Molded artificial polymeric articles using closed-cell metal oxide particles

Abstract

In certain embodiments, polymer compositions comprising closed-cell metal oxide particles and methods of preparing the same are disclosed. In at least one embodiment, the closed-cell metal oxide particles comprise a metal oxide matrix that defines an array of closed cells. Each closed cell encloses a void volume that is inaccessible to the medium. The exterior surface of the closed-cell metal oxide particles is defined by the array of closed cells.

Description

[Technical field]

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 300,385, filed January 18, 2022, the disclosure of which is incorporated herein by reference in its entirety. [Background technology]

[0002] Light stabilizers are used to protect plastics and other materials from degradation due to long-term exposure to light and ultraviolet light. They protect plastics from exposure to ultraviolet light in sunlight, which initiates degradation by a photooxidation process. This process can result in many undesirable effects, including changes in appearance (discoloration, gloss change, and / or chalking), reduced mechanical properties, and the formation of visible defects such as cracks. Fluorescent lights used for interior lighting also emit ultraviolet light, although at a much lower intensity than sunlight.

[0003] There is a need in the art for new light stabilizers and UV boosters for use in polymer compositions. Summary of the Invention [Means for solving the problem]

[0004] In certain embodiments, the present invention relates to the use of closed-cell metal oxide particles as light stabilizers for molded man-made polymeric or plastic articles and corresponding molded man-made polymeric or plastic articles and corresponding extruded, cast, spun, molded or calendered polymeric or plastic compositions.

[0005] The closed cell particles are used to stabilize polymers against degradation, particularly against degradation induced by ultraviolet light. In addition, they may be used for stabilization in combination with other light stabilizers (e.g., for additive or synergistic effects).

[0006] In certain embodiments, the closed cell article may be used as a light stabilizer in a polymeric article in an amount of from 0.1% to about 40% by weight, or from 0.1% to about 20% by weight, or from 0.1% to about 10% by weight, or from 0.1% to about 5% by weight.

[0007] In other embodiments, the closed cell article may be used as a UV booster in a polymeric article in an amount of 0.1% to about 40% by weight, or 0.1% to about 20% by weight, or 0.1% to about 10% by weight, or 0.1% to about 5% by weight, in combination with a light absorber in an amount of 0.1% to about 40% by weight, or 0.1% to about 20% by weight, or 0.1% to about 10% by weight, or 0.1% to about 5% by weight.

[0008] The polymer system may be selected, for example, from polypropylene, polyethylene, polycarbonate (PC), polymethylmethacrylate (PMMA), PET, polystyrene, or combinations thereof.

[0009] Processing techniques for the polymeric articles of the present invention can use, for example, a Brabender, a high speed mixer, a single screw extruder, a twin screw extruder, a film applicator, or a combination thereof.

[0010] In one aspect of the present disclosure, a method for preparing a composition comprising a polymer and closed-cell metal oxide particles is disclosed, where the closed-cell particles are prepared by a method comprising: generating droplets from a particle dispersion comprising first particles comprising a polymeric material and second particles comprising a metal oxide material; drying the droplets to obtain dried particles comprising an array of the first particles; and calcining or sintering the dried particles. In at least one embodiment, each of the first particles is coated with a layer of the second particles. In at least one embodiment, the calcining or sintering densifies the metal oxide material and removes the polymeric material to produce closed-cell metal oxide particles each comprising a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume that is inaccessible to the medium. In at least one embodiment, the outer surface of the closed-cell metal oxide particles is defined by their respective arrays of closed cells.

[0011] In at least one embodiment, the array of closed cells is a regular array. In at least one embodiment, the array of closed cells is an irregular array.

[0012] In at least one embodiment, the first particle comprises a net positively charged surface and the second particle comprises a net negatively charged surface. In at least one embodiment, the first particle comprises a net negatively charged surface and the second particle comprises a net positively charged surface. In at least one embodiment, the surface charge drives the formation of a layer of the second particle on the first particle.

[0013] In at least one embodiment, the polymeric material comprises a polymer selected from poly(meth)acrylic acid, poly(meth)acrylate, polystyrene, polyacrylamide, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, copolymers of methyl methacrylate and [2-(methacryloyloxy)ethyl]trimethylammonium chloride, derivatives thereof, salts thereof, copolymers thereof, or mixtures thereof.

[0014] In at least one embodiment, the first particles have an average diameter of about 50 nm to about 500 nm.

[0015] In at least one embodiment, the metal oxide material comprises a metal oxide selected from silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and combinations thereof, In at least one embodiment, the metal oxide material comprises silica.

[0016] In at least one embodiment, the second particles have an average diameter of from about 1 nm to about 120 nm.

[0017] In at least one embodiment, the closed-cell metal oxide particles have an average diameter of from about 0.5 μm to about 100 μm, or from about 1 μm to about 10 μm.

[0018] In at least one embodiment, generating the droplets is performed using a microfluidic process.

[0019] In at least one embodiment, generating and drying the droplets is performed using a spray drying process.

[0020] In at least one embodiment, generating the droplets is performed using a vibrating nozzle.

[0021] In at least one embodiment, drying the droplets comprises evaporation, microwave irradiation, oven drying, drying under reduced pressure, drying in the presence of a desiccant, or a combination thereof.

[0022] In at least one embodiment, the particle dispersion is an aqueous particle dispersion.

[0023] In at least one embodiment, the weight to weight ratio of the first particles to the second particles is from about 1 / 10 to about 10 / 1.

[0024] In at least one embodiment, the weight to weight ratio of the first particles to the second particles is about 2 / 3, about 1 / 1, about 3 / 2, or about 3 / 1.

[0025] In at least one embodiment, the particle size ratio of the second particles to the first particles is from 1 / 50 to 1 / 5.

[0026] In another aspect of the present disclosure, a method for preparing a composition comprising a polymer and closed-cell metal oxide particles is disclosed, where the closed-cell particles are prepared by a method comprising: generating droplets from a particle dispersion comprising a polymer in a sol-gel matrix of a metal oxide material, where the polymer particles comprise a polymeric material; drying the droplets to obtain dried particles comprising an array of polymer particles; and calcining or sintering the dried particles to obtain closed-cell metal oxide particles. In at least one embodiment, each of the polymer particles is coated with the sol-gel matrix. In at least one embodiment, the calcining or sintering removes the polymeric material and densifies the metal oxide material to produce closed-cell metal oxide particles each comprising a metal oxide matrix that defines an array of closed cells, each closed cell enclosing a void volume that is inaccessible to the medium. In at least one embodiment, the outer surface of the closed-cell metal oxide particles is defined by their respective array of closed cells.

[0027] In at least one embodiment, the polymer particles include a net positively charged surface and the sol-gel matrix of the metal oxide material includes a net negative charge. In at least one embodiment, the polymer particles include a net negatively charged surface and the sol-gel matrix of the metal oxide material includes a net positive charge.

[0028] In another aspect of the present disclosure, closed-cell metal oxide particles for inclusion in a polymer composition are prepared by any of the methods described above or herein.

[0029] In another aspect of the present disclosure, a polymer is disclosed that includes closed-cell metal oxide particles that include a metal oxide matrix that defines an array of closed cells, each closed cell enclosing a void volume that is inaccessible to the medium. In at least one embodiment, an exterior surface of the closed-cell metal oxide particles is defined by the array of closed cells.

[0030] In at least one embodiment, the array of closed cells is a regular array. In at least one embodiment, the array of closed cells is an irregular array.

[0031] In at least one embodiment, the void volume has an average diameter of about 50 nm to about 500 nm.

[0032] In at least one embodiment, the metal oxide matrix comprises a metal oxide selected from silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and combinations thereof, In at least one embodiment, the metal oxide matrix comprises silica.

[0033] In at least one embodiment, the closed-cell metal oxide particles used in the present invention are derived at least in part from polymer particles having an average diameter of about 50 nm to about 500 nm. In at least one embodiment, the closed-cell metal oxide particles are derived at least in part from metal oxide particles having an average diameter of about 1 nm to about 120 nm.

[0034] In at least one embodiment, the closed-cell metal oxide particles employed in the present invention are derived from a metal oxide precursor selected from silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and combinations thereof.

[0035] In another aspect of the present disclosure, a composition is disclosed that includes a polymer of any of the above embodiments or any of the embodiments described herein and closed-cell metal oxide particles. In at least one embodiment, the closed-cell metal oxide particles have an average diameter in the range of about 0.5 μm to about 100 μm. In at least one embodiment, the closed-cell oxide particles of any of the embodiments described herein further include a light absorber. In at least one embodiment, the light absorber is present at 0.1 wt % to about 40.0 wt %. In at least one embodiment, the light absorber includes carbon black. In at least one embodiment, the light absorber includes one or more ionic species.

[0036] Also, as used herein, the term "of" can mean "comprising." For example, "a liquid dispersion of" can be interpreted as "a liquid dispersion comprising."

[0037] Also, as used herein, the terms "particle," "microsphere," "microparticle," "nanosphere," "nanoparticle," "droplet," and the like may refer to, for example, a plurality thereof, a collection thereof, a population thereof, a sample thereof, or a bulk sample thereof.

[0038] Also, as used herein, the terms "micro" or "microscale", for example, when referring to a particle, means from 1 micrometer (μm) to less than 1000 μm. The terms "nano" or "nanoscale", for example, when referring to a particle, means from 1 nanometer (nm) to less than 1000 nm.

[0039] Also, as used herein, the term "monodisperse" with respect to a population of particles means particles having a nearly uniform shape and a nearly uniform diameter. This monodisperse population of particles can have, for example, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% of the particles by number having a diameter within ±7%, ±6%, ±5%, ±4%, ±3%, ±2%, or ±1% of the average diameter of the population.

[0040] Also, as used herein, the term "medium inaccessible" with respect to a volume means that the volume is protected from penetration by large molecules (e.g., molecules such as polymers and oligomers having a molecular weight greater than 5000 g / mol). The volume may be accessible to solvents such as water, toluene, hexane, and ethanol.

[0041] Also, as used herein, the term "substantially free of other components" means containing, for example, ≦5%, ≦4%, ≦3%, ≦2%, ≦1%, ≦0.5%, ≦0.4%, ≦0.3%, ≦0.2%, or ≦0.1% by weight of other components.

[0042] As used herein, the articles "a" and "an" refer to one or to more than one (e.g., to at least one) of the grammatical object of the article. Any ranges cited herein are inclusive.

[0043] Also, as used herein, the term "about" is used to describe and account for slight variations. For example, "about" can mean that a numerical value may vary by ±5%, ±4%, ±3%, ±2%, ±1%, ±0.5%, ±0.4%, ±0.3%, ±0.2%, ±0.1%, or ±0.05%. All numerical values, whether expressly stated or not, are modified by the term "about". Numeric values ​​modified by the term "about" include the specific identified value. For example, "about 5.0" includes 5.0.

[0044] All parts and percentages are by weight unless otherwise indicated. Weight percent (wt%) is based on total composition without volatile materials, i.e., on dry solids, unless otherwise indicated.

[0045] The disclosure described herein is illustrated by way of example and not by way of limitation in the accompanying drawings. [Brief description of the drawings]

[0046] [Figure 1A] 1 illustrates metal oxide particles having closed cell morphology that may be used in polymer compositions according to some embodiments of the present disclosure. [Figure 1B] 3 shows comparative metal oxide particles having a porous exterior surface. [Diagram 2] 1 illustrates a method for preparing metal oxide particles having a closed cell morphology that may be used in plastic compositions according to some embodiments of the present disclosure. [Diagram 3] FIG. 1 shows a schematic diagram of an exemplary spray drying system that may be used to prepare plastic compositions used in accordance with various embodiments of the present disclosure. [Figure 4] 1 shows a scanning electron microscope (SEM) image of closed-cell metal oxide particles that may be used in a plastic composition according to an embodiment of the present disclosure. [Diagram 5] Photographs are shown comparing closed-cell silica particles that may be used in a plastic composition according to one embodiment of the present disclosure with porous particles to demonstrate the prevention of oil penetration into the voids of closed-cell silica particles. [Figure 6] 1 shows an SEM image of closed-cell metal oxide particles that may be used in a plastic composition according to a further embodiment of the present disclosure. [Figure 7] 1 is a plot of the UV-Vis spectrum of a sample produced according to one embodiment that may be used in the plastic composition of the present disclosure, showing a reflectance peak at 440 nm, which corresponds to a blue color. [Figure 8] 1 is a plot of the UV-Vis spectrum of a sample produced according to one embodiment that may be used in the plastic composition of the present disclosure, showing a reflectance peak at 520 nm, which corresponds to green color. [Figure 9] 1 is a plot of UV-Vis spectra showing relative attenuation values ​​in the UV range for closed-cell silica particles and silica nanoparticles produced according to embodiments that may be used in plastic compositions of the present disclosure. [Figure 10]1 shows an SEM image of closed-cell titania particles that may be used in plastic compositions produced according to further embodiments of the present disclosure. [Figure 11] 1 shows an SEM image of closed-cell silica particles that may be used in plastic compositions produced by a sol-gel process according to embodiments of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0047] An embodiment of the present disclosure relates to a composition comprising closed-cell metal oxide particles comprising a plastic material and a metal oxide matrix having an array of substantially uniformly sized pores (referred to as "void volume" or "voids" and may contain air) formed therein, as illustrated by the cross-sectional view in Figure 1A. As shown, the closed-cell metal oxide particles are formed from a metal oxide matrix that defines an array of "closed cells" that enclose void volumes that are inaccessible to media. The exterior surface of the closed-cell metal oxide particles (shown as the overcoated surface formed by the metal oxide) is defined by an array of closed cells, such that the surface is substantially free of open pores of a size similar to the closed cells.

[0048] In contrast to this embodiment, the porous metal oxide particles shown in FIG. 1B have pores on their outer surface and internally connected pores. When incorporated into a medium, the medium penetrates these pores, and the color effect in downstream formulations is lost due to the refractive index match between the medium and the matrix material. This greatly limits the application of the porous particles in various formulations. The closed-cell metal oxide particles of this embodiment are impermeable to polymers and large molecules that are often used in such formulations, preventing them from entering the pores and retaining air within the pores. Thus, the closed-cell metal oxide particles advantageously maintain a constant net refractive index between the matrix and the voids, regardless of the surrounding medium during application.

[0049] FIG. 2 shows an exemplary process for forming closed-cell metal oxide particles used in the polymer composition of the present invention. In certain embodiments, the closed-cell metal oxide particles are produced by drying droplets of a formulation that includes a matrix of metal oxide particles about 1-120 nm in diameter and polymer particles about 50-500 nm in diameter, which act as a template. In certain embodiments, the two particle species are oppositely charged (e.g., positively charged polymer particles and negatively charged metal oxide particles), facilitating the formation of a coating of metal oxide particles on the polymer particles. In certain embodiments, spray drying or a microfluidic process is used to generate droplets (e.g., aqueous droplets), which are dried to remove their solvent. In certain embodiments using a spray drying process, the generation and drying of the droplets are performed one after the other. During the drying process, the polymer particles and metal oxide particles self-assemble to form microspheres containing polymer particles embedded in a metal oxide matrix. For example, by sintering the matrix nanoparticles in a muffle furnace, the matrix nanoparticles are densified to form a stable matrix around the polymer particles. During this process, the polymer particles are removed by baking, resulting in the final closed-cell particles having an array of closed cells formed therein.

[0050] The resulting closed-cell metal oxide particles may be microscale, for example, having an average diameter of about 0.5 μm to about 100 μm. In certain embodiments, the closed-cell metal oxide particles have an average diameter of about 0.5 μm, about 0.6 μm, about 0.7 μm, about 0.8 μm, about 0.9 μm, about 1.0 μm, about 5.0 μm, about 10 μm, about 20 μm, about 30 μm, about 40 μm, about 50 μm, about 60 μm, about 70 μm, about 80 μm, about 90 μm, about 100 μm, or within any range defined by any of these average diameters (e.g., about 1.0 μm to about 20 μm, about 5.0 μm to about 50 μm, etc.). The metal oxide used may also be in particulate form and may be nanoscale. The metal oxide matrix particles may have an average diameter of, for example, about 1 nm to about 120 nm. The polymeric template particles can have an average diameter of, for example, about 50 nm to about 500 nm. One or more of the polymer particles or the metal oxide particles can be polydisperse or monodisperse. In certain embodiments, the metal oxide can be provided as metal oxide particles or can be formed from a metal oxide precursor, for example, via sol-gel techniques.

[0051] Certain embodiments of the closed-cell metal oxide particles exhibit colors in the visible spectrum in wavelength ranges selected from the group consisting of 380 nm to 450 nm, 451 nm to 495 nm, 496 nm to 570 nm, 571 nm to 590 nm, 591 nm to 620 nm, 621 nm to 750 nm, 751 nm to 800 nm, and any ranges defined therebetween (e.g., 496 nm to 620 nm, 450 nm to 750 nm, etc.). In some embodiments, the particles exhibit wavelength ranges in the ultraviolet spectrum selected from the group consisting of 100 nm to 400 nm, 100 nm to 200 nm, 200 nm to 300 nm, and 300 nm to 400 nm.

[0052] In certain embodiments, the closed-cell metal oxide particles may have, for example, one or more of an average diameter of about 0.5 μm to about 100 μm, an average porosity of greater than about 0.1, greater than about 0.2, greater than about 0.3, greater than about 0.4, greater than about 0.5, greater than about 0.6, greater than about 0.7, greater than about 0.8, or greater than about 0.10 to about 0.80, and an average pore size of about 50 nm to about 500 nm. In other embodiments, the particles may have, for example, one or more of an average diameter of about 1 μm to about 75 μm, an average porosity of about 0.10 to about 0.40, and an average pore size of about 50 nm to about 800 nm.

[0053] In certain embodiments, the closed-cell metal oxide particles have an average diameter of, for example, about 1 μm to about 75 μm, about 2 μm to about 70 μm, about 3 μm to about 65 μm, about 4 μm to about 60 μm, about 5 μm to about 55 μm, or about 5 μm to about 50 μm; for example, about 5 μm, about 6 μm, about 7 μm, about 8 μm, about 9 μm, about 10 μm, about 11 μm, about 12 μm, about 13 μm, about 14 μm, or about 15 μm, to about 16 μm, about 17 μm, about 18 μm, about 19 μm, about 20 μm, about 21 μm, about 22 μm, about 23 μm, about 24 μm, or about 25 μm. Other embodiments may have an average diameter of from about 4.5 μm, about 4.8 μm, about 5.1 μm, about 5.4 μm, about 5.7 μm, about 6.0 μm, about 6.3 μm, about 6.6 μm, about 6.9 μm, about 7.2 μm, or about 7.5 μm to about 7.8 μm about 8.1 μm, about 8.4 μm, about 8.7 μm, about 9.0 μm, about 9.3 μm, about 9.6 μm, or about 9.9 μm.

[0054] In certain embodiments, the closed cell metal oxide particles may have a molecular weight of, for example, about 0.10, about 0.12, about 0.14, about 0.16, about 0.18, about 0.20, about 0.22, about 0.24, about 0.26, about 0.28, about 0.30, about 0.32, about 0.34, about 0.36, about 0.38, about 0.40, about 0.42, about 0.44, about 0.46, about 0.48 The average porosity may range from about 0.50, about 0.52, about 0.54, about 0.56, about 0.58, or about 0.60 to about 0.62, about 0.64, about 0.66, about 0.68, about 0.70, about 0.72, about 0.74, about 0.76, about 0.78, about 0.80, or about 0.90. Other embodiments may have an average porosity from about 0.45, about 0.47, about 0.49, about 0.51, about 0.53, about 0.55, or about 0.57 to about 0.59, about 0.61, about 0.63, or about 0.65. In other embodiments, the porosity is from about 0.10 to about 0.80 or from about 0.1 to about 0.4.

[0055] In some embodiments, the closed-cell metal oxide particles have an average pore size of about 3 nm, about 4 nm, about 5 nm, about 10 nm, about 20 nm, or about 25 nm to about 30 nm, about 35 nm, about 40 nm, about 45 nm, or about 50 nm. In other embodiments, the metal oxide particles have an average pore size of about 10 nm, about 20 nm, about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 100 nm, about 120 nm, about 140 nm, about 160 nm, about 180 nm, about 200 nm, about 220 nm, about 240 nm, about 260 nm, about 280 nm, about 300 nm, about 320 nm, about 340 nm, about 360 nm, about 380 nm, for example. , about 400 nm, about 420 nm, or about 440 nm, to about 460 nm, about 480 nm, about 500 nm, about 520 nm, about 540 nm, about 560 nm, about 580 nm, about 600 nm, about 620 nm, about 640 nm, about 660 nm, about 680 nm, about 700 nm, about 720 nm, about 740 nm, about 760 nm, about 780 nm, or about 800 nm. Other embodiments may have an average pore size of about 220 nm, about 225 nm, about 230 nm, about 235 nm, about 240 nm, about 245 nm, or about 250 nm to about 255 nm, about 260 nm, about 265 nm, about 270 nm, about 275 nm, about 280 nm, about 285 nm, about 290 nm, about 295 nm, or about 300 nm. In other embodiments, the average pore size is about 50 nm to about 999 nm or about 100 nm to about 350 nm.

[0056] In certain embodiments, the metal oxide material of the closed-cell metal oxide particles is selected from silica, titania, alumina, zirconia, ceria, cerium oxide, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, or combinations thereof, hi certain embodiments, the metal oxide comprises titania, silica, or combinations thereof.

[0057] In certain embodiments, the polymer of the polymeric particles is selected from poly(meth)acrylic acid, poly(meth)acrylate, polystyrene, polyacrylamide, polyvinyl alcohol, polyvinyl acetate, polyester, polyurethane, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, polyvinyl ether, derivatives thereof, salts thereof, copolymers thereof, or combinations thereof. For example, the polymer is selected from the group consisting of polymethyl methacrylate, polyethyl methacrylate, poly(n-butyl methacrylate), polystyrene, poly(chloro-styrene), poly(α-methylstyrene), poly(N-methylolacrylamide), styrene / methyl methacrylate copolymer, polyalkylated acrylates, polyhydroxyl acrylates, polyaminoacrylates, polycyanoacrylates, polyfluorinated acrylates, poly(N-methylolacrylamide), polyacrylic acid, polymethacrylic acid, methyl methacrylate / ethyl acrylate / acrylic acid copolymer, styrene / methyl methacrylate / acrylic acid copolymer, polyvinyl acetate, polyvinylpyrrolidone, polyvinylcaprolactone, polyvinylcaprolactam, copolymers of methyl methacrylate and [2-(methacryloyloxy)ethyl]trimethylammonium chloride, derivatives thereof, salts thereof, or combinations thereof.

[0058] In certain embodiments, the weight to weight ratio of metal oxide particles to polymer particles is about 1 / 10, about 2 / 10, about 3 / 10, about 4 / 10, about 5 / 10 about 6 / 10, about 7 / 10, about 8 / 10, about 9 / 10, to about 10 / 9, about 10 / 8, about 10 / 7, about 10 / 6, about 10 / 5, about 10 / 4, about 10 / 3, about 10 / 2, or about 10 / 1. In certain embodiments, the weight to weight ratio of metal oxide particles to polymer particles is 1 / 3, 2 / 3, 1 / 1, or 3 / 2.

[0059] In further embodiments, the closed-cell metal oxide particles can have, for example, from about 60.0% to about 99.9% by weight of metal oxide, based on the total weight of the closed-cell metal oxide particles. In other embodiments, the closed-cell metal oxide particles include from about 0.1% to about 40.0% by weight of one or more light absorbers, based on the total weight of the closed-cell metal oxide particles. In other embodiments, the metal oxide is from about 60.0 wt%, about 64.0 wt%, about 67.0 wt%, about 70.0 wt%, about 73.0 wt%, about 76.0 wt%, about 79.0 wt%, about 82.0 wt%, or about 85.0 wt%, to about 88.0 wt%, about 91.0 wt%, about 94.0 wt%, about 97.0 wt%, about 98.0 wt%, about 99.0 wt%, or about 99.9 wt%, based on the total weight of the closed-cell metal oxide particles.

[0060] In certain embodiments, the closed-cell metal oxide particles are prepared by a process that includes forming a liquid dispersion of polymer particles and metal oxide particles; forming droplets of the dispersion; drying the droplets to obtain polymer-templated particles that include a polymer and a metal oxide; and removing the polymer to obtain the closed-cell metal oxide particles. In such embodiments, the resulting closed cells (and thus the encapsulated voids) are monodisperse.

[0061] In certain embodiments, the closed-cell metal oxide particles are prepared by a process that includes forming droplets from a particle dispersion comprising metal oxide particles and polymer particles; drying the droplets to obtain dried particles comprising a matrix of metal oxide particles with embedded polymer particles; and calcining or sintering the dried particles to densify the metal oxide particle matrix and remove the polymer particles to obtain the closed-cell metal oxide particles.

[0062] In another embodiment, the closed-cell metal oxide particles are prepared by a method including: generating droplets from a particle dispersion including polymer particles and a sol-gel of a metal oxide; drying the droplets to obtain dried particles including a matrix of the metal oxide with the polymer particles; and calcining or sintering the dried particles to remove the polymer particles to obtain the closed-cell metal oxide particles. An exemplary method is described as follows: droplets are generated from a particle dispersion (e.g., an aqueous particle dispersion having a pH of 3-5) including polymer particles and a precursor of the metal oxide. The precursor can be, for example, tetraethyl orthosilicate (TEOS) or tetramethyl orthosilicate (TMOS) as a silica precursor, titanium propoxide as a titania precursor, or zirconium acetate as a zirconium precursor. The droplets are dried to obtain dried particles including a hydrolyzed precursor of the metal oxide surrounding and coating the polymer particles. The dried particles are then heated to sinter the metal oxide by a condensation reaction of the hydrolyzed precursor and to remove the polymer particles by calcination.

[0063] In some embodiments, evaporation of the liquid medium may be performed in the presence of a self-assembled substrate, such as a conical tube or a silicon wafer. In certain embodiments, the dried particle mixture may be collected, for example, by filtration or centrifugation. In some embodiments, drying includes microwave irradiation, oven drying, drying under reduced pressure, drying in the presence of a desiccant, or a combination thereof.

[0064] In certain embodiments, the formation and collection of droplets is performed in a microfluidic device. The microfluidic device is, for example, a narrow channel device with a microscale droplet junction configured to generate droplets of uniform size, the channel being connected to a collection reservoir. The microfluidic device includes, for example, a droplet junction with a channel width of about 10 μm to about 100 μm. The device can be made, for example, from polydimethylsiloxane (PDMS) and fabricated, for example, by soft lithography. The emulsion can be prepared in the device by pumping an aqueous dispersed phase and an oil continuous phase at a defined rate into the device where mixing occurs to provide emulsion droplets. Alternatively, an oil-in-water emulsion can be used. The continuous oil phase includes, for example, an organic solvent, a silicone oil, or a fluorinated oil. As used herein, "oil" refers to an organic phase (e.g., an organic solvent) that is not miscible with water. Organic solvents include hydrocarbons, for example, heptane, hexane, toluene, xylene, and the like.

[0065] In certain embodiments using droplets, the droplets are formed using a microfluidic device, which may include a droplet junction having a channel width of, for example, about 10 μm, about 15 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm, or about 45 μm, to about 50 μm, about 55 μm, about 60 μm, about 65 μm, about 70 μm, about 75 μm, about 80 μm, about 85 μm, about 90 μm, about 95 μm, or about 100 μm.

[0066] In certain embodiments, the droplets are generated and dried using a spray drying process. FIG. 3 shows a schematic diagram of an exemplary spray drying system 300 used in accordance with various embodiments of the present disclosure. In certain embodiments of the spray drying technique, a liquid solution or dispersion feedstock 302 is fed (e.g., pumped) to a spray nozzle 304 coupled with a compressed gas inlet into which a gas 306 is injected. The feedstock 302 is pumped through the spray nozzle 304 to form droplets 308. The droplets 308 are surrounded by preheated gas in an evaporation chamber 310, which evaporates the solvent to generate dry particles 312. The dry particles 312 are carried by the drying gas through a cyclone 314 and deposited in a collection chamber 316. The gas includes nitrogen and / or air. In one embodiment of the exemplary spray drying process, the liquid feedstock contains a water or oil phase, a metal oxide, and polymer particles. The dry particles 312 include a self-assembled structure of each polymer particle surrounded by a metal oxide particle.

[0067] Air can be considered a continuous phase with a dispersed liquid phase (liquid-in-gas emulsion). In certain embodiments, spray drying involves an inlet temperature of about 100°C, about 105°C, about 110°C, about 115°C, about 120°C, about 130°C, about 140°C, about 150°C, about 160°C, or about 170°C to about 180°C, about 190°C, about 200°C, about 210°C, about 215°C, or about 220°C. In some embodiments, pump rates (delivery flow rates) of about 1 mL / min, about 2 mL / min, about 5 mL / min, about 6 mL / min, about 8 mL / min, about 10 mL / min, about 12 mL / min, about 14 mL / min, or about 16 mL / min to about 18 mL / min, about 20 mL / min, about 22 mL / min, about 24 mL / min, about 26 mL / min, about 28 mL / min, or about 30 mL / min are used.

[0068] In some embodiments, a vibrating nozzle technique can be used for the closed cell particles to be incorporated into the polymeric material of the present invention. In such a technique, a liquid dispersion is prepared, then droplets are formed and dropped into a bath of a continuous phase. The droplets are then dried. Vibrating nozzle devices are available from BUECHI and include, for example, a syringe pump and a pulsating unit. The vibrating nozzle device can also include a pressure regulating valve.

[0069] In certain embodiments, removal of the polymer may be accomplished, for example, by calcination, pyrolysis, or with a solvent (solvent removal). Calcination, in some embodiments, is accomplished at a temperature of at least about 200° C., at least about 500° C., at least about 1000° C., from about 200° C. to about 1200° C., or from about 200° C. to about 700° C. Calcination may be accomplished for a suitable period of time, for example, from about 0.1 hours to about 12 hours, or from about 1 hour to about 8.0 hours. In other embodiments, calcination may be accomplished for at least about 0.1 hours, at least about 1 hour, at least about 5 hours, or at least about 10 hours. In other embodiments, the baking may be carried out at from about 200° C., about 350° C., about 400° C., about 450° C., about 500° C., or about 550° C. to about 600° C., about 650° C., about 700° C., or about 1200° C. for a period of from about 0.1 h (hour), about 1 h, about 1.5 h, about 2.0 h, about 2.5 h, about 3.0 h, about 3.5 h, or about 4.0 h to about 4.5 h, about 5.0 h, about 5.5 h, about 6.0 h, about 6.5 h, about 7.0 h, about 7.5 h, about 8.0 h, or about 12 h. While the polymer is removed during this process, the array of void volumes is substantially maintained by the closed cells left after baking.

[0070] In certain embodiments, the particle size ratio of the metal oxide particles to the polymer particles is 1 / 50 to 1 / 5 (eg, 1 / 10).

[0071] In certain embodiments, the metal oxide particles have an average diameter of about 1 nm, about 5 nm, about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, or about 60 nm to about 65 nm, about 70 nm, about 75 nm, about 80 nm, about 85 nm, about 90 nm, about 95 nm, about 100 nm, about 105 nm, about 110 nm, about 115 nm, or about 120 nm. In other embodiments, the matrix nanoparticles have an average diameter of about 5 nm to about 150 nm, about 50 to about 150 nm, or about 100 to about 150 nm.

[0072] In certain embodiments, the polymer particles have an average diameter of about 50 nm to about 990 nm. In other embodiments, the particles have an average diameter of about 50 nm, about 75 nm, about 100 nm, about 130 nm, about 160 nm, about 190 nm, about 210 nm, about 240 nm, about 270 nm, about 300 nm, about 330 nm, about 360 nm, about 390 nm, about 410 nm, about 440 nm, about 470 nm, about 500 nm, about 530 nm, about 560 nm, about 590 nm, or about 620 nm to about 650 nm, about 680 nm, about 710 nm, about 740 nm, about 770 nm, about 800 nm, about 830 nm, about 860 nm, about 890 nm, about 910 nm, about 940 nm, about 970 nm, or about 990 nm.

[0073] In certain embodiments, removing the polymer particles includes calcining, pyrolysis, or solvent removal. Calcining the polymer particles can be carried out, for example, at a temperature of about 300° C. to about 800° C. for a period of about 1 hour to about 8 hours.

[0074] In certain embodiments, the closed-cell metal oxide particles used in the polymer composition of the present invention mainly comprise metal oxide, i.e., they can consist essentially of or consist of metal oxide. Advantageously, depending on the particle composition, relative size, and shape of the metal oxide particles used, a bulk sample of the closed-cell metal oxide particles can exhibit a color observable by the human eye, appear white, or exhibit characteristics in the UV spectrum. Light absorbers can also be present in the particles, which can provide a more saturated observable color. Absorbers include inorganic and organic materials, such as broadband absorbers, such as carbon black. Absorbers can be added, for example, by physically mixing the particles and absorbers together, or by including the absorber in the droplets to be dried. In certain embodiments, the closed-cell metal oxide particles can exhibit no observable color without the addition of light absorbers, and can exhibit observable color with the addition of light absorbers.

[0075] The closed-cell metal oxide particles described herein may exhibit angle-dependent or angle-independent color. "Angle-dependent" color means that the observed color depends on the angle of incident light to the sample or the angle between the observer and the sample. "Angle-independent" color means that the observed color is substantially independent of the angle of incident light to the sample or the angle between the observer and the sample.

[0076] Angle-dependent color can be achieved, for example, by the use of monodisperse polymer particles. Angle-dependent color can also be achieved when the step of drying the droplets is performed slowly, causing the particles to become regular. Angle-independent color can be achieved when the step of drying the droplets is performed quickly, causing the particles to become non-regular.

[0077] The following embodiments can be used to achieve angle-dependent color due to the regular pores left after polymer removal. As a first example embodiment of angle-dependent color, monodisperse and spherical polymer particles are embedded in metal oxide particles, the metal oxide particles are subsequently densified, and the polymer is removed. The metal oxide particles can be spherical or non-spherical. As a second example embodiment of angle-dependent color, two or more species of polymer particles, collectively monodisperse and spherical, are embedded in metal oxide particles, the metal oxide particles are subsequently densified, and the polymer is removed. The angle-dependent color is achieved independently of the polydispersity and shape of the matrix particles.

[0078] The following embodiments can be used to achieve angle-independent color due to the irregular pores left behind after polymer removal: As a first example embodiment of angle-independent color, polydisperse polymer particles are embedded in metal oxide particles, the metal oxide particles are subsequently densified, and the polymer is removed.

[0079] As a second example embodiment of angle-independent color, two different sizes of polymer particles (i.e., a bimodal distribution of monodisperse polymer particles) are embedded into metal oxide particles, the metal oxide particles are subsequently densified, and the polymer is removed. The metal oxide particles can be spherical or non-spherical.

[0080] As a third example embodiment of angle-independent color, two different sized and polydisperse spherical polymer particles are embedded into metal oxide particles, the metal oxide particles are subsequently densified and the polymer is removed.

[0081] Angle-independent color is achieved independent of the polydispersity and shape of the matrix particles.

[0082] Any of the embodiments that exhibit angle-dependent or angle-independent color can be modified to exhibit whiteness or effects (eg, reflectance, absorbance) in the ultraviolet spectrum.

[0083] In some embodiments, the metal oxide particles may have more complex compositions and / or morphologies. For example, the metal oxide particles may include particles in which each individual particle includes two or more metal oxides (e.g., silica-titania particles). Such particles may include, for example, a mixture of two or more metal oxides.

[0084] In some embodiments, the metal oxide particles and / or polymer particles may include surface functionalization. One example of surface functionalization is a silane coupling agent (e.g., silane-functionalized silica). In some embodiments, the surface functionalization is performed on the metal oxide particles prior to self-assembly and densification. In some embodiments, the surface functionalization is performed on the closed-cell metal oxide particles after densification. In some embodiments, the surface functionalization may be selected to impart a net positive or net negative surface charge to the particles when dispersed in an aqueous solution.

[0085] Particle size as used herein is synonymous with particle diameter, and is determined, for example, by scanning electron microscopy (SEM) or transmission electron microscopy (TEM). Average particle size is synonymous with D50, which means that half of the population is above this point, and the other half is below this point. Particle size refers to primary particles. Particle size can be measured by laser light scattering techniques using dispersions or dry powders.

[0086] Mercury porosimetry analysis can be used to characterize the porosity of particles. Mercury porosimetry applies a controlled pressure to a sample immersed in mercury. An external pressure is applied that is necessary for the mercury to penetrate the voids / pores of the material. The amount of pressure required to invade the voids / pores is inversely proportional to the size of the voids / pores. Mercury porosimetry generates volume and pore size distributions from the pressure vs. intrusion data generated by the instrument using the Washburn equation. For example, a porous silica particle containing voids / pores with an average size of 165 nm has an average porosity of 0.8.

[0087] The closed cell metal oxide spheres are preferably used at a concentration of 0.01% to 40.0%, or 0.01% to 20.0% by weight based on the weight of the molded artificial polymeric article. Other ranges include 0.1% to 20.0%, or a concentration of 0.1% to 10.0%, or 0.25% to 10.0%, or 0.5% to 10.0% by weight.

[0088] The closed-cell metal oxide microspheres may be used in combination with one or more light stabilizers selected from the group consisting of, for example, 2-hydroxyphenyltriazines, benzotriazoles, 2-hydroxybenzophenones, oxalanilides or oxalanilides, acrylates, cinnamates, benzoates, benzoxazinones, Ni-quenchers, HALS (hindered amine light stabilizers) and NOR-HALS.

[0089] The one or more UV absorbers are preferably used in a concentration of 0.01% to 40.0% by weight, especially 0.01% to 20.0% by weight, based on the weight of the molded artificial polymeric article. A concentration of 0.1% to 20.0% by weight, especially 0.1% to 10.0% by weight, is more preferred.

[0090] The benzotriazole in combination with the closed-cell metal oxide microspheres is preferably of formula (Ia): [ka] In the formula, T1 is hydrogen, C1 to C 18 C1-C substituted with alkyl or phenyl 18 is alkyl, or T1 is a group of the formula [ka] In the formula, L1 is a divalent group, such as -(CH2) n -, where n is in the range of 1 to 8; T2 is hydrogen, C1 to C 18 Alkyl or COOT5, C1-C 18Alkoxy, hydroxyl, phenyl or C2-C 18 C1-C substituted with acyloxy 18 alkyl; T3 is hydrogen, halogen, C1-C 18 Alkyl, C1-C 18 Alkoxy, C2-C 18 acyloxy, perfluoroalkyl of 1 to 12 carbon atoms, such as -CF3, or T3 is phenyl; T5 is a C1-C substituted or unsubstituted alkyl group, which is interrupted by one or more O and / or substituted by OH or the following groups: 18 Alkyl or C4-C 50 It is an alkyl. [ka]

[0091] Examples of such benzotriazoles are Tinuvin® PA 328 and Tinuvin® 326 and the corresponding UV absorbers listed below.

[0092] The 2-hydroxybenzophenone for combination with the closed-cell metal oxide microspheres is preferably of formula (Ib): [ka] In the formula, G1, G2 and G3 are independently hydrogen, hydroxy or C1-C 18 It is an alkoxy.

[0093] Examples of such 2-hydroxybenzophenones are Chimassorb® 81 and the corresponding UV absorbers listed below.

[0094] The oxalanilide or oxalanilide for combination with the closed-cell metal oxide microspheres is preferably of formula (Ic): [ka] In the formula, G4, G5, G6 and G7 are independently hydrogen, C1 to C 12 Alkyl or C1-C 12 It is an alkoxy.

[0095] Examples are the corresponding UV absorbers listed below.

[0096] The cinnamate for combination with the closed-cell metal oxide microspheres is preferably of formula (Id): [ka] During the ceremony, m is an integer from 1 to 4; G 15 is hydrogen or phenyl; If m is 1, then G 16 is COO-G 19 and; If m is 2, then G 16 is C2~C 12 is an alkane-dioxycarbonyl; If m is 3, then G 16 is C3~C 12 is an alkane-trioxycarbonyl; If m is 4, then G 16 is C4~C 12 Alkane-tetraoxycarbonyl; G 17 is hydrogen, CN, or COO-G 19 and; G 18 is hydrogen or methoxy; G 19 is C1~C 18 It is an alkyl.

[0097] An example of such a cinnamate is Uvinul® 3035 and the corresponding UV absorbers listed below.

[0098] The benzoates for combination with the closed-cell metal oxide microspheres are preferably of formula (Ie): [ka] wherein k is 1 or 2; when k is 1, G 20 is C1~C 18 Alkyl, phenyl or C1-C 12 is a phenyl substituted with alkyl; 21 is hydrogen; [ka] If k is 2, then G 20 and G 21 together are tetravalent radicals; G 22 and G 24 are independently hydrogen or C1-C8 alkyl; G 23 is hydrogen or hydroxy.

[0099] Examples of such benzoates are the corresponding UV absorbers listed below.

[0100] The 2-hydroxyphenyltriazine for combination with the closed-cell metal oxide microspheres is preferably of formula (If): [ka] During the ceremony, G8 is C1~C 18 C4-C alkyl, COO, OCO, or O-interposed, or O-interposed and substituted with OH 18 is alkyl; G9, G 10 , G 11 and G 12 is independently hydrogen, methyl, hydroxy or OG8; or of formula (Ig), [ka] In the formula, R is C1 to C 12Alkyl, (CH2-CH2-O-) n -R2; -CH2-CH(OH)-CH2-O-R2; or -CH(R3)-CO-O-R4; n is 0 or 1; R2 is C1-C 13 Alkyl or C2-C 20 Alkenyl or C6-C 12 Aryl or CO-C1-C 18 alkyl; R3 is H or C1-C8 alkyl; R4 is C1-C 12 Alkyl or C2-C 12 It is alkenyl or C5-C6 cycloalkyl.

[0101] Examples of such 2-hydroxyphenyltriazines are Tinuvin® 1577 and Tinuvin® 1600 and the corresponding UV absorbers listed below.

[0102] In the context of the indicated definitions including R2, R3 or R4, alkyl is, for example, branched or unbranched alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.

[0103] An alkyl interrupted by two or more O's is, for example, a polyoxyalkylene, such as a polyethylene glycol residue.

[0104] Aryl is generally an aromatic hydrocarbon group, for example phenyl, biphenylyl or naphthyl.

[0105] Within the context of the definition, the indicated alkenyl includes in particular vinyl, allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl, n-octadec-4-enyl.

[0106] Halogen is primarily fluoro, chloro, bromo or iodo, in particular chloro.

[0107] C5-C6 cycloalkyl is primarily cyclopentyl and cyclohexyl.

[0108] C2~C 18 Acyloxy is, for example, alkanoyloxy, benzoyloxy, or alkenoyloxy, such as acryloyloxy or methacryloyloxy.

[0109] Divalent C2~C 12 An example of an alkane-dioxycarbonyl is -COO-CH2CH2-OCO-; Trivalent C3~C 12 An example of an alkane-trioxycarbonyl is -COO-CH-CH(OCO-)CH-OCO-; Tetravalent C4~C 12 An example of an alkane-tetraoxycarbonyl is (-COO-CH2)4C.

[0110] Preferably, the one or more ultraviolet light absorbers for combination with the closed-cell metal oxide microspheres include one or more compounds selected from (i)-(lv): 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol], Transesterification products of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-(2-hydroxyethyl)phenyl)benzotriazole, 2-(2'-hydroxy-5'-(2-methacryloyloxyethyl)phenyl)benzotriazole, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-alkyloxyphenyl)-1,3,5-triazines (wherein alkyl is a mixture of C8-alkyl groups) (CAS Nos. 137759-38-7; 85099-51-0; 85099-50-9); 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine (CAS No. 2725-22-6), 2,4-diphenyl-6-(2-hydroxy-4-[α-ethylhexanoyloxyethyl]phenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-[1-ethoxycarbonylethoxy]phenyl)-1,3,5-triazine, Reaction products of tris(2,4-dihydroxyphenyl)-1,3,5-triazine with a mixture of α-chloropropionic acid esters (made from an isomeric mixture of C7-C9 alcohols); 2-[4-(dodecyloxy / tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(3'-tert.butyl-5'-methyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-sec.butyl-5'-tert.butyl-2'-hydroxyphenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(5'-tert.octyl-2'-hydroxyphenyl)-benzotriazole, 2-(3'-dodecyl-5'-methyl-2'-hydroxyphenyl)-benzotriazole, 2-(3'-tert.butyl-5'-(2-octyloxycarbonylethyl)-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(5'-methyl-2'-hydroxyphenyl)-benzotriazole, 2-(5'-tert.butyl-2'-hydroxyphenyl)-benzotriazole, A compound of the formula [ka] A compound of the formula [ka] 2-Ethylhexyl-p-methoxycinnamate (CAS No. 5466-77-3), 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] A compound of the formula [ka] Dodecanedioic acid, 1,12-bis[2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl] ester (CAS No. 1482217-03-7), A compound of the formula [ka] or A compound of the formula [ka]

[0111] In one embodiment, ultraviolet absorbers i to xx and xlvi are preferred.

[0112] In certain embodiments, ultraviolet absorbers i to iv, vi to xi, xiii to xviii, xx, xxiii to xxxix, xlvi; in particular, ii, iii, iv, vi, vii, viii, xx, xxv, xxxvii, xlvi are preferred.

[0113] In further embodiments, i to x, xii, xiii, xix to xxiii, xxv to xxvii, xxx to xxxvi, xl to xlv and xlvi; in particular i, ii, iii, v, vi, vii, xii, xiii, xix, xx, xxii, xxiii, xxvi, xxx, xxxi, xxxiv, xxxvi, xl, xli, xlii, xliii, xliv, xlv, xlvi are preferred.

[0114] Highly preferred 2-hydroxyphenyltriazines are xii, xlviii and xlvi.

[0115] 2-Hydroxyphenyltriazine, benzotriazole, 2-hydroxybenzophenone and benzoates are preferred, especially 2-hydroxyphenyltriazine, benzotriazole and 2-hydroxybenzophenone. Benzotriazole and 2-hydroxybenzophenone are more preferred, especially benzotriazole.

[0116] Specific examples of synthetic polymers or natural or synthetic elastomers for molded artificial polymeric articles are: Polymers of mono- and diolefins, such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or poly-butadiene, polyhexene, polyoctene, and polymers of cycloolefins, such as polymers of cyclopentene, cyclohexene, cyclooctene or nor-bornene, polyethylenes, which may optionally be crosslinked, such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra-high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

[0117] Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different methods, in particular by the following methods: (a) radical polymerization (usually under high pressure and elevated temperature); or (b) Catalytic polymerization using catalysts that usually contain one or more metals of group IVb, Vb, VIb or VIII of the periodic table. These metals usually have one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls. These metal complexes can be in free form or fixed on substrates, typically activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used alone in the polymerization or can use further activators, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, the metals being elements of group Ia, IIa and / or IIIa of the periodic table. The activators can also be conveniently modified further by ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0118] Mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (e.g. PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (e.g. LDPE / HDPE).

[0119] Copolymers of mono- and diolefins with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and their mixtures with low density polyethylene (LDPE), very low density polyethylene, propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, ethylene / vinylcyclohexane copolymers, ethylene / cycloolefin copolymers (e.g. ethylene / norbornene, such as COC), ethylene / 1-olefin copolymers (wherein the 1-olefin is generated in-situ); propylene / butadiene copolymers, isobutylene / isoprene. copolymers, ethylene / vinylcyclohexene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and their salts (ionomers), as well as terpolymers of ethylene and propylene with dienes, such as, for example, hexadiene, dicyclopentadiene or ethylidene-norbornene; as well as mixtures of the aforementioned copolymers with each other and with the aforementioned polymers, such as, for example, polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers, and mixtures thereof with other polymers, such as polyamides.

[0120] These include hydrocarbon resins (e.g., C5-C9), their hydrogenated modifications (e.g., tackifiers), and mixtures of polyalkylenes and starches. The homopolymers and copolymers can have any stereostructure, such as syndiotactic, isotactic, hemiisotactic, or atactic, with atactic polymers being preferred. Stereoblock polymers are also included. The copolymers can be random or block copolymers, single-phase or heterophase, or highly crystalline homopolymers.

[0121] Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0122] Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene, and vinylanthracene, and mixtures thereof. The homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemiisotactic, or atactic, with atactic polymers being preferred. Stereoblock polymers are also included.

[0123] Copolymers comprising the aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydride, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, such as styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (copolymers), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; mixtures of impact resistant styrene copolymers with other polymers, such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers; and block copolymers of styrene, such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / isoprene / butadiene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene, HIPS, ABS, ASA, AES.

[0124] 6.) Hydrogenated aromatic polymers derived by hydrogenation of the polymers mentioned above, in particular polycyclohexylethylene (PCHE), often called polyvinylcyclohexane (PVCH), prepared by hydrogenation of atactic polystyrene.

[0125] Hydrogenated aromatic polymers derived by hydrogenation of the polymers mentioned under 6a.). The homopolymers and copolymers can have any stereochemistry, such as syndiotactic, isotactic, hemiisotactic or atactic, with atactic polymers being preferred. Stereoblock polymers are also included.

[0126] Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, e.g., styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on butadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, copolymers of styrene and acrylonitrile grafted onto acrylate / butadiene copolymers, and mixtures thereof with the copolymers listed under 6), e.g. copolymers of styrene and acrylonitrile grafted onto copolymer mixtures known as ABS, MBS, ASA or AES polymers.

[0127] Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated and brominated isobutylene-isoprene copolymers (halobutyl rubbers), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers. The polyvinyl chloride may be rigid or flexible (plasticized).

[0128] Polymers derived from α,β-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates; polymethyl methacrylate, polyacrylamide and polyacrylonitrile impact modified with butyl acrylate.

[0129] Copolymers of the above-mentioned monomers with each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.

[0130] Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine, and their copolymers with the abovementioned olefins.

[0131] Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide, etc., or copolymers thereof with bisglycidyl ethers.

[0132] Polyacetals, such as polyoxymethylene and those containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0133] Polyphenylene oxides and sulfides and mixtures of polyphenylene oxides with styrene polymers or with polyamides.

[0134] Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or poly-butadienes on the one hand and aliphatic or aromatic polyisocyanates on the other hand, as well as their precursors: (1) polyurethanes produced by the reaction of diisocyanates with short-chain diols (chain extenders) and (2) diisocyanates with long-chain diols (thermoplastic polyurethanes, TPUs).

[0135] Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6 / 6, 6 / 10, 6 / 9, 6 / 12, 4 / 6, 12 / 12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylylenediamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid, with or without elastomers as modifiers, such as poly-2,4,4,-trimethylhexylamine, polyamide 12 ... poly(m-phenylene isophthalamide); and block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers, chemically bonded or grafted elastomers; or block copolymers of the aforementioned polyamides with polyethers, for example polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). The polyamides may be amorphous.

[0136] Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

[0137] Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones or lactides, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polypropylene terephthalate, polyalkylene naphthalates and polyhydroxybenzoates, and copolyetheresters derived from hydroxyl-terminated polyethers, and also polyesters modified with polycarbonate or MBS. Copolyesters may include, for example, but are not limited to, polybutylene succinate / terephthalate, polybutylene adipate / terephthalate, polytetramethylene adipate / terephthalate, polybutylene succinate / adipate, polybutylene succinate / carbonate, poly-3-hydroxybutyrate / octanoate copolymers, poly-3-hydroxybutyrate / hexanoate / decanoate terpolymers. Further, the aliphatic polyesters may include, for example, but are not limited to, the class of poly(hydroxyalkanoates), particularly poly(propiolactone), poly(butyrolactone), poly(pivalolactone), poly(valerolactone) and poly(caprolactone), polyethylene succinate, polypropylene succinate, polybutylene succinate, polyhexamethylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyhexamethylene oxalate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene furanoate and polylactic acid (PLA), as well as the corresponding polyesters modified with polycarbonate or MBS.The term "polylactic acid (PLA)" refers to homopolymers, preferably poly-L-lactide, and either its blends or alloys with other polymers; copolymers of lactic acid or lactide with other monomers, such as hydroxycarboxylic acids, for example glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and their cyclic forms; the term "lactic acid" or "lactide" includes L-lactic acid, D-lactic acid, mixtures thereof and dimers, i.e. L-lactide, D-lactide, meso-lactide and any mixtures thereof. Preferred polyesters are PET, PET-G, PBT.

[0138] Polycarbonates and polyestercarbonates. The polycarbonates are preferably prepared by reaction of bisphenol compounds with carbonic acid compounds, in particular phosgene, or, in the melt transesterification process, with diphenyl carbonate or dimethyl carbonate. Particularly preferred are homopolycarbonates based on bisphenol A and copolycarbonates based on the monomers bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC). These and further bisphenol and diol compounds that can be used in the polycarbonate synthesis are disclosed, inter alia, in WO 08037364 (p. 7, line 21 to p. 10, line 5), EP 1582549 (

[0018] to

[0034] ), WO 02026862 (p. 2, line 23 to p. 5, line 15), WO 05113639 (p. 2, line 1 to p. 7, line 20). The polycarbonates may be linear or branched. Mixtures of branched and unbranched polycarbonates may be used as well. Suitable branching agents for polycarbonates are known from the literature and are described, for example, in US Pat. No. 4,185,009 and DE Pat. No. 2,500,092 (3,3-bis-(4-hydroxyallyl-oxindole according to the invention, in each case see the entire document), DE Pat. No. 4,240,313 (see page 3, lines 33-55), DE Pat. No. 19,943,642 (see page 5, lines 25-34) and US Pat. No. 5,367,044 and the documents cited therein. The polycarbonates used may be inherently branched or may be branched in nature. and no branching agents are added here for the preparation of polycarbonates. An example of inherent branching is the so-called Fries structure, which is disclosed for melt polycarbonates in EP 1506249. Chain terminators can additionally be used in the preparation of polycarbonates. Phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof are preferably used as chain terminators.The polyester carbonates are obtained by reaction of the aforementioned bisphenols with at least one aromatic dicarboxylic acid and, optionally, carbonic acid equivalent. Suitable aromatic dicarboxylic acids are, for example, phthalic acid, terephthalic acid, isophthalic acid, 3,3'- or 4,4'-diphenyldicarboxylic acid and benzophenone-dicarboxylic acid. Up to 80 mol %, preferably 20 to 50 mol %, of the carbonate groups in the polycarbonate can be replaced with aromatic dicarboxylic acid ester groups.

[0139] Polyketone.

[0140] Polysulfone, polyethersulfone and polyetherketone.

[0141] Crosslinked polymers derived from aldehydes on the one hand and phenols, urea and melamine on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

[0142] Drying and non-drying alkyd resins.

[0143] An unsaturated polyester resin derived from a copolyester of saturated and unsaturated dicarboxylic acids with a polyhydric alcohol and a vinyl compound as a crosslinking agent, and a halogen-containing modified product thereof having low flammability.

[0144] Crosslinkable acrylic resins derived from substituted acrylates, such as epoxy acrylates, urethane acrylates or polyester acrylates.

[0145] Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

[0146] Crosslinked epoxy resins derived from aliphatic, alicyclic, heterocyclic or aromatic glycidyl compounds, such as the diglycidyl ether products of bisphenol A, bisphenol E, and bisphenol F, with or without accelerators, crosslinked with conventional hardeners such as anhydrides or amines.

[0147] Natural polymers such as cellulose, rubber, gelatin and their chemically modified homologous derivatives, for example cellulose ethers such as cellulose acetate, cellulose propionate and cellulose butyrate or methylcellulose, and rosin and its derivatives.

[0148] Blends (polyblends) of the aforementioned polymers, such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

[0149] Natural and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oils and waxes or oils, fats and waxes based on synthetic esters (for example phthalates, adipates, phosphates or trimellitates), as well as mixtures of synthetic esters and mineral oils in any weight ratio, which are typically used as spinning compositions, and aqueous emulsions of such materials.

[0150] Aqueous emulsions of natural or synthetic rubber, such as natural latex or latex of carboxylated styrene / butadiene copolymer. Adhesives, for example, block copolymers such as SIS, SBS, SEBS, SEPS (S stands for styrene, I for isoprene, B for polybutadiene, EB for ethylene / butylene block, EP for polyethylene / polypropylene block).

[0151] Rubbers, for example polymers of conjugated dienes such as polybutadiene or polyisoprene, copolymers of mono- and diolefins with each other or with other vinyl monomers, copolymers of styrene or alpha-methylstyrene with dienes or acrylic derivatives, chlorinated rubbers, natural rubber.

[0152] Elastomers, such as natural polyisoprene (cis-1,4-polyisoprene natural rubber (NR) and trans-1,4-polyisoprene guttapercha), synthetic polyisoprene (IR for isoprene rubber), polybutadiene (BR for butadiene rubber), chloroprene rubber (CR), polychloroprene, neoprene, biprene, etc., butyl rubber (copolymer of isobutylene and isoprene, IIR), halogenated butyl rubber (chlorobutyl rubber: CIIR; bromobutyl rubber: BIIR), styrene-butadiene rubber (copolymer of styrene and butadiene, SBR), nitrile rubber (copolymer of butadiene and acrylonitrile, NBR), hydrogenated nitrile rubber (HNBR), also called Buna N rubber, Therban and Zetpol, EPM (ethylene propylene rubber, copolymer of ethylene and propylene) and EPDM rubber (ethylene propylene diene rubber, copolymer of ethylene Terpolymers of ethylene, propylene and diene components), epichlorohydrin rubber (ECO), polyacrylic rubber (ACM, ABR), silicone rubber (SI, Q, VMQ), fluorosilicone rubber (FVMQ), fluoroelastomers (FKM and FEPM) Viton, Tecnoflon, Fluorel, Aflas and Dai-El, perfluoroelastomers (FFKM) Tecnoflon PFR, Kalrez, Chemraz, Perlast, polyether block amides (PEBA), chlorosulfonated polyethylene (CSM), (Hypalon), ethylene vinyl acetate (EVA), thermoplastic elastomers (TPE), proteins resin and elastin, polysulfide rubber, elastoplastic fibers used in the production of fabrics.

[0153] Thermoplastic elastomers, such as styrenic block copolymers (TPE-s), thermoplastic olefins (TPE-o), elastomeric alloys (TPE-v or TPV), thermoplastic polyurethanes (TPU), thermoplastic copolyesters, thermoplastic polyamides, Reactor TPO's (R-TPO's), polyolefin plastomers (POP's), polyolefin elastomers (POE's).

[0154] Thermoplastic polymers such as polyolefins and their copolymers are most preferred.

[0155] The molded artificial polymeric articles of the invention are prepared, for example, by one of the following processing steps: Injection blow molding, extrusion, blow molding, rotational molding, in-mold decoration (back injection), slush molding, injection molding, co-injection molding, blow molding, molding, compression molding, resin transfer molding, pressing, film extrusion (cast film; blown film), fiber spinning (woven, nonwoven), stretching (uniaxial, biaxial), annealing, deep drawing, calendaring, mechanical deformation, sintering, coextrusion, lamination, crosslinking (radiation, peroxide, silane), deposition, welding, adhesive, vulcanization, thermoforming, pipe extrusion, profile extrusion, sheet extrusion; sheet casting, strapping, foaming, recycling / rework, visbreaking (peroxide, heat), fiber meltblowing, spunbond, surface treatment (corona discharge, flame, plasma), sterilization (by gamma radiation, electron beam), tape extrusion, pultrusion, SMC process or plastisol.

[0156] A further embodiment of the invention is a molded artificial polymeric article, wherein the polymer is a synthetic polymer and / or a natural or synthetic elastomer, and the polymer contains closed-cell metal oxide microspheres as defined herein. With respect to such articles, the definitions and preferences set forth herein shall apply.

[0157] Preferably the shaped man-made polymeric article is an extruded, cast, spun, moulded or calendered shaped man-made polymeric article.

[0158] Examples of articles according to the invention are: Floating devices, marine applications, pontoons, buoys, plastic planks for decking, piers, boats, kayaks, oars and beach reinforcements.

[0159] Automotive applications, interior applications, exterior applications, especially trim, bumpers, dashboards, batteries, rear and front linings, under bonnet mouldings, rear shelves (hat shelf), trunk lining, interior lining, airbag covers, electronic mouldings for parts (lights), dashboard panes, headlight lenses, instrument panels, exterior linings, upholstery, automotive lights, headlights, parking lights, tail lights, stop lights, interior and exterior trim, door panels, gas tanks, front side glazing, rear windows, seat backing, exterior panels, wire insulation, sealing profile extrusions, cladding, pillar covers, chassis parts, exhaust systems, fuel filters / filler caps, fuel pumps, fuel tanks, side door belt mouldings, convertible tops, side mirrors, exterior trim, fasteners / fixtures, front end modules, glass, hinges, locking systems, luggage / roof racks, pressed / stamped parts, seals, side impact protection, sound deadening / insulation and sunroofs, door medallions, consoles, instrument panels, seats, frames, skins, reinforced automotive applications, reinforced automotive fibres, filled polymer automotive applications, unfilled polymer automotive applications.

[0160] Road traffic devices, especially guide sign posts, road marking posts, car accessories, warning triangles, medical cases, helmets, and tires.

[0161] Devices for transport or public transport: devices for aircraft, trains, motor vehicles (cars, motorcycles), trucks, light trucks, buses, trams, bicycles (including accessories);

[0162] Devices for space applications, in particular rockets and satellites, for example re-entry shields.

[0163] Devices for architecture and design, mining applications, soundproofing systems, street refuges and shelters.

[0164] Appliances, general purpose and electrical / electronic device cases and covers (personal computers, telephones, mobile phones, printers, televisions, audio and video devices), flower pots, satellite receivers, and panel devices.

[0165] Jackets of steel and other materials such as textiles.

[0166] Insulation for devices for the electronic industry, especially plugs, especially computer plugs, cases for electrical and electronic components, printed circuit boards, and materials for electronic data storage such as chips, check cards or credit cards.

[0167] Home appliance applications, especially washing machines, tumble dryers, ovens (microwaves), dishwashers, mixers and irons.

[0168] Covers for lighting (e.g. street lamps, lampshades).

[0169] Wire and cable applications (semiconductors, insulation and cable jackets).

[0170] Capacitor foil, refrigerators, heating appliances, air conditioners, sealing of electronic devices, semiconductors, coffee makers and vacuum cleaners.

[0171] Technical parts such as cogwheels (gears), slide fittings, spacers, screws, bolts, handles, knobs, etc.

[0172] Rotating blades, ventilators and windmill blades, solar panels, closets, wardrobes, partition walls, slat walls, folding walls, roofs, shutters (e.g. roller shutters), fittings, connections between pipes, sleeves and conveyor belts.

[0173] Sanitary articles, in particular portable toilets, shower rooms, toilet seats, covers, and sinks.

[0174] Hygiene products, especially diapers (baby and adult incontinence), feminine hygiene products, shower curtains, brushes, mats, bathtubs, portable toilets, toothbrushes, and bedpans.

[0175] Water, wastewater and chemical pipes (whether or not bridged), pipes for protecting electric wires and cables, gas, oil and sewage pipes, gutters, downpipes and drainage systems.

[0176] All shapes and sizes of profiles (glazing), cladding and siding.

[0177] Glass replacements, especially extruded plates, architectural glazing (monolithic, twin or multi-wall), aircraft, schools, extruded sheets, window films for architectural glazing, trains, transit, and sanitary products.

[0178] Plates (walls, cutting boards), silos, wood substitutes, plastic lumber, wood composites, walls, facings, furniture, decorative foils, flooring (interior and exterior), flooring, duckboard and tiles.

[0179] Intake and exhaust manifolds.

[0180] Cement, concrete, composite applications and covers, siding and cladding, hand rails, balustrades, kitchen counters, roofing, roofing sheets, tiles and waterproofing sheets.

[0181] Plates (walls and cutting boards), trays, artificial grass, astroturf, artificial roofs for athletics stadiums (athletics), artificial flooring and tapes for athletics stadiums (athletics).

[0182] Continuous and staple fibre fabrics, textiles (carpets / sanitary / geotextiles / monofilaments / filters / wipes / curtains (shades) / medical), bulk textiles (for applications such as gowns / protective clothing), nets, ropes, cables, strings, cords, threads, safety seat belts, clothing, underwear, gloves; boots, rubber boots, innerwear, clothing, swimwear, sportswear, umbrellas (parasols, sunshades), parachutes, paragliders, sails, "balloon silk", camping equipment, tents, airbeds, sunbeds, bulk bags and bags.

[0183] Roofing Membranes, Insulation, Covers & Seals, Geomembranes, Tunnels, Dumps, Ponds, Wall Roofing Membranes, Geomembranes, Swimming Pools, Swimming Pool Liners, Swimming Pool Liners, Pond Liners, Curtains / Sun Shields, Awnings, Canopies, Wallpaper, Food Packaging & Wrapping (Flexible & Solid), Medical Packaging (Flexible & Solid), Air Bags / Safety Belts, Arm Rests & Head Rests, Carpets, Centre Consoles, Dashboards, Cockpits, Doors, Overhead Console Modules, Door Trims, Headliners, Interior Lighting, Interior Mirrors, Parcel Shelves, Rear Luggage Covers, Seats, Steering Columns, Steering Wheels, Textiles and Trunk Trims.

[0184] Films (packaging, rigid packaging, dump, laminate, bale wrap, swimming pool, trash bags, wallpaper, stretch film, raffia, desalination film, batteries and connectors.

[0185] In particular, agricultural films (greenhouse covers, tunnels, mulch tunnels, microtunnels, "raspa y amagado" (raspberry vineyards), in the presence of intensive application of pesticides) amagado", multi-span, low walk-in tunnel, high tunnel, mulch, silage, silo-bag, silo-stretch, fumigation, air bubble, keder, solawrap, thermal, bale wrap, stretch bale wrap, seedbed, film tube); other agricultural applications (e.g., nonwoven soil cover, netting (made from tapes, multifilaments and combinations thereof), tarpaulins. Such agricultural films can be either single layer or multi-layered, typically made from three, five or seven layers. This can result in film structures such as ABA, ABC, ABCBA, ABCBD, ABCDCBA, AABCBAA, where A, B, C, D represent different polymers and tackifiers. However, adjacent layers can also be joined such that the final film article can be made from an even number of layers, i.e., two, four or six layers, e.g., AABA, AABB, AABAA, ABBAA, AABCB, AABCAA, etc.

[0186] tape Foams (sealants, insulation, barriers), sports and leisure mats.

[0187] Sealant Food packaging and wrapping (flexible and solid), BOPP, BOPET, bottles.

[0188] Storage systems such as boxes (crates), luggage, chests, household boxes, pallets, containers, shelves, trucks, screw boxes, packs, cans etc.

[0189] Cartridges, syringes, medical applications, transport containers, waste paper baskets and bins, garbage bags, bins, dust bins, trash bin liner, wheeled bins, containers in general, tanks for water / used water / chemicals / gas / oil / petrol / diesel, tank liners, boxes, crates, battery cases, troughs, medical devices e.g. pistons, ophthalmic applications, diagnostic equipment and pharmaceutical blister packaging.

[0190] Household items of all kinds (e.g. household appliances, thermoses / clothes hangers), fastening systems such as plugs, wire and cable clamps, zippers, closures, locks, and snap closers.

[0191] Support devices, leisure articles such as sports and fitness devices, gymnastics mats, ski boots, in-line skates, skis, bigfoot, sports surfaces (eg tennis courts), screw tops, bottle and can tops and stoppers.

[0192] General furniture, foam products (cushions, shock absorbing materials), foam, sponges, dish wipes, mats, garden chairs, stadium seats, tables, sofas, toys, building kits (boards / figures / balls), playhouses, slides, and play cars.

[0193] Materials for optical and magnetic data storage.

[0194] Kitchen supplies (eating, cooking, storage).

[0195] Boxes for CDs, cassettes and video tapes; DVDs, electronic goods, all kinds of office supplies (ballpoint pens, stamps and ink pads, mice, shelves, trucks), bottles of all capacities and contents (drinks, detergents, cosmetics such as perfumes) and adhesive tapes.

[0196] Footwear (shoes / soles), insoles, spats, adhesives, structural adhesives, food boxes (fruit, vegetables, meat, fish), synthetic paper, bottle labels, benches, artificial joints (human), printing plates (flexo), printed circuit boards, and display technology.

[0197] Filled polymer devices (talc, chalk, china clay (kaolin), wollastonite, pigments, carbon black, TiO2, mica, nanocomposites, dolomite, silicates, glass, asbestos).

[0198] Preferred are shaped man-made polymeric articles which are films, tubes, cables, tapes, sheets, containers, frames, fibres or monofilaments.

[0199] Another preferred embodiment of the present invention is a thin film, typically obtained by using extrusion blowing technology. Single layer films or multilayer films with three, five or seven layers are particularly of interest. The most important application of thin plastic films in agriculture is as covers for greenhouses and tunnels for growing crops in a protected environment.

[0200] A further embodiment of the present invention is an extruded, cast, spun, molded or calendered polymeric composition comprising a synthetic polymer and / or a natural or synthetic elastomer and closed-cell metal oxide microspheres as defined herein. With respect to such compositions, the definitions and preferences set forth herein shall apply.

[0201] The closed-cell metal oxide spheres are preferably present in the extruded, cast, spun, molded or calendered polymer composition in an amount of 0.01% to 40.0% by weight, especially 0.01% to 20.0% by weight, based on the weight of the composition. A concentration of 0.1% to 20.0% by weight, especially 0.1% to 10.0% by weight, is more preferred. A concentration of 0.25% to 10.0% by weight, especially 0.5% to 10.0% by weight, is highly preferred.

[0202] The extruded, cast, spun, molded or calendered polymer compositions and molded artificial polymer articles may comprise at least one further additive in an amount of 0.001% to 30%, preferably 0.005% to 20%, in particular 0.005% to 10%, by weight, relative to the weight of the extruded, cast, spun, molded or calendered polymer composition or article. Examples are listed below:

[0203] Antioxidants Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, nonylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

[0204] Alkylthiomethylphenols, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

[0205] Hydroquinone and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

[0206] Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

[0207] Hydroxylated thiodiphenyl ethers, such as 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0208] Alkylidene bisphenols, for example, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4, 6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butadiene , 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene terephthalate, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0209] O-, N-, and S-benzyl compounds, such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxy-benzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

[0210] Hydroxybenzylated malonates, such as dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0211] Aromatic hydroxybenzyl compounds, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0212] Triazine compounds, such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-phenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5 -Tris(3,5-di-tert-butyl-4-hydroxy-benzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0213] Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salts of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0214] Acylaminophenols, for example, 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0215] Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as, for example, esters of methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0216] Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanate, Nurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; esters with 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0217] Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as, for example, methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0218] Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, such as, for example, methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0219] Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard® XL-1 supplied by Uniroyal).

[0220] Ascorbic Acid (Vitamin C) Amine antioxidants, for example, N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, amine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine Nylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, Phenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of mono- and di-alkylated tert-butyl / tert-octyldiphenylamines, mixtures of mono- and di-alkylated nonyldiphenylamines, mixtures of mono- and di-alkylated dodecyldiphenylamines, mixtures of mono- and di-alkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of mono- and di-alkylated tert-butyl / tert-octylphenothiazines, mixtures of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.,

[0221] UV absorbers and light stabilizers 2-(2'-hydroxyphenyl)benzotriazoles, such as 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3' -tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy -5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3' -tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole transesterification product with polyethylene glycol 300;, [ka] (wherein R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole; and 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl]benzotriazole).

[0222] Hydroxybenzophenones, such as the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl-oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy, and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0223] Esters of substituted and unsubstituted benzoic acids, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0224] Acrylates, for example, ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N-(α-carbomethoxy-α-cyanovinyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-diphenylacrylate).

[0225] Nickel compounds, such as nickel complexes of 2,2'-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], for example the 1:1 or 1:2 complexes (with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine), nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, for example the methyl or ethyl ester, nickel complexes of ketoximes, for example nickel complexes of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole (with or without additional ligands).

[0226] Sterically hindered amines, such as carbonic acid bis(1-undecyloxy-2,2,6,6-tetramethyl-4-piperidyl) ester, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) succinate, tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensation product, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine Linear or cyclic condensation products of amines with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethyl) rupiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]Decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro- Condensation product of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine with 1,2-bis(3-aminopropylamino)ethane, condensation product of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine with 1,2-bis(3-aminopropylamino)ethane, condensation product of 8-acetyl-3- Decyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethyl- Mixtures of methylpiperidines, condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation products of 1,2-bis(3-aminopropylamino)ethane with 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); condensation products of 1,6-hexanediamine with 2,4,6-trichloro-1,3,5-triazine and N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[192268-64-7];N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa -3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin reaction products, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene diesters with pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, reaction products of maleic anhydride-α-olefin copolymers with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS Reg.No.106917-31-1], 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, reaction products of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine with N,N'-bis(3-aminopropyl)ethylenediamine), 1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-one-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazin-3-one-4-yl)amino)-s-triazine. [ka]

[0227] Reaction products of 1,3,5-triazine-2,4,6-triamine, N,N'''-1,6-hexanediylbis[N',N''-dibutyl-N,N',N''-tris(2,2,6,6-tetramethyl-4-piperidinyl) with 3-bromo-1-propene, oxide, hydride, 1,3,5-triazine-2,4,6-triamine, N,N'''-1,6-hexanediylbis[N',N''-dibutyl-N,N',N''-tris(2, 2,6,6-tetramethyl-4-piperidinyl)-, 4-piperidinol, 2,2,6,6-tetramethyl-1-(undecyloxy)-, 4,4'-carbonate, 1,3,5-triazine-2,4,6-triamine, N2,N2'-1,6-hexanediylbis[N4,N6-dibutyl-N2,N4,N6-tris(2,2,6,6-tetramethyl-4-piperidinyl)-, N-allyl derivatives, oxides, hydrides and combinations thereof.

[0228] Oxamides, such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy disubstituted oxanilides, and mixtures of o- and p-ethoxy disubstituted oxanilides.

[0229] 2-(2-hydroxyphenyl)-1,3,5-triazines, such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2 -(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[ 2-Hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy / tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxypropyloxy)phenyl 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2-(4,6-bis-biphenyl-4-yl-1,3,5-triazin-2-yl)-5-(2-ethyl-(n)-hexyloxy)phenol; dodecanedioic acid, 1,12-bis[2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl] ester (CAS No. 1482217-03-7). ,

[0230] Metal deactivators, such as N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis-(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

[0231] Phosphites and phosphonites, such as triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di -cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-Biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2',2''-nitrilo[to triethyl tris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane, phosphoric acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters (CAS No.939402-02-5), Phosphoric acid, triphenyl ester, polymer with α-hydro-ω-hydroxypoly[oxy(methyl-1,2-ethanediyl)], C10-16-alkyl ester (CAS No. 1227937-46-3).

[0232] The following phosphites are particularly preferred: Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168, Ciba Specialty Chemicals Inc.), tris(nonylphenyl)phosphite, [ka]

[0233] Hydroxylamines, such as N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

[0234] Nitrones such as N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecyl nitrone, nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

[0235] Thiosynergists, such as dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis[3-(dodecylthio)propionate] or distearyl disulfide.

[0236] Peroxide scavengers, such as esters of β-thiodipropionic acid, such as the lauryl, stearyl, myristyl or tridecyl ester, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmecapto)propionate.

[0237] Polyamide stabilizers, such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

[0238] Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

[0239] PVC heat stabilizers, such as mixed metal stabilizers (such as barium / zinc, calcium / zinc types), organotin stabilizers (such as organotin mercaptoesters, organotin carboxylates, organotin sulfides), lead stabilizers (such as tribasic lead sulfate, dibasic lead stearate, dibasic lead phthalate, dibasic lead phosphate, lead stearate, etc.), organic stabilizers and combinations thereof.

[0240] Nucleating agents, for example, inorganic substances such as talcum, metal oxides, for example titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably of alkaline earth metals, organic compounds, for example, mono- or polycarboxylic acids and their salts, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate, polymeric compounds, for example, ionic copolymers (ionomers). Particularly preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol and 1,3:2,4-di(benzylidene)sorbitol.

[0241] Fillers and reinforcing agents, such as calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and other natural product flours or fibers, synthetic fibers.

[0242] A plasticizer, wherein said plasticizer is selected from the group consisting of di(2-ethylhexyl)phthalate, diisononyl phthalate, diisodecyl phthalate, dipropylheptyl phthalate, trioctyl trimellitate, tri(isononyl) trimellitate, epoxidized soybean oil, di(isononyl)cyclohexane-1,2-dicarboxylate, 2,4,4-trimethyl 1,3-pentanediol diisobutyrate.

[0243] Plasticizers used according to the invention may also include those selected from the group consisting of phthalates, trimellitates, aliphatic dibasic esters, polyesters, polymeric epoxides, phosphates. In a preferred embodiment, the plasticizer is selected from the group consisting of benzyl butyl phthalate, butyl 2-ethylhexyl phthalate, diisohexyl phthalate, diisoheptyl phthalate, di(2-ethylhexyl) phthalate, diisooctyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, diisooct ... sototridecyl, diiso(C11, C12, C13)phthalate, di(n-butyl)phthalate, di(n-C7, C9)phthalate, di(n-C6, C8, C10)phthalate, diiso(n-nonyl)phthalate, di(n-C7, C9, C11)phthalate, di(n-C9, C11)phthalate, di(n-undecyl)phthalate, tri(n-C8, C10)trimellitate, tri(2-ethylhexyl)phthalate di(n-C7,C9) adipate, di(2-ethylhexyl) adipate, di(isooctyl) adipate, di(isononyl) adipate, polyesters of adipic acid or glutaric acid with propylene glycol or butylene glycol or 2,2-dimethyl-1,3-propanediol, epoxidized oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil, octyl epoxythalate, 2-ethylhexyl epoxythalate, isodecyl diphenyl phosphate, tri(2-ethylhexyl) phosphate, tricresyl phosphate, di(2-ethylhexyl) terephthalate, di(isononyl) cyclohexane-1,2-dicarboxylate, and combinations thereof.In a particularly preferred embodiment, the plasticizer is selected from the group consisting of diisohexyl phthalate, diisoheptyl phthalate, di(2-ethylhexyl)phthalate, diisooctyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, diisotridecyl phthalate, diiso(C11, C12, C13)phthalate, di(n-butyl)phthalate, di(n-C7, C9)phthalate, di(n-C6, C8, C10)phthalate, diiso(n-nonyl)phthalate, di(n-C7, C9, C11)phthalate, di(n-C9, C11)phthalate, di(n-undecyl)phthalate, tri(n-C8,C10) trimellitate, tri(2-ethylhexyl)trimellitate, tri(isooctyl)trimellitate, tri(isononyl)trimellitate, di(n-C7,C9)adipate, di(2-ethylhexyl)adipate, di(isooctyl)adipate, di(isononyl)adipate, polyesters of adipic acid or glutaric acid with propylene glycol or butylene glycol or 2,2-dimethyl-1,3-propanediol, epoxidized oils such as epoxidized soybean oil, di(isononyl)cyclohexane-1,2-dicarboxylate, and combinations thereof.

[0244] Other additives such as plasticizers, lubricants, emulsifiers, pigments, antioxidants, thermal fillers, rheology additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and foaming agents.

[0245] Benzofuranones and indolinones, for example those described in U.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643, DE-A-4316611, DE-A-4316622, DE-A-4316 876, EP-A-0589839, EP-A-0591102, EP-A-1291384, or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, )phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.

[0246] In certain embodiments, the optical materials disclosed herein with UV absorbing functionality can be coated on or incorporated into substrates such as plastics, wood, fibers or fabrics, ceramics, glass, metals, and composites thereof.

[0247] The scope and interest of the present invention will be better understood based on the following examples, which are intended to be illustrative of specific embodiments of the invention and are not limiting. EXAMPLES

[0248] The following examples are provided to aid in the understanding of the disclosed embodiments and should not be construed as specifically limiting the embodiments described and claimed herein. Such variations of the embodiments and changes in formulation or slight changes in experimental design, including the substitution of all equivalents now known or later developed that would be within the scope of those skilled in the art, should be considered to fall within the scope of the embodiments incorporated herein.

[0249] Example 1: Preparation of closed-cell silica particles by microfluidic technology An aqueous dispersion of positively charged poly(meth)acrylate nanoparticles was diluted to 1 wt% with deionized water, and 3 wt% of negatively charged silica nanoparticles were added. The mixture was sonicated for 30 seconds to prevent aggregation. The aqueous nanoparticle dispersion and the oil phase (continuous oil phase containing 2 wt% polyethylene glycol-co-perfluoropolyester surfactant in fluorinated oil) were each injected into a microfluidic device with a 50 μm droplet junction via a syringe pump. The system was allowed to equilibrate until monodispersed droplets were generated. The droplets were collected in a reservoir.

[0250] The collected droplets were dried in an oven at 50° C. for 4 hours. The dried powder was placed on a silicon wafer and calcined by heating from room temperature to 500° C. over a period of 4 hours, holding at 500° C. for 2 hours, and cooling to room temperature over a period of 4 hours. This procedure yielded monodispersed closed-cell silica particles with a diameter of 15 micrometers.

[0251] FIG. 4 shows an SEM image of a closed-cell metal oxide particle produced according to a microfluidic process (top image), as well as a cross-section of a closed-cell metal oxide particle (bottom image) showing that the internal structure comprises an array of closed-cell metal oxide shells each surrounding a relatively monodisperse void.

[0252] Example 2: Closed-cell silica particles encapsulate media inaccessible void volumes The powder product from Example 1 is dispersed in mineral oil at a mass concentration of 3 wt%. For comparison, porous silica particles of the same concentration were also dispersed in mineral oil. Figure 5 shows photographs of (a) the powder product of closed-cell silica particles, (b) the closed-cell silica particles in mineral oil, (c) the powder product of porous silica particles, and (d) the porous silica particles in mineral oil. The suspension of closed-cell silica particles exhibited a cloudy appearance. The closed-cell silica particles did not disappear in mineral oil with a refractive index of 1.46 to 1.47, demonstrating that the closed-cell morphology can prevent the medium from penetrating into the voids in which it is enclosed. In comparison, the suspension of porous silica particles exhibited a transparent appearance. Due to the refractive index match between silica (which has a refractive index of about 1.47) and mineral oil, the porous particles disappear after the oil penetrates into the voids.

[0253] Example 3: Closed-cell silica particles with regular voids produced by spray drying An aqueous suspension of positively charged spherical polymer nanoparticles (copolymer of methyl methacrylate and 2-(methacryloyloxy)ethyl]trimethylammonium chloride nanoparticles with an average diameter of 254 nm) and negatively charged silica nanoparticles (with an average diameter of 7 nm) was prepared. The polymer nanoparticles were present at 1.8 wt % and the silica nanoparticles were present at 0.6 wt % based on the weight of the aqueous suspension (3:1 weight-to-weight ratio of polymer nanoparticles to metal oxide nanoparticles). The aqueous suspension was spray dried using a BUECHI lab-scale spray dryer under an inert atmosphere (nitrogen) at an inlet temperature of 100° C., an atomizing gas pressure of 40 mm, a suction speed of 100%, and a flow rate of 30% (approximately 10 mL / min).

[0254] The spray-dried powder was removed from the collection chamber of the spray dryer and spread onto a silicon wafer for sintering. The spray-dried powder was then fired in a muffle furnace using a batch sintering process to sinter and densify the silica nanoparticles and remove the polymer to produce closed-cell silica particles. The heating parameters were as follows: the particles were heated from room temperature to 550°C over a period of 5 hours, held at 550°C for 2 hours, and then cooled to room temperature over a period of 3 hours.

[0255] FIG. 6 shows an SEM image of a closed-cell silica particle produced according to a spray drying process (left image), as well as a cross-section of a closed-cell silica particle (right image) showing that the internal structure comprises an array of closed-cell silica shells each surrounding a relatively monodisperse and regular void.

[0256] Example 4: Closed-cell silica particles containing light absorbers The product of Example 1 was physically mixed with carbon black or an aqueous dispersion of carbon black powder at various weight levels. The resulting closed cell silica particles contained carbon black at levels of 0.5%, 1%, 2%, 3%, 4% and 5% by weight based on the total weight of the particles.

[0257] Example 5: Visible color in bulk samples The closed-cell silica particles (0.5 mg) of Example 1 were placed in a 6 cm 2 The solution was uniformly dispensed into a 20 mL clear glass vial having a bottom of 1.5 mm. The sample exhibited a distinct blue color observable by the human eye. Figure 7 is a plot of the UV-Vis spectrum for this sample, which shows a reflectance peak at 440 nm corresponding to a blue color.

[0258] A sample of closed-cell silica particles was produced in a manner similar to Example 1, except that the weight-to-weight ratio of polymer to silica was 2:1. The sample exhibited a distinct green color observable by the human eye. Figure 8 is a plot of the UV-Vis spectrum for this sample, which shows a reflectance peak at 520 nm corresponding to the color green.

[0259] Example 6: Closed-cell silica particles demonstrating UV reflection A sample of closed-cell silica particles was produced in a manner similar to Example 1, except that PMMA nanoparticles with a diameter of 140 nm were used and the weight-to-weight ratio of polymer to silica was 3:1. The sample showed attenuation in the UV range. The closed-cell silica particles showed attenuation in the UV. The UV attenuation of the silica nanoparticles was used as a control sample, and its relatively low attenuation value suggested that the UV attenuation of the closed-cell silica particles was not due to the silica nanoparticles.

[0260] FIG. 9 is a plot showing the relative attenuation values ​​of closed-cell silica particles and silica nanoparticles in the UV range.

[0261] Example 7: Closed-cell titania particles An aqueous suspension of negatively charged spherical polystyrene nanoparticles (having an average diameter of 197 nm) and positively charged titania nanoparticles (having an average diameter of 15 nm) was prepared. The polymer nanoparticles were present at 1.8 wt % and the titania nanoparticles were present at 1.2 wt % based on the weight of the aqueous suspension (a 3:2 weight-to-weight ratio of polymer nanoparticles to metal oxide nanoparticles). The aqueous suspension was spray dried using a BUECHI lab-scale spray dryer under an inert atmosphere (nitrogen) at an inlet temperature of 100° C., an atomizing gas pressure of 55 mm, a suction speed of 100%, and a flow rate of 30% (approximately 10 mL / min).

[0262] The spray-dried powder was removed from the collection chamber of the spray dryer and spread onto a silicon wafer for sintering. The spray-dried powder was then fired in a muffle furnace using a batch sintering process to densify and stabilize the closed-cell metal oxide particles. The heating parameters were as follows: the particles were heated from room temperature to 300°C over a period of 4 hours, held at 300°C for 6 hours, then heated to 550°C over a period of 2 hours, held at 550°C for 2 hours, and cooled to room temperature over a period of 4 hours.

[0263] FIG. 10 shows an SEM image of a closed-cell titania particle produced according to a spray drying process (left image), as well as a cross-section of a closed-cell titania particle (right image) showing that the internal structure comprises an array of closed-cell titania shells each surrounding a relatively monodisperse void.

[0264] Example 8: Preparation of closed-cell silica particles by sol-gel process Aqueous suspensions of positively charged spherical polymer nanoparticles (copolymer of methyl methacrylate and 2-(methacryloyloxy)ethyltrimethylammonium chloride nanoparticles with an average diameter of 254 nm) and the silica precursor tetramethyl orthosilicate (TMOS) were mixed in the pH range of 2-5. The polymer nanoparticles were present at 1.8 wt % and the TMOS was present at 3.6 wt % based on the weight of the aqueous suspension (1:3 weight-to-weight ratio of polymer nanoparticles to metal oxide precursor). The aqueous suspension was spray dried using a BUECHI lab-scale spray dryer under an inert atmosphere (nitrogen) at an inlet temperature of 100 °C, atomizing gas pressure of 40 mm, suction speed of 100%, and flow rate of 30% (approximately 10 mL / min).

[0265] The spray-dried powder was removed from the collection chamber of the spray dryer and spread on a silicon wafer for sintering.The spray-dried powder was then calcined in a muffle furnace using a batch sintering process to convert the silica precursor into silica nanoparticles, densify the silica, and remove the polymer to produce closed-cell silica particles.The heating parameters were as follows: the particles were heated from room temperature to 200°C over a period of 3 hours, held at 200°C for 2 hours, then heated to 550°C over a period of 2 hours, held at 550°C for 2 hours, and cooled to room temperature over a period of 3 hours.Figure 11 shows an SEM image of the product produced in Example 8.

[0266] Example 9: Closed-cell silica particles with irregular voids An aqueous suspension of positively charged spherical polymeric nanoparticles (copolymer of methyl methacrylate and 2-(methacryloyloxy)ethyltrimethylammonium chloride nanoparticles) of two different sizes (254 nm and 142 nm diameter, respectively) and negatively charged silica nanoparticles (with an average diameter of 7 nm) was prepared. The polymeric nanoparticles were present at a total of 1.8 wt % (0.9 wt % each) based on the weight of the aqueous suspension, and the silica nanoparticles were present at 0.6 wt %. The aqueous suspension was spray dried using a BUECHI laboratory-scale spray dryer under an inert atmosphere (nitrogen) at an inlet temperature of 100° C., an atomizing gas pressure of 40 mm, a suction speed of 100%, and a flow rate of 30% (approximately 10 mL / min).

[0267] The spray-dried powder was removed from the collection chamber of the spray dryer and spread onto a silicon wafer for sintering. The spray-dried powder was then fired in a muffle furnace using a batch sintering process to densify and stabilize the closed-cell metal oxide particles. The heating parameters were as follows: the particles were heated from room temperature to 550°C over a period of 6 hours, held at 550°C for 2 hours, and then cooled to room temperature over a period of 4 hours.

[0268] The closed-cell silica particles (0.5 mg) of Example 9 were placed in a 6 cm 2 The solution was uniformly dispensed into a 20 mL clear glass vial with a 1.2 mm bottom. The sample exhibited an angle-independent blue color observable by the human eye.

[0269] Predictive Application Examples 1-3 Polypropylene powder (Profax 6301, 12g / 10min melt flow rate) is weighed into a 240ml cup. Antioxidant (Irganox B 215) and closed cell particles of any of the above examples are weighed and mixed with the powder. The weights of the ingredients for each sample are listed in Table 1 below.

[0270] [Table 1]

[0271] The polymer mixture is placed into a CW Brabender Plasti-Corder preheated at 210°C and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C for 3 minutes under low pressure followed by 3 minutes under high pressure to a thickness of 250 μm. The mold is then cooled in the compression molder for 3 minutes. A 5 cm x 5 cm square is cut from the sheet for UV-Vis measurements.

[0272] Irganox B215 is a mixture of compounds of the formula: [ka]

[0273] Predictive Application Examples 4-7 Polypropylene powder (Profax 6301, melt flow rate of 12 g / 10 min) is weighed into a 240 ml cup. Antioxidant (Irganox B 215), ultraviolet light absorber (Tinuvin® PA 328), and closed cell particles of any of the above examples are weighed and mixed with the powder. The weights of the ingredients for each sample are listed in Table 2 below.

[0274] [Table 2]

[0275] The polymer mixture is placed into a CW Brabender Plasti-Corder preheated at 210°C and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C for 3 minutes under low pressure followed by 3 minutes under high pressure to a thickness of 250 μm. The mold is then cooled in the compression molder for 3 minutes. A 5 cm x 5 cm square is cut from the sheet for UV-Vis measurements.

[0276] Tinuvin® PA 328 is a compound of the formula: [ka]

[0277] Predictive Application Examples 8 and 9 Polypropylene powder (Profax 6301, melt flow rate of 12 g / 10 min) is weighed into a 240 ml cup. Antioxidant (Irganox B 215), ultraviolet light absorber (Tinuvin® 326), and closed cell particles of any of the above examples are weighed and mixed with the powder. The weights of the ingredients for each sample are listed in Table 3 below.

[0278] [Table 3]

[0279] The polymer mixture is placed into a CW Brabender Plasti-Corder preheated at 210°C and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C for 3 minutes under low pressure followed by 3 minutes under high pressure to a thickness of 250 μm. The mold is then cooled in the compression molder for 3 minutes. A 5 cm x 5 cm square is cut from the sheet for UV-Vis measurements.

[0280] Tinuvin 326® is a compound of the formula: [ka]

[0281] Predictive Application Examples 10 and 11 Polypropylene powder (Profax 6301, 12 g / 10 min melt flow rate) is weighed into a 240 ml cup. Antioxidant (Irganox B 215), ultraviolet light absorber (Chimassorb® 81), and closed cell particles of any of the above examples are weighed and mixed with the powder. The weights of the ingredients for each sample are listed in Table 4 below.

[0282] [Table 4]

[0283] The polymer mixture is placed into a CW Brabender Plasti-Corder preheated at 210°C and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C for 3 minutes under low pressure followed by 3 minutes under high pressure to a thickness of 250 μm. The mold is then cooled in the compression molder for 3 minutes. A 5 cm x 5 cm square is cut from the sheet for UV-Vis measurements.

[0284] Chimassorb® 81 is a compound of the formula: [ka]

[0285] Predictive Application Examples 12 and 13 Polypropylene powder (Profax 6301, melt flow rate of 12 g / 10 min) is weighed into a 240 ml cup. Antioxidant (Irganox B 215), ultraviolet light absorber (Tinuvin® 1577), and closed cell particles of any of the above examples are weighed and mixed with the powder. The weights of the ingredients for each sample are listed in Table 5 below.

[0286] [Table 5]

[0287] The polymer mixture is placed into a CW Brabender Plasti-Corder preheated at 210°C and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C for 3 minutes under low pressure followed by 3 minutes under high pressure to a thickness of 250 μm. The mold is then cooled in the compression molder for 3 minutes. A 5 cm x 5 cm square is cut from the sheet for UV-Vis measurements.

[0288] Tinuvin® 1577 is a compound of the formula: [ka]

[0289] Predictive Application Examples 14 and 15 Polypropylene powder (Profax 6301, melt flow rate of 12 g / 10 min) is weighed into a 240 ml cup. Antioxidant (Irganox B 215), ultraviolet light absorber (Uvinul® 3035), and closed cell particles of any of the above examples are weighed and mixed with the powder. The weights of the ingredients for each sample are listed in Table 6 below.

[0290] [Table 6]

[0291] The polymer mixture is placed into a CW Brabender Plasti-Corder preheated at 210°C and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C for 3 minutes under low pressure followed by 3 minutes under high pressure to a thickness of 250 μm. The mold is then cooled in the compression molder for 3 minutes. A 5 cm x 5 cm square is cut from the sheet for UV-Vis measurements.

[0292] Uvinul® 3035 is a compound of the following formula: [ka]

[0293] Predictive Application Examples 16 and 17 Polyethylene powder (Microthene MN 700 LDPE, 20g / 10min melt flow rate) is weighed into a 240ml cup. Antioxidant (Irganox B 215), ultraviolet light absorber (Tinuvin® 326), and closed cell particles of any of the above examples are weighed and mixed with the powder. The weights of the ingredients for each sample are listed in Table 7 below.

[0294] [Table 7]

[0295] The polymer mixture is placed into a CW Brabender Plasti-Corder preheated at 210°C and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C for 3 minutes under low pressure followed by 3 minutes under high pressure to a thickness of 250 μm. The mold is then cooled in the compression molder for 3 minutes. A 5 cm x 5 cm square is cut from the sheet for UV-Vis measurements.

[0296] Predictive Application Examples 18 and 19 Polyethylene powder (Microthene MN 700 LDPE, 20g / 10min melt flow rate) is weighed into a 240ml cup. Antioxidant (Irganox B 215), ultraviolet light absorber (Chimassorb® 81), and closed cell particles of any of the above examples are weighed and mixed with the powder. The weights of the ingredients for each sample are listed in Table 8 below.

[0297] [Table 8]

[0298] The polymer mixture is placed into a CW Brabender Plasti-Corder preheated at 210°C and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C for 3 minutes under low pressure followed by 3 minutes under high pressure to a thickness of 250 μm. The mold is then cooled in the compression molder for 3 minutes. A 5 cm x 5 cm square is cut from the sheet for UV-Vis measurements.

[0299] Predicted elongation at break The sample in the application example is an Atlas Weather-O-Meter (WOM, compliant with ASTM G155, 0.35 W / m at 340 nm). 2 The films can be exposed to accelerated light weathering (heat cycle, dry cycle). After exposure, specimens of the film samples are taken at regular intervals and tensile tested. The residual tensile strength is measured using a Zwick® Z1.0 Isokinetic Tensiometer (according to ISO 527) to assess the loss of mechanical properties of the samples due to post-oxidative polymer degradation.

[0300] Further Prophetic Example 1 Parameters: Average microsphere diameter: 1-10μm; Average pore size: 150-180nm; Metal oxide matrix: Silica; Method / Technique used: Cast film; Amount of microspheres used: 1.5wt%; Organic light absorber: None; Polymer used: Plexi-glas DR 101; Performance data: UV-Vis transmittance curves.

[0301] Further Prophetic Example 2 Average microsphere diameter: 1-10 μm; Average pore size: 150-180 nm; Metal oxide matrix: Silica; Method / Technique used: Cast film; Amount of microspheres used: 1.5 wt%; Organic light absorber: 0.1 wt% Tinuvin 326; Polymer used: Plexi-glas DR 101; Performance data: UV-Vis transmittance curves.

[0302] Further Prophetic Example 3 Average microsphere diameter: 1-10 μm; Average pore size: 150-180 nm; Metal oxide matrix: Silica; Method / Technique used: Twin screw extrusion; Amount of microspheres used: 1.5 wt%; Organic light absorber: 0.1 wt% Tinuvin 326; Polymer used: Homopolypropylene PP 6301; Performance data: Table of UV-Visible transmittance curves and accelerated weathering results.

[0303] Analytical testing methods for the articles of the present invention can be performed using, for example, UV-Vis for UV transmittance or absorbance analysis, SEM or TEM for characterization of microspheres in polymer film matrices, QUV and Xeon Weatherometer for accelerated weathering tests, long term weathering tests with outdoor panels, or combinations thereof.

[0304] Example 1 Plastic films were prepared to compare the effects of weathering on a control sample with a sample containing closed-cell microspheres prepared according to embodiments described herein. A formulation was prepared from the following components (with values ​​given in weight percent):

[0305] [Table 9]

[0306] Weathering tests were carried out according to the following: (1) ASTM G154 (Standard Practice for Operating Fluorescent Ultraviolet (UV) Lamp Apparatus for Exposure of Nonmetallic Materials) Cycle 1 (0.89 W / m at 340 nm) 2 8 hours UV at 60°C and 4 hours condensation at 50°C); and (2) ASTM G155 (Standard Practice for Operating Xenon Arc Lamp Apparatus for Exposure of Materials) Cycle 1 (0.35 W / m at 340 nm) 2 ;102 minutes light, 18 minutes light + spray).

[0307] The weathering test results are summarized below and show improved performance in both tests for the samples according to the invention compared to the control samples.

[0308] [Table 10]

[0309] In the foregoing description, numerous specific details are set forth, such as specific materials, dimensions, process parameters, etc., to provide a detailed understanding of the embodiments of the present disclosure. The particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. The term "example" or "exemplary" is used herein to mean serving as an example, illustration, or illustration. Any aspect or design described herein as "example" or "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word "example" or "exemplary" is intended to present concepts in a specific manner.

[0310] As used in this application, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise specified or clear from the context, "X includes A or B" is intended to mean any of the natural inclusive arrangements. That is, if X includes A; X includes B; or X includes both A and B, then "X includes A or B" is satisfied under any of the foregoing examples. Furthermore, the articles "a" and "an" as used in this application and the appended claims should generally be construed to mean "one or more" unless otherwise specified or clear from the context that the singular form is intended.

[0311] Throughout this specification, a reference to an "embodiment," "a particular embodiment," or "one embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment is included in at least one embodiment. Thus, the appearances of the phrases "embodiment," "a particular embodiment," or "one embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, and such references mean "at least one."

[0312] It should be understood that the above description is intended to be illustrative, and not limiting. Many other embodiments will be apparent to those skilled in the art upon reading and understanding the above description. The scope of the present disclosure should therefore be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims

1. 1. A method of preparing a composition comprising incorporating closed-cell metal oxide particles into a polymer, wherein the closed-cell metal oxide particles comprise: generating droplets from the particle dispersion comprising first particles comprising a polymeric material and second particles comprising a metal oxide material; drying the droplets to obtain dried particles comprising an array of the first particles, each of the first particles being coated with a layer of the second particles; and calcining or sintering the dried particles, wherein the calcining or sintering densifies the metal oxide material and removes the polymeric material to produce the closed-cell metal oxide particles, each comprising a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume inaccessible to a medium, the outer surface of the closed-cell metal oxide particles being defined by their respective array of closed cells, and the closed cells being present in an amount of 0.1% to about 40% by weight. The method is prepared by a method comprising:

2. The method of claim 1 , wherein the array of closed cells is a regular array.

3. The method of claim 1 , wherein the array of closed cells is an irregular array.

4. The method of claim 1 , wherein the first particles comprise a net positively charged surface and the second particles comprise a net negatively charged surface.

5. The method of claim 1 , wherein the first particles comprise a net negatively charged surface and the second particles comprise a net positively charged surface.

6. The method of claim 4 , wherein the surface charge drives the formation of a layer of the second particles on the first particles.

7. 10. The method of claim 1, wherein the polymeric material comprises a polymer selected from poly(meth)acrylic acid, poly(meth)acrylate, polystyrene, polyacrylamide, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, copolymers of methyl methacrylate and [2-(methacryloyloxy)ethyl]trimethylammonium chloride, derivatives thereof, salts thereof, copolymers thereof, or mixtures thereof.

8. The method of claim 1 , wherein the first particles have an average diameter of about 50 nm to about 500 nm.

9. 10. The method of claim 1, wherein the metal oxide material comprises a metal oxide selected from silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and combinations thereof.

10. The method of claim 1 , wherein the metal oxide material comprises silica.

11. The method of claim 1 , wherein the second particles have an average diameter of about 1 nm to about 120 nm.

12. The method of claim 1 , wherein the closed-cell metal oxide particles have an average diameter of about 0.5 μm to about 100 μm.

13. The method of claim 1 , wherein generating the droplets is performed using a microfluidic process.

14. 10. The method of claim 1, wherein the generating and drying of the droplets is performed using a spray drying process.

15. The method of claim 1 , wherein generating the droplets is performed using a vibrating nozzle.

16. 10. The method of claim 1, wherein drying the droplets comprises evaporation, microwave irradiation, oven drying, drying under vacuum, drying in the presence of a desiccant, or a combination thereof.

17. The method of claim 1 , wherein the particle dispersion is an aqueous particle dispersion.

18. The method of claim 1 , wherein a weight to weight ratio of the first particles to the second particles is from about 1 / 10 to about 10 / 1.

19. 10. The method of claim 1, wherein a weight to weight ratio of the first particles to the second particles is about 2 / 3, about 1 / 1, about 3 / 2, or about 3 / 1.

20. 2. The method of claim 1, wherein the particle size ratio of the second particles to the first particles is 1 / 50 to 1 / 5.

21. 1. A method of preparing a composition comprising incorporating closed-cell metal oxide particles into a polymer, wherein the closed-cell metal oxide particles comprise: generating droplets from a particle dispersion comprising a polymer in a sol-gel matrix of a metal oxide material, the polymer particles comprising a polymeric material; drying the droplets to obtain dried particles comprising an array of the polymer particles, each of the polymer particles being coated with the sol-gel matrix; and calcining or sintering the dried particles to obtain the closed-cell metal oxide particles, wherein the calcining or sintering removes the polymeric material and densifies the metal oxide material to produce the closed-cell metal oxide particles each comprising a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume inaccessible to a medium, and wherein an outer surface of the closed-cell metal oxide particles is defined by their respective array of closed cells. The method is prepared by a method comprising:

22. 22. The method of claim 21, wherein the polymer particles comprise a net positively charged surface and the sol-gel matrix of the metal oxide material comprises a net negative charge.

23. 22. The method of claim 21, wherein the polymer particles comprise a net negatively charged surface and the sol-gel matrix of the metal oxide material comprises a net positive charge.

24. A composition prepared by the method of any one of claims 1 to 23.

25. 1. A composition comprising closed-cell metal oxide particles incorporated into a polymer, wherein the closed-cell metal oxide particles comprise a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume inaccessible to a medium, and an outer surface of the closed-cell metal oxide particles being defined by the array of closed cells.

26. 26. The composition of claim 25, wherein the array of closed cells is a regular array.

27. 26. The composition of claim 25, wherein the array of closed cells is an irregular array.

28. 26. The composition of claim 25, wherein the void volume has an average diameter of about 50 nm to about 500 nm.

29. 26. The composition of claim 25, wherein the metal oxide matrix comprises a metal oxide selected from silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and combinations thereof.

30. 26. The composition of claim 25, wherein the metal oxide matrix comprises silica.

31. 26. The composition of claim 25, at least partially derived from polymer particles having an average diameter of from about 50 nm to about 500 nm.

32. 26. The composition of claim 25, at least partially derived from metal oxide particles having an average diameter of from about 1 nm to about 120 nm.

33. 26. The composition of claim 25, derived from a metal oxide precursor selected from silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and combinations thereof.

34. 1. Use of closed-cell metal oxide particles as a light stabilizer for molded artificial polymeric articles, comprising: the polymer is a synthetic polymer and / or a natural or synthetic elastomer, The closed-cell metal oxide particles are generating droplets from the particle dispersion comprising first particles comprising a polymeric material and second particles comprising a metal oxide material; drying the droplets to obtain dried particles comprising an array of the first particles, each of the first particles being coated with a layer of the second particles; and calcining or sintering the dried particles, wherein the calcining or sintering densifies the metal oxide material and removes the polymeric material to produce the closed-cell metal oxide particles, each comprising a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume inaccessible to a medium, and wherein an exterior surface of the closed-cell metal oxide particles is defined by their respective array of closed cells. The use, prepared by a method comprising:

35. 35. The use of claim 34, wherein the closed-cell particles are used at a concentration of 0.01% to 40.0% by weight, based on the weight of the molded artificial polymeric article.

36. 35. The use of claim 34, wherein the closed-cell particles are used in combination with one or more ultraviolet absorbers, the ultraviolet absorbers being selected from the group consisting of 2-hydroxyphenyltriazines, benzotriazoles, 2-hydroxybenzophenones, oxalanilides, cinnamates, and benzoates.

37. 37. The use of claim 36, wherein the one or more ultraviolet light absorbers are used at a concentration of 0.01% to 40.0% by weight, based on the weight of the molded artificial polymeric article.

38. 35. The use of claim 34, wherein the molded artificial polymeric article comprises hindered amine light stabilizers (HALS).

39. 35. The use according to claim 34, wherein the shaped artificial polymeric article is an extruded, cast, spun, moulded or calendered shaped artificial polymeric article.

40. 35. The use according to claim 34, wherein the shaped artificial polymeric article is a film, a tube, a cable, a tape, a sheet, a container, a frame, a fiber or a monofilament.

41. A molded artificial polymeric article, wherein said polymer is a synthetic polymer and / or a natural or synthetic elastomer, said polymer containing closed-cell particles as disclosed herein.

42. 1. An extruded, cast, spun, molded or calendered polymer composition, wherein the polymer is a synthetic polymer and / or a natural or synthetic elastomer, and the polymer contains the closed-cell particles disclosed herein.

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