Stretchable multilayer film

Abstract

A stretchable multilayer film is disclosed, comprising a thermoplastic polyurethane substrate and a thermoset coating applied to the thermoplastic polyurethane substrate. The thermoset coating may comprise a reaction product of an oligomeric polyester resin comprising a reaction product of a diol or polyol, in each case comprising about 30 to about 99 mol % trimethylolpropane and about 1 mol % to about 70 mol % neopentyl glycol, based on the total molar amount of the reacted diols and polyols, with a dicarboxylic acid or polycarboxylic acid, in each case comprising about 1 mol % to about 70 mol % one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms, based on the total molar amount of the reacted dicarboxylic acid and polycarboxylic acid.

Description

Technical Field

[0001]

[0001] The present invention generally relates to stretchable multilayer films useful as protective films, particularly paint protection films.

Background Art

[0002]

[0002] Paint protection films, which are stretchable films used to protect stretchable films, such as automotive panels and coated wood, generally consist of a thermoplastic elastomer, a thermosetting coating applied to one main surface, and an adhesive on the opposite main surface. These protective films are desired to be stretchable so that they can conform to three-dimensional objects and resistant to environmental factors such as ultraviolet light, acid rain, and tree sap. Resistance to environmental factors is generally provided by the outermost layer of this thermosetting coating.

[0003]

[0003] U.S. Patent No. 10,265,932 discloses stretchable multilayer protective sheets. These are useful for various indoor and outdoor applications, for example in the industries of transportation, construction, and sports goods. The protective sheet can be advantageously applied to at least a part of the surface of any article for which protection is desired. In one aspect, the stretchable multilayer protective sheet may include a carrier layer and an essentially uncrosslinked topcoat layer. According to a further embodiment of the latter, the topcoat layer can be based on polyurethane.

[0004]

[0004] There is an existing market for paint protection films, while on the other hand, the resistance to environmental factors provided by automotive topcoats on automotive body panels is generally quite good. These topcoats are thermosetting, pigment-free transparent coats obtained by reacting a crosslinking agent containing isocyanate with a hydroxyl-functional resin. These coatings are typically developed to exhibit desired performance at a coating thickness of about 50 - 70 microns.

[0005]

[0005] It would be desirable for the protective film to have environmental resistance comparable to that of the automotive clear coating. However, while the clear coating formulation is rigid, the outermost coating of the protective film needs to be designed to maintain the extensibility of the underlying thermoplastic elastomer substrate for the purpose of application. Furthermore, the thickness of the protective film, which is typically 5 to 15 microns, is much thinner than that of the automotive coating. Due to these design constraints, the resistance of the protective film to environmental factors is generally inferior to that of the automotive coating. [Overview of the project] [Problems that the invention aims to solve]

[0006]

[0006] There is still a need for the discovery of stretchable multilayer films containing a protective topcoat and thermoplastic polyurethane that provide improved sap resistance, while simultaneously providing more than 50% elongation at break and reducing tensile strength at low strain values. [Means for solving the problem]

[0007]

[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 oligomeric polyester resin and an aliphatic isocyanate or isocyanurate. The oligomeric polyester resin comprises a reaction product of a diol or polyol comprising about 30 to about 99 mol% trimethylolpropane and about 1 mol to about 70 mol% neopentyl glycol, relative to the total molar amount of the reacted diol and polyol; and a reaction product of a dicarboxylic acid or polycarboxylic acid comprising about 1 mol to about 70 mol% of one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms, relative to the total molar amount of the reacted dicarboxylic acid and polycarboxylic acid. The stretchable multilayer film exhibits a break elongation of more than 50% and an elongation load of less than 0.358 kg / cm (2 lb / in) at a strain of 5% when measured within one week of the preparation of the multilayer film.centimeter It possesses sap resistance exceeding 45°C.

[0008]

[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, allophanate, or biuret reacted with an oligomeric polyester. The oligomer polyester is a reaction product of monomers containing 30-70 mol% of trimethylolpropane (TMP) relative to the total moles of a-c, 1-70 mol% of neopentyl glycol (NPG) relative to the total moles of a-c, 0-69 mol% of a diol other than NPG relative to the total moles of a-c, 30-100 mol% of one or more cyclic or acyclic fatty acids having 2-12 carbon atoms relative to the total moles of d-e, and 0-70 mol% of one or more additional dicarboxylic acids relative to the total moles of d-e. The oligomer polyester resin has a glass transition temperature (Tg) of -40-55°C, an acid value of 0-15 mgKOH / g, a hydroxyl value of 100-370 mgKOH / g, a number-average molecular weight of 500-10,000 mgKOH / g, and a weight-average molecular weight of 1,000-25,000. In this embodiment, the stretchable multilayer film exhibits a break elongation of more than 50% and, when measured within one week of the preparation of the multilayer film, has a stretch load of less than 0.358 kg / cm (2 lb / in) at a strain of 5%. centimeter It possesses sap resistance exceeding 45°C.

[0009]

[0009] Further aspects of the present invention are disclosed herein and claimed. [Brief explanation of the drawing]

[0010] [Figure 1] This figure shows the NPG and adipic acid content in Example (X) and Comparative Example (O) of the present invention. [Figure 2]This figure shows the sap resistance and load / in at 5% strain for Example (X) and Comparative Example (O) of the present invention. [Modes for carrying out the invention]

[0011]

[0010] In one embodiment, the present invention relates to a stretchable multilayer film comprising a thermoplastic elastomer substrate, such as thermoplastic polyurethane, coated with a crosslinked thermosetting coating. The thermosetting coating is a reaction product of an oligomeric polyester resin containing, as described elsewhere in this specification, about 30 mol% to about 99 mol% of trimethylolpropane (TMP) and about 1 mol% to about 70 mol% of neopentyl glycol (NPG) as the diol or polyol, relative to the total molar amount of the reacted diol or polyol. The oligomeric polyester resin of the present invention may contain other diols or polyols. The oligomeric polyester resin further contains, as described elsewhere in this specification, about 1 mol% to about 60 mol% of cyclic or acyclic aliphatic dicarboxylic acids, particularly adipic acid, having 1 to 12 carbon atoms, relative to the total molar amount of the dicarboxylic acid or polycarboxylic acid. The oligomeric polyester resin of the present invention may contain other dicarboxylic acids or polycarboxylic acids.

[0012]

[0011] The oligomer polyester resin of the present invention is reacted with an aliphatic isocyanate, isocyanurate, allophanate, or biuret to obtain a thermosetting coating. The stretchable multilayer film may further include an adhesive layer on the opposite side of the thermosetting coating for use as, for example, a paint protective film. This adhesive may be a pressure-sensitive adhesive. The stretchable multilayer film including the coating layer exhibits a break elongation of more than 50% and, when tested within one week of the preparation of the multilayer film, with a stretch load of less than 0.358 kg / cm (2 lb / in) at a strain of 5% / centimeter It has the following properties and is sap-tolerant above 45°C, or as further specified herein.

[0013]

[0012] We have found that stretchable multilayer films can be formed from thermoplastic elastomer substrates that have a thermosetting coating that maintains the integrity of the coating layer when stretched. Thermoplastic elastomer substrates, typically thermoplastic polyurethane, are suitable for use as paint protective films or autowraps and are therefore stretchable with an elongation of up to 50%. Although thermoplastic polyurethane is known to have an elastic structure, the inventors of this patent enable the entire multilayer film to be stretched to a 50% break point elongation and, when tested within one week of the preparation of the multilayer film, to a stretch load of less than 0.358 kg / cm (2 lb / in) with a strain of 5% / centimeter Unexpectedly, we have developed a stretchable multilayer film having a thermosetting coating that possesses sap resistance exceeding 45°C. Thermosetting coatings similar to those described herein are known to be useful, for example, as metal coatings for automobiles or as coatings for cans, but typically do not stretch to any noticeable degree.

[0014]

[0013] In the present invention, the “stretchable multilayer film” can be reversibly stretched without cracking up to at least 50% of its original strain. A further aspect of the “stretchable film” is that it requires less force to reversibly stretch the film, because this makes it easier for the installer to align the film with the surface of the automobile.

[0015]

[0014] Unless otherwise indicated, all numbers used in this specification and in the claims to represent quantities, properties, etc., of components, such as molecular weight, reaction conditions, etc., shall be understood in all examples to be modified by the term “approximately”. Unless otherwise indicated, the numerical parameters described herein and in the appended claims are approximations, and such approximations may vary depending on the desired properties to be obtained by the present invention. At a minimum, each numerical parameter should be interpreted by applying a normal rounding method, taking into account the number of significant figures reported. Furthermore, the ranges described in this disclosure and in the claims are intended to specifically include the entire range, not just the endpoints. For example, the range described as 0 to 10 is intended to disclose all integers from 0 to 10, e.g., 1, 2, 3, 4, etc., all decimals from 0 to 10, e.g., 1.5, 2.3, 4.57, 6.1113, etc., as well as the endpoints 0 and 10. Furthermore, the scope of chemical substituents, such as "C1-C5 diols," is intended to specifically include and disclose C1, C2, C3, C4, and C5 diols.

[0016]

[0015] The numerical ranges and parameters described in the broad scope of the present invention are approximations, but the numerical values ​​described in the specific examples are reported as accurately as possible. However, each numerical value inherently contains a certain error that inevitably arises from the standard deviation found in each test measurement.

[0017]

[0016] Where used herein and in the appended claims, the singular forms “a,” “an,” and “the” include their plural nouns unless the context clearly indicates otherwise. 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 both singular and plural polyesters, dicarboxylic acids, or residues. In addition, references to compositions “comprising,” “containing,” “having,” or “including” one component or one polyester are intended to include other components or other polyesters, respectively, in addition to the specifically identified component or residue. Therefore, the terms “contain,” “have,” or “include” are intended to be synonymous with and may be used interchangeably with the term “comprising,” meaning that at least the listed 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, or method steps, even if they have the same function as those listed, unless expressly excluded in the claims.

[0018]

[0017] It should also be understood that reference to one or more process steps does not exclude the existence of additional process steps before or after the combined described steps, or process steps intervening between explicitly identified steps. Furthermore, descriptions of process steps or components are a convenient means of identifying individual activities or components, and the described descriptions may be arranged in any order unless otherwise indicated.

[0019]

[0018] Accordingly, the stretchable multilayer film of the present invention comprises a thermosetting coating and a thermoplastic elastomer substrate coated with the thermosetting coating. The thermosetting coating is made from an oligomeric polyester resin having a considerable aliphatic content, comprising residues of trimethylolpropane, neopentyl glycol, and an aliphatic dibasic acid, such as adipic acid. The oligomeric polyester resin useful according to the present invention may also contain further amounts of diols or polyols and further amounts of dicarboxylic acids or polycarboxylic acids.

[0020]

[0019] The oligomeric polyester resins of the present invention are prepared by polycondensation of one or more acid components and one or more hydroxyl components. These acid components are understood to have at least two carboxylic acid units and are therefore optionally either dicarboxylic acids or polycarboxylic acids. Similarly, these hydroxyl components are understood to have at least two hydroxyl units and are therefore optionally either diols or polyols. As used herein, the term "polyol" refers to monomer units used to construct the oligomeric polyester resin and includes monomer units having two or more hydroxyl groups. Similarly, as used herein, the term "polycarboxylic acid" refers to monomer units used to construct the oligomeric polyester resin and includes monomer units having two or more carboxylic acid groups. For convenience, we will often refer to the terms "diol or polyol" and "dicarboxylic acid or polycarboxylic acid" as two reactants used to form the oligomeric polyester resins of the present invention. As used throughout, the molar percentage of each diol or polyol is relative to the total moles of diols or polyols present. Similarly, the molar percentage of each dicarboxylic acid or polycarboxylic acid is given in relation to the total moles of dicarboxylic acid or polycarboxylic acid present.

[0021]

[0020] As used herein, the oligomeric polyester resins of the present invention are distinguished from thermosetting coatings formed by reaction with aliphatic isocyanates, isocyanurates, allophanates, or biuret. The oligomeric polyester resins of the present invention are relatively low molecular weight aliphatic thermoplastic polyesters that act as polyol reactants when reacted with aliphatic isocyanates or isocyanurates to form the thermosetting coatings of the present invention. Depending on the context, the term isocyanate may include isocyanurates, allophanates, or biuret.

[0022]

[0021] Accordingly, the thermosetting coatings of the present invention are thermosetting polymers and are suitable for coating thermoplastic elastomers. That is, the oligomeric polyester resin is compounded with an aliphatic isocyanate or isocyanurate and optionally a small amount of aromatic isocyanate, and as a result the thermosetting coating is suitable for use in protecting thermoplastic elastomer substrates while maintaining desirable stretchability and sap resistance. Therefore, these oligomeric polyester resins are not considered suitable as autopolymers for the manufacture of films, sheets, and other molded products by extrusion, casting, blow molding, and other thermoforming processes commonly used for high molecular weight thermoplastic polymers. The oligomeric polyester resin has reactive functional groups, which are hydroxyl groups and / or carboxyl groups, which subsequently react with the aliphatic isocyanates in the coating formulation. The functional groups of the oligomeric polyester resin are controlled by having either an excess of polyol or polycarboxylic acid in the oligomeric polyester resin composition. Whether the polyester resin is hydroxyl-terminated or carboxylic acid-terminated will determine the desired crosslinking pathway. This concept is publicly known to those skilled in the art, for example, as described in *Organic Coatings Science and Technology*, 2nd edition, pp. 246-257, by Z. Wicks, F. Jones, and S. Pappas, Wiley, New York, 1999, the entire disclosure of which is incorporated herein by reference.

[0023]

[0022] The acid component of the oligomeric polyester resin is prepared from dicarboxylic acids and polycarboxylic acids having 1 to 12 carbon atoms. Typically, the acid component generically referred to as polycarboxylic acid herein contains at least one dicarboxylic acid and may optionally contain polycarboxylic acid. The acid component is essentially an aliphatic polycarboxylic acid, but may contain residues derived from trace amounts of aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, phthalic acid, or phthalic anhydride, but this is not preferred. In some embodiments, the amount of aromatic acid content may be 5 mol% or less, or 3 mol% or less, or 2 mol% or less, or 1 mol% or less, or 0.5 mol% or less, or may be an aromatic acid content of substantially zero.

[0024]

[0023] These aliphatic polycarboxylic acids can be further divided into acyclic and cyclic variants. The acyclic aliphatic dicarboxylic acid accounts for 1 to 60 mol%, 1 to 50 mol%, 1 to 40 mol%, 1 to 30 mol%, 1 to 20 mol%, 1 to 10 mol%, 10 to 60 mol%, 10 to 50 mol%, 10 to 40 mol%, 10 to 30 mol%, 10 to 20 mol%, 20 to 60 mol%, 20 to 50 mol%, 20 to 40 mol%, 20 to 30 mol%, 30 to 60 mol%, 30 to 50 mol%, 30 to 40 mol%, 40 to 60 mol%, 40 to 50 mol%, or 50 to 60 mol% based on the total mol of acyclic aliphatic and cyclic aliphatic dibasic acids.

[0025]

[0024] Therefore, useful acyclic aliphatic acids according to the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, undecanedioic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, dodecanedioic acid, sebacic acid, azelaic acid, acetylenedicarboxylic acid, glutaconic acid, traumatic acid, dimer acid, hydrogenated dimer acid, etc., or residues thereof. Adipic acid is a desirable acyclic aliphatic acid.

[0026]

[0025] Useful cyclic aliphatic acids according to the present invention include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride (HHPA), methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, 2,3-norbornanedicarboxylic acid anhydride, and mixtures thereof, or residues thereof. HHPA is a desirable cyclic aliphatic dibasic acid.

[0027]

[0026] The hydroxyl components of oligomer polyester resins are prepared from diols and polyols that typically have 2 to 20 carbon atoms. As mentioned above, the term polyol includes diols depending on the context.

[0028]

[0027] Diols useful according to the present invention include diols having two hydroxyl groups, which are branched or linear, saturated or unsaturated aliphatic or alicyclic C2-C20 compounds, wherein the hydroxyl groups are primary, secondary, and / or tertiary, preferably primary. Therefore, useful diols and polyols according to the present invention include 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalylhydroxypivalate, 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, as well as mixtures thereof or residues thereof.

[0029]

[0028] Polyols useful according to the present invention may include polyols having three or more hydroxyl groups, which are saturated or unsaturated aliphatic or alicyclic C2-C20 compounds, wherein the hydroxyl groups are primary, secondary, and / or tertiary, and preferably at least two of the hydroxyl groups are primary. Preferably, the polyol is a hydrocarbon and does not contain atoms other than hydrogen, carbon, and oxygen. Examples of these polyols include 1,1,1-trimethylolpropane (TMP), 1,1,1-trimethylolethane, glycerin, pentaerythritol, erythritol, treitol, di-pentaerythritol, sorbitol, and mixtures thereof, or residues thereof.

[0030]

[0029] In other embodiments, the oligomer polyester resin of the present invention may further contain one or more alicyclic diols, for example, 2,2,4,4-tetramethyl-1,3-cyclobutanediol. In other embodiments, the oligomer polyester resin of the present invention may contain little to no 2,2,4,4-tetramethyl-1,3-cyclobutanediol, for example, 15 mol% or less, or 10 mol% or less, or 5 mol% or less, or 2 mol% or less.

[0031]

[0030] In one embodiment, the oligomer polyester resin of the present invention is composed of both trimethylolpropane and neopentyl glycol as monomer polyols.

[0031] In one embodiment, trimethylolpropane may be present in the oligomer polyester resin in an amount of about 30 or 30-99 mol%, or 30-80 mol%, or 30-70 mol%, or 30-50 mol%, or 30-40 mol%, or 40-99%, or 40-80 mol%, or 40-70 mol%, or 40-60 mol%, or 40-50 mol%, or 50-99 mol%, or 50-80 mol%, or 50-70 mol%, or 60-99%, or 60-80 mol%, or 60-70 mol%, or 70-99%, or 70-80 mol%, or 80-99%, relative to the total moles of TMP and other diols and polyols.

[0032]

[0032] In a further embodiment, the 2,2-dimethyl-1,3-propanediol (neopentyl glycol) (NPG) in the oligomer polyester resin is 1-70%, or 10-70%, or 20-70 mol%, or 30-70 mol%, or 40-70 mol%, or 50-70 mol%, or 60-70 mol%, or 1-60%, or 10-60%, or based on the total moles of NPG and other diols and polyols. It accounts for 20-60 mol%, or 30-60 mol%, or 40-60 mol%, or 50-60 mol%, 1-50%, or 10-50%, or 20-50 mol%, or 30-50 mol%, or 40-50%, or 1-40%, or 10-40%, or 20-40 mol%, or 30-40 mol%, 1-30%, or 10-30%, or 20-30 mol%, or 1-20%, or 10-20%, or 1-10%.

[0033]

[0033] A catalyst may be used to accelerate the rate of the polycondensation reaction for forming the oligomeric polyester resin.

[0034] Examples of additional acid and hydroxyl components include, but are not limited to, those known to those skilled in the art, including those discussed below, and various documents known to those skilled in the art, such as Resins for Surface Coatings, Vol. III, pp. 63–167, edited by PkToldring and G. Hayward, SITA Technology, London, UK, 1987, which is incorporated herein by reference.

[0034]

[0035] When used herein in relation to the oligomeric polyester resins of the present invention, the term “residue” means any organic structure incorporated into the polymer by polycondensation or ring-opening reaction involving the corresponding monomer. It will also be understood by those skilled in the art that residues bonded to the various curable polyesters of the present invention may be derived from the parent monomer compound itself or any derivative of the parent compound. For example, dicarboxylic acid residues referred to in the polymers of the present invention may be derived from dicarboxylic acids, or their associated acid halides, esters, salts, anhydrides, or mixtures thereof. Thus, when used herein, the term “polycarboxylic acid” is intended in its broadest sense to include polycarboxylic acids useful in polycondensation processes with diols for producing curable aliphatic polyesters, and any derivatives of polycarboxylic acids, such as their associated acid halides, esters, semi-esters, salts, semi-salts, anhydrides, and mixtures thereof.

[0035]

[0036] Therefore, when the inventors of this patent state that a residue exists, they mean that the residue exists as a reaction product of the monomer used. The inventors assume that the amount reacted is the amount present in the reacted materials.

[0036]

[0037] The term “aliphatic” has its general meaning as is expected to be understood by those skilled in the art, i.e., it is intended to be acyclic or cyclic saturated or unsaturated carbon compounds, excluding benzenoids or other aromatic systems. As used herein, the terms “alicyclic” or “cyclic aliphatic” are intended to mean cyclic aliphatic compounds. As used herein, the term “aliphatic polyester” is understood to mean a polyester containing, for example, 90 mol% or more of aliphatic dibasic acid or diol residues relative to the total moles of dibasic acid or diol residues. Small amounts of aromatic dicarboxylic acid or aromatic diol residues, e.g., 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%, may also be present in the curable aliphatic polyester. Preferably, the curable aliphatic oligomer polyester resin is essentially free of aromatic dibasic acid and / or aromatic diol residues, i.e., has less than 1 mol% of aromatic dibasic acid and / or aromatic diol residues.

[0037]

[0038] Tree sap is an aggressive substance known to damage car paint over time. The inventors of this patent have found that resistance of a coating to tree sap is typically achieved by increasing the crosslinking density and glass transition temperature of the coating, both of which negatively affect the stretchability, of course, a very desirable feature of the protective film of this invention. Therefore, it is very desirable for a paint protective film to achieve good resistance to tree sap while maintaining the required stretchability.

[0038]

[0039] Accordingly, in various embodiments, the present invention provides a thermosetting coating applied to a thermoplastic elastomer substrate of the present invention, which is made from an oligomeric polyester resin to obtain the stretchable multilayer film of the present invention. In one embodiment, the film of the present invention exhibits sap resistance above 45°C, above 50°C, above 60°C, or above 70°C when measured by the method described herein.

[0039]

[0040] In another embodiment, the stretchable multilayer film of the present invention exhibits a break elongation of more than 50%, more than 60%, or more than 65% when measured by the method described herein.

[0040]

[0041] In a further embodiment, the stretchable multilayer film of the present invention exhibits a tensile strength of less than 2% at a strain of 5%, when measured by the method described herein, in each case, when the coating has a thickness of about 0.1 to 25 microns, or 0.1 to 20 microns, or 0.1 to 15 microns, or 0.1 to 10 microns, or 0.5 to 25 microns, or 0.5 to 20 microns, or 0.5 to 15 microns, or 0.5 to 10 microns, or 1 to 25 microns, or 1 to 20 microns, or 1 to 15 microns, or 1 to 10 microns, or 1 to 5 microns, or 2 to 25 microns, or 2 to 20 microns, or 2 to 15 microns, or 2 to 10 microns, or 3 to 8 microns.

[0041]

[0042] The oligomeric polyester resin of the present invention has a hydroxyl value of approximately 100 to approximately 370, or 125 to 300, or 150 to 300, or 170 to 330, or 180 to 280, or 190 to 240 mgKOH / g, and an acid value of 0 to 15 mgKOH / g or 1 to 10 mgKOH / g.

[0042]

[0043] The number-average molecular weight (Mn) of the oligomeric polyester resin of the present invention may be about 500 to about 10,000, or 800 to 6,000, or 1,000 to 4,000 g / mol. The weight-average molecular weight (Mw) of the curable oligomeric polyester resin of the present invention may be about 1,000 to about 40,000, 1,000 to 25,000, or 2,000 to 20,000 g / mol. The molecular weight is measured by gel permeation chromatography (GPC) using polystyrene equivalent molecular weight and tetrahydrofuran (THF) as the solvent. In other embodiments, the Mw molecular weight 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 about 22,000, or up to about 24,000, or up to about 25,000, or up to about 40,000.

[0043]

[0044] The glass transition temperature (Tg) of the oligomer polyester resin of the present invention may be -40°C to 55°C, -30°C to 25°C, or -10°C to 10°C.

[0045] The isocyanate crosslinking agent for thermosetting coatings is preferably an aliphatic isocyanate or an aliphatic polymer isocyanate. Suitable isocyanates include, but are not limited to, methylenebis-4,4'-isocyanatocyclohexane, isophorone diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, pentane-1,5-diisocyanate, and 1,4-bis(isocyanatomethyl)cyclohexane. The isocyanate crosslinking agent for thermosetting coatings also includes polymer isocyanates of the monomer isocyanates listed above. This includes, but is not limited to, isocyanurates, allophanates, and biuretes. Diols and polyols, such as isocyanate-terminated adducts of ethylene glycol, 1,4-butylene glycol, and trimethylolpropane, may also be used. These are formed by reacting more than 1 mole of diisocyanate, for example the diisocyanate mentioned above, with 1 mole of diol or polyol to form a higher molecular weight isocyanate prepolymer having 2-3 functionalities. Examples include the isocyanate crosslinkers Desmodur and Mondur, trade names of Covestro LLC. When isocyanates are used as crosslinkers, aliphatic isocyanates are preferred because they provide better outdoor durability and color stability to the cured coating. Examples include 1,6-hexamethylene diisocyanate, 1,4-butylene diisocyanate, methylenebis(4-cyclohexyl isocyanate), and isophorone diisocyanate. Mixtures of isocyanate crosslinkers may also be used. Desirable isocyanate crosslinkers also include modified isocyanates, such as carbodiimide-modified isocyanates, silane-modified isocyanates, and blocked isocyanates.

[0044]

[0046] The general structure of the desirable isocyanate constituent unit is shown below.

[0045] [ka]

[0046]

[0047] As used herein, allophanate is a reaction product of an isocyanate and urethane as disclosed herein. Biuret is a reaction product of two or more isocyanates as disclosed herein.

[0047]

[0048] Trace amounts of aromatic isocyanates may include toluene diisocyanate, methylenediphenyl isocyanate, and polymer allophanates, isocyanurates, and biuret of these materials.

[0048]

[0049] The thermosetting coating composition of the present invention may further contain one or more other crosslinking agents known to those skilled in the art, which can react with the hydroxyl groups or remaining acid groups of the polyester of the present invention. One example is melamine or an "amino" type crosslinking agent that can react with the hydroxyl groups. Another example is an epoxide that can react with the remaining acid groups.

[0049]

[0050] Stoichiometric calculations of the reaction between polyester resin and isocyanate are 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 are incorporated herein by reference. Theoretically, crosslinking between polyester resin and isocyanate reaches its maximum molecular weight and optimal molecular weight properties when 1 equivalent of isocyanate (NCO) reacts with 1 equivalent of hydroxyl (OH) (when the NCO to OH ratio is 1.0 / 1.0). It is common practice to use a small excess of approximately 5-10% isocyanate to account for the potential consumption of isocyanate by moisture from the air, solvent, and pigment. It may be desirable to change the NCO to OH ratio to less than 1.0 / 1.0 to improve flexibility, or to change it to greater than 1.0 / 1.0 for a harder, more chemically resistant, and more weather-resistant coating.

[0050]

[0051] 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.

[0051]

[0052] In another embodiment, the present invention further provides a thermosetting coating composition which may further comprise one or more crosslinking catalysts. Useful catalysts include tertiary amines, such as triethylenediamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, 1-methyl-4-dimethylaminoethylpiperazine, 3-methoxy-N-dimethylpropylamine, N-dimethyl-N'-methylisopropylpropylenediamine, N,N-diethyl-3-diethylaminopropylamine, N,N-dimethylbenzylamine, dicyclohexylmethylamine, 2,4,6-trisdimethylaminomethylphenol, N,N-dimethylcyclohexylamine, triethylamine, tri-n-butylamine, 1,8-diaza-bichloro[5,40]-undecene-7-N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, and 1,4-diaza-bicyclo-[2,2,2]-octane N-methyl-N-dimethylaminoethyl-piperazine, bis-(N,N-diethylaminoethyl) adipate, N,N-diethylbenzylamine, pentamethyldiethylenetriamine, 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 dichloride, dibutyltin diacetic acid, dibutyltin oxide, tributyltin acetate, tetramethyltin, dimethyldioctyltin, tin ethylhexanoate, tin laurate, dibutyltin maleate, dioctyltin diacetic acid; other metal-organic compounds, such as zinc octanoate, phenylmercury propionate, lead octanoate, lead naphthenate, and copper naphthenate. Dibutyltin dilaurate (DBTDL) is particularly useful in this invention. The useful amount of catalyst is approximately 0.01 to 5% of the total weight of the resin solid.

[0052]

[0053] Thermosetting coating compositions may also contain one or more leveling, rheological, and flow-controlling agents, such as silicones, fluorocarbons, or cellulose-based materials; wetting agents; matting agents; pigment wetting and dispersing agents; surfactants; ultraviolet (UV) absorbers; UV light stabilizers; coloring pigments; defoaming and antifoaming agents; anti-settling, anti-sagging, and thickening agents; anti-skinning agents; anti-separation and anti-fading agents; bactericides and antifungal agents; corrosion inhibitors; thickeners; flowing agents; rheological control agents; slip agents; oleophobic agents; superhydrophobic agents; or fusion aids. 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.

[0053]

[0054] In some useful embodiments, the thermosetting coating compositions described herein may contain a matting agent. The matting agent is generally a small solid particle of a water-insoluble material that is effective in reducing gloss. Preferably, the matting agent particles are about 0.05 to about 10 microns in size, but may exist in clumps or aggregates up to about 50 microns. The matting agent particles may be inorganic or organic. Suitable inorganic matting agents include silicates, e.g., talc, and various forms of silica, e.g., amorphous, aerogel, diatom, hydrogel, and fumed silica. Suitable organic matting agents include insoluble urea-formaldehyde resins, polyethylene, polypropylene, cellulose fibers, and polyurethane / polyurea copolymers.

[0054]

[0055] Some examples of UV absorbers and UV light stabilizers are substituted benzophenones, substituted benzotriazoles, hindered amines, and hindered benzoates; diethyl-3-acetyl-4-hydroxybenzyl-phosphonate; 4-dodecyloxy-2-hydroxybenzophenone, and resorcinol monobenzoate, available from Cytec Specialty Chemicals as CYASORB® UV and from Ciba Specialty Chemicals as TINUVIN®.

[0055]

[0056] If desired, the thermosetting coating composition may include other functional materials, such as dyes, colorants, pigments, abrasion-resistant particles (such as NANOBYK® additives from BYK Chemie), antioxidants, thixotropes, and fillers. Examples of pigments include those commonly recognized by those skilled in the art of surface coatings. For example, the pigments may be typical organic or inorganic pigments, particularly those listed in the Colour Index, 3rd edition, 2nd revision, 1982, published by the Society of Dyers and Colourists in association with the American Association of Textile Chemists and Colorists. Other 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, such as phthalocyanine blue, molybdenum orange, or carbon black, may also be added to the thermosetting coating composition.

[0056]

[0057] The thermosetting coating composition of the present invention may further contain a hydrophobicity enhancer, such as a hydroxyl, amino, or epoxy functional monofunctional silicone component. If a monofunctional material is used, it may act as a chain arrester during polymerization or crosslinking.

[0057]

[0058] Therefore, the additives are monoglycidyl ether-terminated poly(dimethylsiloxane), diglycidyl ether-terminated poly(dimethylsiloxane), bis(3-aminopropyl)-terminated poly(dimethylsiloxane) (DMS-A11 available from Gelest), (aminopropylmethylsiloxane (sioxane))-dimethylsiloxane copolymer (e.g., AMS-132, AMS-152, AMS-162, AMS-163, AMS-191, or AMS-1203 available from Gelest), (aminoethylaminopropylmethylsiloxane (sioxane))-dimethylsiloxane copolymer The material may be one or more of the following: lusiloxane copolymers (e.g., AMS-2202, AMS-233, or AMS-242 available from Gelest), monohydroxyl-terminated polydimethylsiloxanes (e.g., MCS-C11, MCR-C12, MCR-C18, MCR-C22, or MCS-C13 available from Gelest), hydroxyl-terminated polydimethylsiloxanes (e.g., DMS-C15 or DMS-C16 available from Gelest), and silanol-terminated polydimethylsiloxanes (e.g., DMS-S12 available from Gelest).

[0058]

[0059] Any solvent that allows the formulation to be coated onto the substrate may be used, and these are well known to those skilled in the art. Suitable organic solvents include glycols, glycol ether alcohols, alcohols, ketones, and aromatics, such as xylene and toluene, acetates, petroleum spirits, naphtha, and / or mixtures thereof. "Acetate" includes glycol ether acetate. The amount of organic solvent can be up to 60% by weight of the total weight of the thermosetting coating composition.

[0059]

[0060] Examples of dispersants, though not limited to them, include sodium bis(tridecyl)sodium sulfosuccinate, sodium di(2-ethylhexyl)sodium sulfosuccinate, sodium dihexyl sulfosuccinate, sodium dicyclohexyl sulfosuccinate, sodium diamyl sulfosuccinate, sodium diisobutyl (dusobutyl)sodium sulfosuccinate, disodium isodecyl sulfosuccinate, disodium ethoxylated alcohol hemiester of sulfosuccinate, disodium alkylamide polyethoxysulfosuccinate, tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinamic acid, disodium N-octasulfosuccinamic acid, sulfated ethoxylated nonylphenol, and 2-amino-2-methyl-1-propanol.

[0060]

[0061] Examples of viscosity, suspension, and flow control agents include polyaminoamide phosphates, high molecular weight carboxylates of polyamineamides, and alkyleneamine salts of unsaturated fatty acids, all of which are available from BYK Chemie USA under the ANTI TERRA® trademark. Further examples, but not limited to, include polysiloxane copolymers, polyacrylate solutions, cellulose esters, hydroxyethylcellulose, hydroxypropylcellulose, polyamide waxes, polyolefin waxes, hydroxypropylmethylcellulose, and polyethylene oxide.

[0061]

[0062] Several marked antifoaming agents are commercially available, but are not limited to: BUBREAK™ from Buckman Laboratories Inc., BYK™ from BYK Chemie, USA, FOAMASTER™ and NOPCO™ from Henckel Corporation Coating Chemicals, DREWPLUS™ from Ashland Chemical Company's Drew Industrial Division, TRYSOL™ and TROYKYD™ from Troy Chemical Corporation, and SAG™ from Union Carbide Corporation.

[0062]

[0063] Some examples of UV absorbers and UV light stabilizers are substituted benzophenones, substituted benzotriazoles, hindered amines, and hindered benzoates; diethyl-3-acetyl-4-hydroxybenzyl phosphonates; 4-dodecyloxy-2-hydroxybenzophenones, and resorcinol monobenzoate, available from Cytec Specialty Chemicals as CYASORB® UV and from Ciba Specialty Chemicals as TINUVIN®.

[0063]

[0064] As used herein, the thermoplastic elastomer substrate may include several thermoplastic elastomers, such as polyurethane, styrene block copolymer, polyacrylate, polyolefin, vinyl chloride polymer, polyether ester, polyamide, ionomer, silicone, and fluoropolymer. The thermoplastic elastomer substrate of the present invention is partially characterized by its elasticity.

[0064]

[0065] In one embodiment, the thermoplastic elastomer substrate includes thermoplastic polyurethane, i.e., TPU. TPU is divided into three chemical classes: polyester, polyether, and polycaprolactone. Polyester TPU is generally compatible with PVC and other polar plastics, provides excellent abrasion resistance, results in a good balance of physical properties, and is useful in polymer blends. Polyether TPU provides flexibility at lower temperatures, as well as good abrasion and tear resistance. They also have good hydrolysis stability. Polycaprolactone TPU has inherent toughness and the resistance of polyester TPU, as well as good low-temperature performance and hydrolysis stability.

[0065]

[0066] TPUs can be further divided into aromatic TPUs and aliphatic TPUs, and here we will refer to the diisocyanates used. Aromatic TPUs based on isocyanates, such as toluene diisocyanate (TDI) and methylenediphenyl diisocyanate (MDI), make up the majority of TPUs and are used when strength, flexibility, and toughness are required. However, these are typically not very weather-resistant. Aliphatic TPUs based on isocyanates, such as 4,4'-methylenedicyclohexyl diisocyanate (H12 MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI), are photostability and provide excellent transparency. These are commonly used in automotive interior and exterior applications and can be used to bond safety glass. The inventors of this patent have found that aliphatic polycaprolactone-based TPU provides a good balance of weather resistance, flexibility at low temperatures, and impact resistance required for many automotive exterior applications, and is particularly useful according to the present invention.

[0066]

[0067] In certain embodiments, the thermoplastic polyurethane useful as a thermoplastic elastomer substrate according to the present invention may be an aliphatic polycaprolactone-based thermoplastic polyurethane composed of a polycaprolactone-based polymer diol reacted with an aliphatic diisocyanate. In this embodiment, the aliphatic diisocyanate may be selected from, for example, 4,4'-methylenedicyclohexyl diisocyanate (H12 MDI or HMDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). In this embodiment, the polycaprolactone-based polymer diol is composed of a caprolactone unit, a glycol, such as ethylene glycol, propylene glycol, neopentyl glycol, or butanediol, and may start with a glycol, such as ethylene glycol, diethylene glycol, hexanediol, neopentyl glycol, or butanediol. In a preferred embodiment, the thermoplastic polyurethane contains HMDI, 1,4-butanediol, and caprolactone residues. The polycaprolactone-based polymer 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 about 900 to about 3000, or about 1000 to about 2500.

[0067]

[0068] Other properties of aliphatic polycaprolactone-based thermoplastic polyurethanes include inherent toughness, resistance to polyester-based TPUs, good low-temperature performance, good weather resistance, light resistance, and hydrolysis stability.

[0068]

[0069] Examples of TPUs useful as thermoplastic elastomer substrates according to the present invention include the TPUs disclosed and claimed in U.S. Patent No. 10,265,932, which are incorporated herein by reference. They are polymers containing urethane (also known as carbamate) bonds, urea bonds, or a combination thereof (i.e., in the case of poly(urethane-urea)). Thus, polyurethanes useful according to the present invention contain at least urethane bonds and optionally urea bonds. In one embodiment, the polyurethane layer of the present invention is polyurethane-based, with a backbone of at least about 80% urethane and / or urea repeating bonds formed during polymerization.

[0069]

[0070] According to the present invention, TPUs useful as thermoplastic elastomer substrates may include polyurethane polymers, i.e., polymer blends, of the same or different chemicals. Polyurethanes generally contain reaction products of at least one isocyanate-reactive component, at least one isocyanate-functional component, and one or more optional components, such as emulsifiers and chain extenders.

[0070]

[0071] According to the present invention, useful isocyanate-reactive components in TPU include at least one active hydrogen, such as amines, thiols, and polymer diols, particularly polymer diols that, when reacted with hydroxyl-functional materials, such as isocyanate-functional components, result in urethane bonding. Specific polymer diols of interest include polyester polymer diols (e.g., lactone polymer diols) and their alkylene oxide adducts (e.g., ethylene oxide; 1,2-epoxypropane; 1,2-epoxybutane; 2,3-epoxybutane; isobutylene oxide; and epichlorohydrin), polyether polymer diols (e.g., polyoxyalkylene polymer diols, such as polypropylene oxide polymer diols, polyethylene oxide polymer diols, polypropylene oxide polyethylene oxide copolymer polymer diols, and polyoxytetramethylene polymer diols; polyoxycycloalkylene polymer diols; polythioethers; and their alkylene oxide adducts), polyalkylene polymer diols, polycarbonate polymer diols, mixtures thereof, and copolymers thereof. Further target polymer diols are derived from caprolactone and are referred to herein as polycaprolactone-based polymer diols.

[0071]

[0072] Therefore, the isocyanate-reactive component of the thermoplastic elastomer substrate of the present invention reacts with the isocyanate-functional component to form a TPU. The isocyanate-functional component may contain one isocyanate-functional material or a mixture thereof. Polyisocyanates (hereinafter collectively referred to as "polyisocyanates"), including derivatives of polyisocyanates (e.g., urea, biuret, allophanate, dimers and trimers of polyisocyanates, and mixtures thereof), are preferred isocyanate-functional materials for the isocyanate-functional component. Polyisocyanates have at least two isocyanate functional groups and, when reacted with the hydroxy-functional isocyanate-reactive component, result in urethane bonding. In one embodiment, a polyisocyanate useful for preparing polyurethane is one or a combination of aliphatic or optionally aromatic polyisocyanates used to prepare polyurethane.

[0072]

[0073] The isocyanates of TPUs are typically diisocyanates, including aromatic diisocyanates, aromatic-aliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and other compounds with two isocyanate functional groups at the end (e.g., diurethanes of toluene-2,4-diisocyanate-terminated polypropylene oxide polymer diols). Therefore, useful diisocyanates according to the present invention include 2,6-toluene diisocyanate; 2,5-toluene diisocyanate; 2,4-toluene diisocyanate; phenylenedi diisocyanate; 5-chloro-2,4-toluene diisocyanate; 1-chloromethyl-2,4-diisocyanatobenzene; xylylene diisocyanate; tetramethyl-xylylene diisocyanate; 1,4-diisocyanatobutane; 1,6-diisocyanatohexane; 1,12-diisocyanatododecane; 2-methyl-1,5-diisocyanatopentane; methylenedicyclohexylene-4,4'-diisocyanate; 3-isocyanatomethyl-3,5,5'-trimethylcyclohexyl isocyanate (isophorone diisocyanate); 2,2,4-trimethyl Examples include hexyl diisocyanate; cyclohexylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; tetramethylene-1,4-diisocyanate; cyclohexane-1,4-diisocyanate; naphthalene-1,5-diisocyanate; diphenylmethane-4,4'-diisocyanate; hexahydroxylylene diisocyanate; 1,4-benzene diisocyanate; 3,3'-dimethoxy-4,4'-diphenyl diisocyanate; phenylene diisocyanate; isophorone diisocyanate; polymethylene polyphenyl isocyanate; 4,4'-biphenylene diisocyanate; 4-isocyanatocyclohexyl-4'-isocyanatophenylmethane; and p-isocyanatomethylphenyl isocyanate.

[0073]

[0074] The components of these polyurethanes will be further described below with reference to specific hydrocarbon groups and their polymeric versions. Thus, the prefix "poly" is attached to the corresponding hydrocarbon group. The hydrocarbon group may contain one or more heteroatoms in addition to carbon, and may also contain functional groups, such as oximes, esters, carbonates, amides, imides, ethers, urethanes, ureas, carbonyls, or mixtures thereof.

[0074]

[0075] In one embodiment, a TPU useful as a thermoplastic elastomer substrate according to the present invention includes a TPU made from an aliphatic isocyanate and an oligomeric polyester resin. The term “aliphatic” means a saturated or unsaturated linear, branched, or cyclic hydrocarbon group. This term includes alkylene (e.g., oxyalkylene), aralkylene, and cycloalkylene groups. The term “alkylene group” means a saturated linear or branched divalent hydrocarbon group. A preferred alkylene group is the oxyalkylene group, which is a saturated linear or branched divalent hydrocarbon group having a terminal oxygen atom. An “aralkylene group” is a saturated linear or branched divalent hydrocarbon group having at least one aromatic group. The term “cycloalkylene group” means a saturated linear or branched divalent hydrocarbon group having at least one cyclic group. The term "oxycycloalkylene group" refers to a saturated linear or branched divalent hydrocarbon group having at least one cyclic group and a terminal oxygen atom. The term "aromatic group" refers to a monocyclic or polycyclic aromatic hydrocarbon group. This term includes arylene groups. The term "arylene group" refers to a divalent aromatic group.

[0075]

[0076] Therefore, the aliphatic isocyanate useful in the thermoplastic elastomer substrate according to the present invention contains an aliphatic group, and the aliphatic group may be an alkyl group, an alkenyl group, an alkynyl group, etc., and may be branched or linear, with linear being advantageous. The aliphatic group may contain 2 to 30 carbon atoms, or 3 to 12 carbon atoms, or 4 to 10 carbon atoms. Examples include 1,12-diisocyanatododecane; 2-methyl-1,5-diisocyanatopentane; methylenedicyclohexylene-4,4'-diisocyanate; 3-isocyanatomethyl-3,5,5'-trimethylcyclohexyl isocyanate (isophorone diisocyanate); 2,2,4-trimethylhexyl diisocyanate; cyclohexylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; tetramethylene-1,4-diisocyanate; cyclohexane-1,4-diisocyanate; and isophorone diisocyanate.

[0076]

[0077] In the preparation of the thermoplastic elastomer substrate of the present invention, one or more chain extenders may also be used. For example, such chain extenders may be any or a combination of aliphatic polymer diols, aliphatic polyamines, or aromatic polyamines used to prepare polyurethanes. Therefore, useful chain extenders according to the present invention include: 1,4-butanediol; propylene glycol; ethylene glycol; 1,6-hexanediol; glycerin; trimethylolpropane; pentaerythritol; 1,4-cyclohexanedimethanol; and phenyldiethanolamine. 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 contain aromatic rings, but are considered aliphatic polymer diols in the present invention. Aliphatic diols with 2 to 10 carbon atoms are preferred. Particularly preferred is 1,4-butanediol.

[0077]

[0078] According to the present invention, the stretchable multilayer film of the present invention exhibits an improved balance of sap resistance and stretchability. In various embodiments, the stretchable multilayer film of the present invention, when determined as described below, has sap resistance above 45°C, exhibits a break elongation of more than 50%, and, when tested within one week of the preparation of the multilayer film, exhibits a stretch load of less than 0.358 kg / cm (2 lb / in) at a strain of 5% / centimeter It has.

[0078]

[0079] The stretchable multilayer film of the present invention may further include a pressure-sensitive adhesive (PSA) provided to help set the film on the surface to which it is bonded. These pressure-sensitive adhesives may be applied, for example, by a release liner or coated onto a thermoplastic elastomer substrate. A useful pressure-sensitive adhesive according to the present invention is the pressure-sensitive adhesive disclosed in U.S. Patent No. 5,883,149, which is incorporated herein by reference in its entirety.

[0079]

[0080] An example of a pressure-sensitive adhesive useful according to the present invention is an acrylate pressure-sensitive adhesive containing an acrylic polymer, which may be characterized by its glass transition temperature (Tg). The Tg of the polymer may be about -55°C to about 15°C, or -30°C to 5°C, or -25°C to 0°C. The adhesive according to the present invention may contain about 25 to about 98 parts, or 60 to 95 parts, of an acrylic acid ester having a homopolymer Tg of less than 0°C, particularly less than -20°C; about 2 to about 75 parts, or 5 to 45 parts, of an ethylenically unsaturated monomer having a homopolymer Tg of more than 0°C or more than 10°C; or 0 to about 15 parts, or 0 to 10 parts, of a polar ethylenically unsaturated monomer having an acid or hydroxyl. Optionally, the adhesive polymer may be blended with 0 to about 50 parts, or 10 to 30 parts, of a tackifier.

[0080]

[0081] The acrylic acid esters useful according to the present invention are monofunctional acrylic acid esters of monohydric alcohols having about 4 to about 18 carbon atoms in the alcohol portion, and their homopolymers have a Tg of less than 0°C. This class of acrylic acid esters includes isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, isodecyl 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 so that crystallization of the side chain does not occur at room temperature.

[0081]

[0082] Examples of ethylenically unsaturated monomers having a Tg of 0°C or 10°C for homopolymers include, but are not limited to, 3,3,5-trimethylcyclohexyl acrylate, cyclohexyl acrylate, isobornyl acrylate, N-octylacrylamide, t-butyl 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.

[0082]

[0083] Examples of useful acids or monomers having hydroxyl groups according to the present invention include, but are not limited to, acrylic acid, methacrylic acid, methyl acrylate, beta-carboxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate.

[0083]

[0084] These adhesive polymers may optionally contain crosslinking agents, which may include, but are not limited to, metal chelates such as aluminum acetylacetonate and various titanates. Other crosslinking agents may include, but are not limited to, polyfunctional epoxies, silanes, aziridines, isocyanates, and / or (meth)acrylates. Optionally, the PSA may also contain other additives, such as tackifiers, plasticizers, UV absorbers / stabilizers, and antioxidants.

[0084]

[0085] Although the compositions of the present invention have been described in detail above with respect to two exemplary embodiments having practical applications in two end uses, it will be understood by those skilled in the art that the compositions of the present invention can be used in a wide variety of end-use applications and may contain chelating agents in any amount desired to achieve the desired performance in those applications. For example, the compositions of the present invention may be useful in other cleaning applications, such as interior decorating cleaners, carpet cleaners, hard surface cleaners, and in applications such as water treatment, pulp and paper manufacturing, and pesticide treatment.

[0085]

[0086] The following examples describe preferred and / or preferred methods and results according to the present invention. However, these examples are provided for illustrative purposes only, and it should be understood that nothing in the examples should be taken as limiting the entire scope of the invention. Unless otherwise specified, all percentages are by weight. [Examples]

[0086] Preparation of oligomeric polyester resins

[0087] Oligomer polyester resins (Table 1) were prepared according to the following procedure. All resins were prepared in a 2-liter reaction vessel equipped with a heated mantle, mechanical stirrer, thermocouple, nitrogen blanket, oil-heated partial condenser, condensate trap, and water-cooled total condenser.

[0087] Oligomer polyester resin 1 (PE1)

[0088] Step 1 - HHPA, TMCD, triphenyl phosphite, and xylene were charged into the reaction vessel. Additional xylene was used to fill the condensate trap. The temperature was then raised from room temperature to 140°C over 50 minutes. Stirring was started when the molten material reached 100°C. The temperature was maintained at 140°C until a resin with an acid value of 242 mgKOH / g or less was achieved.

[0088]

[0089] In step 2, NPG, half the total amount of TMP, AD, and Fascat 4100 catalyst were added to the reactor and heated to 230°C for 6 hours.

[0090] Step 3 - The remaining TMP was added, and the reaction mixture was maintained at 230°C until a resin with a final acid value of 8 mg KOH / g was achieved. The resin was cooled to 190°C and poured into a metal paint can through a medium-mesh paint filter.

[0089] Oligomer polyester resin 2 (PE2)

[0091] Step 1 - HHPA, NPG, and triphenyl phosphite were charged into the reaction vessel. Additional xylene was used to fill the condensate trap. The temperature was then raised from room temperature to 140°C over 50 minutes. Stirring was started when the molten material reached 75°C. The temperature was maintained at 190°C until a resin with an acid value of 193 mgKOH / g or less was achieved. The temperature was then cooled to 165°C.

[0090]

[0092] Step 2 - Half of the total amount of TMP, AD, and catalyst were added to the reactor, then heated to 140°C and maintained overnight. The reaction mixture was then heated to 230°C over 6 hours.

[0093] Step 3 - The remaining TMP was added to the reactor, and the reaction was maintained at 230°C until a final acid value of 8 mg KOH / g resin was achieved. The resin was cooled to 190°C and poured into a metal paint can through a medium-mesh paint filter.

[0091] Oligomer polyester resin 3 (PE3)

[0094] Step 1 - HHPA, NPG, and triphenyl phosphite were charged into the reaction vessel. Additional xylene was used to fill the condensate trap. The temperature was raised from room temperature to 100°C over 1 hour. Stirring was started when the molten material reached 100°C. The temperature was maintained at 130°C until a resin with an acid value of 272 mgKOH / g or less was achieved.

[0092]

[0095] Step 2 - TMP and Fascat 4100 catalyst were added to the reactor and heated to 230°C over 4 hours. The reaction was maintained at 230°C until a resin with a final acid value of 2 mg KOH / g was achieved. The resin was then cooled to 190°C and poured into a metal paint can through a medium-mesh paint filter.

[0093] Oligomer polyester resin 4 (PE4)

[0096] Step 1 - HHPA, TMCD, triphenyl phosphite, and xylene were charged into the reaction vessel. Additional xylene was used to fill the condensate trap. The temperature was raised from room temperature to 100°C over 1 hour. Stirring was started when the molten material reached 100°C. The temperature was maintained at 140°C until a resin with an acid value of 376 mgKOH / g or less was achieved.

[0094]

[0097] Step 2-NPG, half the total amount of TMP, adipic acid, and Fascat 4100 catalyst were added to the reactor and heated to 230°C for 6 hours.

[0098] Step 3 - The remaining TMP was added. The reaction mixture was maintained at 230°C until a resin with a final acid value of 5 mg KOH / g was achieved. The resin was then cooled to 190°C and poured into a metal paint can through a medium-mesh paint filter.

[0095] Oligomer polyester resin 5 (PE5)

[0099] Step 1 - HHPA, TMCD, adipic acid, triphenyl phosphite, and Fascat 4100 catalyst were charged into the reaction vessel. The temperature was raised from room temperature to 100°C over 1 hour. Stirring was started when the molten material reached 100°C. The temperature was maintained at 200°C until a resin with an acid value of 283 mgKOH / g or less was achieved.

[0096]

[0100] Step 2 - TMP and catalyst were added, and the reaction mixture was heated to 150°C. The temperature was raised to 225°C over 4 hours and maintained at that temperature until a resin with a final acid value of 2 mg KOH / g was achieved. The resin was then cooled to 170°C and poured into a metal paint can through a medium-mesh paint filter.

[0097] Oligomer polyester resin 6 (PE6)

[0101] Step 1 - HHPA, TMCD, TMP, adipic acid, triphenyl phosphite, and xylene were charged into the reaction vessel. Additional xylene was used to fill the condensate trap. The temperature was raised from room temperature to 100°C over 1 hour. Stirring was started when the molten material reached 100°C. The temperature was maintained at 195°C until a resin with an acid value of 245 mgKOH / g or less was achieved.

[0098]

[0102] Step 2 - NPG, TMP, and Fascat 4100 catalyst were added, and the reaction mixture was heated to 150°C. The temperature was increased to 230°C over 4 hours and maintained at that temperature until a resin with a final acid value of 8 mg KOH / g was achieved. The resin was then cooled to 190°C and poured into a metal paint can through a medium-mesh paint filter.

[0099] Oligomer polyester resin 7 (PE7)

[0103] Step 1 - NPG, TMCD, half the total amount of TMP, AD, Fascat 4100 catalyst, triphenyl phosphite, and xylene were charged into the reaction vessel. Additional xylene was used to fill the condensate trap. The temperature was raised from room temperature to 100°C over 1 hour. Stirring was started when the molten material reached 100°C. The temperature was maintained at 220°C for 2 hours until half of the water for esterification was obtained.

[0100]

[0104] Step 2 - The remaining TMP was added, and the temperature was maintained at 220°C until a resin with a final acid value of 4 mg KOH / g was achieved. The resin was then cooled to 190°C and poured into a metal paint can through a medium-mesh paint filter.

[0101] Oligomer polyester resin 8 (PE8)

[0105] Step 1 - HHPA, TMCD, triphenyl phosphite, and xylene were charged into the reaction vessel. Additional xylene was used to fill the condensate trap. The temperature was then raised from room temperature to 150°C over 2 hours. Stirring was started when the molten material reached 100°C. The temperature was maintained at 150°C until a resin with an acid value of 248 mgKOH / g or less was achieved.

[0102]

[0106] Step 2 - TMP and Fascat 4100 catalyst were added to the reactor and heated to 230°C for 2.5 hours. The reaction mixture was maintained at 230°C until a resin with a final acid value of 4 mg KOH / g was achieved. The resin was cooled to 110°C and adjusted to a 75 wt% solid state using n-butyl acetate. It was then poured into a metal paint can through a medium-mesh paint filter.

[0103] Properties of oligomer polyester resins

[0107] Table 1 shows the acid value (abbreviated as "AN"), hydroxyl value (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 polyesters.

[0104]

[0108] The acid value was determined using the ASTM method D1639.

[0109] The hydroxyl value was determined by esterifying the resin by reacting it with excess acetic anhydride in pyridine, followed by decomposition of the unreacted anhydride with water. The resulting acetic acid was then titrated with KOH standard solution. The number of milligrams of KOH equivalent to 1 gram of the resin sample is reported as the hydroxyl value.

[0105]

[0110] The molecular weight was determined by gel permeation chromatography using a polystyrene standard and a refractive index detector.

[0111] Residual solvents remaining in the resin from solvent treatment can artificially lower the Tg measurement. To obtain a more accurate Tg, the resin sample was first pre-conditioned in a drying oven. Approximately 0.3 g of resin was placed in a small aluminum weighing dish 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 rapidly cooled to -50°C. In 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 is reported as the Tg of the sample.

[0106] [Table 1]

[0107] Preparation and evaluation of thermosetting properties Preparation of 2K transparent coating

[0112] Part A of both the example and comparative example 2K transparent coatings were prepared by mixing the components listed in Table 2. The oligomer polyester resin samples prepared in Table 1 were pre-dissolved in n-butyl acetate to form a 75% solid solution. Part A and Part B were mixed together immediately before coating the film. The solvent amounts of 4 parts by weight of n-butyl acetate and 1 part by weight of PM acetate were adjusted to achieve the desired solid content of 40% by weight of the formulation.

[0108] [Table 2-1]

[0109] [Table 2-2]

[0110] Preparation of composite films

[0113] Multilayer films were prepared by applying a transparent coating to one main surface of a 0.15 mm (6 mil) thick elastomer polyurethane film. The coating was applied using a gravure roll with a TecMaster® lab coater. The solid percentage of the transparent coating solution and the process conditions in the TecMaster® were adjusted to achieve a final coating thickness of 5–15 microns. All coatings were post-cured in a convection oven at 60°C for 15 hours to ensure complete curing before evaluation.

[0111] Test panel preparation

[0114] The multilayer film was placed on a substrate that mimicked the surface of an automotive topcoat. The test panel was prepared as follows: A 0.813 mm (0.032 inch) thick polished cold-rolled steel test panel with an electrodeposited coating overlaid with a gray primer was purchased from ACT Test Panel LLC. The panel was further coated with a commercially available water-based black basecoat, hard-baked, and then spray-applied with an automotive-grade 2K clear coat to obtain a clear coat with a dry film thickness of 40 microns. The coated panel was flushed at room temperature for 10 minutes and then cured at 140°C for 30 minutes.

[0112]

[0115] The multilayer film was applied to the test panel by hand with moderate pressure. A 2 percent soap solution was used as the application fluid. The film, placed on the substrate, was dried under ambient conditions for at least 24 hours before testing.

[0113] Test method

[0116] The tensile strength at 5% strain was measured by first cutting the multilayer film into strips 2.54 cm (1 inch) wide. The strips were placed at 5.08 cm (2 inch) intervals on the grips of a Mark-10 Tensile Tester equipped with a Series 5 Force gauge (maximum load 22.7 kg (50 lb)). The film was pulled at a speed of 25.4 cm (10 inches) per minute until 50% elongation was achieved. 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 preparation of the multilayer film.

[0114]

[0117] Sap resistance was measured using an Erichsen Model 432 gradient oven. The temperature range was set to 30°C to 75°C. The test was conducted according to DIN EN ISO 2812-5:2007-05. Sap resistance is reported as the temperature at which the coating sustained irreparable damage from sap.

[0115] 2K Transparent Coating Evaluation Results

[0118] Table 3 reports the monomer compositions of oligomeric polyester resins and their performance in 2K transparent coatings.

[0116] [Table 3] The present invention includes the following embodiments. [1] Thermoplastic polyurethane substrate, and Thermosetting coating applied to a thermoplastic polyurethane substrate. A stretchable multilayer film comprising a thermosetting coating, i) a. In each case, the diol or polyol is reacted with a mixture containing approximately 30 to 99 mol% trimethylolpropane and approximately 1 mol to 70 mol% neopentyl glycol relative to the total molar amount of the reacted diol and polyol. b. The dicarboxylic acid or polycarboxylic acid contains approximately 1 mol% to approximately 70 mol% of one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms, relative to the total molar amount of the reacted dicarboxylic acid and polycarboxylic acid. Oligomer polyester resin containing the reaction product and (ii) Aliphatic isocyanates, isocyanurates, allophanates, or biuret The reaction product includes, The oligomer polyester resin has a glass transition temperature (Tg) of -40 to 55°C, an acid value of 0 to 15 mg KOH / g, a hydroxyl value 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 40,000. The stretchable multilayer film exhibited a break elongation of more than 50% and, when measured within one week of the preparation of the multilayer film, under a stretch load of less than 0.358 kg / cm (2 lb / in) at a strain of 5%. centimeter It has sap resistance exceeding 45°C, Stretchable multilayer film. [2] The stretchable multilayer film according to [1], wherein the oligomer polyester resin has an acid value of 0 to 10 mg KOH / g, a hydroxyl value of 125 to 300 mg KOH / g, a number average molecular weight of 1,000 to 4,000 mg KOH / g, and a weight average molecular weight of 1,000 to 25,000. [3] The stretchable multilayer film according to [1] or [2], wherein the amount of trimethylolpropane is about 40 to about 70 mol%, the amount of neopentyl glycol is about 30 mol% to about 60 mol%, and the amount of one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms is about 20 mol% to about 70 mol%. [4] An extensible multilayer film according to any one of [1] to [3], comprising adipic acid as one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms. [5] A stretchable multilayer film according to any one of [1] to [4], further comprising a diol or polyol TMCD. [6] A stretchable multilayer film according to any one of [1] to [5], further comprising one or more of HHPA or CHDA, in which a dicarboxylic acid or polydicarboxylic acid is present in an amount of 50 mol% to 100 mol%. [7] When measured within one week of preparation of the multilayer film, the tensile load is greater than 0.179 kg / cm (1 lb / in) at 5% strain and less than 0.358 kg / cm (2 lb / in) at 5% strain. centimeter An extensible multilayer film according to any one of [1] to [6], which exhibits sap resistance at 45°C to 70°C. [8] A stretchable multilayer film according to any one of [1] to [7], wherein the thickness of the thermosetting coating is 0.1 to 25 microns. [9] A stretchable multilayer film according to any one of [1] to [8], wherein the coating thickness is 1 to 10 microns.

[10] An aliphatic diisocyanate is present, and one or more of the following are selected: methylenebis-4,4'-isocyanatocyclohexane, 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(isocyanatomethyl)cyclohexane, or polyisocyanate. The stretchable multilayer film according to any one of [1] to [9].

[11] Aliphatic diisocyanates exist, with the following structure: [ka] A stretchable multilayer film according to any one of [1] to

[10] , corresponding to one of the above.

[12] A stretchable multilayer film according to any one of [1] to

[11] , further comprising less than 30 mol% of TMCD, wherein a diol or polyol of an oligomer polyester resin.

[13] An stretchable multilayer film according to any one of [1] to

[12] , wherein the dicarboxylic acid or polycarboxylic acid of the oligomer polyester resin contains 5 mol% or less of an aromatic dicarboxylic acid.

[14] An stretchable multilayer film according to any one of [1] to

[13] , wherein the molar ratio of the oligomer polyester resin to the aliphatic isocyanate or isocyanurate is 0.95 to 1.05.

[15] Thermoplastic polyurethane substrates, and Thermosetting coating applied to a thermoplastic polyurethane substrate. A stretchable multilayer film comprising a thermosetting coating, i) For the total moles of aa~c, add 30~70 mol% of trimethylolpropane (TMP). For the total moles of ba~c, add 1 to 70 mol% of neopentyl glycol (NPG). For the total moles of ca~c, 0 to 69 mol% of diols other than NPG, With respect to the total moles of dd~e, 30~100 mol% of one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms, and One or more additional dicarboxylic acids in an amount of 0 to 70 mol% relative to the total moles of ed to e. The reaction product of monomers containing, oligomeric polyester, (ii) Aliphatic isocyanates, isocyanurates, allophanates, or biuret The reaction product includes, The oligomer polyester resin has a glass transition temperature (Tg) of -40 to 55°C, an acid value of 0 to 15 mg KOH / g, a hydroxyl value 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. The stretchable multilayer film exhibited a break elongation of more than 50% and, when measured within one week of the preparation of the multilayer film, under a stretch load of less than 0.358 kg / cm (2 lb / in) at a strain of 5%. centimeter It has sap resistance exceeding 45°C, Stretchable multilayer film.

[16] A stretchable multilayer film according to any one of [1] to

[15] , wherein the amount of trimethylolpropane is about 40 to about 70 mol%, the amount of neopentyl glycol is about 30 mol% to about 60 mol%, and the amount of one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms is about 20 mol% to about 70 mol%.

[17] An extensible multilayer film according to any one of [1] to

[16] , comprising adipic acid as one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms.

[18] A stretchable multilayer film according to any one of [1] to

[17] , further comprising a diol or polyol TMCD.

[19] A stretchable multilayer film according to any one of [1] to

[18] , further comprising one or more of HHPA or CHDA, in which a dicarboxylic acid or polydicarboxylic acid is present in an amount of 50 mol% to 100 mol%.

[20] When measured within one week of preparation of the multilayer film, the tensile load is greater than 0.179 kg / cm (1 lb / in) at 5% strain and less than 0.358 kg / cm (2 lb / in) at 5% strain. centimeter An extensible multilayer film according to any one of [1] to

[19] , which exhibits sap resistance at 45°C to 70°C.

[21] A stretchable multilayer film according to any one of [1] to

[20] , wherein the thickness of the thermosetting coating is 0.1 to 25 microns.

[22] A stretchable multilayer film according to any one of [1] to

[21] , wherein the coating thickness is 1 to 10 microns.

[23] An aliphatic diisocyanate is present, and one or more of the following are selected: methylenebis-4,4'-isocyanatocyclohexane, 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(isocyanatomethyl)cyclohexane, or polyisocyanate. The stretchable multilayer film according to any one of [1] to

[22] .

[24] Aliphatic diisocyanates exist, with the following structure: [ka] An extensible multilayer film according to any one of [1] to

[23] , corresponding to one of the above.

[25] An stretchable multilayer film according to any one of [1] to

[24] , wherein the oligomeric polyester resin further comprises less than 30 mol% of TMCD as a polyol.

[26] An stretchable multilayer film according to any one of [1] to

[25] , wherein the oligomeric polyester resin further comprises 5 mol% or less of an aromatic dicarboxylic acid as a polycarboxylic acid.

[27] An stretchable multilayer film according to any one of [1] to

[26] , wherein the molar ratio of the oligomer polyester resin to the aliphatic isocyanate or isocyanurate is 0.95 to 1.05.

Claims

1. Thermoplastic polyurethane substrate, and Thermosetting coating applied to a thermoplastic polyurethane substrate. A stretchable multilayer film comprising a thermosetting coating, i) a. In each case, the diol or polyol is reacted with a solution containing 30 to 99 mol% trimethylolpropane and 1 mol to 70 mol% neopentyl glycol relative to the total molar amount of the reacted diol and polyol. b. A dicarboxylic acid or polycarboxylic acid containing 1 mol% to 70 mol% of one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms, relative to the total molar amount of the reacted dicarboxylic acid and polycarboxylic acid. Oligomer polyester resin containing the reaction product and (ii) Aliphatic isocyanates, isocyanurates, allophanates, or biuret The reaction product includes, The oligomer polyester resin has a glass transition temperature (Tg) of -40 to 55°C, an acid value of 0 to 15 mg KOH / g, a hydroxyl value of 100 to 370 mg KOH / g, a number-average molecular weight of 500 to 10,000 g / mol, and a weight-average molecular weight of 1,000 to 40,000 g / mol. The stretchable multilayer film exhibits a break elongation of more than 50%, has an elongation load / centimeter of less than 0.358 kg / cm (2 lb / in) at 5% strain when measured within one week of the preparation of the multilayer film, and has sap resistance above 45°C. Stretchable multilayer film.

2. The stretchable multilayer film according to claim 1, wherein the oligomeric polyester resin has an acid value of 0 to 10 mg KOH / g, a hydroxyl value of 125 to 300 mg KOH / g, a number-average molecular weight of 1,000 to 4,000 g / mol, and a weight-average molecular weight of 1,000 to 25,000 g / mol.

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

4. The stretchable multilayer film according to any one of claims 1 to 3, wherein one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms contain adipic acid.

5. The stretchable multilayer film according to any one of claims 1 to 4, further comprising a diol or polyol TMCD.

6. The stretchable multilayer film according to any one of claims 1 to 5, further comprising one or more HHPA or CHDA, in which a dicarboxylic acid or polydicarboxylic acid is present in an amount of 50 mol% to 100 mol%.

7. An extensible multilayer film according to any one of claims 1 to 6, which exhibits an elongation load / centimeter greater than 0.179 kg / cm (1 lb / in) and less than 0.358 kg / cm (2 lb / in) at 5% strain when measured within one week of the preparation of the multilayer film, and has sap resistance from 45°C to 70°C.

8. A stretchable multilayer film according to any one of claims 1 to 7, wherein the thickness of the coating is 1 to 10 microns.

9. An stretchable multilayer film according to any one of claims 1 to 8, comprising an aliphatic diisocyanate, selected from one or more of the following: methylenebis-4,4'-isocyanatocyclohexane, 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(isocyanatomethyl)cyclohexane, or polyisocyanate.

10. Aliphatic diisocyanates exist, with the following structure: 【Chemistry 1】 An extensible multilayer film according to any one of claims 1 to 9, which corresponds to one of the above.

11. The stretchable multilayer film according to any one of claims 1 to 10, further comprising less than 30 mol% of TMCD, which is a diol or polyol of an oligomer polyester resin.

12. Thermoplastic polyurethane substrate, and Thermosetting coating applied to a thermoplastic polyurethane substrate. A stretchable multilayer film comprising a thermosetting coating, i) a. Trimethylolpropane (TMP) in an amount of 30 to 70 mol% relative to the total moles of a to c. b. Neopentyl glycol (NPG) in an amount of 1 to 70 mol% relative to the total moles of a to c. c. Diols other than NPG in amounts of 0 to 69 mol% relative to the total moles of a to c, d. One or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms in an amount of 30 to 100 mol% relative to the total moles of d to e, and e. One or more additional dicarboxylic acids in an amount of 0 to 70 mol% relative to the total moles of d to e. The reaction product of monomers containing, oligomeric polyester, (ii) Aliphatic isocyanates, isocyanurates, allophanates, or biuret The reaction product includes, The oligomeric polyester resin has a glass transition temperature (Tg) of -40 to 55°C, an acid value of 0 to 15 mg KOH / g, a hydroxyl value of 100 to 370 mg KOH / g, a number-average molecular weight of 500 to 10,000 g / mol, and a weight-average molecular weight of 1,000 to 25,000 g / mol. The stretchable multilayer film exhibits a break elongation of more than 50%, has an elongation load / centimeter of less than 0.358 kg / cm (2 lb / in) at 5% strain when measured within one week of the preparation of the multilayer film, and has sap resistance above 45°C. Stretchable multilayer film.

13. The stretchable multilayer film according to any one of claims 1 to 12, wherein the amount of trimethylolpropane is 40 to 70 mol%, the amount of neopentyl glycol is 30 to 60 mol%, and the amount of one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms is 20 to 70 mol%.

14. The stretchable multilayer film according to any one of claims 1 to 13, wherein one or more cyclic or acyclic fatty acids having 2 to 12 carbon atoms contain adipic acid.

15. The stretchable multilayer film according to any one of claims 1 to 14, further comprising a diol or polyol TMCD.

16. An extensible multilayer film according to any one of claims 1 to 15, which exhibits an elongation load / centimeter greater than 0.179 kg / cm (1 lb / in) and less than 0.358 kg / cm (2 lb / in) at 5% strain when measured within one week of the preparation of the multilayer film, and has sap resistance from 45°C to 70°C.

17. A stretchable multilayer film according to any one of claims 1 to 16, wherein the thickness of the thermosetting coating is 0.1 to 25 microns.

18. A stretchable multilayer film according to any one of claims 1 to 17, wherein the thickness of the coating is 1 to 10 microns.

19. Aliphatic diisocyanates exist, with the following structure: 【Chemistry 2】 An extensible multilayer film according to any one of claims 1 to 18, which corresponds to one of the above.

20. The stretchable multilayer film according to any one of claims 1 to 19, wherein the oligomer polyester resin further comprises TMCD in an amount of less than 30 mol% as a polyol.

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