt% 20nm S1O2 nanoparticles..
  • the coating on PET had a Transmission of 92.7%, Haze of 0.63%, and Clarity of 99.9%.
  • a coating solution was made by mixing 1319 grams of the 15wt% dispersion of SURLYN 9120 from Preparatory Example 5 and 431 grams of carboxylic acid modified S1O2 nanodispersion from Preparatory Example 3.
  • a film was made by coating the ionic elastomer nanocomposite dispersion onto the unprimed side of a 75 pm polyester substrate (PET). The dispersion was applied to the PET substrate in a roll to roll process where the solution was metered through a slot die onto the moving web. Thickness was controlled by the use of a metering pump and a mass flow meter and solution was filtered through a Roki HT-40 filter (ROKI TECHNO Co., Ltd., Tokyo, Japan).
  • the volatile components of the dispersion were removed by drying in a three- zone air flotation zoned oven (ovens temperatures set to 66°C, 93 °C and 135°C).
  • the dried coating had a thickness of ⁇ 10 pm and the film was wound into a roll.
  • the dried film had 40wt% 20nm S1O2 nanoparticles..
  • the coating on PET had a Transmission of 92.8%, Haze of 0.54%, and Clarity of 99.9%.
  • a coating solution was made by mixing 1326 grams of the 15wt% 44/56 PRIMACOR5980i/SURLYN 9120 aqueous dispersion from Preparatory Example 6 and 424 grams of carboxylic acid modified S1O2 nanodispersion from Preparatory Example 3.
  • a film was made by coating the ionic elastomer nanocomposite dispersion onto the unprimed side of a 75 pm polyester substrate (PET). The dispersion was applied to the PET substrate in a roll to roll process where the solution was metered through a slot die onto the moving web.
  • Thickness was controlled by the use of a metering pump and a mass flow meter and solution was filtered through a Roki HT-40 filter (ROKI TECHNO Co., Ltd., Tokyo, Japan).
  • the volatile components of the dispersion were removed by drying in a three-zone air flotation zoned oven (ovens temperatures set to 66°C, 93°C and 135°C).
  • the dried coating had a thickness of ⁇ 10pm and the film was wound into a roll.
  • the dried film had 40wt% 20nm S1O2 nanoparticles..
  • the coating on PET had a Transmission of 92.9%, Haze of 0.53%, and Clarity of 99.9%.
  • a coating solution was made by mixing 1319 grams of the 15wt% dispersion of SURLYN 8150 from Preparatory Example 7 and 431grams of carboxylic acid modified S1O2 nanodispersion from Preparatory Example 3.
  • a film was made by coating the ionic elastomer nanocomposite dispersion onto the unprimed side of a 75 pm polyester substrate (PET). The dispersion was applied to the PET substrate in a roll to roll process where the solution was metered through a slot die onto the moving web. Thickness was controlled by the use of a metering pump and a mass flow meter and solution was filtered through a Roki HT-40 filter (ROKI TECHNO Co., Ltd., Tokyo, Japan).
  • the volatile components of the dispersion were removed by drying in a three- zone air flotation zoned oven (ovens temperatures set to 66°C, 93 °C and 135°C).
  • the dried coating had a thickness of ⁇ 10pm and the film was wound into a roll.
  • the dried film had 40wt% 20nm S1O2 nanoparticles..
  • the coating on PET had a Transmission of 93.0%, Haze of 0.59%, and Clarity of 99.9%.
  • a coating solution was made by mixing 1319 grams of the 15wt% dispersion of SURLYN 7940 from Preparatory Example 8 and 431grams of carboxylic acid modified S1O2 nanodispersion from Preparatory Example 3.
  • a film was made by coating the ionic elastomer nanocomposite dispersion onto the unprimed side of a 75 pm polyester substrate (PET). The dispersion was applied to the PET substrate in a roll to roll process where the solution was metered through a slot die onto the moving web. Thickness was controlled by the use of a metering pump and a mass flow meter and solution was filtered through a Roki HT-40 filter (ROKI TECHNO Co., Ltd., Tokyo, Japan).
  • the volatile components of the dispersion were removed by drying in a three-zone air flotation zoned oven (ovens temperatures set to 66°C, 93°C and 135°C).
  • the dried coating had a thickness of ⁇ 10pm and the film was wound into a roll.
  • the dried film had 40wt% 20nm SiCE nanoparticles..
  • the coating on PET had a Transmission of 92.9%, Haze of 0.66%, and Clarity of 99.8%.
  • a coating solution was made by mixing 1319 grams of the 15wt% dispersion of NUCREL 960 from Preparatory Example 8 and 431 grams of carboxylic acid modified SiCE nanodispersion from Preparatory Example 3.
  • a film was made by coating the ionic elastomer nanocomposite dispersion onto the unprimed side of a 75 pm polyester substrate (PET). The dispersion was applied to the PET substrate in a roll to roll process where the solution was metered through a slot die onto the moving web. Thickness was controlled by the use of a metering pump and a mass flow meter and solution was filtered through a Roki HT-40 filter (ROKI TECHNO Co., Ltd., Tokyo, Japan).
  • the volatile components of the dispersion were removed by drying in a three- zone air flotation zoned oven (ovens temperatures set to 66°C, 93 °C and 135°C).
  • the dried coating had a thickness of ⁇ 10pm and the film was wound into a roll.
  • the dried film had 40wt% 20nm SiCE nanoparticles..
  • the coating on PET had a Transmission of 92.7%, Haze of 0.54%, and Clarity of 99.9%.
  • a coating solution was made by mixing 659.5 grams of the 15wt% dispersion of NUCREL 960 from Preparatory Example 8 and 659.5 grams of the 15wt% dispersion of SURLYN 9120 from Preparatory Example 5 and 431 grams of carboxylic acid modified SiCE nanodispersion from Preparatory Example 3.
  • a film was made by coating the ionic elastomer nanocomposite dispersion onto the unprimed side of a 75 pm polyester substrate (PET). The dispersion was applied to the PET substrate in a roll to roll process where the solution was metered through a slot die onto the moving web.
  • Thickness was controlled by the use of a metering pump and a mass flow meter and solution was filtered through a Roki HT-40 filter (ROKI TECHNO Co., Ltd., Tokyo, Japan).
  • the volatile components of the dispersion were removed by drying in a three- zone air flotation zoned oven (ovens temperatures set to 66°C, 93 °C and 135°C).
  • the dried coating had a thickness of - 1 Omih and the fdm was wound into a roll.
  • the dried fdm had 40wt% 20nm S1O2 nanoparticles.
  • the coating on PET had a Transmission of 92.7%, Haze of 0.62%, and Clarity of 99.9%.
  • a melt-processed monolithic fdm of a SURLYN 9120 ionomer was prepared using a Plasti-corder (C.W. Brabender Instruments, Inc., South Hackensack, NJ). 50.0 grams of SURLYN 9120 pellets was added to the preheated Plasti-corder and was processed for 15 minutes at 150°C and 75 rpm. After processing the melt-processed material was cooled to room temperature. A portion of the melt-processed material was pressed into a fdm using an Auto Series Hot Press (Carver Inc., Wabash, IN). A portion of the melt-processed fdm was placed between two layers of polyimide fdm which were between two polished aluminum plates.
  • the melt-processed material was pressed to 900 kg force at 125°C and held for 5 minutes.
  • the sample was then pressed to 10900 kg force at 125°C and held for 0.1 minutes (6 seconds).
  • the pressed fdm was removed from the press and from between the aluminum plates and cooled to room temperature.
  • the polyimide sheets are removed once the fdm sufficiently cooled.
  • the thickness of the pressed fdm was 7.1 mil (-180 microns) and the fdm had a Transmission of 92.3%, Haze of 3.5%, and Clarity of 96.8%.
  • Films of controlled thickness may be made via known extrusion casting and orientation methods to produce rolls of monolithic fdm at thickness from 25-250 microns.
  • a melt-processed monolithic fdm of a 44wt% PRIMACOR 5980i and 56% SURLYN 9120 ionomer was prepared using a Plasti-corder (C.W. Brabender Instruments, Inc., South Hackensack, NJ). 22.0 grams of PRIMACOR 5980i pellets and 28.0 grams SURLYN 9120 pellets were added to the preheated Plasti-corder and the materials were processed for 15 minutes at 150°C and 75 rpm to form a blend. After processing the melt-processed polymer blend was cooled to room temperature. A portion of the melt-processed material was pressed into a fdm using Auto Series Hot Press (Carver Inc., Wabash, IN).
  • melt-processed fdm was placed between two layers of polyimide fdm which were between two polished aluminum plates.
  • the melt-processed material was pressed to 900 kg force at 125°C and held for 5 minutes.
  • the sample was then pressed to 10900 kg force at 125°C and held for 0.1 minutes (6 seconds).
  • the pressed fdm was removed from the press and from between the aluminum plates and cooled to room temperature.
  • the polyimide sheets are removed once the fdm sufficiently cooled.
  • the thickness of the pressed fdm was 6.5 mil (-165 microns) and the fdm had a Transmission of 92.4%, Haze of 3.1%, and Clarity of 97.1%.
  • Films of controlled thickness may be made via known extrusion casting and orientation methods to produce rolls of monolithic fdm at thickness from 25-250 microns.
  • a melt-processed monolithic nanocomposite fdm with a composition of 20 wt% 20nm S1O2 nanoparticles 40 wt% SURLYN 9120 and 40 wt% NUCREL 699 was prepared using a Plasti-corder (C.W. Brabender Instruments, Inc., South Hackensack, NJ). 25.0 grams of the coating from Preparatory Example S2 was removed from the PET substrate, along with 5.0 grams of SURLYN 9120 pellets and 20.0 grams of NUCREL 699 pellets were added to the preheated Plasti-corder and the materials were processed for 15 minutes at 150°C and 75 rpm to form a nanocomposite blend.
  • a Plasti-corder C.W. Brabender Instruments, Inc., Southhackensack, NJ. 25.0 grams of the coating from Preparatory Example S2 was removed from the PET substrate, along with 5.0 grams of SURLYN 9120 pellets and 20.0 grams of NUCREL 699 pellets were added to
  • melt-processed polymer blend After processing the melt-processed polymer blend was cooled to room temperature. A portion of the melt-processed material was pressed into a film using an Auto Series Hot Press (Carver Inc., Wabash, IN). A portion of the melt-processed fdm was placed between two layers of polyimide fdm which were between two polished aluminum plates. To press the samples, the melt-processed material was pressed to 900 kg force at 125°C and held for 5 minutes. The sample was then pressed to 10900 kg force at 125°C and held for 0.1 minutes (6 seconds). The pressed fdm was removed from the press and from between the aluminum plates and cooled to room temperature. The polyimide sheets are removed once the fdm sufficiently cooled.
  • the thickness of the pressed fdm was 7.7 mil (-196 microns) and the fdm had a Transmission of 93.0%, Haze of 3.4%, and Clarity of 94.3%. Films of controlled thickness may be made via known extrusion casting and orientation methods to produce rolls of monolithic fdm at thickness from 25-250 microns.
  • a melt-processed monolithic nanocomposite fdm with a composition of 20 wt% 20nm S1O2 nanoparticles 40 wt% SURLYN 9120 and 40 wt% PRIMACOR 1410 was prepared using Plasti-corder (C.W. Brabender Instruments, Inc., South Hackensack, NJ). 25.0 grams of the coating from Preparatory example S2 was removed from the PET substrate, along with 5.0 grams of SURLYN 9120 pellets and 20.0 grams of PRIMACOR 1410 pellets were added to the preheated Plasti-corder and the materials were processed for 15 minutes at 150°C and 75 rpm to form a nanocomposite blend.
  • melt-processed polymer blend After processing the melt-processed polymer blend was cooled to room temperature. A portion of the melt-processed material was pressed into a fdm using an Auto Series Hot Press (Carver Inc., Wabash, IN). A portion of the melt-processed fdm was placed between two layers of polyimide fdm which were between two polished aluminum plates. To press the samples, the melt-processed material was pressed to 900 kg force at 125°C and held for 5 minutes. The sample was then pressed to 10900 kg force at 125°C for 0.1 minutes (6 seconds).
  • the pressed film was removed from the press and from between the aluminum plates and cooled to room temperature.
  • the polyimide sheets are removed once the film sufficiently cooled.
  • the thickness of the pressed film was 11.3 mil (-287 microns) and the film had a Transmission of 91.2%, Haze of 3.6%, and Clarity of 96.1%.
  • Films of controlled thickness may be made via known extrusion casting and orientation methods to produce rolls of monolithic film at thickness from 25-250 microns.
  • a melt-processed monolithic nanocomposite film with a composition of 20 wt% 20nm S1O2 nanoparticles 40 wt% SURLYN 8150 and 40 wt% SURLYN 9020 was prepared using a Plasti-corder (C.W. Brabender Instruments, Inc., South Hackensack, NJ). 25.0 grams of the coating from Preparatory example S5 was removed from the PET substrate, along with 5.0 grams of SURLYN 8150 pellets and 20.0 grams of SURLYN 9020 (terpolymer) pellets were added to the preheated Plasti-corder and the materials were processed for 15 minutes at 150°C and 75 rpm to form a nanocomposite blend.
  • a Plasti-corder C.W. Brabender Instruments, Inc., Southhackensack, NJ. 25.0 grams of the coating from Preparatory example S5 was removed from the PET substrate, along with 5.0 grams of SURLYN 8150 pellets and 20.0 grams of SURLYN 90
  • melt-processed polymer blend After processing the melt-processed polymer blend was cooled to room temperature. A portion of the melt-processed material was pressed into a film using an Auto Series Hot Press (Carver Inc., Wabash, IN). A portion of the melt-processed film was placed between two layers of polyimide film which were between two polished aluminum plates. To press the samples, the melt-processed material was pressed to 900 kg force at 125°C andheld for 5 minutes. The sample was then pressed to 10900 kg force at 125°C and held for 0.1 minutes (6 seconds). The pressed film was removed from the press and from between the aluminum plates and cooled to room temperature. The polyimide sheets are removed once the film sufficiently cooled.
  • the thickness of the pressed film was 3.5 mil (-89 microns) and the film had a Transmission of 93.4%, Haze of 3.6%, and Clarity of 94.7%.
  • Films of controlled thickness may be made via known extrusion casting and orientation methods to produce rolls of monolithic film at thickness from 25-250 microns.
  • Samples of shape memory polyurethane (PU) were prepared in a roll to roll process where the isocyanate and polyol with catalyst were mixed using an inline dynamic mixer. The solutions were applied to a moving web between two silicone release liners at an appropriate flow rate to achieve the desired final sample thickness.
  • the polyurethane between films were heated at 70°C and wound into a roll.
  • the fdms were post-baked at 70°C for 24 hours prior to lamination to glass Samples had a range of equivalents of NCO reacted with 1.0 equivalents of -OH, as shown in Table 2 in order to achieve the desired glass transition temperature and crosslink concentration. Relative proportions by mass of Polyol 1 and Polyisocyanate 1 for intermediate fdms PU15-PU22 are shown in Table 2.
  • the coated materials contained about 350ppm dibutyltin dilaurate catalyst.
  • Polyurethane Film Preparative Intermediates PU23-PU26 The polyurethanes for Examples PU23 - PU26, were composed of a polyol 1 (K-FLEX
  • Polyisocyanate 1 contains a uretdione unit that can react with excess OH in the polyol component at elevated temperature to form an allophanate group. For this reason, the table contains two stoichiometric ratio columns. The first calculates the NCO/OH ratio based on only existing NCO content in Polyisocyanate 1 and Polyisocyanate 2 at the beginning of the reaction. The NCO+UD/OH ratio accounts for the ratio after the uretdione is reacted with excess OH of the polyol. The theoretical gel content and crosslink concentration are reported in Table 3.
  • Polyurethane Substrate intermediate PU27 coating was made with an alternative polyol, Fomrez 55-112 in order to provide a film having a lower glass transition temperature.
  • the polyurethane was composed of polyol 2 reacted with Polyisocyanate 1, prepared in the same manner as samples PU15-PU22.
  • the weight ratio Polyol 2 to Polyisocyanate 1 for sample PU27 is shown in Table 4. Ovens were run at 70°C and the samples were post-cured for 24 hours at 70°C
  • the glass transition temperature of the polyurethane coatings was characterized using Q800 DMA from TA Instruments. Samples were cut into strips 6.35 mm wide and about 4 cm long. The thickness of each film was measured. The films were mounted in the tensile grips of a Q800 DMA from TA Instruments with an initial grip separation between 16 mm and 19 mm. The samples were then tested at an oscillation of 0.2% strain and 1 Hz throughout a temperature ramp from -50 °C to 200 °C at a rate of 2 °C per minute. The results are shown in Table 5. The onset of the glass transition was determined by location of peak for E". The temperature at which the Tan Delta signal reached a maximum was recorded as the peak Tan Delta temperature.
  • Example 1 Into a Flacktek Inc. size 40 speedmixer cup was added 27.04g of Polyol 1 containing ⁇ 500ppm of DABCO T-12 and 15. Og of Polyisocyanate 1. The contents were mixed using a Flacktek DAC 150 FVZ-K speedmixer and were mixed at 1500 rpm for 30 seconds. The resulting resin was coated between the elastic ionomer nanocomposite layer of Preparatory Film Substrate Example S2 and a silicone release liner (for example T50 release liner available from Eastman Chemical). The reactive mixture was coated to a desired thickness between the two fdms in a continuous fashion using a notch bar coating method where thickness was controlled by setting a defined gap.
  • a silicone release liner for example T50 release liner available from Eastman Chemical
  • the coated polyurethane film was allowed to cure at room temperature for 12 hours and was then heated at 70°C for 12 hours in a forced air oven.
  • the NCO/OH ratio for the polyurethane reactive mixture was ⁇ 0.7.
  • the silicone liner on the polyurethane side and the PET layer supporting the elastic ionomer nanocomposite was removed to give an -182 micron thick sample of the composite film shown in FIG. 1.
  • the polyurethane side of the film was tacky and easily wet out to a painted metal surface.
  • the Elastic ionomer nanocomposite side of the film was non-tacky and did not wetout the painted metal surface.
  • the film was very flexible and had transmission of 93.8%, haze of 0.22%, and clarity of 96.6%.
  • the film was folded over a mandrel of 2mm diameter. One minute after unfolding the film, the film showed no crease or change in optical properties.
  • the coated polyurethane film was allowed to cure at room temperature for 12 hours and was then heated at 70°C for 12 hours in a forced air oven.
  • the NCO/OH ratio for the polyurethane reactive mixture was - 0.7.
  • the silicone liner on the polyurethane side and the PET layer supporting the elastic ionomer nanocomposite was removed to give an -205 micron thick sample of the composite film shown in FIG. 1.
  • the polyurethane side of the film was tacky and easily wet out to a painted metal surface.
  • the Elastic ionomer nanocomposite side of the film was non-tacky and did not wetout the painted metal surface.
  • the film was very flexible and had transmission of 93.5%, haze of 0.12%, and clarity of 99.9%.
  • the film was folded over a mandrel of 2mm diameter. One minute after unfolding the film, the film showed no crease or change in optical properties.
  • the coated polyurethane film was allowed to cure at room temperature for 12 hours and was then heated at 70°C for 12 hours in a forced air oven.
  • the NCO/OH ratio for the polyurethane reactive mixture was - 0.8.
  • the silicone liner on the polyurethane side and the PET layer supporting the elastic ionomer nanocomposite was removed to give an -165 micron thick sample of the composite film shown in FIG. 1.
  • the polyurethane side of the film was tacky and easily wet out to a painted metal surface.
  • the Elastic ionomer nanocomposite side of the film was non-tacky and did not wetout the painted metal surface.
  • the film was very flexible and had transmission of 91.9%, haze of 0.16%, and clarity of 92.3%.
  • the film was folded over a mandrel of 2mm diameter. Three minute after unfolding the film, the film showed no crease or change in optical properties.
  • the coated polyurethane film was allowed to cure at room temperature for 12 hours and was then heated at 70°C for 12 hours in a forced air oven.
  • the NCO/OH ratio for the polyurethane reactive mixture was - 0.8.
  • the silicone liner on the polyurethane side and the PET layer supporting the elastic ionomer nanocomposite was removed to give an -110 micron thick sample of the composite film shown in FIG. 1.
  • the polyurethane side of the film was tacky and easily wet out to a painted metal surface.
  • the Elastic ionomer nanocomposite side of the fdm was non-tacky and did not wetout the painted metal surface.
  • the film was very flexible and had transmission of 93.8%, haze of 0.61%, and clarity of 96.4%.
  • the film was folded over a mandrel of 2mm diameter. Three minute after unfolding the film, the film showed no crease or change in optical properties.
  • the coated polyurethane film was allowed to cure at room temperature for 12 hours and is then heated at 70°C for 12 hours in a forced air oven.
  • the NCO/OH ratio for the polyurethane reactive mixture is ⁇ 0.7.
  • the PET layer supporting the elastic ionomer nanocomposite layer are removed to give an -120 micron thick sample of the composite film shown in FIG. 2.
  • the Elastic ionomer nanocomposite outer layers of the construction are non- tacky and do not wetout to a smooth painted metal surface.
  • the film is very flexible and is expected to have a transmission of >90%, haze of ⁇ 2%, and clarity of >90%.
  • the film is folded over a mandrel of 2mm diameter and is expected to show no signs of creasing or change in optical properties.
  • the reactive mixture is coated to a desired thickness between the two films in a continuous fashion using a notch bar coating method where thickness is controlled by setting a defined gap.
  • the coated polyurethane film is allowed to cure at room temperature for 12 hours and is then heated at 70°C for 12 hours in a forced air oven.
  • the NCO/OH ratio for the polyurethane reactive mixture is - 0.7.
  • the film is very flexible and is expected to have a transmission of >90%, haze of ⁇ 2%, and clarity of >90%.
  • the film is folded over a mandrel of 2mm diameter and is expected to show no signs of creasing or change in optical properties.
  • Luminous transmission, haze, and clarity were measured using a BYK-Gardner Haze-Gard Plus model 4725 (available from BYK-Gardner Columbia, MD). Reported measurements are the average of three measurements on a given sample. Samples with obvious optical defects in film preparation were not used in optical testing.
  • the aliphatic polyurethanes can be prepared in a roll to roll process where the isocyanate and polyol with catalyst are mixed using an inline dynamic mixer.
  • the solutions can be applied to a moving web between a silicone release liner and an approximately lOum thick ionic elastomer nanocomposite coating from any of the preparatory film substrate SI to S 8 on unprimed PET.
  • the surface of the Ionic elastomer nanocomposite can be activated with an atmospheric plasma.
  • the mixed solutions are delivered at an appropriate flow rate to achieve the desired final sample thickness, for example -lOOum, of aliphatic cross-linked polyurethane layer.
  • the polyurethane between films are heated at 70°C and wound into a roll.
  • the polyurethane bonds strongly with the activated surface of the ionic elastomer film on PET.
  • the PET is removed to give a composite two-layer Film substrate where the ionic elastomer nanocomposite from preparatory film substrate SI to S 8 are disposed directly onto the polyurethane.
  • the samples can have a range of physical properties based on the NCO/OH ratios of the polyurethane layer (properties of which are detailed in PU15-PU27 examples in the Preparatory Examples). Further constructions can be made by using various substrate layers in place of the silicone release liner in the above procedure where the substrate is treated to provide adhesion to the polyurethane layer.

Landscapes

  • Laminated Bodies (AREA)

Abstract

Un film multicouche comprend une couche de polyuréthane réticulée aliphatique et une couche de nanocomposite fixée à la couche de polyuréthane. La couche de nanocomposite comprend au moins un polymère et des nanoparticules d'oxyde métallique dispersées dans le ou les polymères. Le ou les polymères comprennent un premier polymère comprenant des motifs monomères d'acide (méth)acrylique. Les nanoparticules d'oxyde métallique sont modifiées en surface par un agent de modification de surface à base d'acide carboxylique et de silane. Le film multicouche peut comprendre des couches supplémentaires. Le film multicouche peut être un film d'affichage protecteur transparent.
PCT/IB2021/050265 2020-01-29 2021-01-14 Film multicouche avec couche de nanocomposite et couche de polyuréthane WO2021152412A1 (fr)

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JP2008105919A (ja) * 2006-10-27 2008-05-08 Hakuto Co Ltd ポリマー被覆シリカ
WO2014025762A1 (fr) * 2012-08-07 2014-02-13 3M Innovative Properties Company Composition de revêtement pour la prévention et/ou le retrait de calcaire et/ou d'écume de savon
JP2014071419A (ja) * 2012-10-01 2014-04-21 Konica Minolta Inc 光学フィルム及び光学フィルムの製造方法
JP2016103015A (ja) * 2014-11-14 2016-06-02 新日鉄住金化学株式会社 タッチパネル絶縁膜・保護膜形成用の感光性樹脂組成物、並びにこれを用いた硬化膜及びタッチパネル
WO2017015885A1 (fr) * 2015-07-29 2017-02-02 3M Innovative Properties Company Compositions antisalissures contenant des microparticules de silice et des composés silane fonctionnels et articles revêtus associés
JP2017097381A (ja) * 2012-03-05 2017-06-01 味の素株式会社 感光性樹脂組成物
JP2018024717A (ja) * 2016-08-08 2018-02-15 スリーエム イノベイティブ プロパティズ カンパニー アクリル系感圧接着剤、その製造方法、及びマーキングフィルム
JP2019019232A (ja) * 2017-07-18 2019-02-07 第一工業製薬株式会社 酸化ジルコニウム粒子分散体組成物およびその硬化物
US20190112714A1 (en) * 2016-03-30 2019-04-18 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Conversion-coated metal plate for non-condensed thermoplastic resin bonding, surface-treated metal plate for non-condensed thermoplastic resin bonding, composite member, and method for producing conversion-coated metal plate for non-condensed thermoplastic resin bonding

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002241583A (ja) * 2001-02-14 2002-08-28 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及び半導体装置
JP2008105919A (ja) * 2006-10-27 2008-05-08 Hakuto Co Ltd ポリマー被覆シリカ
JP2017097381A (ja) * 2012-03-05 2017-06-01 味の素株式会社 感光性樹脂組成物
WO2014025762A1 (fr) * 2012-08-07 2014-02-13 3M Innovative Properties Company Composition de revêtement pour la prévention et/ou le retrait de calcaire et/ou d'écume de savon
JP2014071419A (ja) * 2012-10-01 2014-04-21 Konica Minolta Inc 光学フィルム及び光学フィルムの製造方法
JP2016103015A (ja) * 2014-11-14 2016-06-02 新日鉄住金化学株式会社 タッチパネル絶縁膜・保護膜形成用の感光性樹脂組成物、並びにこれを用いた硬化膜及びタッチパネル
WO2017015885A1 (fr) * 2015-07-29 2017-02-02 3M Innovative Properties Company Compositions antisalissures contenant des microparticules de silice et des composés silane fonctionnels et articles revêtus associés
US20190112714A1 (en) * 2016-03-30 2019-04-18 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Conversion-coated metal plate for non-condensed thermoplastic resin bonding, surface-treated metal plate for non-condensed thermoplastic resin bonding, composite member, and method for producing conversion-coated metal plate for non-condensed thermoplastic resin bonding
JP2018024717A (ja) * 2016-08-08 2018-02-15 スリーエム イノベイティブ プロパティズ カンパニー アクリル系感圧接着剤、その製造方法、及びマーキングフィルム
JP2019019232A (ja) * 2017-07-18 2019-02-07 第一工業製薬株式会社 酸化ジルコニウム粒子分散体組成物およびその硬化物

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