Thermoplastic polyurethanes

Abstract

Provided is a thermoplastic polyurethane composition(s) including the reaction product of: (a) a polyisocyanate including: (i) from 25 to 80 weight percent of a regular aliphatic isocyanate, based on the total weight of the polyisocyanate component; and (ii) from 20 to 75 weight percent of a second aliphatic isocyanate different from the regular aliphatic isocyanate, based on the total weight of the polyisocyanate component; (b) a polycaprolactone polyol having a molecular weight of from 200 to 6,000 g / mol; and (c) a chain extender having a molecular weight of from 50 to 350 g / mol. Also provided are films including the thermoplastic polyurethane(s) disclosed herein, as well as surface protection films including such films as one layer, further including an adhesive layer and an optional polymer coating layer.

Description

THERMOPLASTIC POLYURETHANES

[0001] The disclosed technology relates to thermoplastic polyurethanes, such as for use in films for surface protection.

[0002] In general, thermoplastic polyurethanes are widely known and used in a multitude of applications. Some thermoplastic polyurethanes rely on 4,4’-diisocyanato dicyclohexylmethane (“H12MDI”) as the major or only polyisocyanate reactant to create the thermoplastic polyurethane, especially in the surface protection market, such as paint protective films (e.g., for use in automotive paint protection). Unfortunately, supply of H12MDI is not always able to keep up with demand, and so there is a need to be able to replace H12MDI with another polyisocyanate(s) without sacrificing the properties of the resulting thermoplastic polyurethane.

[0003] The disclosed technology, therefore, at least partially replaces H12MDI with another polyisocyanate(s) to provide thermoplastic polyurethanes with desirable and possibly improved properties for various applications.

[0004] The subject matter disclosed herein provides a thermoplastic polyurethane composition comprising the reaction product of: (a) a poly isocyanate comprising: (i) from 25 to 80 weight percent of a regular aliphatic isocyanate, based on the total weight of the poly isocyanate component; and (ii) from 20 to 75 weight percent of a second aliphatic isocyanate different from the regular aliphatic isocyanate, based on the total weight of the polyisocyanate component; (b) a polycaprolactone polyol having a molecular weight of from 200 to 6,000 g / mol; and (c) a chain extender having a molecular weight of from 50 to 350 g / mol. Also provided are fdms comprising the thermoplastic polyurethane(s) disclosed herein, as well as surface protection films comprising such films as one layer, further comprising an adhesive layer and an optional polymer coating layer.

[0005] The following embodiments of the present subject matter are contemplated:

[0006] 1. A thermoplastic polyurethane composition comprising the reaction product of:(a) a polyisocyanate comprising: (i) from 25 to 80 weight percent of a regular aliphatic isocyanate, based on the total weight of the polyisocyanate component; and (ii) from 20 to 75 weight percent of a second aliphatic isocyanate different from the regular aliphatic isocyanate, based on the total weight of the polyisocyanate component; (b) a polycaprolactone polyolhaving a molecular weight of from 200 to 6,000 g / mol; and (c) a chain extender having a molecular weight of from 50 to 350 g / mol.[00071 2. The thermoplastic polyurethane composition of embodiment 1, wherein the regular aliphatic isocyanate is a linear aliphatic isocyanate.

[0008] 3. The thermoplastic polyurethane composition of either embodiment 1 or embodiment 2, wherein the regular aliphatic isocyanate comprises hexamethylene diisocyanate.

[0009] 4. The thermoplastic polyurethane composition of any one of embodiments 1 to 3, wherein the second aliphatic isocyanate comprises a cyclic aliphatic isocyanate.

[0010] 5 The thermoplastic polyurethane composition of any one of embodiments 1 to 4, wherein the second aliphatic isocyanate comprises at least one of 4,4’-diisocyanato dicyclohexylmethane or isophorone diisocyanate.

[0011] 6 The thermoplastic polyurethane composition of any one of embodiments 1 to 5, wherein the chain extender comprises at least one of 2-methyl propanediol, 1,4-butanediol, 1,6- hexanediol, 3-methyl pentanediol, 1,4-cyclohexanedimethanol, or 1,12-dodecanediol.

[0012] 7. The thermoplastic polyurethane composition of any one of embodiments 1 to 6, wherein the reaction product is produced from components which are substantially free of polyether polyols.

[0013] 8. The thermoplastic polyurethane composition of any one of embodiments 1 to 7, wherein the polyisocyanate comprises from 5 to 35 weight percent of the reaction product, based on the total weight of the reaction product.

[0014] 9. The thermoplastic polyurethane composition of any one of embodiments 1 to 8, wherein the polycaprolactone comprises from 30 to 90 weight percent of the reaction product, based on the total weight of the reaction product.

[0015] 10. The thermoplastic polyurethane composition of any one of embodiments 1 to 9, wherein the chain extender comprises from 5 to 35 weight percent of the reaction product, based on the total weight of the reaction product.

[0016] 11. The thermoplastic polyurethane composition of any one of embodiments 1 to10, wherein the thermoplastic polyurethane composition has a Shore D hardness of from 20 to 80, as measured by ASTM D2240.

[0017] 12. The thermoplastic polyurethane composition of any one of embodiments 1 to11, wherein the thermoplastic polyurethane composition has a weight average molecular weight of from 40,000 to 200,000 g / mol, as measured by the MW by GPC Test.

[0018] 13. The thermoplastic polyurethane composition of any one of embodiments 1 to12, wherein the thermoplastic polyurethane composition further comprises at least one of a UV additive, an antioxidant, or a lubricant.

[0019] 14. A film comprising the thermoplastic polyurethane composition of any one of embodiments 1 to 13.

[0020] 15. The film of embodiment 14, wherein the film has an initial yellowness index of less than 4, as measured by the Yellowness Index Test.

[0021] 16. The film of either embodiment 14 or embodiment 15, wherein the film has a change in yellowness index of less than 1, as measured by the Accelerated Weathering Test.

[0022] 17. The film of any one of embodiments 14 to 16, wherein the film has a tensile strength at break of from 3,000 to 9,000 psi, as measured according to ASTM D882.

[0023] 18. The film of any one of embodiments 14 to 17, wherein the film has an elongation at break of from 350 to 700 percent, as measured according to ASTM D882.

[0024] 19. A surface protection film composition comprising an optional first layer comprising a polymer coating layer, a second layer comprising the film of any one of embodiments 14 to 18, and a third layer comprising an adhesive.

[0025] 20. The surface protection film composition of embodiment 19, wherein the second layer is, directly or indirectly, between the first layer and the third layer.

[0026] Various features and embodiments of the present subject matter will be described below by way of non-limiting illustration.

[0027] The amount of each chemical component described herein is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated. Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.

[0028] As used herein, the term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group includes at least carbon andhydrogen atoms. If the hydrocarbyl group comprises more than one carbon atom, then those carbons need not necessarily be linked to each other. For example, at least two of the carbons may be linked via a suitable element or group. In various embodiments, the term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group consists of carbon, hydrogen, optionally one or more heteroatoms provided the heteroatoms do not alter the predominantly hydrocarbon nature of the substituent. The heteroatom may link at least two of the carbons in the hydrocarbyl group, and optionally no more than two non-hydrocarbon substituents. Suitable heteroatoms will be apparent to those skilled in the art and include, for instance, sulphur, nitrogen, oxygen, phosphorus and silicon. Where the hydrocarbyl contains heteroatoms, optionally, no more than two heteroatoms will be present for every ten carbon atoms in the hydrocarbyl group. Suitable non-hydrocarbon substituents will also be apparent to those skilled in the art and include, for instance, halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy.

[0029] Examples of hydrocarbyls within the context of the present technology therefore include: (i) hydrocarbon groups selected from aliphatic (e.g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl, cycloalkenyl, cycloalkadienyl), and aromatic groups; (ii) substituted hydrocarbon groups, selected from hydrocarbon groups defined in (i) substituted with no more than two non- hydrocarbon substituents and / or one or more hydrocarbon substituents, the non-hydrocarbon substituents being selected from the group consisting of halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy; and / or (iii) hetero-containing hydrocarbon groups, selected from hydrocarbon groups defined in (i) containing one or more heteroatom in the ring or chain, provided that the group has no more than two heteroatoms present for every ten carbon atoms in the group, the heteroatoms being selected from sulphur, nitrogen, oxygen, phosphorus and silicon. The hetero-containing hydrocarbon groups may be substituted with no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents. In certain embodiments, the term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group consists of carbon and hydrogen atoms.

[0030] It is known that some of the materials described herein may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) may migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the productsformed upon employing the composition of the present subject matter in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present subject matter; the present subject matter encompasses the composition prepared by admixing the components described herein.

[0031] As used herein, the indefinite article “a” / “an” is intended to mean one or more than one. As used herein, the phrase “at least one” means one or more than one of the following terms. Thus, “a” / “an” and “at least one” may be used interchangeably. For example “at least one of A, B or C” means that just one of A, B or C may be included, and any mixture of two or more of A, B and C may be included, in alternative embodiments.

[0032] As used herein, the term “substantially” means that a value of a given quantity is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value.

[0033] As used herein, the term “substantially free of’ means that a component does not include any intentional addition of the material which the component is “substantially free of’. For example, the component may include a material which the component is “substantially free of’ at no more than impurity levels, which may be the result of incomplete chemical reactions and / or unintended / undesired (but perhaps unavoidable) reaction products.

[0034] As used herein, the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps. However, in each recitation of “comprising” herein, it is intended that the term also encompass, as alternative embodiments, the phrases “consisting essentially of’ and “consisting of,” where “consisting of’ excludes any element or step not specified and “consisting essentially of’ permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

[0035] Provided is a thermoplastic polyurethane composition(s) comprising the reaction product of (a) a polyisocyanate comprising: (i) from 25 to 80 (such as from 25 to 75, from 25 to 70, from 25 to 65, from 25 to 60, from 25 to 55, from 25 to 50, from 25 to 45, from 25 to 40, from 25 to 35, from 25 to 30, from 30 to 80, from 30 to 75, from 30 to 70, from 30 to 65, from 30 to 60, from 30 to 55, from 30 to 50, from 30 to 45, from 30 to 40, from 30 to 35, from 35 to80, from 35 to 75, from 35 to 70, from 35 to 65, from 35 to 60, from 35 to 55, from 35 to 50, from 35 to 45, from 35 to 40, from 40 to 80, from 40 to 75, from 40 to 70, from 40 to 65, from 40 to 60, from 40 to 55, from 40 to 50, from 40 to 45, from 45 to 80, from 45 to 75, from 45 to 70, from 45 to 65, from 45 to 60, from 45 to 55, from 45 to 50, from 50 to 80, from 50 to 75, from 50 to 70, from 50 to 65, from 50 to 60, from 50 to 55, from 55 to 80, from 55 to 75, from 55 to 70, from 55 to 65, from 55 to 60, from 60 to 80, from 60 to 75, from 60 to 70, from 60 to 65, from 65 to 80, from 65 to 75, from 65 to 70, from 70 to 80, from 70 to 75, or from 75 to 80) weight percent of a regular aliphatic isocyanate, based on the total weight of the polyisocyanate component; and (ii) from 20 to 75 (such as from 20 to 70, from 20 to 65, from 20 to 60, from 20 to 55, from 20 to 50, from 20 to 45, from 20 to 40, from 20 to 35, from 20 to 30, from 20 to 25, from 25 to 75, from 25 to 70, from 25 to 65, from 25 to 60, from 25 to 55, from 25 to 50, from 25 to 45, from 25 to 40, from 25 to 35, from 25 to 30, from 30 to 75, from 30 to 70, from 30 to 65, from 30 to 60, from 30 to 55, from 30 to 50, from 30 to 45, from 30 to 40, from 30 to 35, from 35 to 75, from 35 to 70, from 35 to 65, from 35 to 60, from 35 to 55, from 35 to 50, from 35 to 45, from 35 to 40, from 40 to 75, from 40 to 70, from 40 to 65, from 40 to 60, from 40 to 55, from 40 to 50, from 40 to 45, from 45 to 75, from 45 to 70, from 45 to 65, from 45 to 60, from 45 to 55, from 45 to 50, from 50 to 75, from 50 to 70, from 50 to 65, from 50 to 60, from 50 to 55, from 55 to 75, from 55 to 70, from 55 to 65, from 55 to 60, from 60 to 75, from 60 to 70, from 60 to 65, from 65 to 75, from 65 to 70, or from 70 to 75) weight percent of a second aliphatic isocyanate different from the regular aliphatic isocyanate, based on the total weight of the poly isocyanate component; (b) a polycaprolactone polyol having a molecular weight of from 200 to 6,000 (such as from 200 to 5,000, from 200 to 4,000, from 200 to 3,500, from 200 to 3,000, from 200 to 2,500, from 200 to 2,000, from 200 to 1,800, from 200 to 1,600, from 200 to 1,400, from 200 to 1,200, from 200 to 1,000, from 300 to 6,000, from 300 to 5,000, from 300 to 4,000, from 300 to 3,500, from 300 to 3,000, from 300 to 2,500, from 300 to 2,000, from 300 to 1,800, from 300 to 1,600, from 300 to 1,400, from 300 to 1,200, from 300 to 1,000, from 400 to 6,000, from 400 to 5,000, from 400 to 4,000, from 400 to 3,500, from 400 to 3,000, from 400 to 2,500, from 400 to 2,000, from 400 to 1,800, from 400 to 1,600, from 400 to 1,400, from 400 to 1,200, from 400 to 1,000, from 500 to 6,000, from 500 to 5,000, from 500 to 4,000, from 500 to 3,500, from 500 to 3,000, from 500 to 2,500, from 500 to 2,000, from 500 to 1,800, from 500 to 1,600, from 500 to 1,400, from 500 to 1,200, from 500 to 1,000, from 600 to 6,000,from 600 to 5,000, from 600 to 4,000, from 600 to 3,500, from 600 to 3,000, from 600 to 2,500, from 600 to 2,000, from 600 to 1,800, from 600 to 1,600, from 600 to 1,400, from 600 to 1,200, from 600 to 1,000, from 700 to 6,000, from 700 to 5,000, from 700 to 4,000, from 700 to 3,500, from 700 to 3,000, from 700 to 2,500, from 700 to 2,000, from 700 to 1,800, from 700 to 1,600, from 700 to 1,400, from 700 to 1,200, from 700 to 1,000, from 800 to 6,000, from 800 to 5,000, from 800 to 4,000, from 800 to 3,500, from 800 to 3,000, from 800 to 2,500, from 800 to 2,000, from 800 to 1,800, from 800 to 1,600, from 800 to 1,400, from 800 to 1,200, from 800 to 1,000, from 900 to 6,000, from 900 to 5,000, from 900 to 4,000, from 900 to 3,500, from 900 to 3,000, from 900 to 2,500, from 900 to 2,000, from 900 to 1,800, from 900 to 1,600, from 900 to 1,400, from 900 to 1,200, or from 900 to 1,000) g / mol; and (c) a chain extender having a molecular weight of from 50 to 350 (such as from 50 to 300, from 50 to 250, from 50 to 200, from 50 to 150, from 50 to 100, from 50 to 90, from 50 to 80, from 50 to 70, from 50 to 60, from 60 to 350, from 60 to 300, from 60 to 250, from 60 to 200, from 60 to 150, from 60 to 100, from 60 to 90, from 60 to 80, from 60 to 70, from 70 to 350, from 70 to 300, from 70 to 250, from 70 to 200, from 70 to 150, from 70 to 100, from 70 to 90, from 70 to 80, from 80 to 350, from 80 to 300, from 80 to 250, from 80 to 200, from 80 to 150, from 80 to 100, from 80 to 90, from 90 to 350, from 90 to 300, from 90 to 250, from 90 to 200, from 90 to 150, from 90 to 100, from 100 to 350, from 100 to 300, from 100 to 250, from 100 to 200, from 100 to 150, from 150 to 350, from 150 to 300, from 150 to 250, from 150 to 200, from 200 to 350, from 200 to 300, from 200 to 250, from 250 to 350, from 250 to 300, or from 300 to 350) g / mol.

[0036] As used in the context of a “regular aliphatic isocyanate”, the term “regular” refers to an isocyanate with straight or branched aliphatic carbon chain(s) with the isocyanate group attached, where the aliphatic chain(s) can vary in length and branching, but the isocyanate does not contain any additional chemical groups or modifications; further, regular aliphatic isocyanates are unmodified and / or unblocked.

[0037] In certain embodiments, the regular aliphatic isocyanate is a linear aliphatic isocyanate. In the context of “linear aliphatic isocyanate”, the term “linear” refers to a regular aliphatic isocyanate with straight aliphatic carbon changes, as opposed to branched aliphatic carbon chains.

[0038] The phrase “second aliphatic isocyanate different from the regular aliphatic isocyanate” means that the second aliphatic isocyanate can be any aliphatic isocyanate whichis different from the specific regular aliphatic isocyanate which is chosen, such that the second aliphatic isocyanate could also be a regular aliphatic isocyanate, as long as it is a different regular aliphatic isocyanate. It is also possible that the second aliphatic isocyanate is not a regular aliphatic isocyanate.

[0039] The molecular weight of the polycaprolactone is determined by measuring the OH value of the polyol, which is standard industrial practice for determining molecular weight polycaprolactones.

[0040] The molecular weight of the chain extender is determined based on the chemical structure of the chain extender. Chain extenders generally have small and / or simple chemical structures which are easy to define and thereby simply add up the various atoms which make up the chain extender to arrive at the molecular weight of the chain extender.

[0041] In certain embodiments, the regular aliphatic isocyanate may comprise at least one of hexamethylene diisocyanate, trans-trans isomer of 4,4’-diisocyanato dicyclohexylmethane, or 1,4-hydrogenated xylylene diisocyanate. In certain embodiments, the regular aliphatic isocyanate comprises hexamethylene diisocyanate.

[0042] In certain embodiments, the second aliphatic isocyanate comprises a cyclic aliphatic isocyanate. In certain embodiments, the second aliphatic isocyanate comprises at least one of 4,4’-diisocyanato dicyclohexylmethane or isophorone diisocyanate.

[0043] In certain embodiments, the chain extender comprises at least one of 2-methyl propanediol, 1,3-propanediol, 1,9-nonanediol, 2-butyl-2-ethyl-l,3-propanediol, 1,4- butanediol, 1,6-hexanediol, 3-methyl pentanediol, 1,4-cyclohexanedimethanol, or 1,12- dodecanediol.

[0044] In certain embodiments, the reaction product is produced from components which are substantially free of, or free of polyether polyols. The reaction product being substantially free of, or free of polyether polyols may provide certain benefits, such as improved UV resistance and / or improved thermal oxidation resistance.

[0045] In certain embodiments, the polyisocyanate comprises from 5 to 35 (such as from 5 to 30, from 5 to 25, from 5 to 20, from 5 to 15, from 5 to 10, from 5 to 9, from 5 to 8, from 5 to 7, from 5 to 6, from 6 to 35, from 6 to 30, from 6 to 25, from 6 to 20, from 6 to 15, from 6 to 10, from 6 to 9, from 6 to 8, from 6 to 7, from 7 to 35, from 7 to 30, from 7 to 25, from 7 to 20, from 7 to 15, from 7 to 10, from 7 to 9, from 7 to 8, from 8 to 35, from 8 to 30, from 8 to 25,from 8 to 20, from 8 to 15, from 8 to 10, from 8 to 9, from 9 to 35, from 9 to 30, from 9 to 25, from 9 to 20, from 9 to 15, from 9 to 10, from 10 to 35, from 10 to 30, from 10 to 25, from 10 to 20, from 10 to 15, from 15 to 35, from 15 to 30, from 15 to 25, from 15 to 20, from 20 to 35, from 20 to 30, from 20 to 25, from 25 to 35, from 25 to 30, or from 30 to 35) weight percent of the reaction product, based on the total weight of the reaction product.

[0046] In certain embodiments, the polycaprolactone comprises from 30 to 90 (such as from 30 to 89, from 30 to 88, from 30 to 87, from 30 to 86, from 30 to 85, from 30 to 80, from 30 to 75, from 30 to 70, from 30 to 65, from 30 to 60, from 30 to 55, from 30 to 50, from 30 to 45, from 30 to 40, from 30 to 35, from 35 to 90, from 35 to 89, from 35 to 88, from 35 to 87, from35 to 86, from 35 to 85, from 35 to 80, from 35 to 75, from 35 to 70, from 35 to 65, from 35 to60, from 35 to 55, from 35 to 50, from 35 to 45, from 35 to 40, from 40 to 90, from 40 to 89, from 40 to 88, from 40 to 87, from 40 to 86, from 40 to 85, from 40 to 80, from 40 to 75, from40 to 70, from 40 to 65, from 40 to 60, from 40 to 55, from 40 to 50, from 40 to 45, from 45 to90, from 45 to 89, from 45 to 88, from 45 to 87, from 45 to 86, from 45 to 85, from 45 to 80, from 45 to 75, from 45 to 70, from 45 to 65, from 45 to 60, from 45 to 55, from 45 to 50, from50 to 90, from 50 to 89, from 50 to 88, from 50 to 87, from 50 to 86, from 50 to 85, from 50 to80, from 50 to 75, from 50 to 70, from 50 to 65, from 50 to 60, from 50 to 55, from 55 to 90, from 55 to 89, from 55 to 88, from 55 to 87, from 55 to 86, from 55 to 85, from 55 to 80, from55 to 75, from 55 to 70, from 55 to 65, from 55 to 60, from 60 to 90, from 60 to 89, from 60 to88, from 60 to 87, from 60 to 86, from 60 to 85, from 60 to 80, from 60 to 75, from 60 to 70, from 60 to 65, from 65 to 90, from 65 to 89, from 65 to 88, from 65 to 87, from 65 to 86, from65 to 85, from 65 to 80, from 65 to 75, from 65 to 70, from 70 to 90, from 70 to 89, from 70 to88, from 70 to 87, from 70 to 86, from 70 to 85, from 70 to 80, from 70 to 75, from 75 to 90, from 75 to 89, from 75 to 88, from 75 to 87, from 75 to 86, from 75 to 85, from 75 to 80, from80 to 90, from 80 to 89, from 80 to 88, from 80 to 87, from 80 to 86, from 80 to 85, from 85 to90, from 85 to 89, from 85 to 88, from 85 to 87, from 85 to 86, from 86 to 90, from 86 to 87, from 86 to 88, from 86 to 87, from 87 to 90, from 87 to 89, from 87 to 88, from 88 to 90, from 88 to 89, or from 89 to 90) weight percent of the reaction product, based on the total weight of the reaction product.

[0047] In certain embodiments, the poly caprolactone may comprise at least one of s- caprolactone, P-propiolactone, P-butyrolactone, ^-butyrolactone, 5-valerolactone, y- valerolactone, 5-caprolactone, 5-decalactone, or s-decalactone.

[0048] In certain embodiments, the chain extender comprises from 5 to 35 (such as from 5 to 30, from 5 to 25, from 5 to 20, from 5 to 15, from 5 to 10, from 5 to 9, from 5 to 8, from 5 to 7, from 5 to 6, from 6 to 35, from 6 to 30, from 6 to 25, from 6 to 20, from 6 to 15, from 6 to 10, from 6 to 9, from 6 to 8, from 6 to 7, from 7 to 35, from 7 to 30, from 7 to 25, from 7 to 20, from 7 to 15, from 7 to 10, from 7 to 9, from 7 to 8, from 8 to 35, from 8 to 30, from 8 to 25, from 8 to 20, from 8 to 15, from 8 to 10, from 8 to 9, from 9 to 35, from 9 to 30, from 9 to 25, from 9 to 20, from 9 to 15, from 9 to 10, from 10 to 35, from 10 to 30, from 10 to 25, from 10 to 20, from 10 to 15, from 15 to 35, from 15 to 30, from 15 to 25, from 15 to 20, from 20 to 35, from 20 to 30, from 20 to 25, from 25 to 35, from 25 to 30, or from 30 to 35) weight percent of the reaction product, based on the total weight of the reaction product.

[0049] When describing amounts of the polyisocyanate, the polycaprolactone, the chain extender, or other optional reactants which make up the reaction product, it is meant that the amount (such as by weight percent) is based on the total weight of reactants which make up the reaction product, since, once reacted, the weight of a particular reactant as a portion of the reaction product may slightly change.

[0050] In certain embodiments, the thermoplastic polyurethane composition has a Shore D hardness of from 20 to 80, as measured by ASTM D2240.

[0051] In certain embodiments, the thermoplastic polyurethane composition has a weight average molecular weight of from 40,000 to 200,000 (such as from 40,000 to 180,000, from 40,000 to 160,000, from 40,000 to 140,000, from 40,000 to 120,000, from 40,000 to 100,000, from 40,000 to 90,000, from 40,000 to 80,000, from 40,000 to 70,000, from 40,000 to 60,000, from 40,000 to 50,000, from 50,000 to 200,000, from 50,000 to 180,000, from 50,000 to 160,000, from 50,000 to 140,000, from 50,000 to 120,000, from 50,000 to 100,000, from 50,000 to 90,000, from 50,000 to 80,000, from 50,000 to 70,000, from 50,000 to 60,000, from 60,000 to 200,000, from 60,000 to 180,000, from 60,000 to 160,000, from 60,000 to 140,000, from 60,000 to 120,000, from 60,000 to 100,000, from 60,000 to 90,000, from 60,000 to 80,000, from 60,000 to 70,000, from 70,000 to 200,000, from 70,000 to 180,000, from 70,000 to 160,000, from 70,000 to 140,000, from 70,000 to 120,000, from 70,000 to 100,000, from 70,000to 90,000, from 70,000 to 80,000, from 80,000 to 200,000, from 80,000 to 180,000, from 80,000 to 160,000, from 80,000 to 140,000, from 80,000 to 120,000, from 80,000 to 100,000, from 80,000 to 90,000, from 90,000 to 200,000, from 90,000 to 180,000, from 90,000 to 160,000, from 90,000 to 140,000, from 90,000 to 120,000, from 90,000 to 100,000, from 100,000 to 200,000, from 100,000 to 180,000, from 100,000 to 160,000, from 100,000 to 140,000, from 100,000 to 120,000, from 120,000 to 200,000, from 120,000 to 180,000, from 120,000 to 160,000, from 120,000 to 140,000, from 140,000 to 200,000, from 140,000 to 180,000, from 140,000 to 160,000, from 160,000 to 200,000, from 160,000 to 180,000, or from 180,000 to 200,000) g / mol, as measured by the MW by GPC Test.

[0052] The MW by GPC test is performed using tetrahydrofuran (THF) as solvent and mobile phase, ImL / min flow rate, and at 40 °C, with polystyrene as calibration standard, as is known by those of ordinary skill in the relevant art.

[0053] In certain embodiments, the thermoplastic polyurethane composition further comprises at least one of a UV additive, an antioxidant, or a lubricant. Other ingredients may also be used as additives and / or reactants in the thermoplastic polyurethane compositions described herein, as is known to those of ordinary skill in the art. Non-limiting examples of such additives and / or reactants may include those described in the following paragraphs.

[0054] These additives may include antioxidants, organic phosphites, phosphines and phosphonites, hindered amines, organic amines, organo sulfur compounds, lactones and hydroxylamine compounds, biocides, fungicides, antimicrobial agents, compatibilizers, electro-dissipative or anti-static additives, fillers and reinforcing agents, such as titanium dixide, alumina, clay and carbon black, flame retardants, such as phosphates, halogenated materials, and metal salts of alkyl benzenesulfonates, impact modifiers, such as methacrylate- butadiene-styrene ("MBS") and methylmethacrylate butylacrylate ("MBA"), lubricants, mold release agents such as waxes, fats and oils, pigments and colorants, plasticizers, polymers, rheology modifiers such as monoamines, polyamide waxes, silicones, and polysiloxanes, slip additives, such as paraffinic waxes, hydrocarbon polyolefins and / or fluorinated polyolefins, and UV additives (such as UV stabilizers). Other additives may be used to enhance the performance of the TPU composition or blended product. All of the additives described above may be used in an effective amount customary for these substances.

[0055] Antioxidants may be added during the polymerization reaction, or blended into the previously-formed thermoplastic polyurethane composition(s) described herein, such as in an amount of from 0.3 to 2 percent by weight, based on the total weight of the thermoplastic polyurethane composition. Suitable antioxidants include phenolic types, organic phosphites, phosphines and phosphonites, hindered amines, organic amines, organo sulfur compounds, lactones and hydroxylamine compounds. For applications in which transparency is desired, the antioxidant is preferably soluble in the thermoplastic polyurethane, or dispersable therein as very fine droplets or particles. Many suitable antioxidant materials are available commercially. These include Irganox™ 1010, Irganox™ MD1024, Irgafos™ 168, Irgafos™ 126, all available from BASF Specialty Chemicals, and the like.

[0056] UV additives, such as UV stabilizers and / or UV absorbers (all of which may be similar or different compositions depending on preferred nomenclature in different circumstances), may be used in the thermoplastic polyurethane compositions described herein. UV additives may be used for many reasons, such as to prevent the thermoplastic polyurethane composition(s) from changing color, losing clarity, and / or impacting mechanical properties.

[0057] Suitable UV light stabilizers include hindered amine light stabilizers (HALS) and UV light absorber (UVA) additives. Blends of HAL and UVA additives are also effective. Representative HALS that can be used in the practice of this invention include, but are not limited to, Sterically hindered amines as well as the N derivatives thereof (e.g., N-alkyl, N- hydroxy, N-alkoxy and N-acyl), such as bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(2,2,6,6tetramethylpiperidin-4-yl) succinate; bis(l, 2,2,6, 6-pentamethylpiperidin-4- yl)sebacate; bis(l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; bis( 1,2, 2,6,6- pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert-butyl-4-hydroxybenzylmalonate; the condensate of l(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; the condensate of N,N’-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert- octylamino-2,6-dichloro-l,3,5-triazine; tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate; tetrakis(2,2,6,6-tetramethylpiperidin-4yl)-l,2,3,4-butanetetracarboxylate; 1,1'-(l,2ethanediyl)bis(3,3,5,5-tetramethylpiperazinone); 4-benzoyl-2,2,6,6-tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine; bis(l, 2,2,6, 6-pentamethylpiperidyl)-2-n-butyL2- (2-hydroxy-3,5-di-tert-butylbenzyl) mal onate; 3-n-octyl-7, 7,9, 9-tetramethyl- 1,3,8- triazaspiro[4.5]decan-2, 4-dione; bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate; bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; the condensate of N, N'-bis(2, 2,6,6- tetramethylpiperidin4-yl) hexamethylenediamine and 4-morpholino-2,6-dichlorol,3,5-triazine; the condensate of 2-chloro-4,6-bis(4-nbutylamino-2,2,6,6-tetramethylpiperidyl)-l,3,5-triazine and l,2-bis(3-aminopropylamino)ethane; the condensate of 2-chloro-4,6-bis(4-n-butylamino- l,2,2,6,6-pentamethylpiperidyl)-l,3,5-triazine and l,2-bis-(3aminopropylamino)ethane; 8- acetyl-3-dodecyl-7,7,9,9-tetramethyl-l,3,8-triazaspiro[4.5]decane-2,4-dione; 3-dodecyl-l- (2,2,6,6-tetramethylpiperidin4-yl)pyrrolidin-2,5-dione; 3-dodecyl-l-(l-ethanoyl-2,2,6,6tetramethylpiperidin-4-yl) pyrrolidin-2, 5-dione; 3-dodecyl-l-(l,2,2,6,6- pentamethylpiperidin-4yl)pyrrolidine-2, 5-dione; a mixture of 4-hexadecyloxyand 4- stearyloxy-2,2,6,6-tetramethylpiperidine; the condensate of N, N'-bis(2, 2,6,6- tetramethylpiperidin-4yl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-l,3,5- triazine; the condensate of l,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-l,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine, 2-undecyl-7,7,9,9-tetramethyl-l-oxa-3,8- diaza-4-oxospiro[4.5]decane; oxo-piperanzinyl-triazines and similar materials disclosed in US5071981; photobondable HALS and similar materials disclosed in GB-A-2269819; and the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-l-oxa-3,8-diaza-4oxospiro[4.5]decane and epichlorohydrin. See also generally US4619956, US5106891, GB-A-2269819, EP- A0309400, EP-A-0309401, EP-A-0309402 and EP-A-0434608. Some commercially available examples of HALS additives are Tinuvin® 123, Tinuvin 123-DW, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622-SF, Tinuvin 770-DF, Tinuvin 5100 (the Tinuvin® series of additives are available from BASF), Chimassorb® 119, Chimassorb 2020 (the Chimassorb® series of additives are available from BASF), Lowilite® 76, Lowilite 62 (the Lowilite® series of additives are available from Addivant), Uvinul® 4050FF (BASF), LA-52, LA-576, LA-63P, 68, 72, 77Y, 77G, 81, 82, 87, 4042F, 502XP (the LA series of additives are available from Adeka Corporation), Hostavin® N30, Hostavin N845PP, Hostavin 3050, Hostavin 3051, Hostavin 3052, Hostavin 3053, Hostavin 3055, Hostavin 3058, Hostavin 3065, Hostavin PR- 31 (the Hostavin® series of additives are available from Clariant), and Nylostab® S-EED® (available from Clariant), Additional preferred hindered amine light stabilizer may be listed in the Plastics Additives Handbook 6th Edition, Hans Zweifel, Ralph Maier, Michael Schiller (Hanser Publications, Inc., Cincinnati, Ohio, USA, 2009). If present, then the HALS is typicallypresent in an amount of greater than 0 to 4, more typically of 0.2 to 3 and even more typically of 0.5 to 2, wt% based on the weight of the composition.

[0058] Without being bound by theory, typically a UV stabilizer works by scavenging the free radicals and / or hydroperoxides formed by UV light damage while a UV absorber works by absorbing and dissipation the UV radiation. Suitable UV absorbers include, but are not limited to, triazines, benzoxazinones, benzotriazoles, benzophenones, benzoates, formamidines, cinnamates / propenoates, aromatic propanediones, benzimidazoles, cycloaliphatic ketones, formanilides (including oxamides), cyanoacrylates, benzopyranones, salicylates, and mixtures of two or more of these.

[0059] Suitable benzophenone UV absorbers include, but are not limited to, 2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone or sulisobenzone, 2-(4- benzoyl-3-hydroxyphenoxy)-2-propenoic acid ethyl ester, homopolymer of 4-(2- acryloyloxyethoxy)-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone or dioxybenzone, 2-hy droxy-4-(2 -hydroxy-3 -decyl oxypropoxy) benzophenone and 2-hydroxy-4- (2-hydroxy-3 -octyl oxypropoxy) benzophenone, 2,4,4'-trihydroxybenzophenone, 2-hydroxy-4- (isooctyloxy) benzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4,4'- dimethoxy-5,5'-disulfobenzophenone, disodium salt, 2,4-dihydroxybenzophenone or 4- benzoylresorcinol, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2, 2', 4,4'- tetrahydroxybenzophenone, 2,2'-dihydroxy-4-(2-hydroxyethoxy)benzophenone, 2-hydroxy-4- benzyloxybenzophenone, and mixtures of two or more of these. MAXGARD® 300, MAXGARD® 400, MAXGARD® 500, MAXGARD® 600, MAXGARD® 700, MAXGARD® 900, MAXGARD® 1000 MAXGARD® 1800, (The Maxgard series of chemicals can be obtained from Lycus LTD)

[0060] Suitable benzopyranone UV absorbers include, but are not limited to, 3, 3', 4', 5,7- pentahydroxyflavone or quercetin.

[0061] Suitable benzotriazole UV absorbers include, but are not limited to, 2-[2-hydroxy- 5-(l,l,3,3-tetramethylbutyl)phenyl]benzotriazole, 2-(2'-hydroxy-5'-(2- hydroxyethyl))benzotriazole, 2-(2'-hydroxy-5'-methacrylyloxyethylphenyl)-2H-benzotriazole, 1,1,1 -tri s(hydroxyphenyl) ethane benzotri azole, 5-t-butyl-3-(5-chloro-2H-benzotriazol-2-yl)-4- hy dr oxy benzenepropanoic acid octyl ester and 3-(5-chloro-2H-benzotriazol-2-yl)-5-t-butyl-4- hydroxybenzenepropanoic acid octyl ester, a-[3-[3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]-! -ox opropyl]-co-hydroxy poly(oxy-l,2-ethanediyl) and a-[3-[3-(2H- benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]-l-oxopropyl]-w-[3-[3-(2H-benzotriazol-2-yl)- 5-t-butyl-4-hydroxyphenyl]-l-oxopropoxy]poly(oxy-l,2-ethanediyl), 2-(2 -Hydroxy-3, 5-di-t- butylphenyl) benzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chloro-2H- benzotriazole, 2-(3'-5'-di-t-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2 -Hydroxy-3, 5- di-t-amylphenyl)benzotriazole, 3-(2H-benzotriazol-2-yl)-5-t-butyl-4- hydroxybenzenepropanoic acid, 2-(2H-benzotriazol-2-yl)-4-methyl-6-dodecylphenol, 3-(2H- benzotriazol-2-yl)-5-t-butyl-4-hydroxy-l,6-hexanediyl ester of benzenepropanoic acid and 3- (2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxy-methyl ester of benzenepropanoic acid, 2-[2- hydroxy-3,5-bis-(l, 1 -dimethylbenzyl) phenyl]-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-6- ( 1 -methyl- 1 -phenylethyl)-4-( 1 , 1 ,3,3 -tetramethylbutyl) phenol, 3 -(2H-benzotriazol-2-yl)-5-t- butyl-4-hydroxybenzenepropanoic acid, C7-9 branched and linear alkyl esters, 2-(2-hydroxy- 5-methylphenyl) benzotriazole, 2-(2'-hydroxy-3'-sec-butyl-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, bis[2-hydroxy-3-(2H-benzotriazol-2-yl)-5- octylphenyl]methane, and mixtures of two or more of these. Some commercially avaialable examples of suitable benzotriazole UV absorbers include, but are not limited to TINUVIN® 99, TINUVIN 109, TINUVIN 328, TINUVIN 350, TINUVIN 360 TINUVIN 384-2, TINUVIN 571, TINUVIN 1130, and TINUVIN P. (The Tinuvin series of additives are available from BASF).

[0062] Suitable benzoate UV absorbers include, but are not limited to, hexadecyl 3,5-dit- butyl-4-hydroxybenzoate, 3 -hydroxyphenylbenzoate, ethyl -4-[[(ethylphenylamino)methylene] amino]benzoate, phenyl 2-hydroxybenzoate or phenylsalicylate, 2,4-di-t-butylphenyl-3,5-di-t- butyl-4-hydroxybenzoate, 4-bis(polyethoxy)amino acid polyethoxy ethyl ester, 4-t-butylphenyl 2-hydroxybenzoate or 4-t-butylphenylsalicylate, and mixtures of two or more of these. Some commercially available examples of suitable UV absorbers of this type include, but are not limited to SEESORB 300; SEESORB 201; SEESORB 202 (The SEESORB UV absorbers are available from Shipro Kasei Kaisha, Ltd.); TINUVIN 120 (available from BASF); UVINUL® P 25 (available from BASF).

[0063] Suitable benzoxazinone UV absorbers include, but are not limited to, 2,2'-(p- phenylene) di-3,l-benzoxazin-4-one. A commercially available example of a suitable UV absorbers of this type includes, but is not limited to CYASORB 3638 (from Syensqo).

[0064] Suitable cinnamates or propenoate UV absorbers include, but are not limited to, dimethyl (p-methoxybenzylidene) mal onate, and 3-(4-methoxyphenyl)-2-propenoic acid 2- ethylhexyl ester or octyl p-methoxycinnamate.

[0065] Suitable cyanoacrylate UV absorbers include, but are not limited to, ethyl -2-cyano- 3,3-diphenylacrylate,; 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, l,3-bis-[(2'-cyano-3,3'- diphenylacryloyl)oxy]-2,2-bis-{ [(2-cyano-3',3'-diphenylacryloyl)oxy]methyl}propane, and 2- cyano-3-(2-methylindolinyl) methylacrylate, Some commercially available examples of suitable UV absorbers of this type include, but are not limited to UVINUL® 3030, UVINUL 3035, and UVINUL 3039. The Uvinul series of additives are available from BASF.

[0066] Suitable cycloaliphatic ketone UV absorbers include, but are not limited to, 3-(4- methylbenzylidene)-D,L-camphor.

[0067] Suitable formamidine UV absorbers include, but are not limited to, ethyl-4- [[(methylphenylamino)methylene]amino]benzoate.

[0068] Suitable formanilide (including oxamide) UV absorbers include, but are not limited to, N-(2-ethoxyphenyl)-N'-(4-isododecylphenyl) oxamide, N-[5-t-Butyl-2-ethoxyphenyl)-N'- (2-ethylphenyl) oxamide, N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) oxamide, 2H- benzimidazole-2-carboxylic acid (4-ethoxyphenyl) amide, and mixtures of two or more of these. Some commercially avaialable examples of these types of additives are Hostavin® 3206 from Clariant and TINUVIN® 312 from BASF.

[0069] Suitable triazine UV absorbers include, but are not limited to, 2-[4,6-bis(2,4- dimethylphenyl)-l,3,5-triazin-2-yl]-5-octyloxyphenol, 2-(4,6-diphenyl-l,3,5-triazin-2-yl)-5- hexyloxyphenol, 2-[4-((2-Hydroxy-3-dodecyloxy-propyl)oxy)-2-hydroxyphenyl]-4,6-bis(2,4- dimethylphenyl)-l,3,5-triazine, 2,4,6-Trianilino-p-(carbo-2'-ethylhexyl-r-oxy)-l,3,5-triazine, and mixtures of two or more of these. TINUVIN® 400; TINUVIN 1577 ED; UVINUL T-150 from BASF.

[0070] Suitable salicylate UV absorbers include, but are not limited to, 3,3,5- trimethylcyclohexylsalicylate or homomethyl salicylate, and menthyl-o-aminobenzoate. Some commercially available examples of these types of additives are NEO HELIOPAN® HMS and NEO HELIOPAN® MA available from Symrise AG.

[0071] If present, then the UV additive may be present in an amount of from greater than 0 to 4, from 0.2 to 3, or from 0.3 to 2 weight percent, based on the total weight of the thermoplastic polyurethane composition.

[0072] Lubricants may be added to the thermoplastic polyurethane composition(s) described herein for various reasons, such as to aid in processing, to reduce friction, for wear resistance, to improve thermal stability, and / or to enhance mechanical properties, such as in an amount of from 0.1 to 1.5 percent by weight, based on the total weight of the thermoplastic polyurethane composition. Lubricants may act as processing aids by reducing the melt viscosity of TPUs, enhancing flow properties during processing, and may help in improving melt stability and preventing melt fracture, resulting in smoother processing and reducing the risk of surface defects. Lubricants may reduce friction between polymer chains, enhancing the slip and release properties of TPUs, which may improve the surface quality of molded parts, facilitates demolding, and prevents sticking or blocking issues. Certain lubricants, such as metallic stearates, may improve the wear resistance of TPUs, such as by forming a lubricating layer on the surface, reducing frictional forces and preventing excessive wear and abrasion. Lubricants may contribute to the thermal stability of TPUs by acting as stabilizers; metallic stearates, for example, may provide thermal stability by scavenging free radicals and preventing degradation during processing or long-term use. In some cases, lubricants may improve the mechanical properties of TPUs, such as by modifying the hardness, tensile strength, and / or elongation at break of the material, depending on the type and amount of lubricant used.

[0073] Methods of manufacturing thermoplastic urethanes are well known to those of ordinary skill in the art, and the thermoplastic polyurethane composition(s) described herein may be made according to such methods.

[0074] Thermoplastic polyurethanes have a wide variety of uses, which are well known to those of ordinary skill in the art. The thermoplastic polyurethane composition(s) described herein may be used in any known application for thermoplastic polyurethanes which would be suitable or desirable, but may be particularly useful, for example, in forming films which may be used as protective layers over substrates, such as painted automotive substrates, as described in more detail below.

[0075] Also provided is a film(s) comprising the thermoplastic polyurethane composition(s) described herein. Such films may be produced by any known methods whichmay be suitable, such as via a cast extrusion process, as is known in the art. In certain embodiments, the film has an initial yellowness index of less than 4, as measured by the Yellowness Index Test. In certain embodiments, the film has a change in yellowness index of less than 1, as measured by the Accelerated Weathering Test. In certain embodiments, the film has a tensile strength at break of from 3,000 to 9,000 psi, as measured according to ASTM D882. In certain embodiments, the film has an elongation at break of from 350 to 700 percent, as measured according to ASTM D882.

[0076] The Yellowness Index Test is performed using an X-Rite Exact™ spectrophotometer using D65 illuminant and 10° viewing angle conditions. Measurements are taken by placing 5 mil TPU film on top of a white Leneta card backing sheet, and the instrument reports the Yellow Index value.

[0077] The Haze Test is performed using a BYK Haze-Gard Plus haze meter following ASTM DI 003 test method. This instrument measures total transmittance, transmission haze and clarity of films. Measurements are taken on 5 mil TPU film without any backing material and haze values reported.

[0078] The Accelerated Weathering Test is performed using an Applied Optix SUV-W161 Super UV Solar Simulation Weathering Chamber. The test is run at continuous irradiation of 1500 W / m2and chamber temperature of 63 °C and 50% relative humidity. The exposure time was set for about 168 hours. The TPU films were applied to aluminum test panels and evaluated at several exposure intervals. The Yellow Index of a sample may then be taken again to determine how much the Yellow Index is impacted by the Accelerated Weathering Test.

[0079] Also provided is a surface protection film(s) composition comprising an optional first layer comprising a polymer coating layer, a second layer comprising the film(s) described herein, and a third layer comprising an adhesive. Such surface protections film(s) may be made according to known methods, examples of which are provided in WO 2008 / 042883 A2 and WO 2022 / 003447 Al. In certain embodiments, the second layer is, directly or indirectly, between the first layer and the third layer.

[0080] The subject matter disclosed herein may be better understood with reference to the following examples, which are set forth merely to further illustrate the subject matter disclosed herein. The illustrative examples should not be construed as limiting the subject matter in any manner.

[0081] Samples were prepared using the compositions set forth in Table 1 , below, by known one-shot procedures known in the art to react the polyol(s) with the isocyanate. Each composition listed in Table 1 also included the same antioxidant and UV additive(s) in the same amounts.

[0082] As can be seen in Table 1, Comparative Example 1 (“CE1”) included 4,4’- diisocyanato dicyclohexylmethane (“H12MDI”) as the only isocyanate. Examples 1 through 5 included mixtures of H12MDI and either hexamethylene diisocyanate (“HDI”) or isophorone diisocyanate (“IPDI”), in the relative amounts shown in Table 1. Table 1 also indicates the chain extender(s) used in each sample, with relative amounts shown in cases where more than one chain extender was used. Each sample also included a 1000 g / mol polycaprolactone diol. Each sample had a hard segment content of 50 percent, which is calculated by dividing the sum of the weight of isocyanate and chain extender by the sum of the weight of chain extender, isocyanate and diol; this provides relative amounts of reactants used to create each sample.Table 1

[0083] Films were made from the samples via a compression molding process, as is known in the art. Results of testing of certain properties, as follows, are reported in Table 2. Yellow Index (“YI”) and Haze are obtained using the Yellowness Index Test described above. Tensile strength (“TS”, reported in psi) and elongation at break (“EAB”, also referred to as ultimate elongation, reported in %) are measured according to ASTM D882. Each film was subjected to the Accelerated Weathering Test described above, after which it was again tested for Yellow Index according to the Yellowness Index Test described above, which result was compared with the original Yellow Index to provide the change in Yellow Index (“AYI”).Table 2

[0084] Blooming of each film was also measured by examining the surface of each film after being placed in a humidity chamber at 50 °C and 50% relative humidity for 72 hours. If there is no additional substance on the surface (e g., powder or oily layer), it is deemed as not having blooming; otherwise, it is deemed as having blooming. None of the films exhibited blooming.

[0085] Overall, these data show that films made according to the present subject matter exhibit similar performance to films made from TPUs using only H12MDI as the isocyanate, showing that H12MDI may be partially replaced with other isocyanates which are easier to obtain and / or are cheaper to procure.

[0086] Except in the Examples, or where otherwise explicitly indicated or required by context, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word “about”. As used herein, the term “about” means that a value of a given quantity is within ±20% of the stated value. In other embodiments, the value is within ±15% of the stated value. In other embodiments, the value is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value. In other embodiments, the value is within a range of the explicitly-described value which would be understood by those of ordinary skill, based on the disclosures provided herein, to perform substantially similarly to compositions including the literal amounts described herein.

[0087] It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined, and that any amount within a disclosed range is contemplated to provide a minimum or maximum of a narrower range in alternativeembodiments (with the proviso, of course, that the minimum amount of a range must be lower than the maximum amount of the same range). Similarly, the ranges and amounts for each element of the subject matter disclosed herein may be used together with ranges or amounts for any of the other elements.

[0088] While certain representative embodiments and details have been shown for the purpose of illustrating the subject matter disclosed herein, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the scope of the subject matter. In this regard, the scope of the invention is to be limited only by the following claims.

Claims

What is claimed is:

1. A thermoplastic polyurethane composition comprising the reaction product of: a. a polyisocyanate comprising: i. from 25 to 80 weight percent of a regular aliphatic isocyanate, based on the total weight of the polyisocyanate component; and ii. from 20 to 75 weight percent of a second aliphatic isocyanate different from the regular aliphatic isocyanate, based on the total weight of the polyisocyanate component; b. a polycaprolactone polyol having a molecular weight of from 200 to 6,000 g / mol; and c. a chain extender having a molecular weight of from 50 to 350 g / mol.

2. The thermoplastic polyurethane composition of claim 1, wherein the regular aliphatic isocyanate is a linear aliphatic isocyanate.

3. The thermoplastic polyurethane composition of either claim 1 or claim 2, wherein the regular aliphatic isocyanate comprises hexamethylene diisocyanate.

4. The thermoplastic polyurethane composition of any one of claims 1 to 3, wherein the second aliphatic isocyanate comprises a cyclic aliphatic isocyanate.

5. The thermoplastic polyurethane composition of any one of claims 1 to 4, wherein the second aliphatic isocyanate comprises at least one of 4,4’-diisocyanato dicyclohexylmethane or isophorone diisocyanate.

6. The thermoplastic polyurethane composition of any one of claims 1 to 5, wherein the chain extender comprises at least one of 2-methyl propanediol, 1,4-butanediol, 1,6-hexanediol, 3-methyl pentanediol, 1,4-cyclohexanedimethanol, or 1,12-dodecanediol.

7. The thermoplastic polyurethane composition of any one of claims 1 to 6, wherein the reaction product is produced from components which are substantially free of poly ether polyols.

8. The thermoplastic polyurethane composition of any one of claims 1 to 7, wherein the polyisocyanate comprises from 5 to 35 weight percent of the reaction product, based on the total weight of the reaction product.

9. The thermoplastic polyurethane composition of any one of claims 1 to 8, wherein the polycaprolactone comprises from 30 to 90 weight percent of the reaction product, based on the total weight of the reaction product.

10. The thermoplastic polyurethane composition of any one of claims 1 to 9, wherein the chain extender comprises from 5 to 35 weight percent of the reaction product, based on the total weight of the reaction product.

11. The thermoplastic polyurethane composition of any one of claims 1 to 10, wherein the thermoplastic polyurethane composition has a Shore D hardness of from 20 to 80, as measured by ASTM D2240.

12. The thermoplastic polyurethane composition of any one of claims 1 to 11, wherein the thermoplastic polyurethane composition has a weight average molecular weight of from 40,000 to 200,000 g / mol, as measured by the MW by GPC Test.

13. The thermoplastic polyurethane composition of any one of claims 1 to 12, wherein the thermoplastic polyurethane composition further comprises at least one of a UV additive, an antioxidant, or a lubricant.

14. A film comprising the thermoplastic polyurethane composition of any one of claims 1 to 13.

15. The film of claim 14, wherein the film has an initial yellowness index of less than 4, as measured by the Yellowness Index Test.

16. The film of either claim 14 or claim 15, wherein the film has a change in yellowness index of less than 1, as measured by the Accelerated Weathering Test.

17. The film of any one of claims 14 to 16, wherein the film has a tensile strength at break of from 3,000 to 9,000 psi, as measured according to ASTM D882.

18. The film of any one of claims 14 to 17, wherein the film has an elongation at break of from 350 to 700 percent, as measured according to ASTM D882.

19. A surface protection film composition comprising an optional first layer comprising a polymer coating layer, a second layer comprising the film of any one of claims 14 to 18, and a third layer comprising an adhesive.

20. The surface protection film composition of claim 19, wherein the second layer is, directly or indirectly, between the first layer and the third layer.

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