Resin composition for optical films

Abstract

The present disclosure relates to compositions, laminates, films, and / or composites made from thermoplastic polymers such as thermoplastic polyurethanes (TPUs). The films have one or more optical layers made from materials that allow visible light transmission and reflect or absorb UV light. The optical films are made from one or more TPU resins containing a first UV absorber from the benzotriazole family or the triazine family, a light stabilizer, and a second UV absorber selected from the group consisting of benzotriazole, benzophenone, triazine, or benzylidene malonate. The second UV absorber can be present in a basic resin combined with the TPU resin. The optical films are capable of blocking at least 99% of light having a wavelength in the range of about 380 nm to about 400 nm and have a YI value of 2.5 or less.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 62 / 876,171, filed July 19, 2019, the entire disclosure of which is incorporated herein by reference for all purposes. The field of the disclosure relates to compositions, composites, laminates, and / or films having one or more optical materials or layers that are substantially transparent to visible light while blocking UV radiation. [Background technology]

[0002] Films and laminates that have high optical transmission to visible light are desirable in many applications, for example, films with high optical transmission are used in vehicle windshields and sunroofs, food packaging, optical disk devices, residential and commercial windows, and the like.

[0003] Solar radiation is radiant (electromagnetic) energy from the sun. Solar radiation provides light and heat to the earth, as well as energy for photosynthesis. This radiant energy is necessary for the metabolism of the environment and its inhabitants. The solar radiation spectrum is divided into different radiation regions defined by wavelength bands. Generally, the human eye can detect visible light with wavelengths ranging from about 400nm to 700nm. Invisible light includes infrared rays with wavelengths ranging from about 700nm to 1m, and ultraviolet rays with wavelengths ranging from about 10nm to 400nm. The solar spectrum of various radiation regions can have different effects on the environment and humans. Although small amounts of UV light can be beneficial to humans, prolonged exposure to UV radiation can damage human skin and lead to acute and chronic health problems. Similarly, prolonged exposure to UV light can also damage or discolor items such as interior decoration materials and furniture. Therefore, while the irradiation of sunlight brings natural light to buildings or automobiles through windows, it also brings unwanted effects from UV radiation, which causes direct harm and damage to objects within the interior of the space. Therefore, functional windows that block UV light while transmitting visible light are essential for buildings and automobiles to reduce the electrical burden and protect all objects and users inside.

[0004] Laminated glass windows with polymer interlayers are commonly used due to safety concerns and improved energy efficiency, with polyvinyl butyral (PVB) resin sheets being the most common glass laminate. Conventional automotive or architectural glass windows or window structures often include a laminate typically made of two rigid glass or plastic sheets and an interlayer of plasticized polyvinyl butyral (PVB). PVB sheets are generally used because they can hold sharp glass fragments in place when the glass is broken. Therefore, PVB laminated safety glass is widely applied in architectural and automotive windows, display cases, and other places where human interaction is highly involved. An optical filter is a device that selectively transmits and / or blocks different wavelengths of light. Optical properties of filters are fully described by their frequency response, which defines how the magnitude and phase of each frequency component of an input signal is modified by the filter. Optical layers or filters can be placed within or between the PVB sheets to block UV light passing through the laminated window. However, PVB layers have certain drawbacks in laminates such as glass windows. For example, a large amount of moisture can be absorbed into the PVB layer during use. This moisture can eventually cause the laminate to break or reduce the quality of the visible light passing through the window. In addition, PVB generally has a high modulus and low tensile strength, which can negatively affect the performance of glass windows in applications such as windows and automobile windshields. Furthermore, PVB interlayers can bleed at the edges between the film layers, creating sufficient space to create a very tinted pearlescent luster, called "edge gloss." Edge gloss is not a desirable feature in this type of glass laminate. Therefore, there is a need for improved compositions comprising optical layers, such as films, composites, or laminates for vehicle and building windows that are more durable and less susceptible to moisture transmission and / or runoff, while still providing protection from the adverse effects of UV radiation and still being thin enough to support low material costs in competitive markets. Summary of the Invention

[0005] The following presents a simplified summary of the claimed subject matter in order to provide a basic understanding of some aspects of the claimed subject matter. This summary is not an extensive overview of the claimed subject matter. It is not intended to identify key or critical elements of the claimed subject matter, nor is it intended to delineate the scope of the claimed subject matter. The sole purpose of the summary is to present some concepts of the claimed subject matter in a simplified form as a guide to the more detailed description that is presented later.

[0006] The present disclosure relates to films, compositions, laminates, and / or composites made from thermoplastic polymers, preferably thermoplastic polyurethanes (TPUs). The films have one or more optical materials and / or layers made from materials that allow the transmission of visible light and reflect or absorb UV light. In certain embodiments, the present disclosure relates to compositions made from one or more resins, at least one of which is an aliphatic thermoplastic polyurethane (TPU) resin. In other embodiments, the present disclosure relates to glass composites, such as window glass, that include TPUs and optical materials in the TPUs. The films and compositions of the present invention are less susceptible to moisture absorption into the TPU layer, resulting in a more durable optical composition and improving the quality of visible light passing through the optical composition. TPU also has the desirable property of allowing the TPU to be etched into plastic. Furthermore, the TPU composition of the present disclosure is less susceptible to bleeding at the edges between film layers, which reduces the gloss of the edges. The TPU layer is preferably selected from materials that provide sufficient transparency to visible light and exhibit suitable adhesion to glass, polycarbonate, acrylic, cellulose acetate butyrate, or other surfaces that the layer may contact. In certain embodiments, the TPU layer preferably has a storage modulus sufficient to substantially absorb and dissipate the kinetic energy of air particles that contact the surface of the TPU layer, such as rain, hail, wind, dust, and other pollutants. At the same time, the TPU material preferably has substantial tear and abrasion resistance, thereby protecting the film from adverse environmental conditions.

[0007] In one aspect of the present invention, an optical film made from an aliphatic thermoplastic polyurethane (TPU) resin composition is provided. The resin composition includes an aliphatic thermoplastic polyurethane (TPU) resin, a first UV absorber selected from the group consisting of a benzotriazole family or a triazine family, a light stabilizer, and a second UV absorber. The second UV absorber is preferably selected from the group consisting of a benzotriazole, a benzophenone, a triazine, or a benzylidene malonate. In certain embodiments, the TPU resin is present in an amount of about 95% to about 99.99% by weight. The first UV absorber is present in the TPU resin in an amount of about 0.1% to about 1.0% by weight. The second US absorber is present in an amount of about 0.01% to about 2.0% by weight. In a preferred embodiment, the first and second UV absorbers are present in a combined amount of about 0.1% to about 3% by weight. In certain embodiments, the second UV absorber is selected from the group consisting of benzotriazole-type absorbers or benzophenone-type absorbers. In certain embodiments, the light stabilizer comprises an amine light stabilizer (HALS or NOR-HALS). In an exemplary embodiment, the light stabilizer can be made by mixing bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate. In some embodiments, the bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate are mixed in a ratio of 3:1. In certain embodiments, the second UV absorber is base As a concentrate in resin, it is combined with one or more TPU resins and base The resin ratio ranges from about 20:1 to about 3:1. base The loading percentage of the concentrate in the resin ranges from about 0.5% to about 10%. In one exemplary embodiment, the loading percentage of the second UV absorber as a concentrate is: base In another exemplary embodiment, the concentration loading of the second UV absorber is about 8.5 PPH and the film thickness is less than or equal to 15 mils.

[0008] The optical films of the present invention are preferably capable of blocking at least about 95% of light having a wavelength in the range of about 100 nm to about 410 nanometers, preferably about 380 to about 410 nanometers. In exemplary embodiments, the optical films are capable of blocking greater than about 99.9% of light having a wavelength in the range of about 380 nm to about 400 nm, or at least 99% of light having a wavelength of about 400 nm. In certain embodiments, the optical film has a Yellowness Index (YI value) of about 3.0 or less, preferably about 2.5 or less, hi certain embodiments, the YI value is less than 2.0. In certain embodiments, the thickness of the film and the concentration of the second UV absorber are optimized. In one embodiment, the loading percentage of the second UV absorber as a concentrate is: base In another embodiment, the concentration loading of the second UV absorber is about 8.5 PPH and the film thickness is 15 mils or less.

[0009] In another aspect of the invention, a composition comprises an aliphatic thermoplastic polyurethane (TPU) comprising a first UV absorber selected from the group consisting of the benzotriazole family or the triazine family, and a light stabilizer. base The second UV absorber is preferably selected from the group consisting of benzotriazoles, benzophenones, triazines, or benzylidene malonates. In certain embodiments, base The resin includes a second TPU resin. The resin includes a TPU resin and a second UV absorber. base The resin ratio ranges from about 20:1 to about 3:1, preferably from about 10:1 to about 7:1. base The loading percentage of the concentrate in the resin ranges from about 0.5% to about 10%. In one exemplary embodiment, the loading percentage of the second UV absorber as a concentrate is: baseIn another exemplary embodiment, the concentration loading of the second UV absorber is about 8.5 PPH and the film thickness is less than or equal to 15 mils.

[0010] In another aspect, the present disclosure relates to a composite material including a first layer of glass, a second layer of glass, and a film between the first layer of glass and the second layer of glass, the film being made from a thermoplastic polyurethane (TPU) resin composition, a first UV absorber from the benzotriazole family or the triazine family, a light stabilizer, and a second UV absorber. In certain embodiments, the second UV absorber is base The resin is combined with the TPU resin as a concentrate, and includes the TPU resin and a second UV absorber concentrate. base The resin ratio ranges from about 20:1 to about 3:1. base The loading percentage of the concentrate in the resin ranges from about 0.5% to about 10%. In one exemplary embodiment, the loading percentage of the second UV absorber as a concentrate is: base In another exemplary embodiment, the concentration loading of the second UV absorber is about 8.5 PPH and the film thickness is less than or equal to 15 mils.

[0011] The composite materials of the present invention are preferably capable of blocking at least about 95% of light having a wavelength in the range of about 100 nm to about 410 nanometers, preferably about 380 to about 410 nanometers. In exemplary embodiments, the composite materials are capable of blocking greater than about 99.9% of light having a wavelength in the range of about 380 nm to about 400 nm, or at least 99% of light having a wavelength of about 400 nm.

[0012] In another aspect, the present disclosure relates to a method for producing an optical film, the method includes preparing a mixture by combining a) a first resin composition having a TPU, a first UV absorber of a benzotriazole family or a triazine family, and a light stabilizer, and b) a concentrate containing a second UV absorber combined with a second resin, melting and extruding the mixture of the first and second resins, and feeding the mixture containing the first and second resins through a die to produce an optical film. In a particular embodiment, the loading concentration of the second UV absorber in the second resin is about 10 PPH. In an exemplary embodiment, the concentrate comprises Tinubin 326. In certain embodiments, the combining comprises dry blending at least 7% of the second resin into the first resin.

[0013] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure. Additional features of the present disclosure will be set forth in part in the description which follows or may be learned by the practice of the present disclosure. The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the present disclosure and, together with the description, serve to explain the principles of the disclosure. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is a cross-sectional view of a composite glass including one of the optical films of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present specification and the accompanying drawings represent exemplary embodiments and should not be understood as limiting, with the claims defining the scope of the present disclosure, including equivalents. Various mechanical, compositional, structural, and operational changes can be made without departing from the scope of the present specification and claims, including equivalents. In some cases, well-known structures and techniques have not been shown or described in detail so as not to obscure the present disclosure. Like numbers in two or more figures represent the same or similar elements. Furthermore, an element described in detail with reference to one embodiment, and its associated aspects, may, whenever practical, be included in other embodiments that are not specifically shown or described. For example, if an element is described in detail with reference to one embodiment and not described with reference to a second embodiment, the element may still be claimed as being included in the second embodiment. Furthermore, the description herein is for illustrative purposes only and does not necessarily reflect the actual shape, size, or dimensions of the system or illustrated components. As used in this specification and the appended claims, it should be noted that the singular forms "a," "an," and "the," as well as the use of any word in the singular, include plural references unless expressly and unambiguously limited to a particular referent. As used herein, the term "comprises," and grammatical variations thereof, are intended to be open-ended, such that the recitation of items in a list does not exclude other similar items that may be substituted for or added to the items in the list.

[0016] The optical films are made from a thermoplastic polyurethane (TPU) resin composition that includes a first UV absorber, a light stabilizer, and a second UV absorber. Films made from such TPU resin compositions have desirable optical properties that result from the combination of UV absorbers. The TPU resin composition according to the present disclosure can include an aliphatic polyether-based TPU that provides sufficient transparency and can exhibit suitable adhesion to glass, polycarbonate, acrylic, cellulose acetate butyrate, or other surfaces with which the film may come into contact. In embodiments, a suitable TPU resin can be polyether-based and made from methylene diphenyl diisocyanate (MDI), polyether polyol, and butanediol. In embodiments, the TPU resin can be Estane AG-8451 resin sold by Lubrizol. In embodiments, the TPU resin can be present in the resin composition in an amount of about 95 to about 99.99% by weight, in certain embodiments, about 98 to about 99.99% by weight, and in other embodiments, about 99.5% to about 99.99%. The TPU resin composition according to the present disclosure also includes a first UV absorber. In embodiments, the first UV absorber can be present in the TPU resin composition in an amount of from about 0.1 to about 1 weight percent, and in embodiments, from about 0.3 to about 0.5 weight percent.

[0017] In certain embodiments, the first UV absorber can be any suitable UV absorber made from the benzotriazole family of compounds. Non-limiting examples of benzotriazole-type UV absorbers include compounds of the formula: [ka] In the formula, R 9 , R 10 , and R 11 are individually hydrogen, a H b N c O d S e[In the formula, a, b, c, d, and e are each an integer of 0 to 30], and halogen. Non-limiting examples of benzotriazole-type UV absorbers that can 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-tetramethyl-butyl) 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-dimethylethyl)-4-hydroxy-benzenepropanoic acid octyl ester;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;Methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / PEG 300; 2-(2'-hydroxy-5'-(2-hydroxyethyl))-benzotriazole; 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole; 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol; or any combination thereof. In other embodiments, the first UV absorber may be from the benzophenone family.Non-limiting examples of benzophenone-type UV absorbers that can be used as the first UV absorber include 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-n-(octyloxy)benzophenone; 2,2',4,4'-tetrahydroxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; sulisobenzone; 2-hydroxy-4-n-octylbenzophenone; 2,2'-dihydroxy-4-methoxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 2,2',4,4'-tetrahydroxybenzophenone; and combinations thereof. In other embodiments, the first UV absorber may be of the triazine family. Non-limiting examples of triazine-type UV absorbers that can be used as the first UV absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol. In other embodiments, the first UV absorber may be of the benzylidene malonate family. A non-limiting example of a benzylidene malonate type UV absorber that can be used as the first UV absorber includes propanedioic acid [(4-methoxyphenyl)-methylene]-dimethyl ester. Other non-limiting examples of benzophenone-type UV absorbers that can be used as the first UV absorber include 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-n-(octyloxy)benzophenone; 2,2',4,4'-tetrahydroxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; sulisobenzone; 2-hydroxy-4-n-octylbenzophenone; 2,2'-dihydroxy-4-methoxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 2,2',4,4'-tetrahydroxybenzophenone; and combinations thereof.

[0018] The TPU resin composition according to the present disclosure also includes a light stabilizer. Suitable light stabilizers primarily protect the polymer of the optical film from the adverse effects of photo-oxidation caused by exposure to UV radiation. In embodiments, the light stabilizer may perform a second function, acting as a heat stabilizer against low to moderate heating. In embodiments, the light stabilizer of the resin composition according to the present disclosure may be included in an amount of about 0.1 to about 1 wt.%, in embodiments, about 0.1 to about 0.2 wt.%. In certain embodiments, the light stabilizer can be a derivative of tetramethylpiperidine.In some embodiments, the light stabilizer can be any suitable hindered amine light stabilizer (HALS or NOR-HALS).In certain embodiments, the light stabilizer can be made by combining bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate with methyl-1,2,2,6,6-pentamethyl-4-piperidylsebacate. Non-limiting examples of light stabilizers useful in the resin composition of the present disclosure include bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate; propanedioic acid, [(4-methoxyphenyl)-methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) ester; 4-hydroxy-2,2,6,6-tetramethyl-1- 10% by weight of dimethyl succinate polymer with piperidine ethanol and N,N″′-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]]bis[N′N″-dibutyl-N′N″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)]-1, or combinations thereof. In embodiments, the light stabilizer is Double Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate in combination with methyl-1,2,2,6,6-pentamethyl-4-piperidylsebacate, i.e., Chisorb 292, sold by 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.

[0019] The TPU resin composition according to the present disclosure also includes a second UV absorber that, when combined with the TPU resin, imparts a particular combination of optical properties to a film made from the resin composition, i.e., the resulting film is capable of blocking about 95% of light having a wavelength in the range of about 10 to about 410 nm, preferably about 380 to about 410 nm. In certain embodiments, the film is capable of blocking greater than 99.9% of light having a wavelength in the range of about 380 nm to about 400 nm and has a Yellowness Index (YI value) of 3.0 or less, preferably 2.5 or less. In other embodiments, the film is capable of blocking greater than 99% of light having a wavelength of about 400 nm. In some embodiments, the second UV absorber is present in an amount of about 0.001% to about 2.0% by weight, and in some embodiments, the second UV absorber is present in the resin composition in an amount of about 0.5% to about 1.0% by weight. In certain embodiments, the second UV absorber can be any suitable UV absorber from the benzotriazole family, the benzophenone family, the triazine family, or the benzylidene malonate family that imparts the combination of optical properties described above, such as the list of compounds listed above for the first UV absorber. Non-limiting examples of benzotriazole-type UV absorbers suitable for use as the second UV absorber include compounds of the following formula: [ka] In the formula, R 9 , R 10 , and R 11 are individually hydrogen, a H b N c O d S e [wherein a, b, c, d, and e are each 0 to 30], and halogen; 9 , R 10 , or R 11At least one of is a halogen. In some embodiments, the second UV absorber is phenol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl.

[0020] The resin composition can be prepared by preparing a composition comprising one or more TPU resins, a first UV absorber, and a light stabilizer. The composition can be prepared by preparing a composition comprising the same or different TPU resins. base In some embodiments, the resin is combined with a concentrate containing a second UV absorber. base The resin and concentrate are dry blended. In some embodiments, the TPU resin and base The resin ratio is from about 20:1 to about 3:1, preferably from about 10:1 to about 7:1. The second UV absorber can be present in the concentrate in an amount of about 9.5% by weight.

[0021] The optical film preferably 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 15 mils or less. In another embodiment, the concentration of the second UV absorber is about 0.5% by weight and the thickness of the film is 25 mils or less. In exemplary embodiments, optical films according to the present disclosure may have a thickness ranging from about 1 mil to about 50 mils, and in some embodiments, from about 15 mils to about 30 mils; a UV cutoff of about 300 nm to about 500 nm, and preferably about 350 nm to 400 nm; an optical transmittance of 0.5% to 10% or less at a wavelength of 400 nm, and in some embodiments, an optical transmittance of about 1% to 5% or less at a wavelength of 400 nm; and a YI (ASTM E313) value of 2.5 or less, preferably 2.0 or less.

[0022] The optical films can be prepared by a single screw cast film extrusion process or any other suitable extrusion process within the purview of one skilled in the art. In some embodiments, the process comprises extruding a concentrate containing a second UV absorber with a fluororesin as described above. base Start by dry blending with the resin to produce a mixture. base The resin and concentrate mixture is then melted and mixed by an extruder. The molten resin composition is then filtered and fed into a die system. The resulting homogenous blend of molten polymers is then moved through a flat die system to conform to the 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 known to those skilled in the art. The film is then fed downstream where the edges may be trimmed and the film is rolled up onto a shaft to create a roll of material. EXAMPLES

[0023] An optical film is prepared by single screw extrusion of the following components: a light stabilizer made of reaction masses of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate (equivalent to Tinuvin 292, CAS number 1065336-91-5, sold by BASF), and a TPU resin (AG-8451, sold by Lubrizol) containing 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)-phenol (equivalent to Tinuvin 328, CAS number 25973-55-1, sold by BASF) as the first UV absorber. This film is 0.762 mm (30 mils) thick and is identified as the control film in Table 1 below. Five additional films (films 1-5) were prepared by compression molding melt blends prepared in a heated Brabender high shear mixer from a light stabilizer made of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate (equivalent to Tinuvin 292, CAS number 1065336-91-5, sold by BASF) and a TPU resin (AG-8451, sold by Lubrizol) containing 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)-phenol (equivalent to Tinuvin 328, CAS number 25973-55-1, sold by BASF) as a first UV absorber, and 0.5% of a second UV absorber. The added UV absorbers present in each of Films 1-5 are identified in Table 1 below.

[0024] [Table 1] TIFF0007603052000004.tif57157

[0025] Table 1 shows that the addition of a concentrate containing Tinuvin 326 can achieve optical films with a UV cutoff of about 400 nm. As used herein, UV cutoff generally refers to the wavelength at which substantially all of the UV light, typically absorbed by organic molecules and converted to heat, is blocked by the UV absorber. The percentage of light blocked at 400 nm by the added Tinuvin 326 is greater than the films with alternative additives. Although the film treated with Tinuvin 360 has a UV cutoff closer to 400 than the other films, the YI value is surprisingly greater than that of film 2, even though film 2 has a higher UV cutoff and light blocking percentage. The higher YI values ​​of films 1-5 than the control film are achieved by processing films 1-5 using a laboratory-prepared Brabender high shear mixer. In contrast, the control film was made by commercial single screw extrusion, showing less thermal oxidation effects contributed to the process.

[0026] In another exemplary embodiment, an optical film was prepared from the following components: a light stabilizer made of reaction masses of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate (equivalent to Tinuvin 292, CAS number 1065336-91-5, sold by BASF), and 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)-phenol (equivalent to Tinuvin 328, CAS number 25973-55-1, sold by BASF) as a first UV absorber. base TPU resin (AG-8451 sold by Lubrizol) and 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 number 3896-11-5, sold by Lubrizol), blended into the TPU resin of AG-8451. Three different films (1-3) having a thickness of 0.381 mm (15 mils) were prepared with different loadings of Tinuvin 326 concentrate. The properties of the three films are included below in Table 2. The addition of Tinuvin 326 concentrate to the resin composition has been shown to still block most of the UV light at 400 nm while maintaining the desired transparency with a YI value below 2.0, even when thinner films are made.

[0027] [Table 2] TIFF0007603052000006.tif41146

[0028] Referring now to Figure 1, a composite material 10 according to the present disclosure includes first and second layers of glass 12, 14 and a film 16 between the first layer of glass and the second layer of glass. The film 16 can include any of the compositions described above. In certain embodiments, a window is provided that includes the composite material. The film 16 can be laminated between at least two sheets of glass substrates facing each other to reflect light having certain wavelengths in the infrared region. Glass layers 12, 14 may comprise any clear or ultra clear glass of the type suitable for use in image sensors, electronic display screens for computers and mobile devices, food packaging, optical disk drives, appliances, and the like. Examples include PPG clear glass, Solarphire.RTM glass, or PPG Starphire.RTM glass. Clear glass is preferred because when sunlight shines on a window, glass layer 12 absorbs less energy from the IR light and reflects more energy back out of the window from the outer layers. Ultra clear glass is more preferred because it absorbs less energy from the IR light than clear glass and its high transmittance allows more light to be reflected. Of course, there are other substantially transparent materials that can be used as layers 12, 14 and provide stiffness and strength to the optical sheet. These alternative materials include, for example, polymeric materials such as acrylic, polyethylene terephthalate (PET), or polycarbonate. The glass window components can be substantially flat or have some curvature. The glass window components can be provided in a variety of shapes, such as domes, cones, or other configurations and cross sections with various surface topographies. It is not intended that the present invention be necessarily limited to the use of any particular glass window component material or structure.

[0029] Those skilled in the art will understand that the products and methods specifically described herein are non-limiting exemplary embodiments. Features illustrated or described in connection with one exemplary embodiment can be combined with features of other embodiments. Various alternatives and modifications can be devised by those skilled in the art without departing from the present disclosure. Thus, the present disclosure is intended to embrace all such alternatives, modifications, and variances. Similarly, those skilled in the art will appreciate further features and advantages of the present disclosure based on the above-described embodiments. Thus, the present disclosure is not limited by what has been specifically shown and described, except as indicated by the appended claims. Any and all issued patents, published patent applications, and non-patent publications referred to in this specification are hereby 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 was specifically and individually indicated to be incorporated by reference. Although several embodiments of the present disclosure have been shown in the drawings, it is not intended that the present disclosure be limited thereto, as the disclosure is intended to be as broad as the art allows and the specification is read as such. Therefore, the above description should not be considered as limiting, but should be understood merely as an exemplification of the embodiments disclosed herein. Therefore, the scope of the embodiments should be determined by the appended claims and their legal equivalents, and not by the examples given. Those skilled in the art will understand that the apparatus and method specifically described herein and shown in the accompanying drawings are non-limiting exemplary embodiments. Features illustrated or described in connection with one exemplary embodiment may be combined with features of other embodiments. Various alternatives and modifications may be devised by those skilled in the art without departing from the disclosure. Thus, the disclosure is intended to embrace all such alternatives, modifications, and variances. Similarly, those skilled in the art will appreciate further features and advantages of the disclosure based on the above-described embodiments. Thus, the disclosure is not limited by what has been specifically shown and described, except as indicated by the appended claims. Yet another aspect of the present invention may be as follows. [1] An optical film, a first UV absorber selected from the group consisting of the benzotriazole family or the triazine family; A light stabilizer; a second UV absorber selected from the group consisting of benzotriazoles, benzophenones, triazines, or benzylidene malonates; An optical film comprising one or more thermoplastic polyurethane (TPU) resins. [2] The optical film according to [1], wherein at least one of the TPU resins contains an aliphatic TPU resin in an amount of about 95% by mass to about 99.99% by mass. [3] The optical film according to [1], wherein the first UV absorber is present in the TPU resin in an amount of about 0.1 to about 1% by mass. [4] The optical film according to [1], wherein the light stabilizer is an amine light stabilizer (HALS). [5] The optical film according to [1], wherein the light stabilizer is made of 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. [6] The optical film according to [1] above, wherein the thickness of the film is from about 0.127 mm (5 mils) to about 1.27 mm (50 mils). [7] The optical film according to [1] above, wherein the thickness of the film is about 0.381 mm (15 mils) to about 0.762 mm (30 mils). [8] The optical film according to [1], wherein the combination of the first and second UV absorbers is present in an amount of about 0.1 to about 3% by mass. [9] The optical film according to [1], wherein the second UV absorber is present in an amount of about 0.01 to about 2% by mass.

[10] The optical film according to [1], wherein the film is capable of blocking at least about 95% of light having a wavelength in the range of about 380 nm to about 410 nm.

[11] The optical film according to [1], wherein the YI value of the film is about 4.5 or less.

[12] The optical film described in [1] above, wherein the YI value of the film is about 2.0 or less.

[13] The optical film according to [1], wherein the film is capable of blocking at least about 99.5% of light having a wavelength in the range of about 380 nm to about 400 nm, and the YI value of the film is less than about 2.0.

[14] The optical film according to [1], wherein the film is capable of blocking 99.5% or more of light having a wavelength of about 400 nm. 14. The second UV absorber is base As a concentrate in resin, the one or more TPU resins are combined with the one or more TPU resins, base The optical film according to the above item [1], wherein the resin ratio is in the range of about 20:1 to about 3:1.

[15] The second UV absorber, baseadded to said one or more TPU resins as a concentrate in said resin; base The optical film according to the above [1], wherein the filling ratio of the concentrate in the resin is in the range of about 0.5% to about 10%. 15. The loading ratio of the second UV absorber as a concentrate is: base The optical film according to [1], wherein the content is about 0.5% by weight in the resin and the thickness of the film is 0.762 mm (30 mils) or less.

[16] The optical film described in [1], wherein the concentration loading of the second UV absorber is about 8.5 PPH and the thickness of the film is 0.381 mm (15 mils) or less.

[17] An optical film, a first UV absorber selected from the group consisting of the benzotriazole family or the triazine family, and Light stabilizers A thermoplastic polyurethane (TPU) resin comprising A second UV absorber selected from the group consisting of benzotriazoles, benzophenones, triazines, or benzylidene malonates. base Resin and An optical film comprising:

[18] Ibid. base The optical film according to

[17] above, wherein the resin comprises a thermoplastic polyurethane (TPU) resin.

[19] The TPU resin and the base The optical film according to the above item

[17] , wherein the resin ratio is about 20:1 to about 3:1.

[20] The TPU resin and the base The optical film according to the above item

[17] , wherein the resin ratio is about 10:1 to about 7:1.

[21] The second UV absorber is a concentrate of the base The resin is added base The optical film according to the above

[17] , wherein the filling ratio of the concentrate in the resin is in the range of about 0.5% to about 10%.

[22] A composite material comprising: a first layer of glass; a second layer of glass; a film between the first layer of glass and the second layer of glass; wherein the film is made from one or more resins comprising a first UV absorber selected from the group consisting of the benzotriazole family or the triazine family, a light stabilizer, and a second UV absorber selected from the group consisting of benzotriazole, benzophenone, triazine, or benzylidene malonate.

[23] The composite material described in

[22] , wherein at least one of the resins comprises a thermoplastic polyurethane (TPU) resin, the TPU resin comprising at least the first UV absorber and the light stabilizer.

[24] The composite material according to

[23] , wherein the TPU resin contains an aliphatic TPU resin in an amount of about 95% by mass to about 99.99% by mass.

[25] The composite material according to

[23] , wherein the first UV absorber is present in the TPU resin in an amount of about 0.1 to about 1% by mass.

[26] The composite material according to

[22] , wherein the thickness of the film is from about 0.127 mm (5 mils) to about 1.27 mm (50 mils).

[27] The second UV absorber base The composite material according to

[22] , which is present in a resin.

[28] Ibid. base The composite material according to claim 27, wherein the resin comprises a second TPU resin.

[29] The TPU resin and the base The composite material according to

[27] above, wherein the resin ratio is about 20:1 to about 3:1.

[30] The TPU resin and the base The composite material according to

[27] above, wherein the resin ratio is about 10:1 to about 7:1.

[31] The second UV absorber is a concentrate of the base The resin is added base The composite material according to

[27] , wherein the loading ratio of the concentrate in the resin is in the range of about 0.5% to about 10%.

[32] A vehicle window comprising the composition according to

[22] above.

[33] A method for preparing a resin for extruding an optical film, comprising the steps of: Preparing a mixture by combining a) a first resin composition having a TPU, a first UV absorber of the benzotriazole family or the triazine family, and a light stabilizer, and b) a concentrate containing a second UV absorber combined with a second resin; melting and extruding the mixture of the first and second resins; feeding the mixture containing the first and second resins through a die to form an optical film. A method comprising:

[34] The method according to

[33] , wherein the loading concentration of the second UV absorber in the second resin is about 10 PPH.

[35] The method according to

[33] , wherein the concentrate contains Tinuvin 326.

[36] The method of

[33] , wherein the combining step includes dry blending at least 7% of the second resin into the first resin.

Claims

1. An optical film comprising a resin composition, the resin composition comprising: one or more thermoplastic polyurethane (TPU) resins; formula: wherein R 9 , R 10 , and R 11 are independently selected from hydrogen and a group having the formula C a H b N c O d S e , where a, b, c, d, and e are 0 to 30. and a first UV absorber of the benzotriazole family having the formula: formula: wherein R 9 , R 10 , and R 11 are independently selected from hydrogen, a group having the formula C a H b N c O d S e , where a, b, c, d, and e are 0-30, and halogen, and at least one of R 9 , R 10 , and R 11 is halogen. and a second UV absorber of the benzotriazole family having the formula: A light stabilizer; The optical film comprises: Blocks at least 95% of light having a wavelength between 380 nm and 410 nm, or has a Yellowness Index (YI) value of 4.5 or less; and Blocks 99.5% or more of light having a wavelength between 380 nm and 400 nm, or An optical film that blocks more than 99.5% of light having a wavelength of 400 nm.

2. An optical film comprising a resin composition, the resin composition comprising: one or more thermoplastic polyurethane (TPU) resins; formula: wherein R 9 , R 10 , and R 11 are independently selected from hydrogen and a group having the formula C a H b N c O d S e , where a, b, c, d, and e are 0 to 30. and a first UV absorber of the benzotriazole family having the formula: A light stabilizer; formula: wherein R 9 , R 10 , and R 11 are independently selected from hydrogen, a group having the formula C a H b N c O d S e , where a, b, c, d, and e are 0-30, and halogen, and at least one of R 9 , R 10 , and R 11 is halogen. and a base resin comprising a second UV absorber of the benzotriazole family having The optical film comprises: Blocks at least 95% of light having a wavelength between 380 nm and 410 nm, or has a Yellowness Index (YI) value of 4.5 or less; and Blocks 99.5% or more of light having a wavelength between 380 nm and 400 nm, or An optical film that blocks more than 99.5% of light having a wavelength of 400 nm.

3. 3. The optical film of claim 1, wherein at least one of the TPU resins comprises an aliphatic TPU resin in an amount of 95% to 99.99% by weight.

4. The optical film according to any one of claims 1 to 3, wherein the first UV absorber is present in the resin composition in an amount of 0.1 to 1% by weight.

5. The optical film according to any one of claims 1 to 4, wherein the light stabilizer is a hindered amine light stabilizer (HALS).

6. The optical film according to any one of claims 1 to 5, wherein the light stabilizer is made of the reaction product of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate.

7. The optical film of any one of claims 1 to 6, wherein the film has a thickness of from 0.127 mm (5 mils) to 1.27 mm (50 mils).

8. The optical film of any one of claims 1 to 7, wherein the film has a thickness of from 15 mils to 30 mils.

9. 9. The optical film of any one of claims 1 to 8, wherein the combination of the first UV absorber and the second UV absorber is present in an amount of 0.1 to 3 wt. %.

10. The optical film of any one of claims 1 to 9, wherein the second UV absorber is present in an amount of 0.01 to 2 wt %.

11. The optical film according to any one of claims 1 to 10, wherein the YI value of the optical film is 2.0 or less.

12. An optical film described in any one of claims 1 to 11, wherein the YI value of the optical film is less than 2.

0.

13. The optical film according to any one of claims 1 to 12, wherein the optical film blocks 99.5% or more of light having a wavelength of 400 nm.

14. 3. The optical film of claim 2, wherein the second UV absorber is combined with the one or more TPU resins as a concentrate in the base resin, and the ratio of the one or more TPU resins to the base resin ranges from 20:1 to 3:

1.

15. The optical film described in claim 14, wherein the ratio of the one or more TPU resins to the base resin is 10:1 to 7:

1.

16. 3. The optical film of claim 2, wherein the second UV absorber is added to the one or more TPU resins as a concentrate in the base resin, and the loading percentage of the concentrate in the base resin ranges from 0.5% to 10%.

17. 3. The optical film of claim 2, wherein the loading level of the second UV absorber as a concentrate is 0.5 wt% in the base resin and the optical film has a thickness of 0.762 mm (30 mils) or less.

18. 3. The optical film of claim 2, wherein the loading fraction of the second UV absorber is 8.5 PPH and the film has a thickness of 15 mils or less.

19. 19. The optical film of any one of claims 2 and 14 to 18, wherein the base resin comprises a thermoplastic polyurethane (TPU) resin.

20. 20. The optical film of any one of claims 1 to 19, wherein the second UV absorber comprises 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol.

21. 21. The optical film of any one of claims 1 to 20, wherein the first UV absorber comprises 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)-phenol.

22. A first layer of glass. a second layer of glass; and 22. The optical film according to any one of claims 1 to 21, disposed between the first layer of glass and the second layer of glass. Composite material comprising:

23. 23. A vehicle window comprising the composite material of claim 22.

24. A method for making an optical film, comprising: preparing a first composition comprising combining with one another a first resin, a first UV absorber of the benzotriazole family, and a light stabilizer; preparing a second composition comprising combining a second resin and a second UV absorber of the benzotriazole family; combining the first composition with the second composition to form a mixture; Melting the mixture of the first composition and the second composition; and extruding the mixture of the first composition and the second composition to prepare an optical film; the first resin is a thermoplastic polyurethane; The first UV absorber has the formula: wherein R 9 , R 10 , and R 11 are independently selected from hydrogen and a group having the formula C a H b N c O d S e , where a, b, c, d, and e are 0 to 30. Including, The second UV absorber has the formula: wherein R 9 , R 10 , and R 11 are independently selected from hydrogen, a group having the formula C a H b N c O d S e , where a, b, c, d, and e are 0-30, and halogen, and at least one of R 9 , R 10 , and R 11 is halogen. Including, The optical film is Blocks at least 95% of light having a wavelength between 380 nm and 410 nm, or has a Yellowness Index (YI) value of 4.5 or less; and Blocks 99.5% or more of light having a wavelength between 380 nm and 400 nm, or Blocks more than 99.5% of light having a wavelength of 400 nm. method.

25. 25. The method of claim 24, wherein the loading concentration of the second UV absorber in the second resin is 10 PPH.

26. 25. The method of claim 24, wherein combining the first composition with the second composition comprises dry blending at least 7% of the second composition into the first composition.

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