Protective structure of laminated material

Abstract

Protective structures for laminates and laminates including the same are provided that can be used in a variety of different applications, such as crush resistant windows for vehicles and buildings. The protective structure includes a first layer including polycarbonate (PC), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), acrylics, or a combination thereof, and having a first surface and a second surface opposite the first surface. The structure also includes a hard coat layer on the first surface of the first layer and a second layer in contact with the second surface of the first layer, the second layer including a thermoplastic polyurethane (TPU). Fabricating the protective structure into a single film or layer reduces material handling steps and reduces costs. In addition, the number of independent webs of the structure is smaller, and the structure can be made to be thinner, thereby further reducing the manufacturing cost.

Description

Cross-reference to related applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 519,422, filed August 14, 2023, the full disclosure of which is incorporated herein by reference for all purposes. Technical Field

[0002] This specification generally relates to protective structures for laminated components, such as membranes, layers, coatings, or overlays, and more specifically to external safety films for shatterproof windows. Background Technology

[0003] Debris refers to fragments or pieces that break off from a pane of glass when it shatters. When a vehicle or building window is hit by strong winds or an external object, this debris can fly inwards and cause serious cuts. Injuries from broken glass can be life-threatening, result in permanent scarring, or lead to limb loss.

[0004] Safety or “peel-resistant” window films provide an extra barrier, improving the glass’s resistance to breakage and / or penetration, thereby enhancing the window’s bulletproof performance and security. These protective films typically consist of a layer of polyethylene terephthalate (PET) with a scratch-resistant outer hard coating. The PET layer adheres to the outer surface of the glass via an adhesive interlayer to protect people and property from glass peeling. Summary of the Invention

[0005] This application provides a protective structure for laminated materials and the laminated materials themselves, which can be used in a variety of different applications, such as windows in vehicles and buildings. The laminated materials are particularly suitable for applications requiring shatter resistance or impact resistance, such as shatterproof and / or bulletproof glass, skylights, windshields, light bulbs, skylights, security doors, screen protectors, curtain walls, public transportation vehicles, ships, military installations, critical infrastructure, etc.

[0006] In one aspect, a protective structure includes a first layer comprising a material selected from polycarbonate (PC), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), acrylics, and combinations thereof, and having a first surface and a second surface opposite to the first surface. The structure also includes a hard coating layer on the first surface of the first layer, and a second layer in contact with the second surface of the first layer, the second layer comprising thermoplastic polyurethane (TPU).

[0007] In one embodiment, the TPU layer is directly extruded onto the first layer to form a single structure, film, or layer. In an exemplary embodiment, the first layer comprises PET. Forming a protective structure with a single TPU layer and a PET layer reduces material handling steps and costs. Furthermore, the structure has fewer individual webs and can be manufactured in a thinner thickness, further reducing manufacturing costs.

[0008] In one embodiment, the thickness of the structure is approximately 0.015 inches to approximately 0.020 inches, or approximately 0.016 inches to approximately 0.018 inches, or approximately 0.017 inches. The thickness of the first layer can be approximately 0.005 inches to approximately 0.009 inches, or approximately 0.007 inches. The thickness of the second layer can be approximately 0.008 inches to approximately 0.012 inches, or approximately 0.010 inches.

[0009] The TPU layer may comprise any suitable thermoplastic polyurethane, such as polyesters, polyethers, polycaprolactones, etc., which is substantially optically transparent and has sufficient protective properties to bond to various materials, such as glass, polycarbonate, acrylics, etc. In an exemplary embodiment, the TPU layer comprises an aliphatic TPU, preferably a polyether aliphatic TPU. The hardness of the polyether aliphatic TPU can be in the range of about 60 Shore A to about 100 Shore A, or about 70 Shore A to about 85 Shore A.

[0010] In this embodiment, the hard coating is a scratch-resistant "hard" coating comprising one or more materials that prevent scratches from forming on the first layer. Suitable materials for the hard coating include, but are not limited to, silicones, solvent-based acrylics, solvent-free acrylics, diamond-like carbon (DLC), and combinations thereof. Additionally, or alternatively, the hard coating may include additives, fillers, and / or binders that provide scratch resistance.

[0011] The hard coating can be applied to the first layer in any suitable manner, such as drop casting, dip coating, optical deposition, vacuum deposition, electrospinning, electrostatic spraying, layer-by-layer deposition, spin coating, etc. In an exemplary embodiment, the hard coating is sputtered onto the PET layer.

[0012] In this embodiment, the protective structure is substantially optically transparent. Therefore, the haze of the structure can be less than about 4%, or less than about 3%, preferably less than or equal to about 1%. The light transmittance of the structure can be greater than about 50%, or greater than about 70%, preferably greater than or equal to about 90%. The yellowness index (YI) of the structure can be less than about 2 or less than about 1.

[0013] In one embodiment, the protective structure further includes a third layer that contacts the surface of the second layer opposite to the first layer. The third layer includes a release liner, such as interlayer paper, which can be removed from the TPU layer before the structure is applied to a substrate such as glass. The thickness of the interlayer paper can be from about 0.002 inches to about 0.006 inches, or about 0.004 inches.

[0014] In some embodiments, the structure may be adhered to a single transparent substrate or layer, such as glass, polycarbonate, etc. In other embodiments, the structure may be part of a laminated assembly including one or more additional layers adhered to the transparent substrate. The transparent substrate may include any optically transparent material with sufficient rigidity to be suitable for a particular application. Suitable materials for the substrate include, but are not limited to, glass, artificial glass, polycarbonate, acrylic resin, polyester, polyether, and polyurethane. In exemplary embodiments, the transparent substrate includes glass or polycarbonate.

[0015] In another aspect, a laminated material is provided, which includes one of the aforementioned protective structures.

[0016] In another aspect, a window is provided that includes one of the aforementioned protective structures.

[0017] In another aspect, the laminate includes an optically transparent substrate and a protective structure adhered to the substrate. The protective structure includes a first layer comprising a material selected from polycarbonate (PC), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), acrylics, and combinations thereof. The first layer has a first surface and a second surface opposite to the first surface. The structure also includes a hard coating layer on the first surface of the first layer and a second layer in contact with the second surface of the first layer, the second layer comprising thermoplastic polyurethane (TPU). The TPU layer is adhered to the optically transparent substrate.

[0018] In embodiments, the optically transparent substrate may include one of glass, artificial glass, polycarbonate, acrylic resin, polyester, polyether, and / or polyurethane. In an exemplary embodiment, the transparent substrate includes glass or polycarbonate.

[0019] In one embodiment, the protective structure is bonded to a first surface of a transparent substrate, and the laminate further includes an intermediate layer that contacts a second surface of the transparent substrate opposite to the first surface. In another embodiment, the laminate includes a second optically transparent substrate that contacts the intermediate layer and is opposite to the first substrate. The second substrate may include glass, artificial glass, polycarbonate, acrylic resin, polyester, polyether, and / or polyurethane.

[0020] In some embodiments, any other layer of the protective structure and / or laminate may include one or more functional elements with solar energy control properties. Suitable functional elements include, but are not limited to, light emitters, ionomers, and optical elements, such as UV absorbers, UV reflectors, IR absorbers, IR reflectors, etc. In one embodiment, the functional element includes a solar energy control element, such as a heat absorber, a heat reflector, a filter, a photovoltaic module, an electrochromic module, or a combination thereof. Attached Figure Description

[0021] The accompanying drawings, which are incorporated in and form a part of this specification, illustrate several embodiments of the present disclosure and, together with the description, serve to explain the principles of the present disclosure.

[0022] Figure 1 This is a cross-sectional schematic diagram of the protective structure; and Figure 2 It has Figure 1 A schematic diagram of the cross-section of the multilayer laminated material of the protective structure. Detailed Implementation

[0023] This specification and accompanying drawings illustrate exemplary embodiments and should not be considered limiting. The claims (including equivalents) define the scope of this disclosure. Various mechanical, compositional, structural, and operational changes may be made without departing from the scope of this specification and the claims (including equivalents). In some cases, well-known structures and techniques have not been shown or described in detail so as not to obscure this disclosure. Identical numbers in two or more drawings denote identical or similar elements. Furthermore, elements and related aspects described in detail with reference to one embodiment may, where practically feasible, be included in other embodiments where they are not specifically shown or described. For example, if an element is described in detail with reference to one embodiment but not with reference to a second embodiment, that element may still be claimed as included in the second embodiment. Furthermore, the illustrations herein are for illustrative purposes only and do not necessarily reflect the actual shape, size, or dimensions of the system or the components shown.

[0024] It should be noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” as well as the singular use of any word, include plural referents unless explicitly and unambiguously limited to a single referent. As used herein, the term “comprising” and its grammatical variations are intended to be non-restrictive, such that the listing of items does not exclude other similar items that may be substituted for or added to the listed items.

[0025] A protective structure for laminated materials and a laminated material including the protective structure are provided, which can be used in a variety of different applications, such as windows in vehicles and buildings. The laminated material is particularly suitable for applications requiring shatter resistance or impact resistance, such as shatterproof or bulletproof glass, skylights, windshields, light bulbs, skylights, security doors, screen protectors, curtain walls, public transportation vehicles, ships, military installations, critical infrastructure, etc. In some embodiments, the protective structure and / or laminated material may also include solar energy control properties, such as light emitters, ionomers, UV and / or IR light filters, heat filters, etc.

[0026] In some implementations, such as Figure 1 As shown, the protective structure 10 includes a first layer 30 having a hard coating 40 and a second layer 20 of thermoplastic polyurethane (TPU) in contact with the surface of the first layer 30 opposite to the coating 40. The structure 10 may include an optional third layer 50, such as interlayer paper, release liner, etc. The interlayer paper 50 serves to prevent the TPU layer 20 from adhering to other materials such as equipment, packaging, etc., and is typically removed before the structure 10 is applied to a transparent substrate such as a window or door.

[0027] like Figure 1 As shown, the TPU layer 20 is preferably extruded directly onto the first layer 30 to form a single structure, film, or layer 10. Forming a single-layer protective structure reduces material handling steps and costs. Furthermore, this structure has fewer individual webs and can be manufactured in thinner thicknesses, further reducing manufacturing costs.

[0028] Suitable materials for the first layer 30 include, but are not limited to, polycarbonate (PC), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), acrylics, and combinations thereof. In one embodiment, the first layer comprises a blend of TPU and acrylics, which are co-crosslinked to form a harder layer. In another embodiment, the first layer 30 comprises PET.

[0029] In this embodiment, the thickness of structure 10 is approximately 0.015 inches to approximately 0.020 inches, or approximately 0.016 inches to approximately 0.018 inches, or approximately 0.017 inches. The thickness of PET layer 30 may be approximately 0.005 inches to approximately 0.009 inches, or approximately 0.007 inches. The thickness of TPU layer 20 may be approximately 0.008 inches to approximately 0.012 inches, or approximately 0.010 inches.

[0030] Combining the PET and TPU layers into a single layer allows both layers to be thinner than conventional protective films. Manufacturers are typically able to process polymer layers with a thickness of approximately 0.015 inches or more. Therefore, by combining the two layers into a single structure with a thickness of approximately 0.017 inches, the overall thickness of the protective structure can be reduced.

[0031] The second layer 20 includes a TPU that is substantially optically transparent and has sufficient protective properties to adhere to various materials, such as glass, polycarbonate, acrylics, etc. In an exemplary embodiment, the TPU includes an aliphatic TPU, preferably a polyether aliphatic TPU. Aliphatic TPUs are important compounds with excellent optical transparency and generally do not degrade (i.e., yellow) when exposed to UV light. Furthermore, polyether aliphatic TPUs have extremely strong adhesion and can adhere to many different substances, such as polycarbonate, acrylics, etc.

[0032] The hardness of polyether aliphatic TPU can range from about 60 Shore A to about 100 Shore A, or from about 70 Shore A to about 85 Shore A. The tear strength of polyether aliphatic TPU, measured according to ASTM D412, can be at least about 250 psi or higher, or at least about 320 psi or higher, and the ultimate tensile strength of polyether aliphatic TPU, measured according to ASTM D412, can be at least about 6000 psi or at least about 7000 psi.

[0033] In some embodiments, the haze of the protective structure 10 may be less than about 3.5%, or less than about 2%, preferably less than or equal to about 1%. The light transmittance of the structure may be greater than about 50%, or greater than about 50%, preferably greater than or equal to about 90%. The yellowness index (YI) of the structure may be less than about 2 or less than about 1.

[0034] The first layer 30 may include an tackifier to enhance the adhesion between the first layer 30 and the TPU layer 20 and to prevent delamination of the TPU from the first layer. Suitable tackifiers include, but are not limited to, organosilanes, organotitanates, zirconates, zirconium aluminates, alkyl phosphates, organometallic compounds, etc.

[0035] Hard coating 40 is a scratch-resistant "hard" coating comprising one or more materials that prevent scratch formation on the first layer of the protective structure. Suitable materials for the hard coating include, but are not limited to, silicones, solvent-based acrylics, solvent-free acrylics, diamond-like carbon (DLC), and combinations thereof. Additionally, or alternatively, the hard coating may include additives, fillers, and / or adhesives that provide scratch resistance. Suitable adhesives include, but are not limited to, inorganic non-metallic ceramics, polysilazanes, DLCs, organic polymer-based resin adhesives, epoxy resins, polycarbonates, polyethylene, and combinations thereof. Suitable fillers include, but are not limited to, titanium dioxide (TiO2), zirconium dioxide (ZrO2), aluminum hydroxide (AlOOH), silicon monoxide (SiO), and combinations thereof. Suitable additives include, but are not limited to, siloxanes, erucamide, MoS2, graphite, oleamide, zinc oxide (ZnO), barium oxide (BaO), lead dioxide (PbO), and combinations thereof.

[0036] In an exemplary embodiment, the hard coating 40 comprises a solvent-based or solvent-free acrylic. The hard coating 40 can be applied to the first layer 30 in any suitable manner, such as drop casting, dip coating, optical deposition, vacuum deposition, electrospinning, electrostatic spraying, layer-by-layer deposition, spin coating, etc. In an exemplary embodiment, the coating 40 is sputtered onto layer 30.

[0037] In some embodiments, the selected TPU is flexible or moldable to form a deformable or flexural laminate with solar energy control properties. In this embodiment, the laminate can be used with curved glass, polycarbonate, etc., to manufacture, for example, bay windows, arched windows, domed windows, corner windows, pre-bent vehicle windows, curved bulletproof windows, etc.

[0038] Now refer to Figure 2 Another embodiment of the laminate 100 includes an outer layer 110 and a protective structure 10 laminated to the outer layer 110. The protective structure 10 includes a first layer 30 having a hard coating 40, and a second thermoplastic polyurethane (TPU) layer 20 in contact with the surface of the first layer 30 opposite to the coating 40. The TPU layer 20 is also bonded to the surface of the outer layer 110. Before bonding the TPU layer 20 to the outer layer 110, the interlayer paper 50 (see [link to documentation]) has been removed. Figure 1 As with previous embodiments, the first layer 30 may include polycarbonate (PC), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), acrylics and combinations thereof, such as crosslinked blends of acrylics and TPU.

[0039] The outer layer 110 comprises an optically transparent, substantially rigid material. Suitable materials for the outer layer 110 include, but are not limited to, glass, artificial glass, or any well-known glass alternative, such as polycarbonate, acrylic resin, polyester, polyether, and polyurethane.

[0040] In some embodiments, the laminate 100 may further include an additional intermediate layer and / or optically transparent layer adhered to the surface of layer 110 opposite to the protective structure 10. In one such embodiment, the protective structure 10 is bonded to a first surface of the substrate 110, and the laminate further includes an intermediate layer (not shown) bonded to a second surface of the substrate opposite to the first surface. In embodiments, the laminate includes a second optically transparent substrate (not shown) bonded to the intermediate layer and opposite the first substrate. The second substrate may include glass, artificial glass, or any well-known glass alternative, such as polycarbonate, acrylic resin, polyester, polyether, and polyurethane.

[0041] In some embodiments, any other layer of the protective structure 10 or the laminate 100 may include one or more functional elements therein. Suitable functional elements include, but are not limited to, solar control elements, light emitters, ionomers, and optical elements, such as UV absorbers, UV reflectors, IR absorbers, IR reflectors, etc. In one embodiment, the functional element includes a solar control element. Suitable solar control elements include, but are not limited to, heat absorbers, heat reflectors, filters, photovoltaic modules, electrochromic modules, and combinations thereof.

[0042] In some embodiments, any other layer of the protective structure 10 or the laminate 100 may include one or more optical elements, materials, and / or layers made of materials that allow visible light to pass through and reflect or absorb UV and / or IR light. For example, an IR-blocking optical element may be configured to reflect or absorb light with wavelengths from about 700 nm to 1 mm, preferably from about 700 nm to about 1400 nm (i.e., near-infrared wavelengths), more preferably from about 750 nm to about 1200 nm. In one embodiment, the optical element includes an IR-reflective coating. Suitable materials for reflecting light in the IR range include metals or metal-based coatings, such as double or triple silver coatings, liquid crystal materials that selectively transmit or scatter IR light, etc.

[0043] In another embodiment, the optical element includes an IR absorbing material, such as an IR absorbing dye, a copper salt composition (e.g., copper phosphonate), nanoparticles (e.g., zinc oxide, antimony tin oxide (ATO), lanthanum hexaboride (LaB), etc.), an infrared filter (e.g., blue glass), an intermediate layer film including infrared shielding fine particles, etc.

[0044] In yet another embodiment, the IR absorbing element comprises IR absorbing particles (e.g., nanoparticles) dispersed in a TPU layer. In this embodiment, for example, the first TPU layer may comprise a UV blocking material, while the second TPU layer comprises IR blocking particles.

[0045] In some embodiments, any other layer of the protective structure 10 or the laminate 100 may include an optical element, layer, or material capable of reflecting or absorbing UV light. The UV-blocking optical element preferably reflects or absorbs light with wavelengths of about 10 to 410 nanometers, more preferably greater than about 380 nanometers, and even more preferably about 380 to 410 nanometers. The optical element may include any material suitable for being configured to reflect or absorb UV light, such as UV radiation absorbing, blocking, or shielding additives. Suitable UV absorbing, blocking, or shielding additives for this disclosure include combinations of benzophenones, cinnamic acid derivatives, esters of benzoic acid, alicyclic acids, esters of terephthalic acid and isophthalic acid with resorcinol and phenol, pentamethylpiperidine derivatives, salicylates, benzotriazoles, cyanoacrylates, benzylenes, malonates, and oxalamides with nickel chelates and hindered amines.

[0046] Alternatively, UV-blocking optical elements may include a filter layer within a TPU layer. Suitable optical elements for use in this application include sheet polarizers, dichroic reflective filter materials, etc., to provide broadband UV radiation attenuation. For example, blue or green colored glass with significantly reduced UV transmittance, or blue or green colored polymer interlayers, coatings, or layers or polymer films of UV radiation attenuating coatings or varnishes may be suitable as UV-blocking materials.

[0047] In some embodiments, the optical element includes an IR blocking layer capable of reflecting or absorbing IR light and a separate UV blocking element capable of reflecting or absorbing UV light. The IR blocking element is preferably disposed between and in contact with one of the first and second thermoplastic polyurethane layers 130, 140. The IR blocking element is capable of reflecting or absorbing light with wavelengths from about 700 nm to about 1 mm, preferably from about 700 nm to about 1400 nm, more preferably from about 750 nm to about 1200 nm. The UV blocking element is preferably capable of reflecting or absorbing light with wavelengths from about 10 nm to 410 nm, preferably from about 380 nm to 410 nm.

[0048] Alternatively, the optical element may comprise a single material that blocks both UV and IR light. Suitable materials for the optical layer in this embodiment may include a metallic coating, such as a double or triple silver layer. A more complete description of optical elements that absorb or reflect IR and UV light can be found in co-filed International Application No. PCT / US2021 / 40300 (titled “Laminated Materials Having Optical Layers or Materials”), filed July 20, 2021, the full description of which is incorporated herein by reference for all purposes.

[0049] In some embodiments, any other layer of the protective structure or laminate 100 may include one or more light emitters. In an exemplary embodiment, the light emitter is a fluorophore, which is a fluorescent compound configured to re-emit light upon photoexcitation. A fluorophore typically comprises a plurality of combined aromatic groups, or a planar or cyclic molecule having a plurality of π bonds.

[0050] The luminescent material can be configured to absorb most of the NIR or UV photons that pass through the laminated material. In one embodiment, the protective structure comprises a blend of phosphorescent organic molecules or multiple luminescent materials (e.g., quantum dots or organic dyes) to reduce reabsorption loss and improve absorption efficiency across the entire spectrum.

[0051] In some embodiments, any other layer of the protective structure or laminate 100 may comprise an ionomer or a polymer consisting of repeating units of electrically neutral repeating units and ionized units covalently bonded to the polymer backbone as side-group portions. A certain molar percentage (e.g., 15% or less) is ionized. The ionomer may have unique physical properties, such as conductivity and viscosity.

[0052] In some embodiments, any other layer of the protective structure or laminate 100 may include photovoltaic, electrochromic, and / or other functionalities for electrical conductivity. In one such embodiment, the laminate 100 includes a photovoltaic module therein. For example, quantum dots may be provided in any other layer of the protective structure 10 or laminate 100. Another suitable quantum dot alternative for energy generation is organic photovoltaic (OPV) cells, which can be applied here. Organic photovoltaic technology is rapidly emerging due to its improved cell efficiency, extended forward performance lifetime, and the potential for roll-to-roll manufacturing through solution processing. OPV technology is a highly attractive alternative because it can provide absorbers of any color and can fabricate highly efficient transparent devices. Another advantage is that a variety of organic materials can be used to design and synthesize absorbers, acceptors, and interfaces. Organic photovoltaic cells can be applied via film deposition, such as sputtering and pulsed laser deposition, to fabricate this film-type OPV for energy generation. For a more complete description of suitable photovoltaic modules, see co-filed pending U.S. Provisional Patent Application No. 63 / 470,128 (“Functional Glass and Artificial Glass Laminates”), filed May 31, 2023, the full disclosure of which is incorporated herein by reference for all purposes.

[0053] While materials and products formed from these materials have been described in detail herein according to certain preferred embodiments, many modifications and alterations can be made thereto by those skilled in the art. Therefore, the foregoing description should not be construed as limiting, but rather as including the obvious variations described above, and is limited only by the spirit and scope of the following claims.

[0054] For example, in one aspect, a first embodiment is a protective structure comprising a first layer comprising a material selected from polycarbonate (PC), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), acrylics, and combinations thereof, the first layer having a first surface and a second surface opposite to the first surface; a hard coating on the first surface of the first layer; and a second layer comprising thermoplastic polyurethane (TPU) and in contact with the second surface of the first layer.

[0055] The second implementation is the first implementation, wherein the thickness of the structure is about 0.015 inches to about 0.020 inches.

[0056] The third implementation is any combination of the first two implementations, wherein the thickness is about 0.016 inches to about 0.018 inches.

[0057] The fourth implementation is any combination of the first three implementations, wherein the TPU includes aliphatic TPU.

[0058] The fifth embodiment is any combination of the first four embodiments, wherein the aliphatic TPU is a polyether-based aliphatic TPU.

[0059] The sixth embodiment is any combination of the first five embodiments, wherein the thickness of the first layer is about 0.005 inches to about 0.009 inches.

[0060] The seventh implementation is any combination of the first six implementations, wherein the thickness of the second layer is about 0.008 inches to about 0.012 inches.

[0061] The eighth embodiment is any combination of the first seven embodiments, wherein the protective structure is substantially optically transparent.

[0062] The ninth embodiment is any combination of the first eight embodiments, wherein the haze of the protective structure is less than about 1%.

[0063] The tenth embodiment is any combination of the first nine embodiments, wherein the light transmittance of the protective structure is greater than about 90%.

[0064] The eleventh embodiment is any combination of the first ten embodiments, wherein the second layer is extruded onto the first layer.

[0065] The twelfth embodiment is any combination of the preceding eleven embodiments, wherein the hard coating comprises a material selected from silicone and acrylics.

[0066] The thirteenth embodiment is any combination of the first three embodiments, and further includes a third layer that contacts the surface of the second layer opposite to the first layer, the third layer including a release liner.

[0067] The fourteenth embodiment is any combination of the preceding thirteen embodiments, wherein the coating is sputtered onto the first layer.

[0068] The fifteenth embodiment is any combination of the previous fourteen embodiments, wherein the first layer includes PET.

[0069] In another aspect, a laminated material is provided that includes a protective structure comprising any combination of the first fifteen embodiments.

[0070] In another aspect, a window is provided that includes a protective structure comprising any combination of the first fifteen embodiments.

[0071] In another aspect, a shatterproof window is provided, which includes a protective structure comprising any combination of the first fifteen embodiments.

[0072] In another aspect, a first embodiment is a laminated material comprising an optically transparent substrate and a protective structure adhered to the substrate. The protective structure includes a first layer comprising a material selected from polycarbonate (PC), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), acrylics, and combinations thereof, the first layer having a first surface and a second surface opposite to the first surface; a hard coating layer located on the first surface of the first layer; and a second layer in contact with the second surface of the first layer, the second layer comprising thermoplastic polyurethane (TPU). The TPU layer is in contact with the optically transparent substrate.

[0073] The second embodiment is the first embodiment, wherein the substrate comprises a material selected from glass, artificial glass, polycarbonate, acrylic, polyester, polyether and polyurethane.

[0074] The third embodiment is any combination of the first two embodiments, wherein the substrate comprises glass or polycarbonate.

[0075] The fourth embodiment is any combination of the first three embodiments, wherein the thickness of the structure is about 0.015 inches to about 0.020 inches.

[0076] The fifth embodiment is any combination of the first four embodiments, wherein the thickness is about 0.016 inches to about 0.018 inches.

[0077] The sixth implementation is any combination of the first five implementations, wherein the TPU includes aliphatic TPU.

[0078] The seventh embodiment is any combination of the first six embodiments, wherein the thickness of the first layer is about 0.005 inches to about 0.009 inches.

[0079] The eighth embodiment is any combination of the first seven embodiments, wherein the thickness of the second layer is about 0.008 inches to about 0.012 inches.

[0080] The ninth embodiment is any combination of the first eight embodiments, wherein the protective structure is substantially optically transparent.

[0081] The tenth embodiment is any combination of the first nine embodiments, wherein the second layer is extruded onto the first layer.

[0082] The eleventh embodiment is any combination of the preceding ten embodiments, wherein the coating comprises a material selected from acrylics and silicones.

[0083] The twelfth embodiment is any combination of the preceding eleven embodiments, further including a third layer that contacts the surface of the second layer opposite to the first layer, the third layer including a release liner.

[0084] The thirteenth embodiment is any combination of the first twelve embodiments, wherein the coating is sputtered onto the first layer.

[0085] The fourteenth embodiment is any combination of the preceding thirteen embodiments, wherein the protective structure contacts a first surface of the substrate, and the laminate further includes an intermediate layer that contacts a second surface of the substrate opposite the first surface.

[0086] The fifteenth embodiment is any combination of the preceding fourteen embodiments, and further includes a second optically transparent substrate that is in contact with the intermediate layer and opposite to the first substrate.

[0087] The sixteenth embodiment is any combination of the preceding fifteen embodiments, wherein the second substrate comprises glass or polycarbonate.

[0088] The seventeenth embodiment is any combination of the first sixteen embodiments, wherein the laminate is bulletproof.

[0089] The eighteenth embodiment is any combination of the preceding seventeen embodiments, wherein the first layer includes PET.

[0090] In another aspect, a window is provided that comprises a laminated material of any combination of the first eighteen embodiments.

[0091] In another aspect, a shatter-resistant window is provided, comprising a laminate of any combination of the first eighteen embodiments.

Claims

1. A protective structure, comprising: The first layer comprises a material selected from polycarbonate (PC), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), acrylics, and combinations thereof, the first layer having a first surface and a second surface opposite to the first surface; A hard coating layer is located on the first surface of the first layer; and The second layer comprises thermoplastic polyurethane (TPU) and is in contact with the second surface of the first layer.

2. The protective structure of claim 1, wherein the thickness of the structure is from about 0.015 inches to about 0.020 inches.

3. The protective structure of claim 2, wherein the thickness is about 0.016 inches to about 0.018 inches.

4. The protective structure of claim 1, wherein the second layer is extruded onto the first layer to form a single structure.

5. The protective structure of claim 1, wherein the TPU comprises aliphatic TPU.

6. The protective structure of claim 5, wherein the aliphatic TPU is a polyether-based aliphatic TPU.

7. The protective structure of claim 1, wherein the thickness of the first layer is from about 0.005 inches to about 0.009 inches.

8. The protective structure of claim 7, wherein the thickness of the second layer is from about 0.008 inches to about 0.012 inches.

9. The protective structure of claim 1, wherein the protective structure is substantially optically transparent.

10. The protective structure of claim 1, wherein the haze of the protective structure is less than about 1%.

11. The protective structure of claim 1, wherein the light transmittance of the protective structure is greater than about 90%.

12. The protective structure of claim 1, wherein the hard coating comprises a material selected from acrylics and silicones.

13. The protective structure of claim 1 further includes a third layer, the third layer being in contact with the surface of the second layer opposite to the first layer, the third layer including a release liner.

14. The protective structure of claim 1, wherein the hard coating is sputtered onto the first layer.

15. The protective structure of claim 1, wherein the first layer comprises PET.

16. A laminated material comprising the protective structure of claim 1.

17. A window comprising the protective structure of claim 1.

18. A shatterproof window, comprising the protective structure of claim 1.

19. A laminated material, comprising: Optically transparent substrate; as well as A protective structure adhered to the substrate, the protective structure comprising: The first layer comprises a material selected from polycarbonate (PC), polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), acrylics, and combinations thereof, the first layer having a first surface and a second surface opposite to the first surface; A hard coating layer is located on the first surface of the first layer; and The second layer comprises thermoplastic polyurethane (TPU), which contacts the second surface of the first layer and the optically transparent substrate.

20. The laminate of claim 19, wherein the substrate comprises a material selected from glass, artificial glass, polycarbonate, acrylic, polyester, polyether, and polyurethane.

21. The laminate of claim 19, wherein the substrate comprises glass or polycarbonate.

22. The laminate of claim 19, wherein the thickness of the protective structure is from about 0.015 inches to about 0.020 inches.

23. The laminate of claim 22, wherein the thickness is from about 0.016 inches to about 0.018 inches.

24. The laminate of claim 19, wherein the second layer is extruded onto the first layer to form a single structure.

25. The laminated material of claim 19, wherein the TPU comprises aliphatic TPU.

26. The laminate of claim 19, wherein the thickness of the first layer is from about 0.005 inches to about 0.009 inches.

27. The laminate of claim 26, wherein the thickness of the second layer is from about 0.008 inches to about 0.012 inches.

28. The laminate of claim 19, wherein the protective structure is substantially optically transparent.

29. The laminate of claim 19, wherein the hard coating comprises a material selected from acrylics and silicones.

30. The laminate of claim 19 further comprises a third layer, the third layer being in contact with the surface of the second layer opposite to the first layer, the third layer comprising a release liner.

31. The laminate of claim 19, wherein the coating is sputtered onto the first layer.

32. The laminate of claim 19, wherein the protective structure is in contact with a first surface of the substrate, and the laminate further comprises an intermediate layer in contact with a second surface of the substrate opposite to the first surface.

33. The laminated material of claim 32 further includes a second optically transparent substrate, the second optically transparent substrate being in contact with the intermediate layer and opposite to the first substrate.

34. The laminate of claim 33, wherein the second substrate comprises glass or polycarbonate.

35. The laminate of claim 19, wherein the first layer comprises PET.

36. The laminate of claim 19, wherein the laminate is bulletproof.

37. A window comprising the laminated material of claim 19.

38. A shatterproof window comprising the laminate of claim 19.

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