Stretchable multilayer films

Abstract

Stretchable, multilayer films are disclosed that include a thermoplastic polyurethane substrate and a thermoset coating, applied to the thermoplastic polyurethane substrate. The thermoset coating may comprise the reaction product of: an oligomeric polyester resin comprising the reaction product of: diols or polyols comprising from about

Description

[Technical Field]

[0001] This invention relates to a protective film, and specifically to a stretchable multilayer film that can be used as a paint protective film. [Previous Technology]

[0002] Stretchable films (e.g., protective films for automotive panels, coated wood, and similar paint protection) typically comprise a thermoplastic elastomer, wherein a thermosetting coating is applied to a main surface and an adhesive is applied to an opposing main surface. It is desirable that these protective films be stretchable to conform to three-dimensional objects and resist environmental factors such as ultraviolet radiation, acid rain, and tree sap. Resistance to environmental factors is typically provided by the outermost layer of this thermosetting coating.

[0003] U.S. Patent No. 10,265,932 discloses a scalable multilayer protective sheet. It can be used in a range of indoor and outdoor applications, such as in the transportation, construction, and sporting goods industries. The protective sheet can be advantageously applied to at least a portion of the surface of any object to be protected. In one embodiment, the scalable multilayer protective sheet may comprise a carrier layer and a substantially uncrosslinked topcoat. According to other embodiments of the latter, the topcoat may be based on polyurethane.

[0004] Although paint protection films are marketable, automotive topcoats on vehicle body panels typically offer quite good resistance to environmental factors. These topcoats are thermosetting, pigment-free, transparent coatings obtained by reacting hydroxyl-functionalized resins with crosslinking agents containing isocyanates. These coatings are designed to provide the desired performance at a typical coating thickness of about 50-70 micrometers.

[0005] The desired environmental resistance is to match that of the paint protective film and the automotive clear coat. However, the outermost coating of the protective film needs to be designed to maintain the tensile strength of the underlying thermoplastic substrate for the application, while the clear coat formulation is rigid. Furthermore, the thickness of the protective film, typically 5-15 micrometers, is much lower than that of the automotive coating. Due to these design limitations, the environmental resistance of the protective film is generally less than that of the automotive coating.

[0006] There is a continued need to discover stretchable multilayer films containing a protective topcoat and thermoplastic polyurethane that provide improved resin resistance, while providing elongation at break greater than 50% and reducing tensile strength at low strain values. [Summary of the Invention]

[0007] In one embodiment, the present invention relates to a stretchable multilayer film comprising a thermoplastic polyurethane substrate and a thermosetting coating applied to the thermoplastic polyurethane substrate. The thermosetting coating comprises a reaction product of an oligopolyester resin and an aliphatic isocyanate or isocyanurate. The oligopolyester resin itself also comprises reaction products of: a diol or polyol comprising about 30 to about 99 mol% trimethylolpropane and about 1 mol% to about 70 mol% neopentyl glycol, in each case based on the total molar amount of the reacted diol and polyol; and a dicarboxylic acid or polycarboxylic acid comprising about 1 mol% to about 70 mol% of one or more cyclic or acyclic aliphatic acids having 2 to 12 carbons, based on the total molar amount of the reacted dicarboxylic acid and polycarboxylic acid. The stretchable multilayer film exhibits an elongation at break greater than 50%, and when measured within one week of multilayer film preparation, it has a tensile load of less than 2 lb / in at 5% strain and resin resistance greater than 45°C.

[0008] In another embodiment, the present invention relates to a stretchable multilayer film comprising a thermoplastic polyurethane substrate and a thermosetting coating applied to the thermoplastic polyurethane substrate. In this embodiment, the thermosetting coating is a reaction product of an aliphatic isocyanate, isocyanurate, urethane, or biuret with an oligopolyester. The oligopolyester itself is also a reaction product comprising the following monomers: trimethylolpropane (TMP) in an amount of 30 to 70 mol% based on total moles of ac; neopentyl glycol (NPG) in an amount of 1 to 70 mol% based on total moles of ac; diols other than NPG in an amount of 0 to 69 mol% based on total moles of ac; one or more cyclic or acyclic aliphatic acids having 2 to 12 carbons in an amount of 30 to 100 mol% based on total moles of de; and one or more additional dicarboxylic acids in an amount of 0 to 70 mol% based on total moles of de, wherein the oligopolyester resin has a glass transition temperature (Tg) of -40 to 55°C, an acid value of 0 to 15 mg KOH / g, a number of hydroxyl groups of 100 to 370 mg KOH / g, a number average molecular weight of 500 to 10,000 mg KOH / g, and a weight average molecular weight of 1,000 to 25,000. In this sample, the stretchable multilayer film exhibits an elongation at break greater than 50%, and when measured within one week of multilayer film preparation, it has a tensile load of less than 2 lb / in at 5% strain and resin resistance greater than 45°C.

[0009] Other aspects of the present invention are as disclosed and claimed herein.

Implementation Method

[0012] In one embodiment, the present invention relates to a stretchable multilayer film comprising a thermoplastic elastic substrate (e.g., thermoplastic polyurethane) coated with a crosslinked thermosetting coating. The thermosetting coating is a reaction product of an oligopolyester resin, which, based on the total molar amount of the reacted diol or polyol, or as described herein elsewhere, comprises about 30 mol% to about 99 mol% of trimethylolpropane (TMP) and about 1 mol% to about 70 mol% of neopentyl glycol (NPG) as a diol or polyol. The oligopolyester resin of the present invention may contain other diols or polyols. Based on the total molar amount of dicarboxylic acids or polycarboxylic acids, or as described herein elsewhere, the oligopolyester resin further comprises about 1 mol% to about 60 mol% of a cyclic or acyclic aliphatic dicarboxylic acid having 1 to 12 carbons, and specifically adipic acid, as a dicarboxylic acid or polycarboxylic acid. The oligopolyester resin of the present invention may contain other dicarboxylic acids or polycarboxylic acids.

[0013] The oligopolyester resin of the present invention is reacted with aliphatic isocyanates, isocyanurates, urethanes, or biuret to obtain a thermosetting coating. The stretchable multilayer film may further include an adhesive layer opposite the thermosetting coating, which serves as, for example, a paint protective film. This adhesive may be a pressure-sensitive adhesive. The stretchable multilayer film (including the coating) exhibits an elongation at break greater than 50%, has a tensile load / inch of less than 2 lb / in at 5% strain when tested within one week of multilayer film preparation, and has sap resistance greater than 45°C, or as further defined herein.

[0014] According to the present invention, it has been found that stretchable multilayer films can be formed from a thermoplastic elastic substrate provided with a thermosetting coating that maintains the integrity of the coating upon stretching. Thermoplastic elastic substrates, typically thermoplastic polyurethanes, are suitable for use as paint protection films or automotive wrapping materials, and therefore can be stretched, for example, by amounts up to 50% elongation. Although thermoplastic polyurethanes are known to be structurally elastic, stretchable multilayer films with thermosetting coatings have been unexpectedly developed that allow the entire multilayer film to be stretched to up to 50% elongation at break, exhibiting a tensile load of less than 2 lb / in at 5% strain when tested within one week of multilayer film preparation, and resin resistance greater than 45°C. Although thermosetting coatings similar to those described herein are known to be used as metallic coatings (e.g., for automotive applications or as can coatings), they typically cannot be stretched to any perceptible extent.

[0015] For the purposes of this invention, a “stretchable multilayer film” is a multilayer film that can reversibly stretch to at least 50% strain without cracking. Other forms of the “stretchable film” require less force to reversibly stretch the film, thus making it easier for the installer to apply the film to the surface of the vehicle.

[0016] Unless otherwise indicated, all figures used in the specification and claims that represent quantities, properties (e.g., molecular weight), reaction conditions, etc., of ingredients should in all cases be understood to be modified by the term "about". Unless the contrary is stated, the numerical parameters listed in the following specification and the appended claims are approximate values ​​that may vary as the desired properties are sought to be obtained by the present invention. At a minimum, each numerical parameter should be interpreted according to the number of significant digits reported and by applying general rounding techniques. Furthermore, the ranges stated in this disclosure and the claims are intended to specifically include the entire range, and not merely the endpoints. For example, a range stated as 0 to 10 is intended to disclose all integers between 0 and 10 (e.g., 1, 2, 3, 4, etc.), all fractions between 0 and 10 (e.g., 1.5, 2.3, 4.57, 6.1113, etc.), and the endpoints 0 and 10. Furthermore, the range of chemically substituent-related terms such as "C1 to C5 diols" is intended to specifically include and disclose C1, C2, C3, C4, and C5 diols.

[0017] Although the numerical ranges and parameters described in this invention are approximate, the values ​​described in specific examples are reported as precisely as possible. However, any numerical value inherently contains errors that are necessarily caused by the standard deviation present in its respective test measurement.

[0018] Unless the context clearly indicates otherwise, as used in this specification and the appended claims, the singular forms "a (a, an)" and "the" include a plurality of such indicators. For example, references to "polyester," "dicarboxylic acid," and "residue" are synonymous with "at least one" or "one or more" polyesters, dicarboxylic acids, or residues, and are therefore intended to refer to a single or multiple polyesters, dicarboxylic acids, or residues. In addition, references to compositions that "comprise," "contain," "have," or "include" "one" component or "one" polyester, other than specifically identified components or residues, are also intended to include other components or other polyesters. Therefore, the terms "containing," "having," or "including" are intended to be synonymous and can be used interchangeably with the term "comprising," meaning that at least the specified compounds, elements, particles, or method steps are present in the composition, article, or method, but do not exclude the presence of other compounds, catalysts, materials, particles, method steps, etc., even if such other compounds, materials, particles, method steps, etc. have the same function as those specified, unless expressly excluded in the scope of the patent application.

[0019] Moreover, it should be understood that the mention of one or more process steps does not preclude the existence of additional process steps before or after the combined listed steps, or intermediate process steps between those explicitly identified steps. Furthermore, the annotation of process steps or components is a convenient means of identifying discrete activities or components, and unless otherwise indicated, the listed annotations may be arranged in any sequence.

[0020] Therefore, the stretchable multilayer film of the present invention comprises a thermosetting coating and a thermoplastic elastic substrate on which the thermosetting coating is applied. The thermosetting coating is made of an oligopolyester resin having a high aliphatic content and containing residues of trimethylolpropane, neopentyl glycol, and aliphatic diacids (e.g., adipic acid). The oligopolyester resin usable according to the present invention may contain other amounts of diols or polyols and other amounts of dicarboxylic acids or polycarboxylic acids.

[0021] The oligopolyester resin of the present invention is prepared by polycondensation of one or more acid components and one or more hydroxyl components. The acid components should be understood to have at least two carboxylic acid units, and therefore, depending on the case, are dicarboxylic acids or polycarboxylic acids. Similarly, the hydroxyl components should be understood to have at least two hydroxyl units, and therefore, depending on the case, are diols or polyols. As used herein, the term "polyol" refers to a monomer unit used to construct the oligopolyester resin and will include monomer units having two or more hydroxyl groups. Similarly, the term "polycarboxylic acid" refers to a monomer unit used to construct the oligopolyester resin and will include monomer units having two or more carboxylic acid groups. For convenience, the terms "diol or polyol" and "dicarboxylic acid or polycarboxylic acid" are generally referred to as the two types of reactants used to form the oligopolyester resin of the present invention. As used throughout, the mole percentage of each of the diols or polyols is based on the total moles of the diols or polyols present. Similarly, the mole percentage of each of the dicarboxylic acids or polycarboxylic acids is based on the total mole number of the dicarboxylic acids or polycarboxylic acids present.

[0022] As used herein, the oligopolyester resin of the present invention differs from thermosetting coatings that have been reacted with aliphatic isocyanates, isocyanurates, urethanes, or biuret. The oligopolyester resin of the present invention is a relatively low molecular weight aliphatic thermoplastic polyester that serves as a polyol reactant when reacted with aliphatic isocyanates or isocyanurates to form the thermosetting coating of the present invention. Depending on the context, the term isocyanate may include isocyanurates, urethanes, or biuret.

[0023] Therefore, the thermosetting coating of the present invention is a thermosetting polymer and is suitable for coating thermoplastic elastic substrates. That is, the oligopolyester resin is formulated using aliphatic isocyanates or isocyanurates, and, where appropriate, a small amount of aromatic isocyanates, so that the thermosetting coating is suitable for protecting the thermoplastic elastic substrate while maintaining the desired tensile strength and sap resistance. Therefore, these oligopolyester resins are not suitable as standalone polymers for manufacturing films, sheets, and other molded objects by extrusion, casting, blow molding, and other thermoforming processes commonly used for high molecular weight thermoplastic polymers. The oligopolyester resin has reactive functional groups, namely hydroxyl and / or carboxyl groups, which subsequently react with the aliphatic isocyanates in the coating formulation. The functional groups of the oligopolyester resin are controlled by having an excess of polyols or polycarboxylic acids in the oligopolyester resin composition. The desired crosslinking pathway will determine whether the polyester resin is hydroxyl-terminated or carboxylic acid-terminated. This concept is known to those skilled in the art and has been described, for example, in Organic Coatings Science and Technology, 2nd edition, pp. 246-257, Z. Wicks, F. Jones and S. Pappas, Wiley, New York, 1999, the entire disclosure of which is incorporated herein by reference.

[0024] The acid component in the oligopolyester resin is prepared from dicarboxylic acids and polycarboxylic acids having 1 to 12 carbon atoms. Generally, the acid component of the polycarboxylic acid is generally described herein as containing at least one dicarboxylic acid and, where appropriate, including a polycarboxylic acid. The acid component is essentially an aliphatic polycarboxylic acid, but it may contain small amounts of aromatic polycarboxylic acids, such as isophthalic acid, terephthalic acid, phthalic acid, or residues derived from phthalic anhydride, but this is not preferred. In some samples, the amount of aromatic acid content may not exceed 5 mol%, or not exceed 3 mol%, or not exceed 2 mol%, or not exceed 1 mol%, or not exceed 0.5 mol%, or substantially zero aromatic acid content.

[0025] These aliphatic polycarboxylic acids can be further divided into acyclic and cyclic variants. Based on the total moles of acyclic and cyclic aliphatic dicarboxylic acids, the acyclic aliphatic dicarboxylic acid accounts for 1 to 60 moles, 1 to 50 moles, 1 to 40 moles, 1 to 30 moles, 1 to 20 moles, 1 to 10 moles, 10 to 60 moles, 10 to 50 moles, 10 to 40 moles, 10 to 30 moles, 10 to 20 moles, 20 to 60 moles, 20 to 50 moles, 20 to 40 moles, 20 to 30 moles, 30 to 60 moles, 30 to 50 moles, 30 to 40 moles, 40 to 60 moles, 40 to 50 moles, or 50 to 60 moles.

[0026] Therefore, the noncyclic aliphatic acids that can be used according to the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, undecanoic acid, maleic acid, fumaric acid, itconic acid, citraconic acid, dodecanoic acid, sebacic acid, azelaic acid, acetylenic acid, pentenic acid, guaiac acid, dimer acid, hydrogenated dimer acid, and such or residues thereof. Adipic acid is a desirable noncyclic aliphatic acid.

[0027] Cyclic aliphatic acids usable according to the present invention include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride (HHPA), methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 5-norcamphen-2,3-dicarboxylic anhydride, 5-norcamphen-2,3-dicarboxylic acid, 2,3-norcamphenic anhydride, mixtures thereof, or residues thereof. HHPA is a desired cyclic aliphatic diacid.

[0028] The hydroxyl component in the oligopolyester resin is prepared from diols and polyols that typically have 2 to 20 carbon atoms. As indicated, depending on the context, the term polyol includes diols.

[0029] The diols that can be used according to the present invention comprise diols having two hydroxyl groups, such diols being branched or straight-chain, saturated or unsaturated, aliphatic or cycloaliphatic C2-C20 compounds, wherein the hydroxyl groups are primary, secondary and / or tertiary hydroxyl groups, preferably primary hydroxyl groups. Therefore, the diols and polyols that can be used according to the present invention include 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, 1,4-cyclohexanediethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxyneopentyl hydroxypentanoate, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4,4-tetramethyl-1,6-hexanediol, 1,10-decanediol, 1,4-benzenedimethanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol, mixtures thereof or residues thereof.

[0030] The polyols usable according to the present invention may comprise those having three or more hydroxyl groups, which are saturated or unsaturated, aliphatic or cycloaliphatic C2-C20 compounds, wherein the hydroxyl groups are primary, secondary and / or tertiary hydroxyl groups, and preferably at least two hydroxyl groups are primary hydroxyl groups. Preferably, the polyols are hydrocarbons and do not contain atoms other than hydrogen, carbon and oxygen. Examples of such polyols include 1,1,1-trimethylolpropane (TMP), 1,1,1-trimethylolethane, glycerol, neopentyl tertrol, erythritol, threitol, di-neopentrol, sorbitol, mixtures thereof, or residues thereof.

[0031] In other embodiments, the oligopolyester resin of the present invention may further comprise one or more cycloaliphatic diols, such as 2,2,4,4-tetramethyl-1,3-cyclobutanediol. In other embodiments, the oligopolyester resin of the present invention may comprise a small amount or no 2,2,4,4-tetramethyl-1,3-cyclobutanediol, for example, no more than 15 mol%, or no more than 10 mol%, or no more than 5 mol%, or no more than 2 mol%.

[0032] In one embodiment, the oligopolyester resin of the present invention comprises trimethylolpropane and neopentyl glycol as monomeric polyols.

[0033] In one sample, based on the total moles of TMP and other diols and polyols, trimethylolpropane may be present in the oligomeric polyester resin in the following amounts: from 30 to 99 moles, or 30 to 80 moles, or 30 to 70 moles, or 30 to 50 moles, or 30 to 40 moles, or 40 to 99%, or 40 to 80 moles, or 40 to 70 moles, or 40 to 60 moles, or 40 to 50 moles, or 50 to 99 moles, or 50 to 80 moles, or 50 to 70 moles, or 60 to 99%, or 60 to 80 moles, or 60 to 70 moles, or 70 to 99%, or 70 to 80 moles, or 80 to 99%.

[0034] In other samples, based on the total moles of NPG and other diols and polyols, the 2,2-dimethyl-1,3-propanediol (neopentyl glycol) in the oligomeric polyester resin. (NPG) accounts for 1 to 70%, or 10 to 70%, or 20 to 70 mmol%, or 30 to 70 mmol%, or 40 to 70 mmol%, or 50 to 70 mmol%, or 60 to 70 mmol%, or 1 to 60%, or 10 to 60%, or 20 to 60 mmol%, or 30 to 60 mmol%, or 40 to 60 mmol%, or 50 to 60 mmol%, or 1 to 50%, or 10 to 50%, or 20 to 50 mmol%, or 30 to 50 mmol%, or 40 to 50%, or 1 to 40%, or 10 to 40%, or 20 to 40 mmol%, or 30 to 40 mmol%, or 1 to 30%, or 10 to 30%, or 20 to 30 mmol%, or 1 to 20%, or 10 to 20% or 1 to 10%.

[0035] A catalyst may be used to accelerate the rate of the polycondensation reaction to form an oligopolyester resin.

[0036] Additional examples of acid components and hydroxyl components include those known in the art, including (but not limited to) those discussed in various literatures known in the art below, such as Resins for Surface Coatings, Volume III, pp. 63-167, edited by PKT Oldring and G. Hayward, SITA Technology, London, UK, 1987, the disclosure of which is incorporated herein by reference.

[0037] As used herein with respect to the oligopolyester resins of the present invention, the term "residue" means any organic structure incorporated into the polymer by means of a polycondensation or ring-opening reaction involving the respective monomer. Those skilled in the art will also understand that the relevant residues within the various curable polyesters of the present invention can be derived from the parent monomer compound itself or any derivative thereof. For example, the dicarboxylic acid residues mentioned in the polymers of the present invention can be derived from dicarboxylic acids or their associated acetic halides, esters, salts, anhydrides, or mixtures thereof. Therefore, as used herein, the term "polycarboxylic acid" is intended in its broadest sense to include polycarboxylic acids and any derivatives of polycarboxylic acids that can be used with diols in a polycondensation process to obtain curable aliphatic polyesters, including their associated acetic halides, esters, half-esters, salts, half-salts, anhydrides, and mixtures thereof.

[0038] When we say that residues are present, we therefore intend to mean that they are present as a reaction product of the monomers used. We assume that the amount reacted is the amount present in the reactant material.

[0039] The term "aliphatic" is intended to have the common meaning that will be understood by one skilled in the art, namely, acyclic or cyclic, saturated or unsaturated carbon compounds, excluding benzene-like or other aromatic systems. As used herein, the terms "cyclic aliphatic" or "cyclic aliphatic" are intended to refer to cyclic aliphatic compounds. As used herein, the term "aliphatic polyester" should be understood to mean a polyester containing, for example, 90 mol% or more of aliphatic diacid or diol residues in total moles based on diacid or diol residues. Curable aliphatic polyesters may also contain small amounts, for example, less than 10 mol%, or less than 9 mol%, or less than 8 mol%, or less than 5 mol%, or less than 3 mol%, or less than 2 mol%, or less than 1 mol% of aromatic dicarboxylic acid residues or aromatic diol residues. Desiredly, curable aliphatic oligopolyester resins are substantially free of, i.e., contain less than 1 mol% of aromatic diacid and / or aromatic diol residues.

[0040] Resin is an erosive agent that is known to damage vehicle paint over time. Resin resistance in coatings is typically achieved by increasing the crosslinking density and glass transition temperature of the coating. However, we have found that both of these negatively affect tensile strength, which is, of course, a highly desirable characteristic of the protective film of this invention. Therefore, it is highly desirable for the paint protective film to achieve good sin resistance while maintaining the required tensile strength.

[0041] Therefore, in various embodiments, the present invention provides a thermosetting coating applied to the thermoplastic elastic substrate of the present invention, the thermosetting coating being made from an oligomeric polyester resin to obtain the stretchable multilayer film of the present invention. In one sample, the film of the present invention exhibits resin resistance greater than 45°C, or greater than 50°C, or greater than 60°C, or greater than 70°C, as determined by the methods described herein.

[0042] In another embodiment, the stretchable multilayer film of the present invention exhibits an elongation at break of greater than 50%, or greater than 60% or greater than 65%, as determined by the methods described herein.

[0043] In another embodiment, when the coating thickness is about 0.1 to 25 micrometers, or 0.1 to 20 micrometers, or 0.1 to 15 micrometers, or 0.1 to 10 micrometers, or 0.5 to 25 micrometers, or 0.5 to 20 micrometers, or 0.5 to 15 micrometers, or 0.5 to 10 micrometers, or 1 to 25 micrometers, or 1 to 20 micrometers, or 1 to 15 micrometers, or 1 to 10 micrometers, or 1 to 5 micrometers, or 2 to 25 micrometers, or 2 to 20 micrometers, or 2 to 15 micrometers, or 2 to 10 micrometers, or 3 to 8 micrometers, the stretchable multilayer film of the present invention exhibits a tensile strength of less than 2% at 5% strain, as determined in each case by the method described herein.

[0044] The oligopolyester resin of the present invention has a hydroxyl number of about 100 to about 370, or 125 to 300, or 150 to 300, or 170 to 330, or 180 to 280 or 190 to 240 mg KOH / g polyester, and an acid value of 0 to 15 mg KOH / g or 1 to 10 mg KOH / g.

[0045] The number average molecular weight (Mn) of the oligopolyester resin of the present invention can be from about 500 to about 10,000, or 800 to 6,000, or 1,000 to 4,000 g / mole. The weight average molecular weight (Mw) of the curable oligopolyester resin of the present invention can be from about 1,000 to about 40,000, 1,000 to 25,000, or 2,000 to 20,000 g / mole. The molecular weight is determined by gel permeation chromatography (GPC) using the equivalent molecular weight of polystyrene and tetrahydrofuran (THF) as a solvent. In other states, the molecular weight of Mw may be at least about 1,000, or at least 1,500, or at least 2,000, up to about 20,000, or up to about 21,000, or up to 22,000, or up to about 24,000, or up to about 25,000, or up to about 40,000.

[0046] The glass transition temperature (Tg) of the oligopolyester resin of the present invention can be -40°C to 55°C, -30°C to 25°C, or -10°C to 10°C.

[0047] The isocyanate crosslinking agent for thermosetting coatings is preferably an aliphatic isocyanate or an aliphatic polymeric isocyanate. Suitable isocyanates include (but are not limited to) methylene bis-4,4'-isocyanocyclohexane, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, pentane-1,5-diisocyanate, and 1,4-bis(isocyanomethyl)cyclohexane. The isocyanate crosslinking agent for thermosetting coatings also includes polymeric isocyanates of the monomeric isocyanates listed above. This includes (but is not limited to) isocyanurates, urethane esters, and biuret. Isocyanate-terminated adducts of glycols and polyols (e.g., ethylene glycol, 1,4-butanediol, trimethylolpropane, etc.) can also be used. These are formed by reacting more than 1 mole of diisocyanate (such as those mentioned above) with 1 mole of glycol or polyol to form a higher molecular weight isocyanate prepolymer with 2 to 3 functions. Examples include isocyanate crosslinking agents such as Desmodur and Mondur from Covestro LLC. When isocyanates are used as crosslinking agents, aliphatic isocyanates are preferred because they provide better outdoor durability and color stability in the cured coating. Examples include 1,6-hexamethylene diisocyanate, 1,4-endobutyl diisocyanate, methylenebis(4-cyclohexyl isocyanate), and isophorone diisocyanate. Mixtures of isocyanate crosslinking agents may also be used. It is desirable that isocyanate crosslinking agents also include modified isocyanates, such as carbodiimide-modified isocyanates, silane-modified isocyanates, and terminally capped isocyanates.

[0048] The general structure of the desired isocyanate building block is shown below. 1,6-Diisocyanatohexane bis(4-isocyanatocyclohexyl)methane 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane.

[0049] As used herein, urethane esters are reaction products of isocyanates and urethane esters disclosed herein. Biuret is a reaction product of two or more isocyanates disclosed herein.

[0050] Small amounts of aromatic isocyanates may include toluene diisocyanate, methylene diphenyl isocyanate, and polymeric urea, isocyanurate and biuret of such materials.

[0051] The thermosetting coating composition of the present invention may further contain one or more other crosslinking agents known in the art, which can react with the hydroxyl or residual acid groups of the polyester of the present invention. One example is a melamine or "amine" type crosslinking agent that can react with hydroxyl groups. Another example is an epoxide that can react with residual acid groups.

[0052] The stoichiometric calculations for the reaction between polyester resin and isocyanate are well known to those skilled in the art and are described in *The Chemistry of Polyurethane Coatings*, Technical Publication, p. 20, Bayer Material Science, 2005, which is incorporated herein by reference. Theoretically, when 1 equivalent of isocyanate (NCO) reacts with 1 equivalent of hydroxyl group (OH), i.e., when the NCO to OH ratio is 1.0 / 1.0, the crosslinking between the polyester resin and isocyanate reaches its maximum molecular weight and optimal molecular weight-related properties. It is common practice to use a small excess of isocyanate, approximately 5-10%, to account for isocyanate consumption from atmospheric, solvent, and pigment moisture. Sometimes it is desirable to change the NCO to OH ratio to less than 1.0 / 1.0 to improve flexibility, or to make it greater than 1.0 / 1.0 for harder, more chemically resistant, and more weather-resistant coatings.

[0053] In a preferred embodiment, the NCO to OH ratio may be 0.7 to 1.3, or 0.75 to 1.25, or 0.8 to 1.2, or 0.85 to 1.15, or 0.9 to 1.1 or 0.95 to 1.05.

[0054] In another embodiment, the present invention further provides a thermosetting coating composition which may further comprise one or more crosslinking catalysts. Useful catalysts may include tertiary amines, such as triethylenediamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, 1-methyl-4-dimethylaminoethylhexahydropyrazine, 3-methoxy-N-dimethylpropylamine, N-dimethyl-N'-methylisopropylpropanediamine, N,N-diethyl-3-diethylaminopropylamine, N,N-dimethylbenzylamine, dicyclohexylmethylamine, 2,4,6-tris(dimethylaminomethylphenol), N,N-dimethylcyclohexylamine, triethylamine, tri-n-butylamine, 1,8-diaza-dichloro[5,40]-undecene-7 N-Methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylcyclohexylamine, N,N,N'N'-tetramethyl-ethylenediamine, 1,4-diaza-bicyclo-[2,2,2]octane-N-methyl-N-dimethylaminoethyl-hexahydropyrazine, bis-(N,N-diethylaminoethyl) adipic acid ester, N,N-diethylbenzylamine, pentamethyldiethyltriamine, N,N,N',N'-tetramethyl-1,3-butanediamine, 1,2- Dimethylimidazole, 2-methylimidazole; tin compounds, such as stannous chloride, dibutyltin di-2-ethylhexanoate, stannous octanoate, dibutyltin dilaurate, trimethyltin hydroxide, dimethyltin chloride, dibutyltin diacetate, dibutyltin oxide, tributyltin acetate, tetramethyltin, dimethyldioctyltin, stannous ethylhexanoate, stannous laurate, dibutyltin maleate, dioctyltin diacetate; other organometallic compounds, such as zinc octanoate, phenylmercuric propionate, lead octanoate, lead naphthate, and copper naphthate. Dibutyltin dilaurate (DBTDL) is particularly useful in this invention. Based on the total weight of the resin solids, the useful amount of the catalyst will be about 0.01% to 5%.

[0055] Thermosetting coating compositions may also contain one or more leveling agents, rheology modifiers, and flow control agents, such as polysiloxane, fluorocarbon, or cellulose; wetting agents; matting agents; pigment wetting and dispersing agents; surfactants; ultraviolet (UV) absorbers; UV light stabilizers; coloring pigments; defoamers and antifoaming agents; antisettling agents, anti-sagging agents, and compounding agents; anti-skinning agents; anti-flooding and anti-floating agents; fungicides and antifungals; corrosion inhibitors; thickeners; flow aids; rheology control agents; slip agents; oleophobic agents; superhydrophobic agents; or coalescing agents. Specific examples of such additives can be found in the Raw Materials Index, published by the National Paint & Coatings Association, 1500 Rhode Island Avenue, NW, Washington, DC 20005.

[0056] In some useful embodiments, the thermosetting coating composition described herein may include a matting agent. The matting agent is typically a small solid particle of a material that is insoluble in water and effectively reduces gloss. Preferably, the matting agent particles have a size of about 0.05 to about 10 micrometers, but may be present as clumps or aggregates up to about 50 micrometers. The matting agent particles may be inorganic or organic. Examples of suitable inorganic matting agents include silicates (e.g., talc) and various forms of silica, such as amorphous, aerogels, diatomaceous earth, hydrogels, and fuming silica. Examples of suitable organic matting agents include insoluble urea-formaldehyde resins, polyethylene, polypropylene, cellulose fibers, and polyurethane / polyurea copolymers.

[0057] Some examples of UV absorbers and UV light stabilizers are substituted benzophenones, substituted benzotriazoles, hindered amines and hindered benzoic acid esters, which are available from Cytec Specialty Chemicals as CYASORB® UV and from Ciba Specialty Chemicals as TINUVIN®; 3-acetylated-4-hydroxy-benzyl-phosphonate diethyl ester, 4-dodecyloxy-2-hydroxybenzophenone and resorcinol monobenzoate.

[0058] If desired, the thermosetting coating composition may contain other functional materials, such as dye colorants, pigments, abrasion-resistant particles (such as NANOBYK™ additives from BYK Chemie), antioxidants, thixotropic agents, and fillers. Examples of pigments include those generally recognized by those skilled in surface coating techniques. For example, pigments may be typical organic or inorganic pigments, particularly those described in Colour Index, 3rd Edition, 2nd Revision, 1982, jointly published by the Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists. Other examples of suitable pigments include titanium dioxide, barite, clay, calcium carbonate, CI Pigment White 6 (titanium dioxide), CI Pigment Black 7, CI Pigment Black 11, CI Pigment Black 22, CI Pigment Black 27, CI Pigment Black 28, CI Pigment Red 101 (red iron oxide), CI Pigment Yellow 42, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 (copper phthalocyanine); CI Pigment Red 49:1 and CI Pigment Red 57:1. Colorants (e.g., phthalocyanine blue, molybdate orange, or carbon black) may also be added to thermosetting coating compositions.

[0059] The thermosetting coating composition of the present invention may further comprise hydrophobic reinforcing additives, such as monofunctional polysiloxane components having hydroxyl, amine, or epoxy functionalities. If a monofunctional material is used, it can be used as a chain terminator during polymerization or crosslinking.

[0060] Therefore, the additive may be one or more of the following: monoglycidyl ether-terminated poly(dimethylsiloxane), diglycidyl ether-terminated poly(dimethylsiloxane), bis(3-aminopropyl)-terminated poly(dimethylsiloxane) (DMS-A11 purchased from Gelest), (aminopropylmethylsiloxane)-dimethylsiloxane copolymer (e.g., AMS-132, AMS-152, AMS-162, AMS-163, AMS-191 or AMS-1203 purchased from Gelest), (aminoethylaminopropylmethylsiloxane)-dimethylsiloxane copolymer (e.g., AMS-2202, AMS-1203 purchased from Gelest). -233 or AMS-242), monohydroxy-terminated polydimethylsiloxanes (e.g., MCS-C11, MCR-C12, MCR-C18, MCR-C22 or MCS-C13 available from Geleest), hydroxyl-terminated polydimethylsiloxanes (e.g., DMS-C15 or DMS-C16 available from Geleest), and silyl alcohol-terminated polydimethylsiloxanes (e.g., DMS-S12 available from Geleest).

[0061] Any solvent capable of applying the formulation to the substrate may be used, and such solvents will be well known to those skilled in the art. Suitable organic solvents include glycols, glycol ether alcohols, alcohols, ketones and aromatics (e.g., xylene and toluene), acetates, mineral oils, naphtha and / or mixtures thereof. "Acetates" include glycol ether acetates. The amount of organic solvent may be up to 60 wt.% based on the total weight of the thermosetting coating composition.

[0062] Examples of dispersants include (but are not limited to) sodium bis(tridecyl) sulfosuccinate, sodium di(2-ethylhexyl) sulfosuccinate, sodium dihexyl sulfosuccinate, sodium dicyclohexyl sulfosuccinate, sodium dipentyl sulfosuccinate, sodium diisobutyl sulfosuccinate, disodium isodecyl sulfosuccinate, disodium ethoxylated alcohol half ester of sulfosuccinate, disodium acetyl polyethoxylated alkyl sulfosuccinate, tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinate, disodium N-octadecyl sulfosuccinate, sulfated ethoxylated nonylphenol, 2-amino-2-methyl-1-propanol and the like.

[0063] Examples of viscosity, suspension, and flow control agents include polyaminoamide phosphates, high molecular weight carboxylates of polyaminoamides, and alkylamine salts of unsaturated fatty acids, all of which are available from BYK Chemie USA as ANTI TERRA™. Other examples include (but are not limited to) polysiloxane copolymers, polyacrylate solutions, cellulose esters, hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide waxes, polyolefin waxes, hydroxypropyl methylcellulose, polyethylene oxide, and the like.

[0064] Certain patented antifoaming agents are commercially available and include (but are not limited to) BUBREAK™ from Buckman Laboratories Inc., BYK™ from BYK Chemie, USA, FOAMASTER™ and NOPCO™ from Henkel Corporation Coating Chemicals, DREWPLUS™ from Drew Industrial Division of Ashland Chemical Company, TROYSOL™ and TROYKYD™ from Troy Chemical Corporation and SAG™ from Union Carbide Corporation.

[0065] Some examples of UV absorbers and UV light stabilizers are substituted benzophenones, substituted benzotriazoles, hindered amines and hindered benzoic acid esters, which are available from Cytec Specialty Chemicals as CYASORB® UV and from Ciba Specialty Chemicals as TINUVIN®; 3-acetylated-4-hydroxy-benzyl-phosphonate diethyl ester, 4-dodecyloxy-2-hydroxybenzophenone and resorcinol monobenzoate.

[0066] As used herein, the thermoplastic elastic substrate may comprise a variety of thermoplastic elastomers, such as polyurethane, styrene block copolymers, polyacrylates, polyolefins, vinyl chloride polymers, polyether esters, polyamides, ionomers, polysiloxanes, and fluoropolymers. The thermoplastic elastic substrate of the present invention is characterized in part by its elasticity.

[0067] In one embodiment, the thermoplastic elastic substrate comprises thermoplastic polyurethane or TPU. TPU can be classified into three chemical categories: polyester-based, polyether-based, and polycaprolactone-based. Polyester TPU is generally compatible with PVC and other polar plastics and provides excellent abrasion resistance, a good balance of physical properties, and can be used in polymer blends. Polyether-based TPU provides low-temperature flexibility and good abrasion and tear resistance. It also has good hydrolytic stability. Polycaprolactone-based TPU has the inherent toughness and resistance of polyester-based TPU, as well as good low-temperature performance and hydrolytic stability.

[0068] TPU can also be further divided into aromatic and aliphatic TPUs, in which case it refers to the diisocyanate used. Aromatic TPUs based on isocyanates such as toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) constitute the majority of TPUs and are used when strength, flexibility, and toughness are required. However, they are generally not weather-resistant. Aliphatic TPUs based on isocyanates such as 4,4'-methylene dicyclohexyl diisocyanate (H12 MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are light-stable and provide excellent clarity. They are commonly used in automotive interior and exterior applications and can be used to bond safety glass. It has been found that aliphatic polycaprolactone-based TPUs provide a good balance of weather resistance, low-temperature flexibility, and impact resistance required for many automotive exterior applications, and are particularly useful according to the present invention.

[0069] In a specific state, the thermoplastic polyurethane that can be used as a thermoplastic elastic substrate according to the present invention may be a thermoplastic polyurethane based on aliphatic polycaprolactone, which includes a polycaprolactone-based polymeric diol reacted with aliphatic diisocyanate. In this embodiment, the aliphatic diisocyanate may be selected from, for example, 4,4'-methylene dicyclohexyl diisocyanate (H12 MDI or HMDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). In this embodiment, the polycaprolactone-based polymeric diol comprises caprolactone units, a diol (e.g., ethylene glycol, propylene glycol, neopentyl glycol, or butanediol), and may be initiated from a diol (e.g., ethylene glycol, diethylene glycol, hexanediol, neopentyl glycol, or butanediol). In a preferred embodiment, the thermoplastic polyurethane comprises HMDI, 1,4-butanediol, and caprolactone residues. The polycaprolactone-based polymeric diol used to form the thermoplastic polyurethane of the present invention may have a molecular weight of, for example, about 500 to about 5000, or about 800 to about 4000, or 900 to about 3000, or about 1000 to about 2500.

[0070] Other properties of thermoplastic polyurethanes based on aliphatic polycaprolactone include the inherent toughness and resistance of polyester-based TPUs, as well as good low-temperature performance, good weather resistance and light resistance, and hydrolytic stability.

[0071] The TPUs that can be used as thermoplastic elastic substrates according to the present invention include those disclosed and claimed in U.S. Patent No. 10,265,932 (the disclosure of which is incorporated herein by reference). They are polymers containing urethane (also known as carbamate) bonds, urea bonds, or combinations thereof (i.e., in the case of poly(urethane-urea)). Therefore, the polyurethanes that can be used according to the present invention contain at least urethane bonds and, where appropriate, urea bonds. In one embodiment, the polyurethane-based layering of the present invention is based on polyurethane, wherein the main chain has at least about 80% urethane and / or urea repeating bonds formed during its polymerization.

[0072] The TPU that can be used as a thermoplastic elastic substrate according to the present invention may comprise polyurethane polymers with the same or different chemicals, i.e., polymer blends. Polyurethane typically comprises a reaction product of at least one isocyanate reactive component, at least one isocyanate functional component, and one or more optional components (e.g., emulsifiers and chain extenders).

[0073] The isocyanate reactive component that can be used in TPU according to the present invention includes at least one active hydrogen, such as amines, thiols, and polymeric diols, and particularly hydroxyl functional materials, such as polymeric diols that provide urethane-linked bonds when reacting with isocyanate functional components. Specific polymeric diols of interest include polyester polymeric diols (e.g., lactone polymeric diols) and their alkylene oxide adducts (e.g., ethylene oxide; 1,2-epoxypropane; 1,2-epoxybutane; 2,3-epoxybutane; methylepoxypropane; and epichlorohydrin), polyether polymeric diols (e.g., polyoxyethylene polymeric diols, such as polypropylene oxide polymeric diols, polyethylene oxide polymeric diols, polypropylene oxide-ethylene oxide copolymer polymeric diols, and polyoxytetramethylene polymeric diols; polyoxyalkylene polymeric diols; polysulfides; and their alkylene oxide adducts), polyalkylene polymeric diols, polycarbonate polymeric diols, mixtures thereof, and copolymers thereof. Other polydiols of interest that are derived from their own lactones are referred to herein as polycaprolactone-based polydiols.

[0074] The isocyanate reactive component of the thermoplastic elastic substrate of the present invention therefore reacts with the isocyanate functional component to form TPU. The isocyanate functional component may contain an isocyanate functional material or a mixture thereof. Polyisocyanates, including their derivatives (e.g., urea, biuret, urethane, dimers and trimers of polyisocyanates and mixtures thereof) (collectively referred to below as "polyisocyanates") are preferred isocyanate functional materials for use as isocyanate functional components. Polyisocyanates have at least two isocyanate functional groups and provide urethane bonding when reacted with the hydroxyl-functionalized isocyanate reactive component. In one embodiment, the polyisocyanate used to prepare polyurethane is one or a combination of any aliphatic or, where applicable, aromatic polyisocyanates used to prepare polyurethane.

[0075] The isocyanate of TPU is usually a diisocyanate, and includes aromatic diisocyanate, aromatic-aliphatic diisocyanate, aliphatic diisocyanate, cycloaliphatic diisocyanate and other compounds terminated by two isocyanate functional groups (e.g., toluene-2,4-diisocyanate-terminated polyoxypropylene glycol diaminocarbamate). Therefore, the diisocyanates that can be used according to the present invention include: 2,6-toluene diisocyanate; 2,5-toluene diisocyanate; 2,4-toluene diisocyanate; phenyl diisocyanate; 5-chloro-2,4-toluene diisocyanate; 1-chloromethyl-2,4-diisocyanophenyl; phenyl dimethyl diisocyanate; tetramethyl-phenyl dimethyl diisocyanate; 1,4-diisocyanobutane; 1,6-diisocyanohexane; 1,12-diisocyanododecane; 2-methyl-1,5-diisocyanopentane; methylene dicyclohexyl-4,4'-diisocyanate; 3-isocyanomethyl-3,5,5'-trimethylcyclohexyl isocyanate (isophorone diisocyanate). 2,2,4-Trimethylhexyl diisocyanate; cyclohexyl-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; tetramethylene-1,4-diisocyanate; cyclohexane-1,4-diisocyanate; naphthalene-1,5-diisocyanate; diphenylmethane-4,4'-diisocyanate; hexahydrophenyl dimethyl diisocyanate; 1,4-phenyl diisocyanate; 3,3'-dimethoxy-4,4'-diphenyl diisocyanate; phenyl diisocyanate; isophorone diisocyanate; polymethylene polyphenyl isocyanate; 4,4'-phenyl diisocyanate; 4-isocyanocyclohexyl-4'-isocyanophenylmethane; and p-isocyanomethylphenyl isocyanate.

[0076] The components of these polyurethane esters will be further described below with respect to specific hydrocarbon groups and their polymerization methods. Therefore, the prefix "poly" is added to the corresponding hydrocarbon group. The hydrocarbon group may include one or more heteroatoms other than carbon, and may also contain functional groups, such as oxime, ester, carbonate, amide, amideimide, ether, urethane ester, urea, carbonyl, or mixtures thereof.

[0077] In one embodiment, the TPU that can be used as a thermoplastic elastic substrate according to the present invention comprises those derived from aliphatic isocyanates and oligomeric polyester resins. The term "aliphatic" means a saturated or unsaturated, straight-chain, branched, or cyclic hydrocarbon group. This term includes alkyl groups (e.g., oxyalkyl groups), aralkyl groups, and cyclic alkyl groups. The term "alkyl group" means a saturated, straight-chain, or branched, divalent hydrocarbon group. Preferably, alkyl groups include oxyalkyl groups, which are saturated, straight-chain, or branched, divalent hydrocarbon groups having a terminal oxygen atom. "Aralkyl group" is a saturated, straight-chain, or branched, divalent hydrocarbon group having at least one aromatic group. The term "cycloalkyl group" means a saturated, straight-chain, or branched, divalent hydrocarbon group having at least one cyclic group. The term "oxycycloalkyl group" means a saturated, straight-chain, or branched, divalent hydrocarbon group having at least one cyclic group and a terminal oxygen atom. The term "aromatic group" refers to a mononuclear aromatic hydrocarbon group or a polynuclear aromatic hydrocarbon group. This term includes aryl groups. The term "aryl group" refers to a divalent aromatic group.

[0078] Therefore, the aliphatic isocyanate that can be used in the thermoplastic elastic substrate of the present invention includes an aliphatic group, which may be alkyl, alkenyl, alkynyl and the like and may be branched or linear, wherein linear is advantageous. The aliphatic group may contain 2-30 carbon atoms, or 3-12 carbon atoms or 4-10 carbon atoms. Examples include 1,12-diisocyanododecane; 2-methyl-1,5-diisocyanopentane; methylene dicyclohexyl-4,4'-diisocyanate; 3-isocyanomethyl-3,5,5'-trimethylcyclohexyl isocyanate (isophorone diisocyanate); 2,2,4-trimethylhexyl diisocyanate; dicyclohexyl-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; tetramethylene-1,4-diisocyanate; cyclohexane-1,4-diisocyanate; and isophorone diisocyanate.

[0079] One or more chain extenders can also be used to prepare the thermoplastic elastic substrate of the present invention. For example, such chain extenders can be any or a combination of aliphatic polymeric diols, aliphatic polyamines, or aromatic polyamines used to prepare polyurethanes. Therefore, chain extenders that can be used according to the present invention include the following: 1,4-butanediol; propylene glycol; ethylene glycol; 1,6-hexanediol; glycerol; trimethylolpropane; neopentyl tetroxide; 1,4-cyclohexanediol; and phenyl diethanolamine. It should also be noted that diols such as hydroquinone bis(β-hydroxyethyl) ether; tetrachlorohydroquinone-1,4-bis(β-hydroxyethyl) ether; and tetrachlorohydroquinone-1,4-bis(β-hydroxyethyl) sulfide, even if they contain an aromatic ring, are considered aliphatic polymeric diols for the purposes of the present invention. Aliphatic diols with 2-10 carbon atoms are preferred. 1,4-Butanediol is particularly preferred.

[0080] According to the present invention, the stretchable multilayer film of the present invention exhibits a modified balance of sap resistance and tensile properties. In various embodiments, the stretchable multilayer film of the present invention has sap resistance greater than 45°C, as measured below, and exhibits an elongation at break greater than 50%, and has a tensile load of less than 2 lb / in at 5% strain when tested within one week of multilayer film preparation, as measured below.

[0081] The stretchable multilayer film of the present invention may further comprise a pressure-sensitive adhesive (PSA), which is provided to assist in mounting the film to the surface to which it is to be adhered. Such pressure-sensitive adhesives may be applied, for example, by means of a release liner time, or may be applied to a thermoplastic elastic substrate. Pressure-sensitive adhesives that can be used according to the present invention include those disclosed in U.S. Patent No. 5,883,149 (the disclosure of which is incorporated herein by reference in its entirety).

[0082] The PSA that can be used according to the present invention includes an acrylate pressure-sensitive adhesive, which comprises an acrylic polymer characterized by its glass transition temperature (Tg). The Tg of the polymer can be from about -55°C to about 15°C, or from -30°C to 5°C, or from -25°C to 0°C. The adhesive of the present invention may contain about 25 to about 98 parts or 60 to 95 parts of acrylate, the homopolymer of which has a Tg of less than 0°C or particularly less than -20°C; about 2 to about 75 parts or 5 to 45 parts of olefinic unsaturated monomer, the homopolymer of which has a Tg of greater than 0°C or greater than 10°C; and 0 to about 15 parts or 0 to 10 parts of a polar olefinic unsaturated monomer having an acid or hydroxyl group. Depending on the circumstances, the adhesive polymer may be blended with 0 to about 50 parts or 10 to 30 parts of a tackifier.

[0083] The acrylates usable according to the present invention are monofunctional acrylates of a monohydric alcohol having about 4 to about 18 carbon atoms in the alcohol moiety, the homopolymer of which has a Tg of less than 0°C. The category of acrylates includes isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, isodecanyl acrylate, decyl acrylate, lauryl acrylate, hexyl acrylate, butyl acrylate, and octadecyl acrylate, or combinations thereof. In the case of octadecyl acrylate, the amount is selected such that side-chain crystallization does not occur at room temperature.

[0084] Examples of olefinic unsaturated monomers having a Tg greater than 0°C or greater than 10°C include (but are not limited to) 3,3,5-trimethylcyclohexyl acrylate, cyclohexyl acrylate, isocamphenyl acrylate, N-octylacrylamide, tributyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, N,N-dimethylacrylamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, acrylonitrile, tetrahydrofurfuryl acrylate, glycidyl acrylate, 2-phenoxyethyl acrylate, and benzyl acrylate or combinations thereof.

[0085] Monomers having an acid or hydroxyl group that can be used according to the present invention include (but are not limited to) acrylic acid, methacrylic acid, methyl acrylate, β-carboxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.

[0086] These adhesive polymers may include, where appropriate, crosslinking agents, including (but not limited to) metal chelates such as aluminum acetone and various titanates. Other crosslinking agents include (but are not limited to) polyfunctional epoxides, silanes, aziridines, isocyanates and / or (meth)acrylates. Where appropriate, the PSA may also include other additives such as tackifiers, plasticizers, UV absorbers / stabilizers and antioxidants.

[0087] Although the compositions of the present invention have been described in detail above with respect to two exemplary embodiments having two end uses, those skilled in the art will understand that the compositions of the present invention can be used in a wide variety of end applications and may include any amount of chelating agent required to achieve the desired performance in those applications. For example, the compositions of the present invention can be used in other cleaning applications, such as interior cleaners, carpet cleaners, hard surface cleaners, and utilities, such as water treatment, pulp and paper, and agricultural chemical treatment.

[0088] The following examples illustrate suitable and / or preferred methods and results according to the present invention. However, it should be understood that these examples are provided by way of illustration and should not be construed as limiting the overall scope of the invention. Unless otherwise specified, all percentages are by weight. Example: Preparation of oligopolyester resin

[0089] The oligopolyester resins (Table 1) were prepared according to the following procedure. All resins were prepared in a 2-liter reactor equipped with a heating pack, mechanical stirrer, thermocouple, nitrogen layer, oil-heated partial condenser, condenser trap, and water-cooled full condenser. Oligopolyester resin 1 (PE1)

[0090] Stage 1 - HHPA, TMCD, triphenyl phosphite, and xylene are loaded into the reactor. Additional xylene is used to fill the condenser trap. The temperature is then raised from room temperature to 140°C over 50 minutes. Stirring begins when the melt reaches 100°C. The temperature is maintained at 140°C until an acid value ≤ 242 mg KOH / g resin is achieved.

[0091] Stage 2 - Add NPG, half of the total TMP, AD and Fascat 4100 catalyst to the reactor and heat to 230°C for 6 hours.

[0092] Stage 3 - Add the remaining TMP and maintain the reaction at 230°C until a final acid value of 8 mg KOH / g resin is achieved. Cool the resin to 190°C and pour it through a medium-mesh paint sieve into a metal paint can. Oligopolyester Resin 2 (PE2)

[0093] Stage 1 - HHPA, NPG, and triphenyl phosphite are loaded into the reactor. Additional xylene is used to fill the condenser trap. The temperature is then raised from room temperature to 140°C over 50 minutes. Stirring begins when the melt reaches 75°C. The temperature is maintained at 190°C until an acid value ≤ 193 mg KOH / g resin is achieved. The temperature is then cooled to 165°C.

[0094] Stage 2 - Add half of the total TMP, AD and catalyst to the reactor and then heat to 140°C and keep overnight. Then heat the reaction to 230°C after 6 hours.

[0095] Stage 3 - Add the remaining TMP to the reactor and maintain the reaction at 230°C until a final acid value of 8 mg KOH / g resin is achieved. Cool the resin to 190°C and pour it through a medium-mesh paint sieve into a metal paint can. Oligopolyester Resin 3 (PE3)

[0096] Stage 1 - HHPA, NPG, and triphenyl phosphite are loaded into the reactor. Additional xylene is used to fill the condenser trap. The temperature is raised from room temperature to 100°C over 1 hour. Stirring begins when the melt reaches 100°C. The temperature is maintained at 130°C until an acid value ≤ 272 mg KOH / g resin is achieved.

[0097] Stage 2 - TMP and Fascat 4100 catalyst are added to the reactor and heated to 230°C for 4 hours. The reaction is maintained at 230°C until a final acid value of 2 mg KOH / g resin is achieved. The resin is then cooled to 190°C and poured through a medium-mesh paint sieve into a metal paint can. Oligopolyester Resin 4 (PE4)

[0098] Stage 1 - HHPA, TMCD, triphenyl phosphite, and xylene are loaded into the reactor. Additional xylene is used to fill the condenser trap. The temperature is raised from room temperature to 100°C over 1 hour. Stirring begins when the melt reaches 100°C. The temperature is maintained at 140°C until an acid value ≤ 376 mg KOH / g resin is achieved.

[0099] Stage 2 - Add NPG, half of the total TMP, adipic acid and Fascat 4100 catalyst to the reactor and heat to 230°C for 6 hours.

[0100] Stage 3 - Add remaining TMP. Maintain the reaction at 230°C until a final acid value of 5 mg KOH / g resin is achieved. Then cool the resin to 190°C and pour it through a medium-mesh paint sieve into a metal paint can. Oligopolyester Resin 5 (PE5)

[0101] Stage 1 - HHPA, TMCD, adipic acid, triphenyl phosphite, and Fascat 4100 catalyst are loaded into the reactor. The temperature is raised from room temperature to 100°C over 1 hour. Stirring begins when the melt reaches 100°C. The temperature is maintained at 200°C until an acid value ≤ 283 mg KOH / g resin is achieved.

[0102] Stage 2 - Add TMP and catalyst and heat the reaction to 150°C. After 4 hours, raise the temperature to 225°C and maintain this temperature until a final acid value of 2 mg KOH / g resin is achieved. Then cool the resin to 170°C and pour it through a medium-mesh paint sieve into a metal paint can. Oligopolyester Resin 6 (PE6)

[0103] Stage 1 - HHPA, TMCD, TMP, adipic acid, triphenyl phosphite, and xylene are loaded into the reactor. Additional xylene is used to fill the condenser trap. The temperature is raised from room temperature to 100°C over 1 hour. Stirring begins when the melt reaches 100°C. The temperature is maintained at 195°C until an acid value ≤ 245 mg KOH / g resin is achieved.

[0104] Stage 2 - Add NPG, TMP, and Fascat 4100 catalyst and heat the reaction to 150°C. After 4 hours, raise the temperature to 230°C and maintain this temperature until a final acid value of 8 mg KOH / g resin is achieved. Then cool the resin to 190°C and pour it through a medium-mesh paint sieve into a metal paint can. Oligopolyester Resin 7 (PE7)

[0105] Stage 1 - NPG, TMCD, half of the total TMP, AD, Fascat 4100 catalyst, triphenyl phosphite, and xylene are loaded into the reactor. Additional xylene is used to fill the condenser. The temperature is raised from room temperature to 100°C over 1 hour. Stirring is started when the melt reaches 100°C. The temperature is maintained at 220°C for 2 hours and held until half of the esterified water is obtained.

[0106] Stage 2 - Add the remaining TMP and maintain the temperature at 220°C until a final acid value of 4 mg KOH / g resin is achieved. Then cool the resin to 190°C and pour it through a medium-mesh paint sieve into a metal paint can. Oligopolyester Resin 8 (PE8)

[0107] Stage 1 - HHPA, TMCD, triphenyl phosphite, and xylene are loaded into the reactor. Additional xylene is used to fill the condenser trap. The temperature is then raised from room temperature to 150°C over 2 hours. Stirring begins when the melt reaches 100°C. The temperature is maintained at 150°C until an acid value ≤ 248 mg KOH / g resin is achieved.

[0108] Stage 2 - Add TMP and Fascat 4100 catalyst to the reactor and heat to 230°C for 2.5 hours. Maintain the reaction at 230°C until a final acid value of 4 mg KOH / g resin is achieved. Cool the resin to 110°C and adjust to 75% wt% solids using n-butyl acetate. Then pour it through a medium-mesh paint sieve into a metal paint can. Properties of oligopolyester resin

[0109] The acid value (abbreviated as "AN"), number of hydroxyl groups (abbreviated as "OHN"), number average molecular weight (abbreviated as "Mn"), weight average molecular weight (abbreviated as "Mw"), molecular weight distribution polydispersity index (abbreviated as "Mw / Mn"), and glass transition temperature (abbreviated as "Tg") of the polyester are shown in Table 1.

[0110] The acid value is determined using ASTM method D 1639.

[0111] The number of hydroxyl groups is determined by reacting the resin with excess acetic anhydride in pyridine to esterify it, followed by hydrolysis of the unreacted anhydride. The resulting acetic acid is then titrated with a standard KOH solution. The number of milligrams of KOH equivalent to 1 gram of resin sample is reported as the number of hydroxyl groups.

[0112] The molecular weight was determined by gel permeation chromatography using a refractive index detector with polystyrene standards.

[0113] The residual solvent in the resin can be artificially reduced by treating it with a solvent. To obtain a more accurate Tg, the resin sample was first pretreated in an oven. Approximately 0.3 g of resin was placed in a small aluminum weighing pan and heated at 110°C for 1 hour. The sample was then transferred to a differential scanning calorimeter (TA Instruments DSC Q2000 V24.9 Build 121). In the first heating cycle, the sample was heated from -50°C to 140°C at a rate of 20°C / min under a nitrogen atmosphere. The sample was then quenched to -50°C. For the second heating cycle, the sample was heated under the same conditions as in the first heating cycle. The midpoint of the second heating cycle was reported as the Tg of the sample. Table 1: Weight of oligopolyester resin charge (g) and properties of the resin measured. Polyester resin PE 1 PE 2 PE 3 PE 4 PE 5 PE 6 PE 7 PE 8 Phase 1 TMCD (a) 293.91 - - 293.91 377.40 271.21 357.43 397.03 NPG (b),(c) - 535.82 290.75 - - - 258.14 - TMP (d) - - - - - 129.48 205.96 - HHPA (e) 570.98 598.22 860.71 570.98 496.10 631.44 - 810.36 AD (f) - - - - 348.30 322.30 1017.39 - Triphenyl phosphite 1.96 1.97 1.90 1.91 1.94 1.85 2.04 1.89 Fascat4100 catalyst (g) - - - - 1.94 - 0.51 - Xylene process solvent 39.19 - - 38.19 - 46.19 51.12 47.37 Phase 2 NPG 283.70 - - 283.70 - 363.76 - - TMP 205.07 203.82 749.04 205.07 719.04 129.48 205.96 705.23 AD 400.92 427.78 - 400.92 - - - - Fascat4100 catalyst 1.96 1.97 1.90 1.91 - 1.85 - 1.89 Phase 3 TMP 205.07 203.82 - 205.07 - - - - Total charge (solids only) 1959.65 1969.45 1900.50 1959.65 April 1940 1847.67 2044.87 1898.40 Subtract theoretical condensate 159.65 169.45 100.50 159.65 140.85 147.67 244.87 94.62 Production (solids only) 1800.00 1800.00 1800.00 1800.00 1800.00 1700.00 1800.00 1803.78 The properties of the resin were measured AN, mg KOH / g resin 9 9 2 5 2 4 4 2 OHN, mg KOH / g resin 192 190 330 172 275 148 160 304 M w 5076 5293 1684 3914 4073 6971 21083 1988 M n 1465 1471 904 1416 1332 1824 2019 1016 M w / M n 3 4 2 3 3 4 10 2 T g ,℃ -13 -17 7 twenty four 3 8 -30 twenty two (a) 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (Eastman) (b) 2,2-Dimethyl-1,3-propanediol (Eastman) (c) Based on charge amount, add 1 wt. % excess diol (d) Trimethylolpropane (Perstorp) (e) Hexahydrophthalic anhydride (Dixie Chemical) (f) Adipic acid (Ascend Performance Materials) (g) Butyl stannic acid (PMC Organometallix) Preparation and Evaluation of Thermosetting Materials: Preparation of 2K Clear Coating

[0114] The example and comparison of 2K clear coating component A were both prepared by mixing the components listed in Table 2. The oligopolyester resin sample prepared in Table 1 was pre-dissolved in n-butyl acetate to form a 75% solid solution. Components A and B were mixed together just before the film was applied. The amount of solvent was adjusted to four parts by weight of n-butyl acetate and one part by weight of PM acetate to achieve a desired 40% by weight solid formulation. Table 2. 2K Clear Coating Formulation Example CC1 Example CC 2 Example CC 3 Example CC 4 Example CC 5 Example CC 6 Part A PE 1 100 - 50 - - - PE 2 - 100 50 - - - PE 6 - - - 30 10 40 PE 7 - - - - - 20 PE 8 - - - 70 90 40 DBTDL 0.19 0.19 0.19 0.22 0.23 0.20 Acetate acetone 0.32 0.32 0.32 0.36 0.38 0.33 n-Butyl acetate 132 132 132 153 163 139 PM acetate 33 33 33 38 41 35 Part B Desmodur N3300 52 52 52 69 78 57 Total 318 316 317 361 382 331 Table 2. 2K Clear Coating Formulations (Continued) Compare CC 1 Compare CC 2 Compare CC 3 Compare CC 4 Compare CC 5 Compare CC 6 Compare CC 7 Part A PE 3 100 50 - - - - - PE 4 - - 100 - - - - PE 5 - - - 100 - - - PE 6 - - - - - - 100 PE 7 - - - - - 100 - PE 8 - 50 - - 100 - - DBTDL 0.25 0.25 0.18 0.22 0.24 0.18 0.17 Acetate acetone 0.41 0.40 0.30 0.37 0.39 0.30 0.29 n-Butyl acetate 177 173 126 159 168 122 118 PM acetate 44 43 31 40 42 30 29 Part B Desmodur N3300 89 85 46 73 81 43 40 Total 411 402 304 372 393 296 288 Preparation of composite membranes

[0115] The multilayer film system was prepared by applying a transparent coating to a main surface of a 6 mil thick elastic polyurethane film. The coating was applied to a TecMaster™ laboratory coater using a gravure roller. The solids percentage of the transparent coating solution and process conditions were adjusted on the TecMaster™ to achieve a final coating thickness between 5 and 15 micrometers. All coatings were post-cured in a convection oven at 60°C for 15 hours to ensure complete curing before evaluation. Test panel preparation.

[0116] The multilayer film was mounted on a substrate mimicking an automotive surface coating. The test panels were prepared as follows: 0.032-inch thick polished cold-rolled steel test panels with an electrodeposited coating and a top coat of gray primer were purchased from ACT Test Panel LLC. The panels were further coated with commercially available water-based black paint and hard baked, followed by spray application of an automotive-grade 2K clear coat to achieve a 40-micron dry film thickness. The coated panels were flash-evaporated at room temperature for 10 minutes and then cured at 140°C for 30 minutes.

[0117] The multilayer film was manually applied to the test plate using moderate pressure. A 2% soap solution was used as the application solution. The film mounted on the substrate was dried under ambient conditions for at least 24 hours before testing. Test Method

[0118] The tensile strength at 5% strain was measured by first cutting the multilayer film into 1-inch wide strips. The strips were placed in a Mark-10 tension testing machine equipped with a Seres 5 force gauge (50 Lb maximum load) at 2-inch intervals. The film was stretched to 50% elongation at a rate of 10 inches per minute. The load-displacement curve was recorded, and the load / inch at 5% strain was reported. The tensile properties of the film were measured within one week after the multilayer film was prepared.

[0119] Resistance to resin was measured using an Erichsen 432 gradient oven. The temperature range was set from 30°C to 75°C. The test was conducted according to DIN EN ISO 2812-5:2007-05. The temperature at which the coating was permanently damaged by resin was reported as resin resistance. Evaluation results for 2K clear coating.

[0120] The monomer composition of the oligopolyester resin and its performance in 2K transparent coatings are reported in Table 3. Table 3. Monomer composition of oligopolyester resin and its performance as a 2K transparent coating on multilayer films. 2K Clear Coating NPG Mor% TMCD mole% TMP mole% HHPA mole% AD Morphine% OH# of part of resin A mixture Coating thickness (micrometer) Sap resistance (°C) lb / in at 5% strain Example CC 1 35% 26% 39% 57% 43% 192 4.0 53 1.88 Example CC 2 63% 0% 37% 57% 43% 190 3.9 50 1.57 Example CC 3 49% 13% 38% 57% 43% 191 3.0 55 1.47 Example CC 4 14% 30% 56% 90% 11% 231 3.0 62 1.72 Example CC 5 5% 31% 65% 97% 4% 274 2.9 68 1.85 Example CC 6 25% 29% 46% 66% 34% 190 3.4 48 1.31 Compare CC 1 33% 0% 67% 100% 0% 330 5.5 72 2.05 Compare CC 2 17% 16% 68% 100% 0% 316 3.8 74 2.01 Compare CC 3 35% 26% 39% 100% 0% 172 3.0 47 2.40 Comparison CC 4 0% 31% 69% 57% 43% 275 3.8 44 2.54 Compare CC 5 0% 31% 69% 100% 0% 303 4.0 71 2.30 Compare CC 6 31% 31% 38% 0% 100% 160 4.8 31 0.67 Compare CC 7 48% 26% 26% 65% 35% 148 4.8 42 0.65 The composition of the example of the present invention (“X” symbol) relative to the comparative example (“O” symbol) is shown in Figure 1. The resin of the example of the present invention (“X” symbol) relative to the comparative example (“O” symbol) and the load / in value at 5% strain are shown in Figure 2. [Simplified Explanation of the Diagram]

[0010] Figure 1 shows the NPG and adipic acid content in the examples ("X" symbols) and comparative examples ("O" symbols) of the present invention.

[0011] Figure 2 shows the sap resistance and load / in value at 5% strain in the examples ("X" symbols) and comparative examples ("O" symbols) of the present invention.

Claims

1. A stretchable multilayer film comprising: a thermoplastic polyurethane substrate; and a thermosetting coating applied to the thermoplastic polyurethane substrate and comprising a reaction product comprising: i) an oligopolyester resin comprising a reaction product comprising: a. a diol or polyol comprising about 30 to about 99 mol% trimethylolpropane and about 1 mol% to about 70 mol% neopentyl glycol, in each case based on the total molar amount of the reacted diol and polyol; and b. a dicarboxylic acid or polycarboxylic acid comprising about 1 mol% to about 70 mol% of one or more cyclic or acyclic aliphatic acids having 2 to 12 carbons, based on the total molar amount of the reacted dicarboxylic acid and polycarboxylic acid, wherein the oligopolyester resin has a glass transition temperature (Tg) of -40 to 55°C, an acid value of 0 to 15 mg KOH / g, a hydroxyl number of 100 to 370 mg KOH / g, and a pH of 500 to 10,000 mg KOH / g. (ii) a number average molecular weight of KOH / g and a weight average molecular weight of 1,000 to 40,000; and (ii) an aliphatic isocyanate, isocyanurate, urethane, or biuret, wherein the stretchable multilayer exhibits an elongation at break greater than 50%, has a tensile load of less than 2 lb / in at 5% strain when measured within one week of multilayer preparation, and has tree sap resistance greater than 45°C.

2. The stretchable multilayer film of claim 1, wherein the oligopolyester resin has an acid value of 0 to 10 mg KOH / g, a number of hydroxyl groups of 125 to 300 mg KOH / g, a number average molecular weight of 1000 to 4000 mg KOH / g, and a weight average molecular weight of 1000 to 25000.

3. The stretchable multilayer film of claim 1 or 2, wherein the amount of trimethylolpropane is about 40 to about 70 mol% and the amount of neopentyl glycol is about 30 mol% to about 60 mol%, and the amount of one or more cyclic or acyclic aliphatic acids having 2 to 12 carbons is about 20 mol% to about 70 mol%.

4. The stretchable multilayer film of claim 1 or 2, wherein the one or more cyclic or acyclic aliphatic acids having 2 to 12 carbons include adipic acid.

5. The stretchable multilayer film of claim 1 or 2, wherein the diol or polyol further comprises TMCD.

6. The stretchable multilayer film of claim 1 or 2, wherein the dicarboxylic acid or polycarboxylic acid further comprises one or more of HHPA or CHDA present in an amount of 50 mol% to 100 mol%.

7. The stretchable multilayer film as claimed in claim 1 or 2, wherein, when measured within one week of the multilayer film preparation, the stretchable multilayer film exhibits a tensile load per inch greater than 1 lb / in and less than 2 lb / in at 5% strain, and has resin resistance from 45°C to 70°C.

8. The stretchable multilayer film as claimed in claim 1 or 2, wherein the thickness of the thermosetting coating is from 0.1 to 25 micrometers.

9. The stretchable multilayer film of claim 1 or 2, wherein the coating thickness is 1 to 10 micrometers.

10. The stretchable multilayer film of claim 1 or 2, wherein the aliphatic diisocyanate is present and selected from one or more of the following: methylene bis-4,4'-isocyanocyclohexane, isophorone diisocyanate, isocyanurate of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, isocyanurate of 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, pentane-1,5-diisocyanate, 1,4-bis(isocyanomethyl)cyclohexane, or polyisocyanate.

11. The stretchable multilayer film of claim 1 or 2, wherein the aliphatic diisocyanate is present and corresponds to one of the following structures: 1,6-diisocyanatohexane bis(4-isocyanatocyclohexyl)methane 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane.

12. The stretchable multilayer film of claim 1 or 2, wherein the diol or polyol of the oligopolyester resin further comprises less than 30 mol.% of TMCD.

13. The stretchable multilayer film of claim 1 or 2, wherein the dicarboxylic acid or polycarboxylic acid of the oligopolyester resin contains no more than 5 mol% aromatic dicarboxylic acid.

14. The stretchable multilayer film of claim 1 or 2, wherein the molar ratio of oligopolyester resin to aliphatic isocyanate or isocyanurate is 0.95 to 1.

05.

15. A stretchable multilayer film comprising: a thermoplastic polyurethane substrate; and a thermosetting coating applied to the thermoplastic polyurethane substrate and comprising a reaction product comprising: i) an oligopolyester, which is a reaction product comprising monomers comprising: a. 30 to 70 mol% of trimethylolpropane (TMP) based on total moles of ac, b. 1 to 70 mol% of neopentyl glycol (NPG) based on total moles of ac, c. 0 to 69 mol% of diols other than NPG based on total moles of ac, d. one or more cyclic or acyclic aliphatic acids having 2 to 12 carbons based on total moles of de, and e. one or more additional dicarboxylic acids based on total moles of de, and 0 to 70 mol% of total moles of de. The oligopolyester resin has a glass transition temperature (Tg) of -40 to 55°C, an acid value of 0 to 15 mg KOH / g, a number of hydroxyl groups of 100 to 370 mg KOH / g, a number average molecular weight of 500 to 10,000 mg KOH / g, and a weight average molecular weight of 1,000 to 25,000; and (ii) an aliphatic isocyanate, isocyanurate, urethane, or biuret, wherein the stretchable multilayer film exhibits an elongation at break greater than 50%, has a tensile load of less than 2 lb / in at 5% strain when measured within one week of multilayer film preparation, and has sap resistance greater than 45°C.

16. The stretchable multilayer film of claim 15, wherein the amount of trimethylolpropane is about 40 to about 70 mol% and the amount of neopentyl glycol is about 30 mol% to about 60 mol%, and the amount of one or more cyclic or acyclic aliphatic acids having 2 to 12 carbons is about 20 mol% to about 70 mol%.

17. The stretchable multilayer film of claim 15 or 16, wherein the one or more cyclic or acyclic aliphatic acids having 2 to 12 carbons include adipic acid.

18. The stretchable multilayer film of claim 15 or 16, wherein the diol or polyol further comprises TMCD.

19. The stretchable multilayer film of claim 15 or 16, wherein the dicarboxylic acid or polycarboxylic acid further comprises one or more of HHPA or CHDA present in an amount of 50 mol% to 100 mol%.

20. The stretchable multilayer film of claim 15 or 16, wherein, when measured within one week of the multilayer film preparation, the stretchable multilayer film exhibits a tensile load per inch greater than 1 lb / in and less than 2 lb / in at 5% strain, and has resin resistance from 45°C to 70°C.

21. The stretchable multilayer film of claim 15 or 16, wherein the thickness of the thermosetting coating is from 0.1 to 25 micrometers.

22. The stretchable multilayer film as claimed in claim 15 or 16, wherein the coating thickness is 1 to 10 micrometers.

23. The stretchable multilayer film of claim 15 or 16, wherein the aliphatic diisocyanate is present and selected from one or more of the following: methylene bis-4,4'-isocyanocyclohexane, isophorone diisocyanate, isocyanurate of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, isocyanurate of 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, pentane-1,5-diisocyanate, 1,4-bis(isocyanomethyl)cyclohexane, or polyisocyanate.

24. The stretchable multilayer film of claim 15 or 16, wherein the aliphatic diisocyanate is present and corresponds to one of the following structures: 1,6-diisocyanatohexane bis(4-isocyanatocyclohexyl)methane 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane.

25. The stretchable multilayer film of claim 15 or 16, wherein the oligopolyester resin further comprises less than 30 mol.% of TMCD as a polyol.

26. The stretchable multilayer film of claim 15 or 16, wherein the oligopolyester resin further comprises no more than 5 mol% of aromatic dicarboxylic acid as a polycarboxylic acid.

27. The stretchable multilayer film of claim 15 or 16, wherein the molar ratio of oligopolyester resin to aliphatic isocyanate or isocyanurate is 0.95 to 1.05.

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