阅读说明：本技术 挤出的聚氨酯表面膜 (Extruded polyurethane surface film ) 是由 何嘉台 卢永上 约翰·J·亚罗什 杰伊·M·延嫩 瑞安·M·布朗 肖恩·P·艾迪生 特雷 于 2019-08-06 设计创作，主要内容包括：所公开的各种实施方案涉及一种贴面膜。贴面膜包括基底层。基底层包括热塑性聚氨酯膜,该热塑性聚氨酯膜包含二异氰酸酯；具有至少约30℃的熔融温度的聚酯多元醇；以及二醇增链剂的反应混合物的反应产物。使用贴面膜有许多原因,包括通过在挤出机中混合反应混合物而直接挤出基底层来更容易且更高性价比地制造贴面膜。使用贴面膜的另一个原因是膜具有改善的变色抗性。使用膜的另一个原因是膜示出良好的韧性。(Various embodiments disclosed relate to a surfacing film. The overlay film includes a base layer. The substrate layer comprises a thermoplastic polyurethane film comprising a diisocyanate; a polyester polyol having a melting temperature of at least about 30 ℃; and a reaction product of a reaction mixture of a diol chain extender. The use of a mask has many reasons, including the fact that it is easier and more cost effective to manufacture the mask by mixing the reaction mixture in an extruder to directly extrude the base layer. Another reason for using a patch film is that the film has improved resistance to discoloration. Another reason for using a film is that the film shows good toughness.)

1. A facial mask, comprising:

a base layer, the base layer comprising:

a thermoplastic polyurethane film comprising the reaction product of a reaction mixture comprising:

a diisocyanate; and

a polyester polyol having a melting temperature of at least about 30 ℃; and

a diol chain extender.

2. The overlay film of claim 1 wherein the weight average molecular weight of the thermoplastic polyurethane film is in the range of about 80,000 daltons to about 400,000 daltons.

3. The patch film according to any one of claims 1 or 2, wherein the diisocyanate is selected from dicyclohexylmethane-4, 4 '-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate, m-xylene diisocyanate, tolylene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, poly (hexamethylene diisocyanate), 1, 4-cyclohexylene diisocyanate, 4-chloro-6-methyl-1, 3-phenylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane 4,4' -diisocyanate, toluene diisocyanate, and mixtures thereof, 1, 4-diisocyanatobutane, 1, 8-diisocyanatooctane or mixtures thereof.

4. A facial mask according to any one of claims 1-3 wherein the polyester polyol is the product of a condensation reaction.

5. The mask pack according to any one of claims 1 to 4, wherein the polyester polyol is a polyester diol.

6. The facial mask of any of claims 1-5 wherein the polyester polyol comprises one or more of the following: polyglycolic acid, polybutylene succinate, poly (3-hydroxybutyrate-co-3-hydroxyvalerate), polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, poly (1, 4-butylene adipate), poly (1, 6-hexanediol adipate), poly (ethylene adipate), mixtures thereof, and copolymers thereof.

7. The patch film of claim 4, wherein the condensation reaction comprises a reaction between at least one of:

a plurality of carboxylic acids; and

carboxylic acids and polyols.

8. The patch film according to claim 7, wherein the carboxylic acid is selected from glycolic acid, lactic acid, succinic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, terephthalic acid, naphthalenedicarboxylic acid, 4-hydroxybenzoic acid, 6-hydroxynaphthalene-2-carboxylic acid, oxalic acid, malonic acid, adipic acid, pimelic acid, ethonic acid, suberic acid, azelaic acid, sebacic acid, glutaric acid, dodecanedioic acid, brassylic acid, taparic acid, maleic acid, fumaric acid, glutaconic acid, 2-decenoic acid, callus acid, muconic acid, glutinic acid, citraconic acid, mesaconic acid, itaconic acid, malic acid, aspartic acid, glutamic acid, tartaric acid, diaminopimelic acid, saccharic acid, methoxyoxalic acid, oxaloacetic acid, acetonedicarboxylic acid, arabidopic acid, phthalic acid, isophthalic acid, bibenzoic acid, 2, 6-naphthalenedicarboxylic acid or mixtures thereof.

9. The patch film according to any one of claims 1-8, wherein the glycol chain extender is selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol or mixtures thereof.

10. The patch film of any one of claims 1-9, wherein the diol chain extender has a weight average molecular weight of less than about 250 daltons.

11. The overlay film of any of claims 1-10 wherein the thermoplastic polyurethane film comprises hard segments in a range of about 30 wt.% to about 55 wt.%.

12. The overlay film of any of claims 1-11, wherein the base layer has a shore a hardness in the range of about 70A to about 95A.

13. A method of making a facial mask, the method comprising the steps of:

forming a base layer by a process comprising:

introducing components comprising a diisocyanate, a diol chain extender, and a polyester polyol into an extruder to provide a molten thermoplastic polyurethane, wherein the polyester polyol has a melting temperature of at least 30 ℃;

extruding the molten thermoplastic polyurethane through a die as a uniform film onto a carrier web; and

curing the thermoplastic polyurethane film to obtain the substrate layer.

14. The method of claim 13, further comprising laminating a pressure sensitive adhesive layer to the first major surface of the substrate layer.

15. The method of any one of claims 13 or 14, further comprising laminating a varnish coating comprising a thermoset polyurethane onto the second major surface of the substrate layer.

16. The method of any of claims 13-15 wherein the isocyanate index of the components of the thermoplastic polyurethane is in the range of about 0.99 to about 1.20.

17. The method of any of claims 13-16, wherein the thermoplastic polyurethane film has a weight average molecular weight in a range from about 80,000 daltons to about 400,000 daltons.

18. The process of any one of claims 13-17, wherein the diisocyanate is selected from dicyclohexylmethane-4, 4' -diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate, m-xylene diisocyanate, tolylene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, poly (hexamethylene diisocyanate), 1, 4-cyclohexylene diisocyanate, 4-chloro-6-methyl-1, 3-phenylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane 4,4' -diisocyanate, toluene diisocyanate, 4' -diisocyanate, and mixtures thereof, 1, 4-diisocyanatobutane, 1, 8-diisocyanatooctane or mixtures thereof.

19. The method of any one of claims 13-18, wherein the polyester polyol is a product of a condensation reaction.

20. The method of any one of claims 13-19, wherein the polyester polyol comprises one or more of: polyglycolic acid, polybutylene succinate, poly (3-hydroxybutyrate-co-3-hydroxyvalerate), polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, poly (1, 4-butylene adipate), poly (1, 6-hexanediol adipate), poly (ethylene adipate), mixtures thereof, and copolymers thereof.

21. A facer according to any of claims 1 to 12, wherein the facer exhibits a load at 25% strain of no greater than 20N/cm film width, as determined using a tensile test with a crosshead speed of 100 mm/min.

22. The overlay film according to any of claims 1-12 and 21 wherein the overlay film exhibits an elongation at break of at least 150%, the elongation at break being determined with a tensile test using a strain rate of 200%/min.

23. The overlay film of any of claims 1-12 and 21-22 wherein the overlay film further comprises a hardcoat layer that can stretch 25-75% without breaking.

24. The overlay film of any of claims 1-12 and 21-23 wherein the hardcoat layer comprises a polymerized urethane (meth) acrylate oligomer present in an amount in the range of 40 to 100 weight percent based on weight percent solids of the hardcoat.

25. A facial mask as set forth in any one of claims 1-12 and 21-24 wherein said hardcoat layer further comprises polymerized units of an ethylenically unsaturated monomer wherein a homopolymer of said ethylenically unsaturated monomer has a glass transition temperature of greater than 25, 30, 35, 40, 45, 50, 55, 60, or 65 ℃.

26. A overlay film according to any of claims 1 to 12 and 21 to 25 wherein the overlay film further comprises a siliceous layer.

27. A facial mask according to claims 23-26 wherein the facial mask comprises

i) A hard coating layer; or

ii) a hardcoat layer and a siliceous layer; and is

The overlay film exhibits an elongation at break of at least 150%, as determined using a tensile test with a strain rate of 200%/min.

Background

The multilayer film may include one or more layers of polyurethane material. Some of these films are useful in surface protection applications. For example, the multilayer film product may be used to protect the painted surface of selected automotive body parts.

Disclosure of Invention

The present disclosure provides a facial mask. The overlay film includes a base layer. The substrate layer comprises a thermoplastic polyurethane film comprising a diisocyanate; a polyester polyol having a melting temperature of at least about 30 ℃; and a reaction product of a reaction mixture of a diol chain extender.

The present disclosure also provides a method of making a facial mask. The method includes forming a base layer. Forming the base layer includes introducing components including a diisocyanate, a diol chain extender, and a polyester polyol into an extruder to provide a molten thermoplastic polyurethane, wherein the polyester polyol has a melting temperature of at least 30 ℃. The process further comprises extruding the molten thermoplastic polyurethane through a die as a uniform film onto a carrier web. The method further includes curing the thermoplastic polyurethane film to obtain the substrate layer.

There are various reasons for using the patch films of the present disclosure, including the following non-limiting reasons. For example, the thermoplastic polyurethane may be formed directly by mixing and reacting the components of the thermoplastic polyurethane in an extruder that may extrude the thermoplastic polyurethane as a film. This can substantially eliminate the need to form thermoplastic polyurethane, pelletize thermoplastic polyurethane, and deposit pellets into the extruder. This can result in savings in cost and time to prepare the film.

Additionally, according to some examples, the provided thermoplastic polyurethane films may have higher molecular weights than those formed from pelletized polyurethane extruded films. This is because the pelletized thermoplastic polyurethane is formed by extruding polyurethane which is repeatedly cut to form smaller pellets with shortened thermoplastic polyurethane chains which in turn form a lower weight average molecular weight polyurethane film. Such pellet-forming cutting may result in thermoplastic polyurethane films having shorter chains and lower molecular weights than the thermoplastic polyurethane films of the present disclosure. According to some examples, the higher molecular weight of the thermoplastic polyurethane film may help prevent color staining in the polyurethane film by making it more difficult for the color changing agent to penetrate the polyurethane.

Further, according to some examples, the reactive mixture comprises a chain extender having a weight average molecular weight of less than 250 daltons. This may help to reinforce the thermoplastic polyurethane film. For example, the shore a hardness of a thermoplastic polyurethane film can be greater than a corresponding thermoplastic polyurethane film comprising a chain extender having a weight average molecular weight of greater than 250 daltons.

Further, according to some examples, the polyester polyol in the polyurethane-forming reactive mixture has a melting temperature of at least 30 ℃. This can impart high crystallinity to the thermoplastic polyurethane film. High crystallinity can help make the surface film easier to handle because the thermoplastic polyurethane film is more likely to be substantially tack-free at ambient conditions (e.g., 25 ℃ and 1ATM), which can make it easier to roll the surface film prior to storage or application to a substrate.

Drawings

The drawings are generally shown by way of example, and not by way of limitation, to the various embodiments discussed in this document.

Fig. 1 is a cross-sectional view of a surface film according to various embodiments.

Fig. 2 is a cross-sectional view of another surface film according to various embodiments.

Fig. 3-4 are cross-sectional views of other surface films according to various embodiments.

Detailed Description

Reference will now be made in detail to specific embodiments of the presently disclosed subject matter, examples of which are illustrated in the accompanying drawings. While the presently disclosed subject matter will be described in conjunction with the recited claims, it will be understood that the exemplary subject matter is not intended to limit the claims to the presently disclosed subject matter.

Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not only about 0.1% to about 5%, but also include individual values (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. Unless otherwise indicated, the expression "about X to Y" has the same meaning as "about X to about Y". Likewise, unless otherwise indicated, the expression "about X, Y or about Z" has the same meaning as "about X, about Y, or about Z".

In this document, the terms "a", "an" or "the" are used to include one or more than one unless the context clearly indicates otherwise. The term "or" is used to refer to a non-exclusive "or" unless otherwise indicated. The expression "at least one of a and B" has the same meaning as "A, B or a and B". Also, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid in the understanding of the document and should not be construed as limiting; information related to a section header may appear within or outside of that particular section. All publications, patents, and patent documents mentioned in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of the document; for irreconcilable inconsistencies, the usage of the document controls.

In the methods described herein, various actions may be performed in any order, except when a time or sequence of operations is explicitly recited, without departing from the principles of the invention. Further, the acts specified may occur concurrently unless the express claim language implies that they occur separately. For example, the claimed act of performing X and the claimed act of performing Y may be performed simultaneously in a single operation, and the resulting process would fall within the literal scope of the claimed process.

As used herein, the term "about" can allow, for example, a degree of variability in the value or range, e.g., within 10%, within 5%, or within 1% of the stated value or limit of the range, and includes the exact stated value or range.

The term "substantially" as used herein refers to a majority or majority, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.

The term "substituted" as used herein in connection with a molecule, one or more hydrogen atoms contained in the molecule are replaced with one or more non-hydrogen atoms. Examples of substituents or functional groups that may be substituted include, but are not limited to, halogen (e.g., F, Cl, Br, and I); such as the oxygen atoms in the following groups: hydroxyl groups, alkoxy groups, aryloxy groups, aralkoxy groups, oxo (carbonyl) groups, including carboxylic acid, carboxylate salt, and carboxyl groups of carboxylic acid ester; such as the sulfur atom in the following groups: thiol groups, alkyl and aryl thioether groups, sulfoxide groups, sulfone groups, sulfonyl groups and sulfonamide groups; such as the nitrogen atoms in the following groups: amines, hydroxylamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents that can be bonded to a substituted carbon (OR other) atom include F, Cl, Br, I, OR, OC (O) N (R)₂、CN、NO、NO₂、ONO₂Azido group, CF₃、OCF₃R, O (oxo), S (thiocarbonyl), C (O), S (O), methylenedioxy, ethyleneDioxy, N (R)₂、SR、SOR、SO₂R、SO₂N(R)₂、SO₃R、C(O)R、C(O)C(O)R、C(O)CH₂C(O)R、C(S)R、C(O)OR、OC(O)R、C(O)N(R)₂、OC(O)N(R)₂、C(S)N(R)₂、(CH₂)_0-2N(R)C(O)R、(CH₂)_0-2N(R)N(R)₂、N(R)N(R)C(O)R、N(R)N(R)C(O)OR、N(R)N(R)CON(R)₂、N(R)SO₂R、N(R)SO₂N(R)₂、N(R)C(O)OR、N(R)C(O)R、N(R)C(S)R、N(R)C(O)N(R)₂、N(R)C(S)N(R)₂、N(COR)COR、N(OR)R、C(＝NH)N(R)₂C (o) n (or) R and C (═ NOR) R, where R can be hydrogen or a carbon-based moiety; for example, R can be hydrogen, (C)₁-C₁₀₀) Hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or wherein two R groups bonded to a nitrogen atom or to an adjacent nitrogen atom may form a heterocyclic group together with one or more nitrogen atoms.

As used herein, the term "alkyl" refers to straight and branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, from 1 to about 20 carbon atoms, from 1 to 12 carbon atoms, or, in some embodiments, from 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those having 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, isoamyl, and 2, 2-dimethylpropyl groups. As used herein, the term "alkyl" includes n-alkyl, iso-alkyl, and trans-iso-alkyl groups as well as other branched forms of alkyl. Representative substituted alkyl groups can be substituted one or more times with any of the groups listed herein, such as amino, hydroxyl, cyano, carboxyl, nitro, thio, alkoxy, and halogen groups.

The term "alkenyl" as used herein refers to straight and branched chain and cyclic alkyl groups as defined herein, except that at least one double bond is present between two carbon atoms. Thus, alkenyl groups have 2 to 40 carbonsAtoms, or from 2 to about 20 carbon atoms, or from 2 to 12 carbon atoms, or in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to, ethenyl, -CH ═ CH (CH)₃)、-CH＝C(CH₃)₂、-C(CH₃)＝CH₂、-C(CH₃)＝CH(CH₃)、-C(CH₂CH₃)＝CH₂Cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl, and the like.

As used herein, the term "acyl" refers to a group comprising a carbonyl moiety, wherein the group is bonded through the carbonyl carbon atom. The carbonyl carbon atom is bonded to hydrogen to form a "formyl" group or to another carbon atom, which can be alkyl, aryl, aralkylcycloalkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl, and the like. The acyl group can contain 0 to about 12, 0 to about 20, or 0 to about 40 additional carbon atoms bonded to the carbonyl group. Acyl groups may include double or triple bonds within the meaning herein. An acryloyl group is an example of an acyl group. Acyl groups may also include heteroatoms within the meaning of the disclosure. Nicotinoyl groups (pyridyl-3-carbonyl) are one example of acyl groups within the meaning herein. Other examples include acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and acryloyl groups, and the like. When a group containing a carbon atom that is bonded to the carbonyl carbon atom containing a halogen is referred to as a "haloacyl" group. Examples are trifluoroacetyl groups.

As used herein, the term "cycloalkyl" refers to cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, cycloalkyl groups may have 3 to about 8-12 ring members, while in other embodiments the number of ring carbon atoms ranges from 3 to 4,5, 6, or 7. Cycloalkyl groups also include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphene, isobornene, and carenyl groups, as well as fused rings such as, but not limited to, naphthylalkyl and the like. Cycloalkyl groups also include rings substituted with a straight or branched chain alkyl group as defined herein. Representative substituted cycloalkyl groups may be mono-substituted or substituted more than once, such as, but not limited to, 2-, 2,3-, 2,4-, 2,5-, or 2, 6-disubstituted cyclohexyl groups or mono-, di-, or tri-substituted norbornyl or cycloheptyl groups, which groups may be substituted with, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halo groups. The term "cycloalkenyl" alone or in combination denotes a cyclic alkenyl group.

As used herein, the term "aryl" refers to a cyclic aromatic hydrocarbon group that does not contain heteroatoms within the ring. Thus, aryl groups include, but are not limited to, phenyl, azulenyl, heptenylene, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylene, pyrenyl, tetracenyl, chrysenyl, biphenylene, anthracenyl, and naphthyl groups. In some embodiments, the aryl group comprises from about 6 to about 14 carbons in the ring portion of the group. The aryl group may be unsubstituted or substituted, as defined herein. Representative substituted aryl groups may be mono-substituted or substituted more than once, such as, but not limited to, phenyl groups substituted in any one or more of the 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring, or naphthyl groups substituted in any one or more of the 2-to 8-positions thereof.

As used herein, the term "aralkyl" refers to an alkyl group as defined herein, wherein a hydrogen or carbon bond of the alkyl group is replaced by a bond of an aryl group as defined herein. Representative aralkyl groups include benzyl and phenethyl groups and fused (cycloalkylaryl) alkyl groups such as 4-ethyl-indanyl. An aralkenyl group is an alkenyl group as defined herein wherein the hydrogen or carbon bond of the alkyl group is replaced by a bond of the aryl group as defined herein.

The term "alkoxy" as used herein refers to an oxygen atom attached to an alkyl group (including cycloalkyl groups) as defined herein. Examples of linear alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and the like. Examples of branched alkoxy groups include, but are not limited to, isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, isohexyloxy, and the like. Examples of cyclic alkoxy groups include, but are not limited to, cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, and the like. The alkoxy group may contain from about 1 to about 12, from about 1 to about 20, or from about 1 to about 40 carbon atoms bonded to an oxygen atom, and may also contain double or triple bonds, and may also contain heteroatoms. For example, allyloxy groups or methoxyethoxy groups are also alkoxy groups within the meaning of this document, as are methylenedioxy groups in which two adjacent atoms of the structure are substituted therewith.

As used herein, the term "number average molecular weight" (M)_n) Refers to the common arithmetic average molecular weight of the individual molecules in a sample. Which is defined as the total weight of all molecules in the sample divided by the total number of molecules in the sample. Experimentally, it is classified by analysis as having a molecular weight M_iTo formula M_n＝ΣM_in_i/Σn_iN of (A) to (B)_iDetermination of M from samples of the molecular weight fraction of individual molecules of the species i_n。M_nCan be measured by a variety of well-known methods, including gel permeation chromatography, spectroscopic end group analysis, and osmometry. The molecular weights of the polymers given herein are number average molecular weights, if not specified.

The term "weight average molecular weight" as used herein refers to M_wWhich is equal to sigma M_i ²n_i/ΣM_in_iWherein n is_iIs molecular weight M_iThe number of molecules of (c). In various examples, the weight average molecular weight can be determined using light scattering, small angle neutron scattering, X-ray scattering, gel permeation chromatography, and sedimentation velocity.

The term "melting temperature" refers to the temperature or range of temperatures at which a material changes from a solid to a liquid state at a pressure of 1 ATM. The melting temperature can be determined using differential scanning calorimetry, wherein the melting temperature is taken at the end of the endothermic peak measured therein.

The polymers described herein may be terminated in any suitable manner. In some embodiments, the polymer may terminate with end groups independently selected from suitable polymerization initiators-H, -OH, substituted or unsubstituted (C)₁-C₂₀) Hydrocarbyl (e.g., (C)₁-C₁₀) Alkyl or (C)₆-C₂₀) Aryl group), the substituted or unsubstituted (C)₁-C₂₀) The hydrocarbyl group is interrupted by 0, 1,2 or 3 groups independently selected from: -O-, substituted or unsubstituted-NH-and-S-, poly (substituted or unsubstituted (C)₁-C₂₀) Hydrocarbyloxy) and poly (substituted or unsubstituted (C)₁-C₂₀) Hydrocarbyl amino).

According to various examples of the present disclosure, the overlay film or surface protection film comprises a thermoplastic polyurethane film. The thermoplastic polyurethane film may comprise a number of suitable components. Examples of suitable components include thermoplastic polyurethanes that are the reaction product of a reaction mixture comprising a diisocyanate, a polyester polyol having a melting temperature of at least about 30 ℃, and a diol chain extender.

FIG. 1 is a cross-sectional view of a surfacing film 10, which comprises a thermoplastic polyurethane film. As shown, the surfacing film 10 includes an optional thermoset polyurethane or varnish coating 12, a transparent thermoplastic polyurethane film or substrate layer 14, and an optional pressure sensitive adhesive layer 16. An optional releasable carrier web or liner 18 may be releasably bonded to the polyurethane layer 12 along its major surface facing away from the substrate layer 14 so as to protect the surface of the thermosetting polyurethane layer 12. If the thermoset polyurethane layer 12 is not present, the liner 18 may be releasably bonded to the substrate layer 14 along its major surface facing away from the pressure sensitive adhesive layer 16 to protect the substrate layer 14. If a pressure sensitive adhesive layer 16 is present, it may be desirable for the overlay film 10 to also include another release liner 20 releasably bonded thereto as shown in order to protect the pressure sensitive adhesive layer 16. In some examples of the surfacing film 10, none of these components are present. Fig. 2 is a cross-sectional view of another patch film 20 that includes only the substrate layer 14 and the pressure sensitive adhesive layer 16. FIG. 3 is a cross-sectional view of another overlay film 10 comprising a thermoplastic polyurethane film base layer 14 and a hardcoat layer 17. FIG. 4 is a cross-sectional view of another overlay film 10 comprising a thermoplastic polyurethane film base layer 14, a hardcoat layer 17 and a siliceous layer 13.

The thermoplastic polyurethane film can have a molecular weight in the range of from about 80,000 daltons to about 400,000 daltons, from about 80,000 daltons to about 200,000 daltons, or equal to, less than, or greater than about 80,000 daltons; 85,000 daltons; 90,000 daltons; 95,000 daltons; 100,000 daltons; 105,000 daltons; 110,000 daltons; 115,000 daltons; 120,000 daltons; 125,000 daltons; 130,000 daltons; 135,000 daltons; 140,000 daltons; 145,000 daltons; 150,000 daltons; 155,000 daltons; 160,000 daltons; 165,000 daltons; 170,000 daltons; 175,000 daltons; 180,000 daltons; 185,000 daltons; 190,000 daltons; 195,000 daltons; 200,000 daltons; 205,000 daltons; 210,000 daltons; 215,000 daltons; 220,000 daltons; 225,000 daltons; 230,000 daltons; 235,000 daltons; 240,000 daltons; 245,000 daltons; 250,000 daltons; 255,000 daltons; 260,000 daltons; 265,000 daltons; 270,000 daltons; 275,000 daltons; 280,000 daltons; 285,000 daltons; 290,000 daltons; 295,000 daltons; 300,000 daltons; 305,000 daltons; 310,000 daltons; 315,000 daltons; 320,000 daltons; 325,000 daltons; 330,000 daltons; 335,000 daltons; 340,000 daltons; 345,000 daltons; 350,000 daltons; 355,000 daltons; 360,000 daltons; 365,000 daltons; 370,000 daltons; 375,000 daltons; 380,000 daltons; 385,000 daltons; 390,000 daltons; 395,000 daltons; or a weight average molecular weight of 400,000 daltons. The high molecular weight of the thermoplastic polyurethane film may help prevent discoloration of the film, at least in the substrate layer 14. This is because the relatively high molecular weight of thermoplastic polyurethane films can be caused by long chain length polyurethanes. Long chains can result in the substrate layer 14 being relatively tightly packed or highly entangled such that the color-changing compound cannot readily penetrate the substrate layer 14 and cause color change therein. For example, the substrate layer 14 exposed to a 10% asphalt solution for 24 hours has a yellowing color change that is less than the yellowing color change of a corresponding protective film comprising a substrate layer comprising a thermoplastic polyurethane film having a weight average molecular weight of 80,000 daltons or less.

The base layer 14 may be sufficiently hard to withstand abrasion from foreign objects. For example, the base layer 14 may have a shore a hardness in a range of about 70A to about 95A, about 83A to about 90A, or less than, equal to, or greater than about 70A, 75A, 76A, 77A, 78A, 79A, 80A, 81A, 82A, 83A, 84A, 85A, 86A, 87A, 88A, 89A, 90A, 91A, 92A, 93A, 94A, or 95A.

The thickness of the substrate layer 14 may be in the range of about 0.05mm to about 2mm, about 0.5mm to about 1mm, or less than, equal to, or greater than about 0.05mm, 0.1mm, 0.15mm, 0.2mm, 0.25mm, 0.3mm, 0.35mm, 0.4mm, 0.45mm, 0.5mm, 0.55mm, 0.6mm, 0.65mm, 0.7mm, 0.75mm, 0.8mm, 0.85mm, 0.9mm, 0.95mm, 1mm, 1.05mm, 1.1mm, 1.15mm, 1.2mm, 1.25mm, 1.3mm, 1.35mm, 1.4mm, 1.45mm, 1.5mm, 1.55mm, 1.6mm, 1.65mm, 1.7mm, 1.75mm, 1.8mm, 1.85mm, 1.95mm, or 2 mm.

In some embodiments, the base layer 14 is conformable. The conformability of the film can be characterized by a tensile test, as determined by the test method described in the examples with a strain rate of 200%/min.

Conformable films generally have a lower tensile modulus compared to Polyester (PET). For example, PET has a tensile modulus of at least 5000-; while conformable films typically have a tensile modulus of less than 3000 MPa. In some embodiments, the conformable film has a tensile modulus of less than 1000MPa, 750MPa, 500MPa, or 250 MPa. In some embodiments, the compliant film has a tensile modulus of less than 200MPa, 150MPa, or 100 MPa. The conformable film typically has a tensile modulus of at least 25MPa, 30MPa, 35MPa, 40MPa, 45MPa, or 50 MPa.

Conformable films generally have lower ultimate tensile strength compared to Polyester (PET). For example, PET has an ultimate tensile strength of at least 150 MPa; while conformable films typically have an ultimate tensile strength of less than 100 MPa. The conformable film typically has an ultimate tensile strength of at least 10MPa, 15MPa, or 20 MPa.

Conformable films generally have a higher tensile strain at break, or in other words a higher elongation at break, than Polyester (PET). For example, PET has a tensile strain at break of less than 100%; while conformable films typically have a tensile strain at break of at least 150%, 175%, or 200%. In some embodiments, the conformable film has a tensile strain at break of no greater than 500%, 400%, or 300%.

Conformable films generally have lower loads at 25% strain than Polyester (PET). For example, PET has a load of at least 150N/cm film width at 25% strain; while conformable films typically have a load at 25% strain of less than 50N/cm, 40N/cm, 30N/cm, 20N/cm, or 10N/cm of film width. In some embodiments, the conformable film has a load at 25% strain of at least 2N/cm, 3N/cm, 4N/cm, or 5N/cm of film width.

It is speculated that the load at 25% strain/cm film width is important for stretching the film by hand and/or applying the film to an object by hand. If the film has too high a load at the desired strain (e.g., 25%), most people will not be able to stretch or apply such films to objects by hand due to the excessive force required to stretch the film. For example, an average person may apply a force of 50N by hand. This is a force sufficient to stretch a 5cm wide conformable film by 25%. However, most people will not be able to stretch PET films by hand, as this will require over 700N of force to stretch a 5cm wide film by 25%.

As referred to herein, a thermoplastic polyurethane is the reaction product of a reaction mixture comprising a diisocyanate, a polyester polyol having a melting temperature of at least about 30 ℃, and a chain extender. The diisocyanate may be in the range of about 0.5 wt% to about 40 wt%, about 1 wt% to about 10 wt%, about 25 wt% to about 47 wt% of the reaction mixture, or less than, equal to, or greater than about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, 15 wt%, 15.5 wt%, 16 wt%, 16.5 wt%, 17 wt%, 17.5 wt%, 18 wt%, 18.5 wt%, 19 wt% of the reaction mixture, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 42.5, 28, 23.5, 28, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 45.5 wt%, 46 wt%, 46.5 wt% or 47 wt%. The amount of diisocyanate in the reactive mixture may be expressed in terms of the isocyanate index. The isocyanate index is generally understood to mean the ratio of the equivalent amount of isocyanate functional groups used relative to the theoretical equivalent amount of hydroxyl functional groups. A theoretical equivalent amount equal to one equivalent of isocyanate functional groups per equivalent of hydroxyl groups; this is an index of 100. According to various examples, the isocyanate index of the reactive mixture is in the range of about 0.99 to about 1.20, about 1.00 to about 1.10, or less than, equal to, or greater than about 0.99, 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, or 1.20.

Examples of suitable diisocyanates include diisocyanates according to formula I having the following structure:

O＝C＝N-R-N＝C＝O，

formula I.

In formula I, R is selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₄-C₂₀) Arylene radical- (C)₁-C₄₀) Alkylene- (C)₄-C₂₀) Arylene, (C)₄-C₂₀) Cycloalkylene and (C)₄-C₂₀) An aralkylene group. In additional examples, the diisocyanate is selected from the group consisting of dicyclohexylmethane-4, 4' -diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate, m-xylene diisocyanate, tolylene-2, 4-diisocyanate, toluene 2, 6-diisocyanate, poly (hexamethylene diisocyanate), 1, 4-cyclohexylene diisocyanate, 4-chloro-6-methyl-1, 3-phenylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane 4,4' -diisocyanate, 1, 4-diisocyanatobutane, isophorone diisocyanate, hexamethylene diisocyanate, 4' -diisocyanate, 1, 4-diisocyanatobutane, hexamethylene diisocyanate, and mixtures thereof, Octane 1, 8-diisocyanate, 2, 6-tolylene diisocyanate, 2, 5-tolylene diisocyanate, 2, 4-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, methylenebis (o-chlorophenyl diisocyanate, methylenediphenylene-4, 4 '-diisocyanate, (4,4' -diisocyanate-3, 3',5,5' -tetraethyl) diphenylmethane, 4 '-diisocyanate-3, 3' -dimethoxybiphenyl (o-dianisidine diisocyanate), 5-chloro-2, 4-tolylene diisocyanate, 1-chloromethyl-2, 4-diisocyanate benzene, tetramethyl-m-xylene diisocyanate, hexane 1, 6-diisocyanate 1, dodecane 12-diisocyanate, pentane 2-methyl-1, 5-diisocyanate, methylenedicyclohexylene-4, 4' -diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate, 2, 4-trimethylhexyl diisocyanate or mixtures thereof.

The polyester polyol can be in a range of 43 wt% to about 70 wt%, about 50 wt% to about 60 wt% of the reaction mixture, or less than, equal to, or greater than about 43 wt%, 43.5 wt%, 44 wt%, 44.5 wt%, 45 wt%, 45.5 wt%, 46 wt%, 46.5 wt%, 47 wt%, 47.5 wt%, 48 wt%, 48.5 wt%, 49 wt%, 49.5 wt%, 50 wt%, 50.5 wt%, 51 wt%, 51.5 wt%, 52 wt%, 52.5 wt%, 53 wt%, 53.5 wt%, 54 wt%, 54.5 wt%, 55 wt%, 55.5 wt%, 56 wt%, 56.5 wt%, 57 wt%, 57.5 wt%, 58 wt%, 58.5 wt%, 59 wt%, 59.5 wt%, 60 wt%, 60.5 wt%, 61 wt%, 61.5 wt%, 62.5 wt%, 62 wt%, or more than about 43 wt%, 43.5 wt%, 48 wt%, 44 wt%, 44.5 wt%, 45 wt%, 46 wt%, 47.5 wt%, or more than about the reaction mixture, 63 wt%, 63.5 wt%, 64 wt%, 64.5 wt%, 65 wt%, 65.5 wt%, 66 wt%, 66.5 wt%, 67 wt%, 67.5 wt%, 68 wt%, 68.5 wt%, 69 wt%, 69.5 wt%, or 70 wt%. The polyester polyol can comprise any suitable number of hydroxyl groups. For example, the polyester polyol can comprise four hydroxyl groups or three hydroxyl groups. The polyester polyol may even comprise two hydroxyl groups, such that the polyester polyol is a polyester diol. Generally, the polyester polyol can be the product of a condensation reaction, such as a polycondensation reaction. However, polyester polyols are not prepared via ring-opening polymerization products.

In examples where the polyester polyol is made according to a condensation reaction, the reaction may be conducted between one or more carboxylic acids and one or more polyols. Examples of suitable carboxylic acids include carboxylic acids according to formula II, which have the following structure:

in formula II, R¹Selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₄-C₂₀) Cycloalkylene and (C)₄-C₂₀) An aralkylene group. Specific examples of suitable carboxylic acids include glycolic acid (2-hydroxyacetic acid), lactic acid (2-hydroxypropionic acid), succinic acid (succinic acid), 3-hydroxybutyric acid, 3-hydroxyvaleric acid, terephthalic acid (benzene-1, 4-dicarboxylic acid), naphthalenedicarboxylic acid, 4-hydroxybenzoic acid, 6-hydroxynaphthalene-2-carboxylic acid, oxalic acid, malonic acid (malonic acid) (malonic acid)), adipic acid (adipic acid), pimelic acid (pimelic acid), ethonic acid, suberic acid (suberic acid), azelaic acid (azelaic acid) (azelaic acid (nonanedioic acid))d) Sebacic acid (sebacic acid)), glutaric acid (glutaric acid), dodecanedioic acid (decanodioic acid), brassylic acid, naplaic acid, maleic acid ((2Z) -but-2-enedioic acid), fumaric acid ((2E) -but-2-enedioic acid), glutaconic acid (penta-2-enedioic acid), 2-decenedioic acid, callus acid ((2E) -dodec-2-enedioic acid), muconic acid ((2E,4E) -hex-2, 4-dienedioic acid), glutinic acid, citraconic acid ((2Z) -2-methylbut-2-enedioic acid), mesaconic acid ((2E) -2-methyl-2-butenedioic acid) Itaconic acid (2-methylenesuccinic acid), malic acid (2-hydroxysuccinic acid), aspartic acid (2-aminosuccinic acid), glutamic acid (2-aminoglutaric acid), tartaric acid (tartronic acid), tartaric acid (2, 3-dihydroxybutanoic acid), diaminopimelic acid ((2R,6S) -2, 6-diaminopimelic acid), saccharic acid ((2S,3S,4S,5R) -2,3,4, 5-tetrahydroxyadipic acid), methoxyoxalic acid (mexooxalic acid), oxaloacetic acid (oxosuccinic acid), acetonedicarboxylic acid (3-oxopentaalkanedicarboxylic acid), arabinodicarboxylic acid (arbinaic acid), phthalic acid (benzene-1, 2-dicarboxylic acid), isophthalic acid, biphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid or mixtures thereof.

Examples of suitable polyols include polyols according to formula II, which have the following structure:

in formula II, R²Selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₁-C₄₀) Acyl (C)₄-C₂₀) Cycloalkylene, (C)₄-C₂₀) Aralkylene and (C)₁-C₄₀) Alkylene oxide radical, and R³And R⁴Independently selected from-H, -OH, substituted or unsubstituted (C)₁-C₄₀) Alkyl, (C)₂-C₄₀) Alkenyl, (C)₄-C₂₀) Aryl group, (C)₁-C₂₀) Acyl, (C)₄-C₂₀) Cycloalkyl group, (C)₄-C₂₀) Aralkyl and (C)₁-C₄₀) An alkoxy group.

Examples of another suitable polyol include polyols according to formula III, which have the following structure:

in formula III, R⁵And R⁶Independently selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₁-C₄₀) Acyl (C)₄-C₂₀) Cycloalkylene, (C)₄-C₂₀) Aralkylene and (C)₁-C₄₀) Alkylene oxide group, and n is a positive integer greater than or equal to 1.

Examples of another suitable polyol include polyols according to formula IV having the following structure:

in formula IV, R⁷Selected from substituted or unsubstituted (C1-C)₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₁-C₄₀) Acyl (C)₄-C₂₀) Cycloalkylene, (C)₄-C₂₀) Aralkylene and (C)₁-C₄₀) Alkylene oxide group, and n is a positive integer greater than or equal to 1. In particular examples, the polyester polyol includes one or more of the following: polyglycolic acid (poly [ oxo (1-oxo-1, 2-ethanediyl)]) Polybutylene succinate (poly (tetramethylene succinate)), poly (3-hydroxybutyrate-co-3-hydroxyvalerate), polyethylene terephthalate (poly (ethylbenzene-1, 4-dicarboxylate)), polybutylene terephthalate (poly (oxo-1, 4-butylidenyloxycarbonyl-1, 4-phenylenebarbonyl)), polypropylene terephthalate (poly (trimethylene terephthalate)); poly (oxo)-1, 3-propyleneoxycarbonyl-1, 4-phenylenecarbonyl)), polyethylene naphthalate (poly (ethylene 2, 6-naphthalate)), poly (1, 4-butylene adipate), poly (1, 6-hexanediol adipate), poly (ethylene adipate), mixtures thereof, and copolymers thereof. However, the polyester polyol is free of polycaprolactone polyol ((1,7) -polyoxyheterocycloheptan-2-one). The polyester polyol has at least 30 ℃, at least 35 ℃, at least 40 ℃, at least 42 ℃, at least 45 ℃, at least 50 ℃, at least 55 ℃, at least 60 ℃, at least 65 ℃, at least 70 ℃, at least 75 ℃, at least 80 ℃, at least 85 ℃, at least 90 ℃, at least 95 ℃, at least 100 ℃, at least 110 ℃, at least 120 ℃, at least 130 ℃, at least 140 ℃, at least 150 ℃, at least 160 ℃, at least 170 ℃, at least 180 ℃, at least 190 ℃, at least 200 ℃, at least 210 ℃, at least 220 ℃, at least 230 ℃, at least 240 ℃, at least 250 ℃, at least 260 ℃, at least 270 ℃, at least 280 ℃, at least 290 ℃, at least 300 ℃, at least 310 ℃, at least 320 ℃, at least 330 ℃, at least 340 ℃, at least 350 ℃, at least 360 ℃, at least 370 ℃, at least 380 ℃, at least 390 ℃, at least 400, at least 410 ℃, at least 420 ℃, at least 430 ℃, at least 440 ℃, at least 450 ℃, A melting temperature of at least 460 ℃, at least 470 ℃, at least 480 ℃, at least 490 ℃ or at least 500 ℃. Selection of an appropriate melting temperature may help to increase the crystallinity of the base layer 14. Crystallinity can be determined by differential scanning calorimetry and is expressed as a component of crystallinity in the thermoplastic polyurethane film. The crystallinity may range from about 30% to about 70%, about 40% to about 60%, or less than, equal to, or greater than 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%. The crystallinity may enable easier rolling of the substrate layer 14 because it requires a relatively high temperature to begin liquefying the substrate layer 14. As a result, substrate layer 14 is less likely to stick to itself during rolling or storage. Examples of the melting temperatures of some polyester polyols are provided in table 1 herein.

TABLE 1

Polyester polyols	Melting temperature (. degree.C.)
		Polyglycolic acid	225 to 230
Polybutylene succinate	115
		Polyethylene terephthalate	500
Polybutylene terephthalate	433.4

The chain extender may be in the range of about 2 wt% to about 13 wt%, about 1 wt% to about 10 wt% of the reaction mixture, or less than, equal to, or greater than about 2 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%.

The diol chain extender has a weight average molecular weight of less than about 250 daltons. For example, the weight average molecular weight of the diol chain extender may be in the range of from about 30 daltons to about 250 daltons, from about 50 daltons to about 150 daltons, or less than, equal to or greater than about 30 daltons, 35 daltons, 40 daltons, 45 daltons, 50 daltons, 55 daltons, 60 daltons, 65 daltons, 70 daltons, 75 daltons, 80 daltons, 85 daltons, 90 daltons, 95 daltons, 100 daltons, 105 daltons, 110 daltons, 115 daltons, 120 daltons, 125 daltons, 130 daltons, 135 daltons, 140 daltons, 145 daltons, 150 daltons, 155 daltons, 160 daltons, 165 daltons, 170 daltons, 175 daltons, 180 daltons, 185 daltons, 190 daltons, 195 daltons, 200 daltons, 205 daltons, 210 daltons, 215 daltons, 220 daltons, 225 daltons, 230 daltons, 225 daltons, 220 daltons, 225 daltons, 230 daltons, 235 daltons, 240 daltons, 245 daltons, or about 250 daltons. The diol chain extender may comprise any suitable number of carbons. For example, the diol chain extender may comprise a number average number of from about 2 carbons to about 20 carbons, from about 3 carbons to about 10 carbons, or less than, equal to, or greater than about 2 carbons, 3 carbons, 4 carbons, 5 carbons, 6 carbons, 7 carbons, 8 carbons, 9 carbons, 10 carbons, 11 carbons, 12 carbons, 13 carbons, 14 carbons, 15 carbons, 16 carbons, 17 carbons, 18 carbons, 19 carbons, or 20 carbons. Diol chain extenders such as these may help reinforce the substrate layer 14. This may be because the relatively short chains may be stiffer than the longer chain diols. For example, short chain diols may be stiffer because short chain diols are more restricted in rotating about a single bond along the chain. Examples of suitable diol chain extenders include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, or mixtures thereof.

The thermoplastic polyurethane may comprise hard segments. Hard segments generally refer to the harder, less flexible polymer segments resulting from the polymerization of a diisocyanate and a diol chain extender. The amount of hard segments can be determined by calculating the total amount (wt%) of isocyanate, chain extender and crosslinker. This total amount is then divided by the total weight of the thermoplastic polyurethane. The hard segments can range from about 30 wt% to about 55 wt%, about 40 wt% to about 55 wt% of the thermoplastic polyurethane film, or less than, equal to, or greater than about 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, or 55 wt% of the thermoplastic polyurethane film. The hard segments exist as domains that can interact with each other to effectively form crosslinks between them (e.g., through hydrogen bonding). For example, under stress, the hard segments may become aligned in the direction of the stress by mechanical deformation. This alignment in combination with hydrogen bonding can contribute to the stiffness, elastomeric elasticity, or tear resistance of the thermoplastic polymer film.

In some examples, the reactive mixture may include a crosslinking agent. Examples of the crosslinking agent include polyhydroxy group compounds and polyisocyanate compounds. For example, the polyol may contain 3 hydroxyl groups or 4 hydroxyl groups. The polyisocyanate may contain 3 cyano groups or 4 cyano groups. Although there are many suitable crosslinkers, the reactive mixture does not contain an aziridine crosslinker. If present, the cross-linking agent may function to link the different thermoplastic polyurethane chains of substrate layer 14 (e.g., intermolecular cross-linking). Alternatively, the crosslinking agent can function to crosslink different portions of the thermoplastic polyurethane chain (e.g., intramolecular crosslinking).

The overlay film 10 may be applied to a number of suitable substrates. In addition, the overlay film 10 can be cut to precisely match the size of any desired substrate. By way of example, the substrate may be a vehicle body, a window, or a portion thereof. For example, relative to an automobile, the surfacing film 10 may be sized to precisely fit a portion of the hood of a particular make and model of automobile. In addition to the hood, the overlay film 10 can be cut to conform to other features of the automobile, such as fenders, mirrors, doors, roofs, panels, portions thereof.

The overlay film 10 may also be sized to precisely fit a portion of a water craft such as a hull (e.g., to protect the hull during stranding of the craft), a transom (e.g., to protect the transom from damage caused by water skis), or a bulwark (e.g., to prevent damage from lines). Further, the surfacing film 10 may be applied to a train, or even an aerospace vehicle, such as an airplane or helicopter. For example, the surfacing film 10 may be applied to a blade, such as a propeller blade (e.g., to prevent debris from impacting, such as ice), a wing (e.g., a wing or helicopter blade), or a fuselage.

According to various examples, a method of making the mask 10 may include forming the base layer 14. The base layer 14 may be formed from a reactive mixture prepared in an extruder. Examples of suitable extruders include twin screw extruders or planetary extruders. Suitable twin screw extruders include co-rotating twin screw extruders or counter-rotating twin screw extruders. The components of the reactive mixture (e.g., diisocyanate, diol chain extender, and polyester polyol) may be fed into the extruder separately or simultaneously. The process does not involve introducing pellets comprising thermoplastic polyurethane into an extruder. Thus, the reactive mixture does not contain any components required for granulation, such as wax processing aids or anti-tacking agents. The provided methods can help ensure that the thermoplastic polyurethane film has a weight average molecular weight of at least 80,000 daltons. This is because the pellets introduced into the extruder can be subjected to significant shear, which can shorten the thermoplastic polyurethane chains and thus reduce the weight average molecular weight of the resulting film.

The substrate layer 14 comprising molten thermoplastic polyurethane is formed by extrusion and extruded through a die onto a carrier web as a uniform film. One example of a suitable die includes a coating hanger die. The uniform film may be further pressed by a cold roll of the reaction that thermally quenches the polyurethane to shape, thereby curing the thermoplastic polyurethane to obtain the substrate layer 14.

Extrusion may occur at any suitable temperature. For example, the temperature can be in the range of about 40 ℃ to about 230 ℃, about 90 ℃ to about 200 ℃, or less than, equal to, or greater than about 40 ℃, 45 ℃, 50 ℃,55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, or 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃ or 230 ℃. Extrusion may occur for any suitable amount of time. For example, extrusion can occur over a period of time ranging from about 0.5 hours to about 17 hours, about 1 hour to about 6 hours, or less than, equal to, or greater than about 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours, 15 hours, 15.5 hours, 16 hours, 16.5 hours, or 17 hours.

For applying the pressure sensitive adhesive layer 16 to the substrate layer 14, corona treatment (e.g., air or N) may be desired₂Corona treated) and thermally laminating the major surface of the extruded base layer 14 to bond to the pressure sensitive adhesive layer 16. To accomplish this, the major surface of the base layer 14 that is not in contact with the varnish coating 12 is exposed and then corona treated. If a thermal lamination process is used (e.g., extruding the varnish coating 12 onto a strippable carrier web or liner), it may be necessary to first strip the carrier web or liner from the varnish coating 12.

The base layer 14 and the varnish coating 12 may be bonded together, for example, by laminating the layers at elevated temperature and pressure. For example, one major surface of the varnish coating 12 may be cold laminated under pressure to one major surface of the extruded substrate layer 14 while at least one major surface of the substrate layer 14 or both the substrate layer 14 and the varnish coating 12 are at a sufficiently high temperature to promote adequate bonding between the varnish coating 12 and the substrate layer 14. As used herein, cold lamination refers to layers being laminated together between two nip surfaces in an environment of about room or ambient temperature (e.g., the layers are not held in an intentionally heated environment during the lamination process). The nip surface may be two nip rolls, a stationary nip surface (e.g., a low friction surface of a flat or curved plate) and a nip roll, or two stationary nip surfaces. The lamination process may even be performed in a sub-ambient temperature environment (that is, the layers are intentionally cooled during the lamination process). For example, one or both of the nip surfaces may be cooled to a temperature below ambient so as to cool the exposed major surface of the polyurethane layer (that is, the major surface with which the nip surface contacts). The use of such cooled surfaces may eliminate or at least help reduce warping of the layers caused by the lamination process. At the same time, the major surfaces in contact at the interface between the polyurethane layers are still at an elevated temperature for a sufficient time to be sufficiently bonded together by the lamination pressure applied by the nip surface. Such cold lamination may be achieved by laminating the freshly extruded substrate layer 14 directly onto the preformed varnish coating 12, while the substrate layer 14 material remains sufficiently hot from the extrusion process. The varnish coating 12 is still releasably bonded to the carrier web or liner to provide additional structural strength.

Alternatively, one major surface of the varnish coating 12 may also be bonded to one major surface of the extruded base layer 14 by using a thermal lamination process. With respect to this process, the initial temperature of both the varnish coating 12 and the substrate layer 14 is about room temperature, or at least a temperature that is too low to facilitate adequate bonding between the varnish coating 12 and the substrate layer 14. Then, at least one major surface of the substrate layer 14, at least one major surface of the varnish coating 12, or one major surface of both the varnish coating 12 and the substrate layer 14 is heated to an elevated temperature sufficiently higher than room temperature to facilitate adequate bonding between the varnish coating 12 and the substrate layer 14 at the lamination pressure. With respect to the thermal lamination process, the layers are heated prior to or during the application of the lamination pressure. If a thermal lamination process is used, the major surface of the substrate layer 14 may be releasably laminated to an easily releasable carrier web or liner (e.g., a polyester carrier web) directly after the substrate layer 14 is extruded to provide additional structural support to the now-extruded substrate layer 14.

Acceptable minimum temperatures and pressures for bonding the layers together using either a cold lamination process or a hot lamination process have included a temperature of at least about 200 ° f (93 ℃) and a temperature of at least about 15lb/in²Or psi (10.3N/cm)²) The pressure of (a).

In another embodiment, the clear coat layer may be provided by an organic solvent-based coating composition (also referred to as a hardcoat). The hardcoat layer 17 can improve rigidity, dimensional stability, and durability. The hardcoat layer 17 may also improve adhesion between the siliceous layer 13 and the base layer 14. In advantageous embodiments, the hardcoat layer (e.g., having a thickness of 2 to 10 microns (e.g., 5 microns)) can be stretched at a rate of about 2 cm/sec by 25%, 50%, or 75% and held under stretching conditions for 1 hour without cracking.

In some embodiments, the hardcoat layer comprises one or more polymerized urethane (meth) acrylate oligomers. Typically, the urethane (meth) acrylate oligomer is a di (meth) acrylate. The term "(meth) acrylate" is used to refer to both esters of acrylic acid and esters of methacrylic acid.

One suitable urethane (meth) acrylate oligomer that may be employed in the hardcoat composition is available from Sartomer Company (Exton, PA), axton, PA under the trade designation "CN 991".

Other suitable urethane (meth) acrylate oligomers are available from Sartomer Company (Sartomer Company) under the trade designations "CN 9001" and "CN 981B 88". CN981B88 "is an aliphatic urethane (meth) acrylate oligomer available from Sartomer Company (Sartomer Company) under the trade name CN981 (blended with SR238(1,6 hexanediol diacrylate). The physical properties of these aliphatic urethane (meth) acrylate oligomers are set forth below according to the supplier's report:

as reported by the supplier

The reported tensile strength, elongation and glass transition temperature (Tg) characteristics are based on homopolymers prepared from such urethane (meth) acrylate oligomers.

Suitable urethane (meth) acrylate oligomers of the hardcoat can be characterized as having an elongation at break of at least 25% and typically no greater than 150% or 200%; a Tg in the range of about 0 to 30 ℃, 40 ℃, 50 ℃, 60 ℃ or 70 ℃; and a tensile strength of at least 1,000psi (6.9MPa) or at least 5,000psi (34.5 MPa). In some embodiments, the elongation at break of the urethane (meth) acrylate oligomer or hardcoat composition is at least 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or 75%.

The molecular weight of the one or more urethane (meth) acrylate oligomers is typically in the range of 800g/mol to 5000 g/mol; as determined by Gel Permeation Chromatography (GPC) using polystyrene standards. In some embodiments, the molecular weight of the one or more urethane (meth) acrylate oligomers is no more than 4500g/mol, 4000g/mol, or 3500 g/mol.

These particular urethane (meth) acrylate oligomers and other urethane (meth) acrylate oligomers having similar physical properties may be effectively employed at concentrations of at least 40 wt.% or 50 wt.%, based on the wt.% solids of the organic components of the hardcoat composition, ranging up to 100 wt.%. In some embodiments, the concentration of the polymerized urethane (meth) acrylate oligomer is at least 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 weight percent solids of the organic components of the hardcoat composition.

In some embodiments, the urethane (meth) acrylate oligomer is combined with at least one multi (meth) acrylate monomer comprising at least two (meth) acrylate groups. The multi (meth) acrylate monomer generally has a lower molecular weight than the urethane (meth) acrylate oligomer, and thereby increases the crosslink density, as well as increasing adhesion to the organic polymer film and the siliceous layer.

Suitable di (meth) acrylate monomers include, for example, 1, 3-butanediol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol di (meth) acrylate, ethylene glycol diacrylate, alkoxylated aliphatic diacrylates, alkoxylated cyclohexanedimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, cyclohexane dimethanol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated (10) bisphenol A diacrylate, ethoxylated (3) bisphenol A diacrylate, ethoxylated (30) bisphenol A diacrylate, ethylene glycol, Ethoxylated (4) bisphenol A diacrylate, hydroxypivalaldehyde modified trimethylolpropane diacrylate, neopentyl glycol diacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, propoxylated neopentyl glycol diacrylate, tetraethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol diacrylate and tripropylene glycol diacrylate. In some embodiments, the purchased urethane (meth) acrylate oligomer may be premixed with the di (meth) acrylate monomer, such as for CN988B 88.

In some embodiments, the amount of di (meth) acrylate monomer is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 wt% solids of the organic component of the hardcoat composition.

Having a significant concentration of (meth) acrylate monomers greater than two (meth) acrylate groups can reduce the flexibility of the hardcoat layer. Thus, when such monomers are employed, the concentration is typically no greater than 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 wt% solids of the total hardcoat composition. In some embodiments, the hardcoat composition is free of monomers comprising more than two (meth) acrylate groups.

In typical embodiments, the hardcoat layer comprises polymerized units of at least one (e.g., non-polar) high Tg monomer, i.e., polymerized units of a (meth) acrylate monomer, when reacted to form a homopolymer having a Tg greater than 25 ℃. More typically, the high Tg monomer has a Tg of greater than 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C or 80 deg.C. The (e.g., non-polar) high Tg monomer typically has a Tg no greater than. Mixtures of high Tg monomers may be used. In some embodiments, the mixture of monomers has a Tg in the range of about 50 ℃ to 75 ℃. In one embodiment, a mixture of hexanediol diacrylate and isobornyl acrylate is utilized.

In some embodiments, the hardcoat layer further comprises polymerized units of an ethylenically unsaturated compound comprising siloxane or silyl groups, such as a silicone (meth) acrylate additive. The silicone (meth) acrylate additive typically comprises a Polydimethylsiloxane (PDMS) backbone and terminal (meth) acrylate groups. In some embodiments, the silicone (meth) acrylate additive further comprises an alkoxy side chain. Such silicone (meth) acrylate additives are commercially available from various suppliers, such as under the tradenames "TEGO Rad 2100", "TEGO Rad 2250", "TEGO Rad 2300", "TEGO Rad 2500", and "TEGO Rad 2700" from Diego Chemie.

Based on Nuclear Magnetic Resonance (NMR) analysis, "TEGO Rad 2100" is believed to have the following chemical structure:

it is believed that the PDMS backbone is bonded to OSi (CH)₃)₃The combination of groups comprises about 50 wt% of the silicone (meth) acrylate additive; while the alkoxy (meth) acrylate side chains are believed to make up the remaining 50 wt.%.

The silicone (meth) acrylate additive is typically added to the hardcoat composition at a concentration of at least about 0.10, 0.20, 0.30, 0.40, or 0.50 weight percent solids up to 5, 10, or 20 weight percent solids of the organic components of the hardcoat composition.

When such silicone (meth) acrylate additives are present on the exposed surface, such additives may reduce the tendency of lint to be attracted to the surface, as described in WO 2009/029438. However, when such silicone (meth) acrylate additives are present in the hardcoat layer disposed between the organic polymer film and the (e.g., diamond-like glass) siliceous layer, it is surmised that the silicone or silyl groups improve adhesion to the siliceous layer.

In some embodiments, the hardcoat comprises a photoinitiator. Examples include chlorotriazine, benzoin alkyl ethers, diketones, benzophenones, and the like. Commercially available photoinitiators include those available under the trade name Daracur^TM 1173、Darocur^TM4265、Irgacure^TM 651、Irgacure^TM 184、Irgacure^TM 1800、Irgacure^TM 369、Irgacure^TM1700、Irgacure^TM 907、Irgacure^TM819 those commercially available from Ciba Geigy, Ciba refining, Switzerland, and Aceto, Lake Success, NY, under the trade names UVI-6976 and UVI-6992. Phenyl- [ p- (2-hydroxytetradecyloxy) phenyl]Iodonium hexafluoroantimonate is a photoinitiator commercially available from Gelest (Tullytown, Pa.) in Taristine, Pa. Phosphine oxide derivatives including Lucirin^TMTPO, which is 2,4, 6-trimethylbenzoyldiphenylphosphine oxide available from Pasteur (Charlotte, N.C.) BASF (N.C). Difunctional alpha hydroxy ketone photoinitiators are commercially available from lambertian corporation, lambertia USA under the trade designation "ESACURE ONE". Other useful photoinitiators are known in the art. The photoinitiator is used at a concentration of about 0.1 to 10 wt% or about 0.1 to 5 wt%, based on the organic portion of the formulation (parts per hundred grams).

The hardcoat layer may be cured in an inert atmosphere. In some embodiments, the hardcoat layer can be cured with an Ultraviolet (UV) light source under a nitrogen blanket.

The polymerizable hardcoat composition can be formed by: the free-radically polymerizable material is dissolved in a compatible organic solvent and then combined with a nanoparticle dispersion having a solids concentration of about 50% to 70%. One of the aforementioned organic solvents or a blend thereof may be employed.

The hardcoat film compositions can be applied to (e.g., film) substrates in a single layer or multiple layers using conventional film application techniques. The film may be applied using a variety of techniques including dip coating, forward and reverse roll coating, wire wound rod coating and die coating. Die coaters include knife coaters, slot coaters, slide coaters, fluid bearing coaters, slide curtain coaters, drop curtain coaters, and extrusion coaters, among others. Various types of die coaters are described in the literature. Although the substrate is typically conveniently in the form of a roll of continuous web, the coating may be applied to a separate sheet.

The hardcoat composition is dried in an oven to remove the solvent and then cured, preferably under an inert atmosphere (oxygen content below 50ppm), for example by exposure to ultraviolet radiation at the desired wavelength (using an H-bulb or other lamp). This reaction mechanism causes the free-radically polymerizable material to crosslink.

The thickness of the cured hardcoat layer 17 is typically at least 0.5, 1, or 2 microns. The thickness of the hardcoat layer is typically no greater than 10 microns.

In some embodiments, the major surface of the thermoplastic polyurethane substrate layer 14 comprises the siliceous layer 13 on the thermoplastic polyurethane substrate layer 14. In typical embodiments, the hardcoat layer 17 is disposed between the thermoplastic polyurethane base layer 14 and the siliceous layer 13, as shown in FIG. 4.

The siliceous layer is typically a continuous layer having a low level of porosity. For example, when the siliceous layer comprises a dried network of acid-sintered nanoparticles as described in WO2012/173803, the siliceous layer of sintered nanoparticles has a porosity of 20 to 50 volume percent, 25 to 45 volume percent, or 30 to 40 volume percent. Porosity can be calculated from the refractive index of the (sintered nanoparticle) primer coating according to published procedures as in, for example, w.l. bragg and a.b. pipprard, Acta Crystallographica, 6,865 (1953). In contrast, the siliceous layer described herein has a porosity of less than 20%, 15%, or 10% by volume. In some embodiments, the siliceous layer has a porosity of less than 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%.

The refractive index of fused silica is reported to be 1.458. Since the refractive index of air is 1.0, the porous siliceous layer has a lower refractive index than fused silica. For example, when the siliceous layer has a porosity of 20 vol%, the calculated refractive index will be 1.164.

In some embodiments, the siliceous layer further comprises carbon. For example, the siliceous layer may comprise from about 10 atomic% to about 50 atomic% carbon. The siliceous layer may have a refractive index greater than 1.458 (i.e., fused silica) due to the combination of carbon inclusion and low porosity. For example, the refractive index of the siliceous layer may be at least 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, or 1.60. As the carbon content increased from 30 at% to 50 at% carbon, the refractive index also increased. In some embodiments, the refractive index may be in a range of up to 2.2.

The atomic composition of the siliceous layer (e.g., silicon, carbon, oxygen) can be determined by Electron Spectroscopy for Chemical Analysis (ESCA). The presence of Si-C bonding can be determined by Fourier Transform Infrared Spectroscopy (FTIR). Optical properties (e.g., refractive index) can be measured by Ellipsometry (Ellipsometry).

In one advantageous embodiment, the siliceous layer is a diamond like glass ("DLG") film, such as described in U.S. Pat. No. 6,696,157(David et al). An advantage of such materials is that such DLGs may provide improved stiffness, dimensional stability and durability in addition to providing a silicone bondable front surface on the body member. This is particularly beneficial when the components underlying the base member are relatively soft.

Exemplary diamond-like glass materials suitable for use in the present invention comprise a carbon-rich diamond-like amorphous covalent system comprising carbon, silicon, hydrogen, and oxygen. The absence of crystallinity in an amorphous siliceous (e.g. DLG) layer can be determined by X-Ray Diffraction (XRD). DLG is produced by depositing a dense random covalent system comprising carbon, silicon, hydrogen and oxygen under ion bombardment conditions by placing the substrate on an energized electrode in a radio frequency ("RF") chemical reactor. In a particular implementation, DLG is deposited under intense ion bombardment conditions of a tetramethylsilane and oxygen mixture. Generally, DLG exhibits negligible optical absorption in the visible and ultraviolet regions, i.e., about 250 to about 800 nm. Additionally, DLG generally exhibits improved resistance to flex cracking and excellent adhesion to many substrates including ceramics, glass, metals, and polymers compared to other types of carbon-containing films.

DLG typically contains at least about 30 atomic% carbon, at least about 25 atomic% silicon, and less than or equal to about 45 atomic% oxygen. DLG typically contains from about 30 atomic% to about 50 atomic% carbon. In particular implementations, the DLG may include about 25 atomic% to about 35 atomic% silicon. Additionally, in certain implementations, DLG includes about 20 atomic% to about 40 atomic% oxygen. In a particularly advantageous implementation, DLG comprises, on a hydrogen free basis, from about 30 atomic% to about 36 atomic% carbon, from about 26 atomic% to about 32 atomic% silicon, and from about 35 atomic% to about 41 atomic% oxygen. "not counting hydrogen" refers to the atomic composition of a substance determined by a method such as chemical analysis Electron Spectroscopy (ESCA) that does not detect hydrogen even if a large amount of hydrogen is present in the thin film.

The (e.g. DLG) siliceous layer can be made to a specific thickness, typically in the range of at least 50nm, 75nm or 100nm to 10 microns. In some embodiments, the thickness is no greater than 5 microns, 4 microns, 3 microns, 2 microns, or 1 micron. In some embodiments, the thickness is less than 1 micron, 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, or 200 nm.

The urethane (meth) acrylate oligomer and hardcoat composition are synthesized or selected so that they do not detract from the ability to stretch the film by hand. Thus, the load at 25% strain per cm of film width of the compliant base layer 14, which also includes the hardcoat layer, is in the same range as previously described. In some embodiments, the load at 25% strain/cm film width is equal to or less than the load of a separate (e.g., conformable) film at 25% strain/cm film width. Inclusion of a siliceous (e.g. DLG) layer also did not detract from the load at 25% strain/cm film width. Thus, a conformable organic substrate member (e.g., film) that also includes a hardcoat layer and a siliceous (e.g., DLG layer) also has a load at 25% strain per centimeter of film width in the same range as previously described.

The inclusion of the hardcoat layer and DLG can affect the tensile modulus and ultimate tensile strength of the (e.g., conformable) film. These properties may vary by 5MPa, 10MPa, 15MPa or 20MPa but still fall within the ranges previously described.

In some embodiments, the inclusion of the hardcoat layer and the siliceous layer (e.g., DLG) does not detract from the tensile strain at break or otherwise elongation at break of the (e.g., conformable) film. Therefore, the breaking stretch dyeing of the film also comprising these layers is in the same range as previously described.

Examples

Various embodiments of the present invention may be better understood by reference to the following examples, which are provided by way of illustration. The present invention is not limited to the examples given herein.

Examples

Material

TABLE 2

Test method

Gel Permeation Chromatography (GPC) molecular weight measurement

Membrane samples were analyzed by conventional GPC against polystyrene molecular weight standards using Tetrahydrofuran (THF) as the solvent and eluent. The molecular weight results are not absolute, but relative to the hydrodynamic volume of polystyrene in THF. A sample solution of thermoplastic polyurethane ("TPU") resin was prepared in tetrahydrofuran (THF, stabilized with 250ppm of butylated hydroxytoluene) at a concentration ≈ 2 mg/mL. The sample was allowed to dissolve for approximately 3 hours. The sample solution was filtered through a 0.45 micron teflon syringe filter and then analyzed by gas chromatography.

GPC conditions：

Reporting the measured weight average molecular weight ("MW_w”)。

Dynamic mechanical analysis

Dynamic mechanical properties were measured using a Rheometer Solids Analyzer (RSA) from TA Instruments, New Castle, DE, n.ka. The temperature between-50 ℃ and 180 ℃ was monitored at 0.1% strain and 1.0 Hz. The glass transition temperature ("Tg" obtained from the peak of Tan δ) and softening temperature are reported.

Dyeing of 10% bitumen in diesel fluids

Standard bitumen was dissolved in diesel fluid to make a 10 wt% bitumen solution. The film was applied to a white painted panel (steel panel with 648DM640 basecoat and RK8014 clearcoat, from ACT Test Panels, Hillsdale, MI, hill dall, michigan). A 10 wt% bitumen solution was then applied to the surface of the membrane at a diameter of about 1 inch (2.5cm) and left on the membrane surface for 24 hours. After 24 hours, clean with naphtha. The change in the yellowing color ("Δ b") of the film surface before and after staining was measured by a standard colorimeter.

Haze value

For haze values, a thermoplastic polyurethane film sample was laminated to a transfer adhesive (isooctylacrylate/acrylic acid copolymer) and applied to a 6 mil (150 micron) polyester terephthalate (PET) film layer. Initial haze was measured by HAZEGARD and reported. Further, in some cases, the film samples were heat aged at 80 ℃ for 7 days, and then haze was measured again with HAZEGARD and reported as "haze after heat aging at 80 ℃ for 7 days".

In the following examples (EX-1 to EX-3), a twin screw extruded aliphatic Thermoplastic Polyurethane Film (TPF) had a hard segment content maintained at about 48.25 wt.% and a Shore A hardness maintained at about 87A. Shore A hardness measurement according to ASTM Standard D2240-15

Example 1(EX-1)

All ingredients, including 504.7 grams of FOMREZ-44-111 (having a melting temperature of 60 ℃ C.) premelted at 100 ℃,5 grams of IRGANOX-1076, 0.3 grams of T12 dibutyltin dilaurate catalyst, 88.6 grams of 1,4 butanediol, 393.9 grams of DESMODUR W, 3 grams of TINUVIN-292, and 4.5 grams of TINUVIN-571, were fed separately into a twin screw extruder. The extruder settings, conditions and temperature characteristics were similar to those described in example No. 1 and table 1 of U.S. patent 8,551,285. The isocyanate index was NCO/OH ═ 1.01, and the hard segment was 48.25 wt%. The resulting aliphatic Thermoplastic Polyurethane Film (TPF) was extruded as a 150 micron thick layer onto a polyester carrier web. TPF was aged at ambient temperature for 2 weeks prior to testing, and the test results are summarized in table 3.

Example 2(EX-2)：

All ingredients (including 505.2 grams of FOMREZ-44-111 (having a melting temperature of 60 ℃) premelted at 100 ℃,5 grams of IRGANOX-1076, 0.3 grams of T12 dibutyltin dilaurate catalyst, 85.7 grams of 1,4 butanediol, 397.2 grams of DESMODUR W, 3 grams of TINUVIN-292, and 4.5 grams of TINUVIN-571) were fed separately into a twin screw extruder. The extruder settings, conditions and temperature characteristics were similar to those described in example No. 1 and table 1 of U.S. patent 8,551,285. The isocyanate index was NCO/OH ═ 1.04, and the hard segment content was 48.25%. The resulting aliphatic Thermoplastic Polyurethane Film (TPF) was extruded as a 150 micron thick layer onto a polyester carrier web. TPF was aged at ambient temperature for 2 weeks prior to testing, and the test results are summarized in table 3.

Example 3(EX-3)

All ingredients (including 509.7 grams of FOMREZ-44-111 (having a melting temperature of 60 ℃) pre-melted at 100 ℃,5 grams of IRGANOX-1076, 1.0 gram of T12 dibutyltin dilaurate catalyst, 87.1 grams of 1,4 butanediol, 0.9 grams of glycerol, 394.5 grams of DESMODUR W, 3 grams of TINUVIN-292, and 4.5 grams of TINUVIN-571) were fed separately into a twin screw extruder. The extruder settings, conditions and temperature characteristics were similar to those described in example No. 1 and table 1 of U.S. patent 8,551,285. The isocyanate index was NCO/OH ═ 1.01, and the hard segment was 48.25%. The hydroxyl group crosslinking agent was 1.0% based on the total hydroxyl group mole%. The resulting aliphatic Thermoplastic Polyurethane Film (TPF) was extruded as a 150 micron thick layer onto a polyester carrier web. TPF was aged at ambient temperature for 2 weeks prior to testing, and the test results are summarized in table 3.

Comparative example 1(CE-1)

Thermoplastic polyurethane resin pellets ESTANE D91F87MI were prepared by twin screw reactive extrusion followed by pelletizing the resin in an underwater bath. TPU pellets containing processing wax and anti-tacking agent were extruded from the same twin screw extruder onto a polyester carrier web in a 150 micron thick film with similar extrusion temperature characteristics as in example 1. TPF was aged at ambient temperature for 2 weeks prior to testing, and the test results are summarized in table 3.

Comparative example 2(CE-2)

Thermoplastic polyurethane resin pellets ESTANE ALR CL87A-V containing processing wax and anti-tack agent were extruded from the same twin screw extruder onto a polyester carrier web in a 150 micron thick film with similar extrusion temperature profiles as in example 1. TPF was aged at ambient temperature for 2 weeks prior to testing, and the test results are summarized in table 3.

TABLE 3

In Table 3, "ND" — unidentified

Example 4

The hardcoat film was prepared by combining the following components with MEK under stirring to yield a 35% solids solution:

65.2% by weight of CN991 (aliphatic urethane diacrylate Tg 27 ℃ C., from Sartomer America, Exton, Pa., USA),

16.4 wt% SR506 (isobornyl acrylate, Tg 88 ℃, available from Sartomer Americas), and

16.4 wt% SR238 (hexanediol diacrylate, Tg 43 ℃, from Sartomer America)

97.3 wt% of the solution was combined with 2 wt% of Escapure One photoinitiator and 0.6 wt% of Tegorad 2100.

A hardcoat coating composition was applied to the thermoplastic polyurethane film of example 3 using a #12 wire wound rod (available from r.d. specialties, Webster NY) and dried at 65 ℃ for 2 minutes. The coating was then cured using a 500 watt/in Fusion H bulb (available from Fusion UV Systems, Gaithersburg MD) at 40 feet/minute (12.2m/min) under 100% power and nitrogen. The thickness of the cured coating was about 5 microns.

Example 5

A DLG layer was deposited onto the cured hardcoat layer of the film of example 4 using a 2-step beam process. Some modifications were made using the house building plasma processing system detailed in us patent 5,888,594(David et al): the width of the drum electrode was increased to 42.5 inches (108cm) and the partition between the two compartments within the plasma system was removed so that all pumping was done using a turbomolecular pump and thus operated at a process pressure of about 10-50 millitorr (1.33-6.7 Pa).

A film roll with a cured hardcoat film was mounted in the chamber, the film wound around the drum electrode and secured to a take-up roll on the opposite side of the drum. Will unwindAnd the take-up tension was maintained at 8 pounds (13.3N) and 14 pounds (23.3N), respectively. Close the door and pump the chamber to 5x10^-4Torr (6.7Pa) of the reference pressure. For the precipitation step, Hexamethyldisiloxane (HMDSO) and oxygen were introduced at flow rates of 200 and 1000 standard cubic centimeters per minute, respectively, and the operating pressure was nominally at 35 millitorr (4.67 Pa). The plasma was started at 9500 watts of power by applying rf power to the drum and the drum was started to rotate so that the film was transported at a speed of 10 feet per minute (3 meters per minute). The run was continued until the full length of film on the roll was completed.

After the DLG deposition step was completed, the rf power was deactivated, the HMDSO vapor flow was stopped, and the oxygen flow rate was increased to 2000 standard cubic centimeters per minute. At steady flow rates and pressures, the plasma was restarted at 4000 watts and the web was transported in the opposite direction at a speed of 10ft/min (3m/min), with the pressure nominally stabilized at 14 millitorr (1.87 Pa). This second plasma treatment step is to remove the methyl groups from the DLG film and replace them with oxygen-containing functional groups (such as Si-OH groups), which facilitates the grafting of the silane compound to the DLG film.

After the entire roll of film is processed in the manner described above, the rf power is disabled, the oxygen flow is stopped, the chamber is vented to atmosphere, and the roll is removed from the plasma system for further processing. The thickness of the resulting DLG layer was about 60 nm.

Tensile test method

Tensile specimens were cut from the film of example 3, the film of example 4 having a cured hardcoat, and the film of example 5 having a cured hardcoat and a DLG layer using a cutter to obtain specimens 25cm long × 12.7mm wide. Tensile testing was done according to ASTM D882-12 using an Instron 55R1122 model Universal load frame with flat grips. For all samples, the initial clamp spacing was 5.1cm and the crosshead speed was 100 mm/min. The temperature during the test was 20. + -. 2 ℃. Nominal film thickness is used to determine modulus and tensile strength, which ignores adhesive thickness. All results are the average of 5 test samples.

TABLE 4 tensile test results

Although the terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, it being recognized that various modifications are possible within the scope of the embodiments of the invention. Thus, it should be understood that although the present invention has been specifically disclosed by particular embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of embodiments of this invention.

Additional embodiments：

The present invention provides the following exemplary embodiments, the numbering of which should not be construed as specifying the degree of importance:

embodiment 1 provides a surfacing film comprising:

a base layer, the base layer comprising:

a thermoplastic polyurethane film comprising the reaction product of a reaction mixture comprising:

a diisocyanate; and

a polyester polyol having a melting temperature of at least 30 ℃; and

a diol chain extender.

Embodiment 2 provides the overlay film of embodiment 1 wherein the thermoplastic polyurethane film has a weight average molecular weight in the range of from about 80,000 daltons to about 400,000 daltons.

Embodiment 3 provides a patch film according to any of embodiments 1 or 2, wherein the polyester polyol has a melting temperature of at least 40 ℃.

Embodiment 4 provides a facial mask as set forth in any of embodiments 1-3 wherein the diisocyanate has the structure:

O＝C＝N-R-N＝C＝O，

wherein R is selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₄-C₂₀) Arylene radical- (C)₁-C₄₀) Alkylene- (C)₄-C₂₀) Arylene, (C)₄-C₂₀) Cycloalkylene and (C)₄-C₂₀) An aralkylene group.

Embodiment 5 provides a patch film according to any of embodiments 1-4, wherein the diisocyanate is selected from dicyclohexylmethane-4, 4' -diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate, m-xylene diisocyanate, tolylene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, poly (hexamethylene diisocyanate), 1, 4-cyclohexylene diisocyanate, 4-chloro-6-methyl-1, 3-phenylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane 4,4' -diisocyanate, 1, 4-diisocyanatobutane, 1, 8-diisocyanatooctane or mixtures thereof.

Embodiment 6 provides a patch film according to any of embodiments 1-5, wherein the polyester polyol is the product of a condensation reaction.

Embodiment 7 provides a patch film according to any of embodiments 1-6, wherein the polyester polyol is free of ring-opening polymerization reaction products.

Embodiment 8 provides a facial mask as set forth in any of embodiments 1-7 wherein the polyester polyol is a polyester diol.

Embodiment 9 provides a patch film according to any of embodiments 1-8, wherein the polyester polyol comprises one or more of the following: polyglycolic acid, polybutylene succinate, poly (3-hydroxybutyrate-co-3-hydroxyvalerate), polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, and copolymers thereof.

Embodiment 10 provides a patch film according to any of embodiments 6-9, wherein the condensation reaction comprises a reaction between at least one of:

a plurality of carboxylic acids; and

carboxylic acids and polyols.

Embodiment 11 provides the patch film of embodiment 10, wherein the carboxylic acid has the structure:

wherein R is¹Selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₄-C₂₀) Cycloalkylene and (C)₄-C₂₀) An aralkylene group.

Embodiment 12 provides the patch film of any one of embodiments 10 or 11, wherein the carboxylic acid is selected from glycolic acid, lactic acid, succinic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, terephthalic acid, naphthalenedicarboxylic acid, 4-hydroxybenzoic acid, 6-hydroxynaphthalene-2-carboxylic acid, oxalic acid, malonic acid, adipic acid, pimelic acid, ethonic acid, suberic acid, azelaic acid, sebacic acid, glutaric acid, dodecanedioic acid, brassylic acid, tetraprotic acid, maleic acid, fumaric acid, glutaconic acid, 2-decenoic diacid, callus acid, muconic acid, glutinic acid, citraconic acid, mesaconic acid, itaconic acid, malic acid, aspartic acid, glutamic acid, tartaric acid, diaminopimelic acid, saccharic acid, methoxyoxalic acid, oxaloacetic acid, acetonedicarboxylic acid, arabithalic acid, phthalic acid, Isophthalic acid, biphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, or mixtures thereof.

Embodiment 13 provides a facial mask as set forth in any of embodiments 10-12 wherein the polyol has the structure:

wherein R is²Selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₁-C₄₀) Acyl (C)₄-C₂₀) Cycloalkylene, (C)₄-C₂₀) Aralkylene and (C)₁-C₄₀) Alkylene oxide radical, and R³And R⁴Independently selected from-H, -OH, substituted or unsubstituted (C)₁-C₄₀) Alkyl, (C)₂-C₄₀) Alkenyl, (C)₄-C₂₀) Aryl group, (C)₁-C₂₀) Acyl, (C)₄-C₂₀) Cycloalkyl group, (C)₄-C₂₀) Aralkyl and (C)₁-C₄₀) An alkoxy group.

Embodiment 14 provides a patch film according to any of embodiments 1-12, wherein the polyester polyol has the following structure:

wherein R is⁵And R⁶Independently selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₁-C₄₀) Acyl (C)₄-C₂₀) Cycloalkylene, (C)₄-C₂₀) Aralkylene and (C)₁-C₄₀) Alkylene oxide group, and n is a positive integer greater than or equal to 1.

Embodiment 15 provides a patch film according to any of embodiments 1-12, wherein the polyester polyol has the following structure:

wherein R is⁷Selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₁-C₄₀) Acyl (C)₄-C₂₀) Cycloalkylene, (C)₄-C₂₀) Aralkylene and (C)₁-C₄₀) Alkylene oxide group, and n is a positive integer greater than or equal to 1.

Embodiment 16 provides the facial mask of any of embodiments 1-15, wherein the glycol chain extender is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, or mixtures thereof.

Embodiment 17 provides a facial mask as set forth in any of embodiments 1-16 wherein the diol chain extender has a weight average molecular weight of less than about 250 daltons.

Embodiment 18 provides a patch film according to any of embodiments 1-17, wherein the thermoplastic polyurethane comprises hard segments in a range from about 30% to about 55% by weight.

Embodiment 19 provides a overlay film according to any of embodiments 1-18 wherein the thermoplastic polyurethane film comprises hard segments in the range of about 40% to about 55% by weight.

Embodiment 20 provides a facial mask as in any of embodiments 1-19, wherein the base layer is substantially free of at least one of: wax, anti-tacking agent and processing aid.

Embodiment 21 provides the overlay film of embodiment 20, wherein the protective film exposed to the 10% asphalt solution for 24 hours has a yellowing color change less than a corresponding protective film comprising a base layer comprising at least one of: wax, anti-tacking agent and processing aid.

Embodiment 22 provides a patch film according to any of embodiments 1-21, wherein the substrate layer is transparent.

Embodiment 23 provides a patch film according to any of embodiments 1-22, wherein the substrate layer has an initial film haze in the range of 0.7 to about 1.0.

Embodiment 24 provides the surfacing film according to any one of embodiments 1-23 further comprising a varnish coating attached to a second major surface of the substrate layer opposite the first major surface.

Embodiment 25 provides the overlay film of embodiment 24 wherein the varnish coating comprises a thermoset polyurethane.

Embodiment 26 provides a patch film according to any of embodiments 1-25, wherein the polyurethane of the base layer is at least partially crosslinked.

Embodiment 27 provides a patch film according to embodiment 26, wherein the polyurethane is crosslinked with a hydroxyl crosslinking agent.

Embodiment 28 provides a patch film according to any of embodiments 1-27, wherein the polyester polyol is free of polycaprolactone polyol.

Embodiment 29 provides a facial mask according to any one of embodiments 1-28, wherein the facial mask is a surface protective film.

Embodiment 30 provides the surfacing film according to any one of embodiments 1-29 further comprising a pressure sensitive adhesive layer disposed on a major surface of the substrate layer.

Embodiment 31 provides a facial mask as set forth in any of embodiments 1-30 wherein the base layer has a shore a hardness in the range of from about 70A to about 95A.

Embodiment 32 provides a patch film according to any of embodiments 1-31, wherein the base layer has a shore a hardness in the range of about 83A to about 90A.

Embodiment 33 provides an assembly comprising the surfacing film according to any one of embodiments 1-32.

Embodiment 34 provides the assembly of embodiment 33, further comprising a substrate selected from a portion of a vehicle body or window, wherein the surfacing film is attached to the substrate.

Embodiment 35 provides the assembly of embodiment 34, wherein the portion of the vehicle is selected from a hood, fender, mirror, door, roof, panel, portion thereof, hull, propeller, blade, wing, fuselage, or a combination thereof.

Embodiment 36 provides a method of forming a surfacing film according to any one of embodiments 1-35 comprising the steps of:

forming a base layer by a process comprising:

introducing components comprising a diisocyanate, a diol chain extender, and a polyester polyol into an extruder to provide a molten thermoplastic polyurethane, wherein the polyester polyol has a melting temperature of at least 30 ℃;

extruding the molten thermoplastic polyurethane through a die as a uniform film onto a carrier web; and

curing the thermoplastic polyurethane film to obtain the substrate layer.

Embodiment 37 provides a method of making a facial mask, the method comprising the steps of:

forming a base layer by a process comprising:

introducing components comprising a diisocyanate, a diol chain extender, and a polyester polyol into an extruder to provide a molten thermoplastic polyurethane, wherein the polyester polyol has a melting temperature of at least 30 ℃;

extruding the molten thermoplastic polyurethane through a die as a uniform film onto a carrier web; and

curing the thermoplastic polyurethane film to obtain the substrate layer.

Embodiment 38 provides the method of embodiment 37, further comprising laminating a pressure sensitive adhesive layer to the first major surface of the substrate layer.

Embodiment 39 provides the method of embodiment 38, further comprising laminating a varnish coating comprising a thermoset polyurethane onto the second major surface of the substrate layer.

Embodiment 40 provides the method of any of embodiments 37 or 39, wherein the isocyanate index of the components of the thermoplastic polyurethane is in the range of about 0.99 to about 1.20.

Embodiment 41 provides the method of any of embodiments 37-40, wherein the isocyanate index of the components of the thermoplastic polyurethane is in the range of about 1.00 to about 1.10.

Embodiment 42 provides the method of any one of embodiments 37-41, wherein the extruder is a twin screw extruder or a planetary extruder.

Embodiment 43 provides the method of embodiment 42, wherein the twin screw extruder is a co-rotating twin screw extruder or a counter-rotating twin screw extruder.

Embodiment 44 provides the method of any one of embodiments 37-43, wherein the polyurethane film has a weight average molecular weight in the range of from about 80,000 daltons to about 400,000 daltons.

Embodiment 45 provides the method of any one of embodiments 37-44, wherein the weight average molecular weight of the polyurethane film is in the range of about 100,000 daltons to about 250,000 daltons.

Embodiment 46 provides the method of any one of embodiments 37-45, wherein the diisocyanate has the structure:

O＝C＝N-R-N＝C＝O，

wherein R is selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₄-C₂₀) Arylene radical- (C)₁-C₄₀) Alkylene- (C)₄-C₂₀) Arylene, (C)₄-C₂₀) Cycloalkylene and (C)₄-C₂₀) An aralkylene group.

Embodiment 47 provides the method of any one of embodiments 37-46, wherein the diisocyanate is selected from the group consisting of dicyclohexylmethane-4, 4' -diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate, m-xylene diisocyanate, tolylene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, poly (hexamethylene diisocyanate), 1, 4-cyclohexylene diisocyanate, 4-chloro-6-methyl-1, 3-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene, Diphenylmethane 4,4' -diisocyanate, butane 1, 4-diisocyanate, octane 1, 8-diisocyanate or mixtures thereof.

Embodiment 48 provides the method of any one of embodiments 37-47, wherein the polyester polyol is a product of a condensation reaction.

Embodiment 49 provides the method of any one of embodiments 37-48, wherein the polyester polyol is free of a ring-opening polymerization reaction product.

Embodiment 50 provides the method of any one of embodiments 37-49, wherein the polyester polyol is a polyester diol.

Embodiment 51 provides the method of any one of embodiments 37-50, wherein the diol chain extender has a weight average molecular weight of about 250 daltons.

Embodiment 52 provides the method of any one of embodiments 37-51, wherein the polyester polyol comprises one or more of: polyglycolic acid, polybutylene succinate, poly (3-hydroxybutyrate-co-3-hydroxyvalerate), polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, and copolymers thereof.

Embodiment 53 provides a method according to any one of embodiments 48-52, wherein the condensation reaction comprises a reaction between at least one of:

a plurality of carboxylic acids; and

carboxylic acids and polyols.

Embodiment 54 provides the method of embodiment 53, wherein the carboxylic acid has the structure:

wherein R is¹Is selected from (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₄-C₂₀) Cycloalkylene and (C)₄-C₂₀) An aralkylene group.

Embodiment 55 provides the method of any one of embodiments 53 or 54, wherein the carboxylic acid is selected from glycolic acid, lactic acid, succinic acid, 3-hydroxybutyric acid, 3-hydroxypentanoic acid, terephthalic acid, naphthalenedicarboxylic acid, 4-hydroxybenzoic acid, 6-hydroxynaphthalene-2-carboxylic acid, oxalic acid, malonic acid, adipic acid, pimelic acid, ethonic acid, suberic acid, azelaic acid, sebacic acid, glutaric acid, dodecanedioic acid, brassylic acid, tetraprotic acid, maleic acid, fumaric acid, glutaconic acid, 2-decenoic diacid, callus acid, muconic acid, glutinic acid, citraconic acid, mesaconic acid, itaconic acid, malic acid, aspartic acid, glutamic acid, tartronic acid, tartaric acid, diaminopimelic acid, saccharic acid, methoxyoxalic acid, oxaloacetic acid, acetonic acid, arabinodicarboxylic acid, phthalic acid, succinic acid, fumaric acid, citraconic acid, mesaconic acid, glutaric acid, isophthalic acid, biphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, or mixtures thereof.

Embodiment 56 provides the method of any one of embodiments 53-55, wherein the polyol has the structure:

wherein R is²Is selected from (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₁-C₄₀) Acyl (C)₄-C₂₀) Cycloalkylene, (C)₄-C₂₀) Aralkylene and (C)₁-C₄₀) Alkylene oxide radical, and R³And R⁴Independently selected from-H, -OH, (C)₁-C₄₀) Alkyl, (C)₂-C₄₀) Alkenyl, (C)₄-C₂₀) Aryl group, (C)₁-C₂₀) Acyl, (C)₄-C₂₀) Cycloalkyl group, (C)₄-C₄₀) Aralkyl and (C)₁-C₄₀) An alkoxy group.

Embodiment 57 provides the method of any one of embodiments 37-56, wherein the polyester polyol has the following structure:

wherein R is⁵And R⁶Independently selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₁-C₂₀) Acyl (C)₄-C₂₀) Cycloalkylene, (C)₄-C₂₀) Aralkylene and (C)₁-C₄₀) Alkylene oxide group, and n is a positive integer greater than or equal to 1.

Embodiment 58 provides the method of any one of embodiments 37-57, wherein the polyester polyol has the following structure:

wherein R is⁷Selected from substituted or unsubstituted (C)₁-C₄₀) Alkylene, (C)₂-C₄₀) Alkenylene, (C)₄-C₂₀) Arylene, (C)₁-C₄₀) Acyl (C)₄-C₂₀) Cycloalkylene, (C)₄-C₂₀) Aralkylene and (C)₁-C₄₀) Alkylene oxide group, and n is a positive integer greater than or equal to 1.

Embodiment 59 provides the method of any one of embodiments 37-58, wherein the diol chain extender is selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, or mixtures thereof.

Embodiment 60 provides the method of any one of embodiments 37-59, wherein the thermoplastic polyurethane film comprises hard segments in a range of about 30% to about 55%.

Embodiment 61 provides the method of any one of embodiments 37-60, wherein the thermoplastic polyurethane film comprises hard segments in a range of about 40% to about 55%.

Embodiment 62 provides the method of any one of embodiments 37-61, wherein the overlay film is transparent.

Embodiment 63 provides the method of any one of embodiments 37-62, further comprising a varnish coating attached to a second major surface of the substrate layer opposite the first major surface.

Embodiment 64 provides the method of embodiment 63, wherein the clear coat layer comprises a thermoset polyurethane.

Embodiment 65 provides the method of any one of embodiments 37-64, wherein the polyurethane film of the substrate layer is at least partially crosslinked.

Embodiment 66 provides the method of any one of embodiments 37-65, wherein the component comprises a hydroxyl crosslinking agent.

Embodiment 67 provides the method of any one of embodiments 37-66, wherein the component is substantially free of aziridine crosslinking agent.

Embodiment 68 provides a surfacing film formed according to the method of any one of embodiments 37-68.

Embodiment 70 provides a method of using the overlay film according to any of embodiments 1-36, 68 or the overlay film formed using the method of any of embodiments 37-67, the method comprising:

contacting the overlay film with a substrate.

Embodiment 71 provides the method of embodiment 70, further comprising contacting the pressure surface adhesive of the bulk layer with the substrate.

Embodiment 72 provides the method of any one of embodiments 70 or 71, wherein the substrate is selected from a portion of a vehicle body or a window.

Embodiment 73 provides the method of embodiment 72, wherein the portion of the vehicle is selected from a hood, fender, mirror, door, roof, panel, portion thereof, hull, propeller, blade, wing, fuselage, or a combination thereof.

Embodiment 73 provides a facing film according to any of embodiments 1-31, wherein the facing film exhibits a load of no greater than 20N/cm of film width at 25% strain as determined using a tensile test with a crosshead speed of 100 mm/min.

Embodiment 74 provides the overlay film of any of embodiments 1-31 and 73 wherein the overlay film exhibits an elongation at break of at least 150% as determined by the tensile test with a strain rate of 200%/min.

Embodiment 75 provides a facial mask according to any of embodiments 1-31 and 73-74, wherein the facial mask further comprises a hardcoat layer that can stretch 25-75% without breaking.

Embodiment 76 provides the overlay film of any of embodiments 1-31 and 73-75 wherein the hardcoat layer comprises a polymerized urethane (meth) acrylate oligomer present in an amount ranging from 40 to 100 weight percent based on weight percent solids of the hardcoat.

Embodiment 77 provides a facial mask as set forth in any of embodiments 1-31 and 73-76 wherein the hardcoat layer further comprises polymerized units of an ethylenically unsaturated monomer, wherein a homopolymer of the ethylenically unsaturated monomer has a glass transition temperature of greater than 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃,55 ℃, 60 ℃, or 65 ℃.

Embodiment 78 provides a facial mask according to any one of embodiments 1-31 and 73-77, wherein the facial mask further comprises a siliceous layer.

Embodiment 79 provides a facial mask according to any of embodiments 1-31 and 73-78, wherein the facial mask comprises i) a hardcoat layer; or ii) a hardcoat layer and a siliceous layer; and the surfacing film exhibits an elongation at break of at least 150%, as determined with a tensile test using a strain rate of 200%/min.

All cited references, patents, and patent applications in the above application for letters patent are incorporated by reference herein in their entirety in a consistent manner. In the event of inconsistencies or contradictions between the incorporated reference parts and the present application, the information in the preceding description shall prevail. The preceding description, given to enable one of ordinary skill in the art to practice the claimed disclosure, is not to be construed as limiting the scope of the disclosure, which is defined by the claims and all equivalents thereto.