MULTIFUNCTIONAL LAMINATES

Abstract

The present disclosure relates to compositions, laminates, films and/or composites made from polymers, such as thermoplastic polyurethane (TPU), and windows incorporating the same. The films may have one or more optical layers made from materials that allow the transmission of visible light and reflect or absorb ultraviolet (UV) light. A composite having an infrared (IR) cutoff layer, and a polymer layer desirably having UV absorber may be disposed between layers of glass or artificial glass, combined with polycarbonate (PC) or polyethylene terephalate (PET) layers.

Claims

1. A window, comprising: a composite, comprising: a first rigid sheet; a second rigid sheet; a first layer of a thermoplastic polyurethane (TPU) resin composite interposed between the first rigid sheet and the second rigid sheet; and a polyethylene terephthalate (PET) film interposed between the first rigid sheet and the second rigid sheet, wherein the TPU resin composite comprises a TPU resin and one or more of an ultraviolet (UV) absorber, a light absorber, or a combination thereof, wherein the TPU resin composite: blocks greater than 99.9% of light having a wavelength of from 380 nm to 400 nm, blocks greater than 99% of light having a wavelength of about 400 nm, or blocks about 95% of light having a wavelength between about 380 and 410 nm.

2. The window of claim 1, wherein the TPU resin composite comprises a combination of the TPU resin, the UV absorber, and the light absorber.

3. The window of claim 2, wherein the UV absorber comprises a combination of two or more UV absorbers.

4. The window of claim 3, wherein at least one UV absorber of the two or more UV absorbers is represented by formula (1): ##STR00003## wherein R.sub.9, R.sub.10, and R.sub.11 are independently selected from hydrogen, a halogen, and a group having a formula C.sub.aH.sub.bN.sub.cO.sub.dS.sub.e, wherein a, b, c, d, and e are independently from 0 to 30.

5. The window of claim 3, wherein at least one UV absorber of the two or more UV absorbers comprises one or more of 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)-phenol, phenol,2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl, or a combination thereof.

6. The window of claim 3, wherein at least one UV absorber of the two or more UV absorbers is selected from the group consisting of 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)-phenol, phenol,2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl, and combinations thereof.

7. The window of claim 2, wherein the light absorber comprises a reaction mass of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate.

8. The window of claim 1, wherein the composite further comprising an infrared (IR) cutoff layer interposed between the first layer of the TPU resin composite and the PET film.

9. The window of claim 1, wherein the TPU resin composite comprises a yellowness index, as measured according to ASTM E313, of less than or equal to 3.0.

10. The window of claim 1, wherein the composite further comprises a low emissivity (low-E) layer interposed between the PET film and the second rigid sheet.

11. The window of claim 10, wherein the composite further comprises a second layer of the TPU resin composite interposed between the PET film and the low-E layer.

12. The window of claim 11, wherein the composite further comprises a third layer of the TPU resin composite interposed between the low-E layer and the second rigid sheet.

13. The window of claim 8, wherein the composite further comprises transparent electromagnetic interference (EMI) shielding or a transparent antenna in or on the IR cutoff layer.

14. The window of claim 1, wherein the first rigid sheet and the second rigid sheet are layers of glass or films of polycarbonate.

15. The window of claim 2, wherein the TPU resin composite comprising the combination of the TPU resin, the UV absorber, and the light absorber, blocks greater than 99% of light having a wavelength of about 400 nm.

16. The window of claim 2, wherein the TPU resin composite comprising the combination of the TPU resin, the UV absorber, and the light absorber, blocks about 95% of light having a wavelength between about 380 and 410 nm.

17. The window of claim 2, wherein the TPU resin composite comprising the combination of the TPU resin, the UV absorber, and the light absorber, blocks greater than 99.9% of light having a wavelength of from 380 nm to 400 nm.

18. A window, comprising: a composite, comprising: a first rigid sheet; a transparent infrared (IR) cutoff layer disposed directly adjacent the first rigid sheet; a first film of a resin composite disposed directly adjacent the transparent IR cutoff layer, wherein the resin composite comprises a combination of a polymer selected from thermoplastic polyurethane (TPU) or ethylene co-vinyl acetate (EVA), an ultraviolet (UV) absorber, and a light absorber; a first PC sheet disposed adjacent the first film of the resin composite; a second film of the resin composite disposed adjacent the first PC sheet; a second PC sheet disposed adjacent the second film of the resin composite; a third film of the resin composite disposed adjacent the second PC sheet; and a second rigid sheet disposed proximal the third film of the resin composite, wherein the UV absorber comprises a combination of two or more UV absorbers, wherein a first UV absorber is selected from the group consisting of 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)-phenol, phenol,2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl, and combinations thereof, and wherein the TPU resin composite, comprising the combination of the TPU resin, the UV absorber, and the light absorber: blocks greater than 99.9% of light having a wavelength of from 380 nm to 400 nm, blocks greater than 99% of light having a wavelength of about 400 nm, or blocks about 95% of light having a wavelength between about 380 and 410 nm.

19. The window of claim 18, further comprising: a low-E layer interposed between the third film of the resin composite and the second rigid sheet; a top coat on at least one of the first rigid sheet and the second rigid sheet; and a transparent antenna or transparent EMI shielding in or on the transparent IR cutoff layer.

20. The window of claim 18, wherein the first rigid sheet and the second rigid sheet are layers of glass or films of polycarbonate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0074] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.

[0075] FIG. 1 is a cross-sectional view of a composite glass including one of the optical films of the present disclosure;

[0076] FIG. 2 is a cross-sectional view of a composite material according to an embodiment, including a layer of glass;

[0077] FIG. 3 is a cross-sectional view of a composite material according to another embodiment, including a layer of glass;

[0078] FIG. 4 is a cross-sectional view of a composite material according to a further embodiment, including a layer of glass;

[0079] FIG. 5 is a cross-sectional view of a composite material according to another embodiment, including a layer of glass;

[0080] FIG. 6 is a cross-sectional view of a composite material according to an embodiment, including a polymeric layer;

[0081] FIG. 7 is a cross-sectional view of a composite material according to another embodiment, including a polymeric layer;

[0082] FIG. 8 is a cross-sectional view of a composite material according to a further embodiment, including a polymeric layer; and

[0083] FIG. 9 is a cross-sectional view of a composite material according to another embodiment, including a polymeric layer.

DETAILED DESCRIPTION

[0084] This description and the accompanying drawings illustrate exemplary embodiments and should not be taken as limiting, with the claims defining the scope of the present disclosure, including equivalents. Various mechanical, compositional, structural, and operational changes may be made without departing from the scope of this description and the claims, including equivalents. In some instances, well-known structures and techniques have not been shown or described in detail so as not to obscure the disclosure. Like numbers in two or more figures represent the same or similar elements. Furthermore, elements and their associated aspects that are described in detail with reference to one embodiment may, whenever practical, be included in other embodiments in which they are not specifically shown or described. For example, if an element is described in detail with reference to one embodiment and is not described with reference to a second embodiment, the element may nevertheless be claimed as included in the second embodiment. Moreover, the depictions herein are for illustrative purposes only and do not necessarily reflect the actual shape, size, or dimensions of the system or illustrated components.

[0085] It is noted that, as used in this specification and the appended claims, the singular forms a, an, and the, and any singular use of any word, include plural referents unless expressly and unequivocally limited to one referent. As used herein, the term include and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items.

[0086] The present laminates and composite materials include optical films made from polymers, such as ethyl co-vinyl acetate (EVA), a thermoplastic polyurethane (TPU) resin composition, or other polymers. For example, the TPU resin composition can include one or more ultraviolet light (UV) absorbers, and a light stabilizer. The films made from such TPU resin compositions have desirable optical characteristics provided by the combination of UV absorbers.

[0087] Composite materials disclosed herein include layers of glass or artificial glass, which may include an IR cutoff layer, and a polymer layer selected from TPU or EVA. The polymer layer selected from TPU or EVA desirably includes a UV absorber, and/or a UV absorber and light stabilizer, and may include more than one UV absorber. Specific examples of TPU compositions are disclosed.

[0088] The UV absorbing TPU layer may be incorporated in a composite and combined with other layers, such as glass or artificial glass. Referring now to FIG. 1, a composite 10 according to the present disclosure comprises first and second layers of glass 12, 14 and a film 16 between the first layer and the second layer of glass. Film 16 may include any of the optical film compositions described herein. In certain embodiments, a window is provided that includes the composite. Optical film 16 may be laminated between at least two sheets of glass substrates facing each other in order to reflect light rays having particular wavelengths in the infrared region.

[0089] Glass layers 12, 14 may comprise any clear or ultraclear glass of a type that is suitable for use in for image sensors, electronic display screens for computers and mobile devices, food packaging, optical disk devices, appliances and the like. Examples include PPG Clear glass, Solarphire.RTM glass or PPG Starphire.RTM glass. Clear glass is preferred so that when the window is illuminated with sunlight, less energy from IR light will be absorbed in glass layer 12 and more energy will be reflected back out of the outside layer of glass and away from the window. Ultraclear glass is more preferred because it absorbs less energy from IR light than clear glass and because its higher transmittance allows more light to be reflected.

[0090] There are of course, other substantially clear materials that can be used as layers 12, 14 to provide rigidity and strength to an optical sheet. These alternative materials include polymeric materials such as, for example, acrylic, polyethylene teraphthalate (PET) or polycarbonate (PC). A glazing component can be substantially planar or have some curvature. It can be provided in various shapes, such as a dome, conical, or other configuration, and cross-sections, with a variety of surface topographies. The present invention is not intended to necessarily be limited to the use of any particular glazing component material(s) or structure.

[0091] FIG. 2 shows a composite material 100 having a first layer of glass 102, a second layer of glass 104, at least one thermoplastic polyurethane (TPU) resin film 106 between the first layer of glass and the second layer of glass, and a polyethylene teraphthalate (PET) film 108 between the first layer of glass and the second layer of glass. In embodiments, the TPU resin includes one or more TPU resins, an ultraviolet (UV) absorber, and a light stabilizer. The TPU layer 106, and any of the TPU layers in the examples discussed below, can have a UV absorber selected from the group consisting of the benzotriazole family and the triazin family, and can be a TPU layer as discussed below. The TPU layer 106 can have one or more UV absorbers. In other examples, ethylene co-vinyl acetate (EVA) is used as film 106 instead of TPU.

[0092] In an example, the composite material 100 has a first layer of glass 102, a first TPU resin film 106 including a TPU resin, a transparent IR cut-off layer, which may be formed by sputter deposition 107, a polyethylene teraphthalate (PET) film 108, another TPU resin film 110, and a final layer of glass 104 (see FIG. 2). The TPU resin film 110 can be a TPU layer as discussed below, or another TPU layer, which may include a UV absorber. The layers of glass 102 and 104 are between about 1 millimeter and about 2 millimeters in thickness, more preferably about 2.1 millimeters, and the TPU layers are each between about about 350 micrometers and about 400 micrometers, and more preferably about 380 micrometers. The PET layer 108 is between about 20 micrometers and about 30 micrometers, and more preferably about 25 microns, for a total overall thickness of between about 2 to about 6 millimeters for the composite. In an example, the TPU resin film or films include one or more TPU resins, one or more ultraviolet (UV) absorbers, and a light stabilizer.

[0093] In an example of forming a glass composite material, a PET film is coated with the transparent IR cutoff coating, and this coating is formed by sputter deposition, plasma deposition, or other methods. The TPU film is preferably formed by extrusion.

[0094] In another example shown in FIG. 3, the composite material 200 has a first layer of glass 202, a first TPU layer 206, a transparent IR cutoff layer 210, which maybe formed by sputter deposition, a PET film 208, a second TPU layer 212, a low emmisivity (low-E) layer 214, which may be formed by sputter deposition, a third TPU layer 216, and a second layer of glass 204. The composite materials 100 and 200 may be used as a window, windshield, roof, or skylight of an automobile, boat or other vehicle. The IR cut-off and low-E layers are applied by sputter deposition, plasma deposition, or other methods. Examples of TPU resin layers can include one or more TPU resins, one or more ultraviolet (UV) absorbers, and a light stabilizer. The TPU layers may be as discussed below, or other TPU layers, which may include a UV absorber. In further examples, EVA is used instead of TPU.

[0095] The entire disclosures of European Patent No. 2 651 639 and European Patent No. 3 387 050 are hereby incorporated by reference herein, disclosing energy shielding films and low emissivity coatings.

[0096] In an example of forming a glass composite material, a PET film is coated with the transparent IR cutoff coating, and this coating is formed by sputter deposition, plasma deposition, or other methods. The TPU or EVA film is preferably formed by extrusion. The low-emmisivity (low-E) layer 214 layer is preferably formed by sputter deposition on the TPU layer 212. However, other deposition methods could be used.

[0097] The example above, having three TPU layers, desirably includes UV absorbers. This example has the advantage that an additional layer of UV shielding further shields a vehicle from unwanted heat and radiation. These layers being about 300 micrometers thick, they do not significantly add to the thickness of the composite material.

[0098] Vehicles are increasingly incorporating more and more technical features, such as autonomous driving, navigation systems, Bluetooth connectivity to devices such as phones, safety systems, etc. These systems are affected by electromagnetic interference (EMI), and communicate wirelessly in some cases. It is therefore desirable to incorporate EMI shielding in the composite material, so that natural light passes through the composite, but the vehicle is protected from unwanted and even harmful interference.

[0099] In an example shown in FIG. 4, the composite material 300 has a first layer of glass 302, a first TPU resin film 306 including a TPU resin, a transparent infrared (IR) cut-off layer, which may be formed by sputter deposition 307, a PET film 308, a second TPU resin film 310, and a final layer of glass 304. The IR cut-off layer 307 includes transparent EMI shielding. The layers of glass 302 and 304 are between about 1 millimeter and about 2 millimeters in thickness, more preferably about 2.1 mm, and the TPU layers are each between about 350 micrometers and about 400 micrometers, more preferably about 380 micrometers. The PET layer 308 is between about 20 micrometers and about 30 micrometers, and more preferably about 25 microns, for a total overall thickness of between about 2 to about 6 millimeters for the composite. In embodiments, the TPU resin layers include one or more TPU resins, one or more ultraviolet (UV) absorbers and a light stabilizer. The TPU layers may be as discussed below, or can be other TPU layers, which may include a UV absorber.

[0100] In another example shown in FIG. 5, the composite 400 has a first layer of glass 402, a first TPU layer 406, an IR cutoff and transparent EMI shield layer 410, which may be formed by sputter deposition, a PET film 408, a second TPU layer 412, a low-E layer 414, which may be formed by sputter deposition, a third TPU layer 416, and a second layer of glass 404. The sputtered layers can be formed by sputter deposition, plasma deposition, or other methods. The composite material 300 or 400 may be used as a window, windshield, roof, or skylight of an automobile, boat or other vehicle.

[0101] The example above having three TPU layers desirably includes UV absorbers. This example has the advantage that an additional layer of UV shielding further shields a vehicle from unwanted heat and radiation. These layers being about 300 micrometers thick, they do not significantly add to the thickness of the composite material.

[0102] In further examples, the IR cut-off and transparent EMI shielding layers 307 and 410 can include a transparent antenna made from a precious metal like silver, in the form of wires, such as nanowires. The antenna can be formed from semiconductor nanowires. The antenna further protects the technical features built into a vehicle from cross-talk, and other interference. The nanowires can be incorporated into the IR cut-off and EMI shield sputtered material as a composite and deposited in a sputtering process. Alternatively, each of the IR cutoff, EMI shielding, and/or antenna can be sputtered or otherwise deposited in two or three separate layers.

[0103] In another exemplary embodiment, FIG. 6 shows an artificial glass composite material using polycarbonate (PC) sheets having good optical characteristics. Artificial glass made from a polymer has benefits in that the material can more easily be shaped in all three directions, making such composites very good candidates for windshields, sunroofs, windows and other features for vehicles. The following examples utilize PC sheets with a high degree of visible light transmission (VLT), such as 70% and more preferably 80% or higher. The PC sheets desirably have low haze of 3% or less and more preferably less than 1%. The artificial glass desirably includes a top coat to protect from scratches, and chemical and environmental damage. The top coat is made from urethanes, acrylates, methacrylates, such as 2k fluoro, 1k polyethylene, 2k acrylic, 2k urethane, 1k acrylic, or urethane primer with UV acrylic. The top coat can be applied by dispersion. The artificial glass also has the advantage that the polymer layers can be extruded and the handling of molten glass is avoided. Furthermore, artificial glass is lighter than the glass composite material, adding better fuel economy to a vehicle such as an automobile.

[0104] The composite material 500 has a first PC film 502, a second PC film 504, at least one TPU layer 506, and a PC sheet 508. The TPU resin includes one or more TPU resins, and desirably has at least one ultraviolet (UV) absorber, and a light stabilizer. The TPU layer 506, for example, has an UV absorber selected from the group consisting of the benzotriazole family and the triazin family. The TPU layers may be as discussed below, or can be other TPU layers, which may include a UV absorber.

[0105] In an example shown in FIG. 6, the composite material 500 has a first PC film 502, a transparent IR cut-off layer 510, a first TPU layer 506, a PC sheet 508, a second TPU layer 512, and a second PC film 513. The IR cut-off layer is applied by sputter deposition or other methods. The TPU layers have a thermoplastic polyurethane. The TPU layers may be as discussed below, or can be other TPU layers, which may include a UV absorber. The PC sheet has a visible light transmissibility of 80% and more desirably 90%. The PC sheet has low haze of 3% or less, and more preferably less than 1%. Desirably, a top coat is applied to each of the PC films (see top coat 501 and top coat 514), to protect against scratches, environmental damage and the like. The top coats mentioned above can be used.

[0106] In another example, the composite material 600 shown in FIG. 7 has a first PC film 602 a transparent IR cut-off layer 610, which can be applied by sputter deposition or other methods, a first TPU layer 606, a first PC sheet 608, a second TPU layer 612, a second PC sheet 620, a third TPU layer 622, a transparent low-E layer, which may be applied by sputter deposition 624 or other methods, and a second PC film 613. A top coat may be applied to each of the PC films. The top coat may be any of the top coats discussed above. A top coat can be applied to the first layer of PC 602 and the second layer of PC 613 to protect against scratches, environmental and other damage. A top coat 601 is desirably applied to first layer of PC 602 and top coat 614 is desirably applied to second layer of PC 613. The composite 600 may be used as a window, windshield, roof, or skylight of an automobile, boat, or other vehicle.

[0107] The example above, having three TPU layers, desirably includes UV absorbers. This example has the advantage that an additional layer of UV shielding further shields a vehicle from unwanted heat and radiation. These layers being about 300 micrometers thick, they do not significantly add to the thickness of the composite material.

[0108] The TPU layers 606, 612, and 622 can be about 380 micrometers thick. The PC sheets 608 and 620 can be between about 1 millimeter and 3 millimeters, more preferably about 2.1 mm and have a visible light transmission (VLT) of about 70%, more preferably 80%, with a haze less than about 3% more preferably less than about 1%.

[0109] Benefits and features of artificial glass include that the material is lightweight, leading to improved gas mileage for vehicles. In addition, the IR cut-off layer also reduces electrical consumption. Utilizing PC sheets with good optical characteristics, the composite provides a transparent window while being thermoformable and avoiding the handling and forming of molten glass.

[0110] In another exemplary embodiment, FIG. 8 shows an artificial glass using PC sheets having good optical characteristics. In the following examples, the PC sheets have a high degree of visible light transmission and low haze, such as mentioned in examples above. The artificial glass can include a top coat to protect from scratches, and chemical and environmental damage. The top coats are as mentioned above. The artificial glass also has the advantage that the polymer layers can be extruded and the handling of molten glass is avoided. Furthermore, artificial glass is lighter than the glass composite material, adding better fuel economy to a vehicle such as an automobile.

[0111] The composite material 700 has a first PC film 702, a second PC film 713, at least one TPU layer 706, and a PC sheet 708. For example, the TPU resin includes one or more TPU resins, one or more UV absorbers and a light stabilizer. The TPU layer can have an UV absorber selected from the group consisting of the benzotriazole family and the triazin family. The TPU layers may be as discussed below, or can be other TPU layers, which may include a UV absorber.

[0112] In the example shown in FIG. 8, the composite material 700 has a first PC film 702, a transparent IR cut-off layer 710, a first TPU layer 706, a PC sheet 708, a second TPU layer 712, and a second PC film 713. The transparent IR cut-off layer is applied by sputter deposition, plasma deposition, or other methods, and includes transparent EMI shielding. The PC sheet has a visible light transmissibility of about 70%, more preferably 80%, low haze of less than about 3%, more preferably less than 1%, and premium optical requirements. Desirably, a top coat is applied to each of the PC films, to protect against scratches, and chemical and environmental damage. For example, top coat 701 is applied to PC film 702 and top coat 714 is applied to PC film 713. The top coat can be as discussed in the examples above.

[0113] In another example, the composite material 800 shown in FIG. 9 has a first PC film 802 a transparent IR cut-off layer 810 applied by sputter deposition or other methods, a first TPU layer 806, a first PC sheet 808, a second TPU layer 812, a second PC sheet 820, a third TPU layer 822, a transparent low-E layer 824 applied by sputter deposition or other methods, and a second PC film 813. For example, the transparent IR cut-off layer is applied by sputter deposition and includes transparent EMI shielding.

[0114] In the example above, the three TPU layers desirably include UV absorbers. This example has the advantage that an additional layer of UV shielding further shields a vehicle from unwanted heat and radiation. These layers being about 300 micrometers thick, they do not significantly add to the thickness of the composite material.

[0115] A top coat can be applied to the first layer of PC and the second layer of PC to protect against scratches and chemical and environmental damage. For example, a top coat 801 is applied to PC film 802 and top coat 814 is applied to PC film 813. The top coat can be a top coat from any of the examples discussed above. The composite 800 may be used as a window, windshield, roof, or skylight of an automobile, boat, or other vehicle.

[0116] The TPU layers 806, 812, and 822 can be about 380 micrometers in thickness. The PC sheets can be between about 1 millimeter to about 3 millimeters, more preferably about 2.1 mm and have a visible light transmission (VLT) of about 70%, more preferably about 80%, with a haze less than about 3% more preferably less than 1%, and premium optical requirements.

[0117] Benefits and features of artificial glass include that the material is lightweight, leading to improved gas mileage for vehicles. In addition, the IR cut-off layer also reduces electrical consumption. Utilizing PC sheets with good optical characteristics, the composite provides a transparent window while being thermoformable and avoiding the handling and forming of molten glass. With the increasing use of autonomous driving in modern cars, as well as other safety features, protection against electromagnetic interference (EMI), cross-talk and other problems is necessary.

[0118] The examples of FIGS. 8 and 9 can include an IR cut-off layer that is formed by sputtering. The IR cut-off layer can include a low emissivity material and electromagnetic interference (EMI) shielding. The energy shielding plastic films disclosed herein reduce energy consumption. For example, the use of air conditioning can be reduced. In addition, the need for EMI shielding comes from the increasing use of autonomous driving features and other features in modern automobiles.

[0119] In further examples, the IR cut-off and EMI shielding layers 710 and 810 can include an invisible antenna made from a precious metals in the form of wires, such as nanowires. The nanowires are incorporated into the infrared cut-off and EMI shielding sputtered material as a composite and deposited in a sputtering process, or may be deposited in multiple layers.

[0120] In any of the artificial glass embodiments discussed above, the laminate may be formed as follows. The first polycarbonate film is coated with the IR cutoff coating, which is applied by sputter deposition, plasma deposition, or other method. The EVA or TPU film is desirably formed by extrusion. The various layers are laminated together and the top coat is applied by dispersion or other method. In embodiments having the low-E layer, this layer is desirably formed by sputter deposition onto the second polycarbonate film. The top coat material is desirably transparent for mid and far IR radiation.

[0121] The transparent antennas can be printed on polymeric films, such as silver nanowire printed on a polymer film, like the polycarbonate and other films discussed herein. Nanowire transparent antennas for the examples above can be made from transparent conductive oxides, conductive polymers, and nanocarbon.

[0122] Specific examples of TPU compositions include those disclosed below. TPU resin compositions in accordance with this disclosure may include any aliphatic polyether-based TPU that provides sufficient transparency and may exhibit suitable adhesion to glass, polycarbonate, acrylyic, cellulose acetate butyrate, or other surfaces which the films may contact. In embodiments, suitable TPU resins may be polyether-based and made from methylene diphenyl diisocayanate (MDI), polyether polyol, and butanediol. In embodiments, the TPU resin may be Estane AG-8451 Resin sold by Lubrizol. In embodiments the TPU resin may be present in the resin composition in an amount from about 95 to about 99.99% by weight; in certain embodiments, from about 98 to about 99.99% by weight, in other embodiments from about 99.5% to about 99.99%.

[0123] TPU resin compositions in accordance with this disclosure also include a first UV absorber. In embodiments the first UV absorber may be present in the TPU resin composition in an amount from about 0.1 to about 1% by weight; in embodiments, from about 0.3 to about 0.5% by weight.

[0124] In certain embodiments, the first UV absorber may be any suitable UV absorber made from compounds in the benzotriazole family. Non-limiting examples of benzotriazole-type UV absorbers include compounds of the formula:

##STR00001##

wherein R.sub.9, R.sub.10, and R.sub.11 are individually selected from hydrogen, a group having a formula C.sub.aH.sub.bN.sub.cO.sub.dS.sub.e wherein a, b, c, d, and e are from 0 to 30, and halogen. Non-limiting examples of benzotriazole-type UV absorbers which may be used as the first UV absorber include 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)-phenol; phenol, 2,2-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethyl-butyl)); 2-(2-Hydroxy-3,5-di-t-amylphenyl) benzotriazole; 2-Hydroxy-4-methoxybenzophenone; 2-[2-hydroxy-3,5-di (1,1-dimethylbenzyl)phenyl]; 2-(5-tert-Butyl-2-hydroxyphenyl)-2H benzotriazole; 2-(2-hydroxy-5-methylphenyl) benzotriazole; 2-(2H-Benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol; 2,4-Di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)phenol; 2-(2-Hydroxy-3,5-di-tert-butylphenyl)benzotriazole; 3-(2H-Benzotriazolyl)-5-(1,1-di-methylethyl)-4-hydroxy-benzenepropanoic acid octyl esters; methyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate; 2-(2H-Benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol; reaction products of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/PEG 300; 2-(2-Hydroxy-5-(2-hydroxyethyl))-benzotriazole; 2-(2-Hydroxy-5methacryloxyethylphenyl)-2H-benzotriazole; 2-[4,6-Bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy) phenol; or any combinations thereof. In other embodiments, the first UV absorber may be of the benzophenone family. Non-limiting examples of benzophenone-type UV absorbers which may be used as the first UV absorber include: 2,4-dihydroxy benzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-n-(octyloxy) benzophenone; 2,2,4,4-tetrahydroxybenzophenone; 2,2-dihydroxy-,4,4-dimethoxy benzophenone; sulisobenzone; 2-hydroxy-4-n-octoxybenzophenone; 2,2-dihydroxy-4-methoxy benzophenone; 2-hydroxy-4-methoxybenzophenone; 2,2-dihydroxy-4,4-dimethoxy benzophenone; 2,2,4,4-tetrahydroxybenzophenone; and combinations thereof.

[0125] In other embodiments, the first UV absorber may be of the triazin family. Non-limiting examples of triazin-type UV absorbers which may be used as the first UV absorber include: 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol.

[0126] In other embodiments, the first UV absorber may be of the benzylidene malonate family. Non-limiting example of benzylidene malonate-type UV absorbers which may be used as the first UV absorber include: Propanedioic acid [(4-methoxyphenyl)-methylene]-dimethyl ester).

[0127] Other non-limiting examples of benzophenone-type UV absorbers which may be used as the first UV absorber include: 2,4-dihydroxy benzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-n-(octyloxy) benzophenone; 2,2,4,4-tetrahydroxybenzophenone; 2,2-dihydroxy-,4,4-dimethoxy benzophenone; sulisobenzone; 2-hydroxy-4-n-octoxybenzophenone; 2,2-dihydroxy-4-methoxy benzophenone; 2-hydroxy-4-methoxybenzophenone; 2,2-dihydroxy-4,4-dimethoxy benzophenone; 2,21,4,4-tetrahydroxybenzophenone; and combinations thereof.

[0128] TPU resin compositions in examples according to this disclosure can include a light stabilizer. Suitable light stabilizers primarily protect the polymers of the optical film from the adverse effects of photo-oxidation caused by exposure to UV radiation. In embodiments, the light stabilizer may serve a secondary function of acting as a thermal stabilizer, for low to moderate levels of heat. In embodiments, the light stabilizer of a resin composition in accordance with this disclosure may be included in an amount from about 0.1 to about 1% by weight; in embodiments, from about 0.1 to about 0.2% by weight.

[0129] In certain embodiments, suitable light stabilizers may be derivatives of tetramethylpiperidine. In embodiments, the light stabilizer may be any suitable hindered amine light stabilizer (HALS or NOR-HALS). In certain embodiments, the light stabilizer may be made by combining bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate with methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate.

[0130] Non-limiting examples of light stabilizers useful in the resin compositions of the present disclosure include bis-(2,2,6,6-tetramethyl-4-piperidinyl)sebacate; bis-(I,2,2,6,6-pentamethyl-4-piperidinyl)-2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate; propanedioic acid, [(4-methoxyphenyl)-methylene]-bis-(I,2,2,6,6-pentamethyl-4-piperidinyl) ester; 10 wt % of dimethyl succinate polymer with 4-hydroxy-2,2,6,6,-tetramethyl-l-piperidineethanol and 90 wt % of N,N-[1,2-ethanediylbis [[[4,6-bis[butyl(I,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-traizin-2-yl]imino]-3,I-propanediyl]]bis[NN-dibutyl-NN-bis(I,2,2,6,6-pentamethyl-4-piperidinyl)]-I.; or combinations thereof. In embodiments, the light stabilizer is bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate combined with methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate Chisorb 292 sold by Double Bond Chemical Ind. Co., Ltd., Eversorb 93, sold by Everlight Chemical, RIASORB UV-292 sold by Rianion Corp, Thasorb UV-292 sold by Rianlon Corp., Sabostab UV 65, sold by SABO, Westco UV-292 sold by Western Reserve Chemical, UV-292/UV-292HP sold by Performance Solutions, Inc., and FENTASTAB 292 sold by Jiangsu Forpi Chemicals Co., Ltd or any combination thereof.

[0131] Further examples of TPU resin compositions used in embodiments in accordance with this disclosure can include a second UV absorber which, when combined with the TPU resin, light stabilizer and the first UV absorber, imparts a particular combination of optical characteristics to a film made from the resin composition; namely, the resulting film is capable of blocking about 95% of light having a wavelength ranging from about 10 to about 410 nm, preferably about 380 nm to about 410 nm. In certain embodiments, the film is capable of blocking greater than 99.9% of light having a wavelength ranging from about 380 nm to 400 nm and has a yellowness index (YI value) that is no greater than 3.0, preferably no greater than 2.5. In other embodiments, the film is capable of blocking no less than 99% of light having a wavelength of about 400 nm.

[0132] In embodiments, the second UV absorber is present in an amount from about 0.001% to about 2.0% by weight; in embodiments, the second UV absorber is present in the resin composition in an amount from about 0.5% to about 1.0% by weight.

[0133] In certain embodiments, the second UV absorber may be any suitable UV absorber of the benzotriazole family, the benzophenone family, the triazin family or the benzylidene malonate family that provides the foregoing combination of optical characteristics, such as the compounds lists above with respect to the first UV absorber. Non-limiting examples of benzotriazole-type UV absorbers suitable for use as the second UV absorber include compounds of the formula:

##STR00002##

wherein R.sub.9, R.sub.10, and R.sub.11 are individually selected from hydrogen, a group having a formula C.sub.aH.sub.bN.sub.cO.sub.dS.sub.e wherein a, b, c, d, and e are from 0 to 30, and halogen, where at least one of R.sub.9, R.sub.10, or R.sub.11 is halogen. In embodiments, the second UV absorber is phenol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl.

[0134] The resin composition may be prepared by preparing a composition including one or more TPU resins, the first UV absorber and a light stabilizer. The composition is combined with a concentrate containing the second UV absorber in a base resin including the same or a different TPU resin. In embodiments, the base resin and the concentrate are dry blended. In embodiments, the ratio of TPU resin to base resin is from about 20:1 to about 3:1, preferably from about 10:1 to about 7:1. The second UV absorber may be present in the concentrate by an amount of about 9.5% by weight.

[0135] In an example, the optical film has a thickness of about 5 mils to 50 mils. In one embodiment, the concentration of the second UV absorber is about 0.8% by weight and the thickness of the film is no greater than 15 mils. In another embodiment, the concentration of the second UV absorber is about 0.5% by weight and the thickness of the film is no greater than 25 mils.

[0136] In an exemplary embodiment, optical films in accordance with the present disclosure may have: a thickness in the range of from about 1 mil to about 50 mils, in embodiments from about 15 mils to about 30 mils; a UV cutoff of about 300 nm to 500 nm, preferably about 350 nm to 400 nm; a light transmission rate of no more than 0.5% to 10% at a wavelength of 400 nm, in embodiments a light transmission rate of no more than about 1%-5% at a wavelength of 400 nm; and a YI (ASTM E313) value that is no greater than 2.5., preferably no greater than about 2.0.

[0137] The present optical films may be prepared by a single screw cast film extrusion process, or any other suitable extrusion process within the purview of those of skill in the art. In embodiments, the process begins by dry blending a concentrate containing the second UV absorber with a base resin as described above to provide a mixture. The mixture of base resin and concentrate are then melted and mixed by an extruder. The melted resin composition is then filtered and fed to a die system. The resulting homogenous blend of molten polymer then travels through a flat die system to adopt a final flat film shape. Upon exiting the die, the molten web enters a cooling unit, where it is cooled using a water-cooled chill roll or any suitable cooling mechanism as is known by one of skill in the art. The film is then fed downstream where the edges may be trimmed and the film may be rolled up on a shaft to produce a roll of material.

[0138] In a first example, an optical film is prepared by single screw extrusion from the following ingredients: a TPU resin (AG-8451 sold by Lubrizol) containing a light stabilizer produced by a reaction mass of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (equivalent to Tinuvin 292 sold by BASF, CAS No. 1065336-91-5) and 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)-phenol as a first UV absorber (equivalent to Tinuvin 328 sold by BASF, CAS No. 25973-55-1). This film is 30 mils thick and is identified as a control film in Table 1 below.

[0139] Five additional films (films 1-5) were prepared by compression molding from melt blended formulation prepared in a heated Brabender High Shear Mixer from a TPU resin (AG-8451 sold by Lubrizol) containing a light stabilizer produced by a reaction mass of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (equivalent to Tinuvin 292 sold by BASF, CAS No. 1065336-91-5) and 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)-phenol as a first UV absorber (equivalent to Tinuvin 328 sold by BASF, CAS No. 25973-55-1), and 0.5% of a second UV absorber. The added UV absorber present for each of films 1-5 is identified in Table 1 below.

TABLE-US-00001 TABLE 1 UV % Light Avg. % Light Avg. % Light YI Loading Cutoff Blocked Blocked (380- Blocked (390- Avg. % T ASTM Added UV Absorber Thickness (%) (nm) @ 400 nm 400 nm) 410 nm) (400-900 nm) E313 AG8451 None ~30 mils 375.8 21.1 61.15 26.2 92.6 0.54 Control Film 1 2,4-Dihydroxybenzophenone ~30 mils 0.50% 382.3 39.4 78.31 44.2 89.3 2.42 Film 2 Tinuvin 326 ~30 mils 0.50% 401.1 99.6 99.95 94.9 86 4.57 Film 3 Tinuvin 360 ~30 mils 0.50% 390.5 63.7 93.08 64.3 85 4.97 Film 4 Tinuvin 640 ~30 mils 0.50% 387.8 58.5 89.28 57.9 83.6 4.5 Film 5 Cyasorb UV-5411 ~30 mils 0.50% 383.4 33.2 75.56 39.3 88.8 2.18

[0140] Table 1 shows that by adding a concentrate containing Tinuvin 326, an optical film having a UV cutoff of about 400 nm may be achieved. As used herein, UV cutoff generally refers to the wavelength at which substantially all of the UV light is blocked by the UV absorber, typically being absorbed by organic molecules and converted to heat. The percentage of light blocked at 400 nm with the added Tinuvin 326 is greater than the films having the alternative additives. Although the film treated with Tinuvin 360 has a UV cutoff that is closer to 400 than the other films, the YI value is surprisingly greater than Film 2's YI value, despite film 2 having a higher UV cutoff and light blockage percentage. The higher YI values for films 1-5 versus the control film are attributed to processing using the Brabender High Shear Mixer for laboratory preparation of films 1-5. Whereas the control film was produced by commercial single screw extrusion and evidenced less thermal oxidation impact attributed to the process.

[0141] In another exemplary embodiment, an optical film is prepared from the following ingredients: a base TPU resin (AG-8451 sold by Lubrizol) containing a light stabilizer produced by a reaction mass of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (equivalent to Tinuvin 292 sold by BASF, CAS No. 1065336-91-5) and 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)-phenol as a first UV absorber (equivalent to Tinuvin 328 sold by BASF, CAS No. 25973-55-1), and a concentrate containing 9.5% of a second UV absorber, Phenol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl (equivalent to Tinuvin 326, sold by BASF CAS No. 3896 Nov. 5, blended in a TPU resin of AG-8451 sold by Lubrizol.

[0142] Three different films (1-3) having a thickness of 15 mils were prepared with differing loadings of Tinuvin 326 concentrate. The properties of the three films are contained below in Table 2. It is shown that adding Tinuvin 326 concentrate to the resin composition still blocks a large portion of the UV light at 400 nm while maintaining desired transparency with a YI value that is below 2.0 even when making a thinner film.

TABLE-US-00002 TABLE 2 Conc UV % % Light Avg. % Light Avg. % Light Avg. % T YI Film Loading Cutoff Transmission Blocked Blocked (380- Blocked (390- Blocked ASTM Thickness (PPH) (nm) @ 400 nm @ 400 nm 400 nm) 410 nm) (400-900 nm) E313 Film 1 15 mils 7.0 393.4 13.3 86.7 98.1 78.8 90.5 1.39 Film 2 15 mils 8.5 397.4 3.5 96.5 99.6 88.0 90.8 1.93 Film 3 15 mils 10.0 396.8 4.7 95.3 99.5 86.6 90.4 1.79

[0143] Persons skilled in the art will understand that the products and methods specifically described herein are non-limiting exemplary embodiments. The features illustrated or described in connection with one exemplary embodiment may be combined with the features of other embodiments. Various alternatives and modifications can be devised by those skilled in the art without departing from the disclosure. Accordingly, the present disclosure is intended to embrace all such alternatives, modifications and variances. As well, one skilled in the art will appreciate further features and advantages of the present disclosure based on the above-described embodiments. Accordingly, the present disclosure is not to be limited by what has been particularly shown and described, except as indicated by the appended claims.

[0144] Hereby, all issued patents, published patent applications, and non-patent publications that are mentioned in this specification are herein incorporated by reference in their entirety for all purposes, to the same extent as if each individual issued patent, published patent application, or non-patent publication were specifically and individually indicated to be incorporated by reference.

[0145] While several embodiments of the disclosure have been shown in the drawings, it is not intended that the disclosure be limited thereto, as it is intended that the disclosure be as broad in scope as the art will allow and that the specification be read likewise. Therefore, the above description should not be construed as limiting, but merely as exemplifications of presently disclosed embodiments. Thus the scope of the embodiments should be determined by the appended claims and their legal equivalents, rather than by the examples given.

[0146] Persons skilled in the art will understand that the devices and methods specifically described herein and illustrated in the accompanying drawings are non-limiting exemplary embodiments. The features illustrated or described in connection with one exemplary embodiment may be combined with the features of other embodiments. Various alternatives and modifications can be devised by those skilled in the art without departing from the disclosure. Accordingly, the present disclosure is intended to embrace all such alternatives, modifications and variances. As well, one skilled in the art will appreciate further features and advantages of the present disclosure based on the above-described embodiments. Accordingly, the present disclosure is not to be limited by what has been particularly shown and described, except as indicated by the appended claims.