An embossed film and a method of making thereof

Abstract

Described herein is an embossed film comprising a resin derived from a (meth)acrylate-based compound comprising at least one hindered urea. Such resins enable deep embossing features and durable topcoats.

Description

PA102457WO02AN EMBOSSED FILM AND A METHOD OF MAKING THEREOFTECHNICAL FIELD

[0001] A method of making an embossed film is disclosed, wherein the film comprises a reversible urea crosslinking agent, which enables embossed films having large feature heights as well as being durable.SUMMARY

[0002] A decorative film has been used for the purposes of decoration of the interior and exterior of a structure, a vehicle, and the like. For example, a decorative film in which a polyvinyl chloride film including a printed layer and a transparent polyvinyl chloride film are laminated and which has been subjected to embossing is known. Various kinds of material texture such as woodgrain, metallic, textile, or marble texture can be expressed by using various combinations of lamination and embossing.

[0003] For high durability, these decorative films usually require performance top coatings. Typically, there is a tradeoff between coating layers that are able to be embossed with high embossing heights and topcoats that exhibit high scratch and chemical resistance. Thus, there is a desire to identify a material that can be embossed with high embossing heights, while also having high scratch resistance.

[0004] In one aspect, a method of making a decorative film is discussed. The method comprising:(a) providing a cured film, wherein the cured film is derived from:(i) a first (meth)acrylate-based compound comprising at least one hindered urea; and (ii) an initiator, wherein the cured film has a decrosslinking temperature;(b) heating the cured film near the decrosslinking temperature to provide a softened film;(c) contacting the softened film with a patterned substrate to form an imprinted film;(d) releasing the imprinted film from the patterned substrate; and(e) cooling the imprinted film to form the decorative film.

[0005] In another aspect, an embossed film is described comprising a surface layer having a plurality of features, wherein the surface layer is derived from a first (meth)acrylate-based compound comprising at least one hindered urea; and an initiator, wherein at least a portion of the plurality of features has a depth of at least 9 micrometers.

[0006] The above summary is not intended to describe each embodiment. The details of one or more embodiments of the invention are also set forth in the description below. Other features, objects, and advantages will be apparent from the description and from the claims.BRIEF DESCRIPTION OF DRAWINGS

[0007] FIG. 1 is a schematic cross-sectional view of an article of one embodiment of the present disclosure.DETAILED DESCRIPTION

[0008] As used herein, the term“a”, “an”, and “the” are used interchangeably and mean one or more; and“and / or” is used to indicate one or both stated cases may occur, for example A and / or B includes, (A and B) and (A or B): and“ambient temperature” means at a temperature of 25 degrees Celsius.

[0009] As used herein the term “(methjacrylate” refers to an acrylate, a methacrylate, or combinations thereof.

[0010] The term “curable” refers to a composition or component that can be cured. The terms “cured” and “cure” refer to the polymerization of monomers and / or joining polymer chains together by covalent chemical bonds to form a polymeric network. A cured polymeric network is generally characterized by insolubility, but it may be swellable in the presence of an appropriate solvent. The term “crosslinking” is used herein to refer to the process of chemically joining polymer chains together or the curing of polymer chains. In either instance, a chemical reaction takes place, resulting in the increased molecular weight of the polymer chains as they react together leading to a harder, tougher, or more stable linkage or substance.

[0011] As used herein, the term “solids” when used in reference to a percentage refers to the content minus any solvents or water that may be present. Generally, it refers to the resulting polymer and any solid additives that may be present.

[0012] Also herein, recitation of ranges by endpoints includes all numbers subsumed within that range (e.g., 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0013] Also herein, recitation of “at least” followed by a number, includes the specific number and all numbers greater that that specific number. For example, “at least one” includes all numbers of one and greater (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.). The recitation of “at most” followed by a number, includes the specific number and all numbers less that that specific number. For example, “at most ten” includes all numbers of ten and lower (e.g., at most 9, at most 6, at most 1, etc.).

[0014] As used herein, “comprises at least one of’ A, B, and C refers to element A by itself, element B by itself, element C by itself, A and B, A and C, B and C, and a combination of all three.

[0015] In the present disclosure, it has been discovered that hindered ureas can be used in embossing of (meth)acrylate-based layers (or films), resulting in patterned films that can be used as outer-facing topcoats having deep features with good scratch resistance.

[0016] In the present disclosure, the (meth)acrylate-based film is derived from a (meth)acrylate-based compound comprising at least one hindered urea and an initiator.

[0017] The (mcth)acrylarc-bascd compound comprising at least one hindered urea (herein referred to as (methjacrylate -based compound) comprises at least one (methjacrylate moiety. In some embodiments, the (meth)acrylate-based compound may comprise 2, 3, 4, or more (methjacrylate moieties (-C(=O)OCH=CH2 or -C(=O)OCH=CHCH3). In some embodiments, no more than 10, 18, 12, 10, 8, 6, or even 4 (methjacrylate moieties.

[0018] The (meth)acrylate-based compound also comprises at least one hindered urea. A hindered urea is a urea having a bulky group attached to one of the nitrogen atoms to sterically hinder the nitrogen from undergoing easy reaction. For example, a hindered urea can be of the formula -NX-C(=0)-NH-, wherein X is a sterically bulky group such as methyl, ethyl, isopropyl, or tert-butyl group. In some embodiments, the NX portion of the hindered urea forms a ring structure such as divalent 2,2,6,6-tetramethyl piperidyl moiety. In some embodiments, the (meth)acrylate-based compound may comprise 2, 3, 4, or more hindered ureas. In some embodiments, no more than 20, 18, 12, 10, 8, 6, or even 4 hindered ureas.

[0019] The (meth)acrylate portion of the (meth)acrylate-based compound enables crosslinking of the curable composition. The hindered urea groups, on the other hand, may also crosslink, but under specific conditions. These hindered urea groups provide a dynamic covalent chemistry that leverages fast, reversible reactions to exchange covalent bonds under specific conditions. The exchange of covalent crosslinks in a networked material, allows reworkability, thermoformability, recyclability, or self-healing capabilities that cannot be done with traditional crosslinks. The present disclosure employs the use of these dynamic covalent bonds in the crosslinking moiety to achieve good embossing properties (such as deep features) and having a durable topcoat. Specifically, reversible crosslinking allows a fully crosslinked adhesive to ‘de-crosslink’ at elevated temperatures enabling good embossing features. Once coated and cooled to ambient temperatures, this film can ‘re-crosslink’ without additional curing steps.

[0020] In some embodiments, the (meth)acrylate-based compound is of formula (I), (IIA), (IIB), (III) or combinations thereof.0 0 0y l Yt A,-Y2X z- Y °N 0fR1XHR2(J)0 0 0 0<s. Ax xYl -J -.. L A xY2J-L x<A O N N N N 'O YR1xH HX R2(IIA)o o o of AY 01M N A. NrL ■- M N A. N. xY2O A yI H ' ' H ’R1X X R2(IIB)R3(III)where R1, R2, and R3are independently selected from H or CH3; Y1, Y2, and Y ’ are independently selected from a divalent linking group selected from an alkylene, alkenylene ester, cycloalkene, or aromatic alkylenylene group, optionally comprising at least one carbamate group, at least one urea group, or combinations thereof; each X independently comprises a bulky hydrocarbon group, optionally comprising one or more ether linkages; and L1, L2, and L’ are independently selected from a divalent linking group.

[0021] In some embodiments, Y1, Y2, and Y3comprises 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. Exemplary Y1, Y2, and Y3groups include: -(CH2)n-, where n is an integer from 1 to 12.

[0022] In some embodiments, X is represented by formula (IV7) -C(R4)3 w’herein R4is an alkyl group or an alkoxy group comprising 1 to 6 carbon atoms or an aromatic group. Exemplary X groups include: methyl, ethyl, iso-propyl, or tert-butyl. In some embodiments, X is combined in -Y1NX-, or -NXL- to form a ringed amine group comprising 3 to 12 carbon atoms. Such a ringed amine group includes 2, 2,6,6-tetramethyl piperidyl.

[0023] In some preferred embodiments, R1is -H, X is ethyl, and R2is -CH3.

[0024] L1, L2, and L’ are not particularly limited and can be any linking group known in the art, so long as it doesn’t undergo any reaction during the crosslinking or embossing of the resin. Exemplary L1, L2, and L3groups include alkyl groups comprising 1 to 12 carbon atoms, optionally substituted with N (i.e., amine), O (i.e., ether), S (i.e., thiol), or other atoms. L1, L2, and L3may be linear, branch or cyclic in nature. L1, L2, and L3may independently comprise a urethane, carbamate, urea, ester, alkoxy, carbonyl and / or aromatic group. Exemplary L1, L2, and L3include: -CH2-, or -CH2CH2-. As mentioned above L1, L2, and L ’ may be combined with -NX- to form a ringed structure such as 2,2,6,6-tetramethyl-4-piperidyl.

[0025] The (mcth)acrylarc-bascd compounds disclosed herein may be prepared by methods known to those of ordinary skill in the relevant arts, for example, by reaction of a product formed from the reaction of an isocyanatoalkyl (meth)acrylate (e.g., 2-isocyanatoethyl acrylate) and an alkyl ethanolamine (e.g., N-t-butyl ethanolamine) with a (meth)acryloyl acid chloride (e.g., acryloyl chloride).

[0026] Exemplary (meth)acrylate-based compounds include:or combinations thereof, where R is methyl, isopropyl, or t-butyl.

[0027] In some embodiments, the curable composition comprises the (mcth)acrylarc-bascd compound in an amount of at least 30, 40, 50, or even 55% to at most 100, 90, 80, 70, or even 60% parts by weight relative to the total weight of the curable composition.

[0028] The curable composition of the present disclosure also comprises an initiator, which is used to initiate the reaction of the (meth)acrylate-based compound. The initiator can be a photoinitiator or a thermal initiator. Typically, the initiator is a photoinitiator, which can be activated by irradiation with actinic radiation. As used herein, actinic radiation refers to electromagnetic radiation in the ultraviolet, visible, and infrared wavelengths. For example, in one embodiment, the photoinitiator is activated by irradiation of wavelengths from at least 180, 200, 210, 220, 240, 260, or even 280 nm (nanometer); and at most 700, 800, 1000, 1200, or even 1500 nm. In one embodiment, the photoinitiator is activated by irradiation of wavelengths from at least 180, 210, or even 220 nm; and at most 340, 360, 380, 400, 410, 450, or even 500 nm.

[0029] Photoinitiators are known in the art. Examples of suitable free radical photoinitiators include those available under the trade designation OMNIRAD 4265, OMNIRAD 184, OMNIRAD 651, OMNIRAD 1173, OMNIRAD 819, OMNIRAD TPO, and OMNIRAD TPO-L from IGM Resins, Charlotte, NC. Particularly suitable photoinitiators include those that feature high absorbance above 365 nm wavelength. These include the acylphosphine oxide family of photoinitiators such as OMNIRAD TPO, OMNIRAD TPO-L, or OMNIRAD 819.

[0030] In some embodiments, the curable composition comprises an initiator in an amount of at least 0.1, 0.5, 1, or even 2 weight (wt)% and at most 10, 8, 5, 4, or even 3 wt% versus the total weight of the curable composition.

[0031] In addition to the (meth)acrylate-based compound and the initiator, the curable composition may include additional monomers or additives.

[0032] In some embodiments, the curable composition comprises an additional monomer, such as a (meth)acrylate monomer or an oligomer thereof, wherein the oligomer has at least one (meth)acrylate moiety. Exemplary additional (meth)acrylate monomers include alkyl(meth)acrylates comprising at least 1, 2, 4, 6, 8, 10, 12, or even 14 carbon atoms; and at most 16, 18, 20, 25, or even 30 carbon atoms. Such alkyl(meth)acrylates include: 2 -methyl butyl acrylate, isobornyl (meth)acrylate, 2-ethyl hexyl acrylate, butyl acrylate, iso-octyl acrylate, heterocyclic acrylate (e.g., tetrahydrofurfuryl acrylate), or combinations thereof. Exemplary' additional (meth)acrylate monomers include polar (meth)acrylate monomers. Such polar (meth)acrylate monomers include acrylic acid, methacrylic acid, 4-hydroxybutyl (meth)acrylate, hydroxy ethyl (meth)acrylate, tert-octylacrylamide, or combinations thereof. In some embodiments, the cured film is derived at least 10 wt % to at most 70 wt % of the (meth)acrylate monomer or an oligomer thereof.

[0033] Exemplary additives include, for example, fillers, pigments, plasticizers, tackifier (e.g., tackifying resins available commercially under the trade designations FORAL, STAYBELITE, and WINGTACK), a U V absorber, radical scavengers, a photostabilizer, a thermal stabilizer, chain transfer reagent (e.g., isooctyl thioglycolate), a dispersant, a flow enhancing agent, a leveling agent, a flame retardant, or combinations thereof. These additives may be added to adjust the processing, physical properties, and / or mechanical properties of the resulting product.

[0034] The amount of additive present in the curable composition can varying depending on the additive and the desired result. In some embodiments, the curable composition may include at least 0.01, 0.1, 0.5, 1, or even 2 wt% to at most 5, 4, 3, or even 2.5 wt% of the additive. In some embodiments, the curable composition may include at least 5, 10, 12, 15, or even 20 wt% to at most 60, 50, 40, 30, or even 25 wt% of the additive.

[0035] In some embodiments, the curable composition may include U V absorbers and / or hindered amine radical scavengers. UV absorbers and hindered amine radical scavengers are known in the art. The amount of UV absorber and / or hindered amine radical scavenger in the curable composition may be from at least 0.1 weight percent to 2 or even 4 weight percent. Exemplary UV absorbers include: benzotriazole compound, 5-trifluoromethyl-2-(2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl)-2H-benzotriazole, or combinations thereof. Other exemplary benzotriazoles include: 2-(2-hydroxy-3,5-di-alpha-cumylphehyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotiazole, 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, or combinations thereof. Additional exemplary UV-absorbers include 2(-4,6-diphenyl-1-3,5-triazin-2-yl)-5-hexyloxy-phenol, or those available fromBASF, Florham Park, NJ sold under the trade designations “TINUVIN 1577”, “TINUVIN 405”, and “TINUVIN 900”. In addition, UV-absorber(s) can be used in combination with stabilizers such as hindered amine light stabilizer(s) (HALS) and / or anti-oxidants. Stabilizers can eliminate free radicals produced by photo-oxidation of the polymer. Exemplary HALSs include those available from BASF sold under the trade designations “CHIMASSORB 944”, TINUVIN-292, and “TINUVIN 123”.

[0036] Exemplary fillers include flake-shaped filler having an average particle size of greater than approximately 30 pm and less than approximately 1000 p in the range where low gloss appearance is not impaired. Examples of the flake-shaped filler include expandable graphite, an aluminum foil powder pigment, a glass flake powder pigment, or a resin film foil powder pigment. The average particle size of the flake-shaped filler is a particle size having cumulative volume of 50% measured by using a laser diffraction particle size distribution measuring device. The thickness of the flake-shaped filler maybe from approximately 0.5 gm to approximately 30 urn. The aspect ratio (i.e., width to length) of the flake¬ shaped filler may be from approximately 1.0 to approximately 2000.

[0037] In some embodiments, the curable composition is substantially free of a second crosslinker. As used herein, substantially free means that the curable composition is crosslinked primarily by the (meth)acry late -based compound disclosed herein and that a second crosslinker (i.e., a non-hindered amine crosslinker) is not present. For example, the film comprises less than 5, 4, 2, 1, 0.5, or even 0.1 wt % by solids of an additional second crosslinker.

[0038] To enhance workability, coatability, and the like, the curable composition may further include a solvent such as a ketone (e.g., methyl ethyl ketone, methyl isobutyl ketone, or acetyl acetone): an aromatic hydrocarbon (e.g., toluene or xylene); alcohol (e.g., ethanol or isopropyl alcohol): an ester (e.g., ethyl acetate or butyl acetate); an ether (e.g., tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (l-methoxy-2-propyl acetate), or dipropylene glycol monomethyl ether acetate); or combinations thereof. In some embodiments, the curable composition comprises at least 25, 30, 40, 50, or even 55 wt% of the solvent; and at most 70, 65, or even 60 wt% of the solvent.

[0039] The curable composition of the present disclosure may be disposed on a surface. In some embodiments, the curable composition is coated onto a substrate. For example, the curable composition is coated onto a substrate using techniques known in the art including, for example, knife coating, bar coating, blade coating, doctor coating, roll coating, cast coating, and the like.

[0040] In some embodiments, after coating, the curable composition is subsequently, preferably predried with an apparatus such as a hot plate or an oven to remove any solvent, before being exposed to actinic radiation to cure the curable composition.

[0041] In some embodiments, the coating composition of the present disclosure can be cured using actinic radiation, preferably ultraviolet light of UV-B (320 nm to 290 nm) and / or UV-C (290 nm to 100 nm). The irradiation dose of ultraviolet rays is preferably 50 to 500 mill! Joules per square centimeter (mJ / cm2). Any ultraviolet light source, as long as part of the emitted light can be absorbed by thephotoinitiator, may be employed as a radiation source, such as, a high or low pressure mercury lamp, a cold cathode tube, a black light, an ultraviolet LED, an ultraviolet laser, or a flash light.

[0042] In some embodiments, the resulting cured composition has a thickness of at least 0.1, 0.5, 1, 2, 3, 5, 10, 25, 50, 100, 200, or even 400 micrometers (pm) to at most 2, 1, 0.8, 0.6 or even 0.5 millimeters (mm).

[0043] In some embodiments, the cured composition is derived from at least 35, 40, 45, 50, 55, or even 60 wt % to at most 100, 90, 80, 75, 70, or even 65 wt % of the (meth)acrylate-based compound based on the total amount of reactive monomers present. The reactive monomers include those compounds which undergo polymerization or curing to form the finished resin, e.g., ( me th)acry late-based compound and any additional monomers or oligomers.

[0044] The cured composition derived from the (meth)acrylate-based compound has a decrosslinking temperature, which is a temperature at which the composition becomes softened due to the breakage of the hindered urea bonds. In some embodiments, the decrosslinking temperature is at least 70, 80, 90, 100, 110, or even 120°C; and at most 200, 180, 170, 160, 150, 140, or even 125°C as determined by dynamic mechanical thermal analysis.

[0045] The cured composition of the present disclosure is especially useful for making embossed articles. The cured compositions of the present disclosure may be embossed using techniques known in the art. For example, the cured composition is heated within 60, 50, 40, 30, 20, 10, 5, or even 1°C of the decrosslinking temperature to soften the resin. The softened resin is then passed between an embossing roll (such as an engraved wheel) and a back-up roll with the softened resin side facing the embossing roll, and the surface pattern of the embossing roll is transferred to the surface of the softened resin. The embossing is preferably conducted with heating, The appropriate temperature will be dependent in part upon such factors as materials, processing speed, equipment, pressure, etc. and will typically be between about 50° C and about 270° C, though temperatures outside this range might be used. The roil pressure of the embossing will be dependent in part upon such factors as materials, processing speed, equipment, pressure, etc. and will typically be between about 0.4 and about 1.0 megaPascal (Mpa) though pressures outside this range might be used in accordance with the present disclosure.

[0046] The embossing roll is removed from the softened resin, leaving a patterned surface in the softened resin. The embossed resin is then cooled, resulting in a hardened embossed surface.

[0047] An exemplary article according to the present disclosure is shown in Fig. 1, where decorative film 100 is derived from the curable composition as described above. Decorative film 100 includes a surface layer 110 comprising the (meth)acrylate-based film disclosed herein, optional substrate layer 140, and optional adhesive layer 150. Decorative film 100 may be a film formed of only the surface layer 110, that is, the surface layer 110 itself may be a film. The surface layer 110 is embossed and includes a printed pattern 130.

[0048] The substrate layer may be colored or colorless. The substrate layer may be opaque, translucent or transparent. Substrates may include plastics such as polyolefins (e.g., polyethylene, or polypropylene), polyester (e.g., polyethylene terephthalate or polylactic acid), or polyamides, polycarbonate,polymethacrylate, polystyrene, polyolefin, epoxy, melamine, triacetylcellulose, acrylonitrile- butadienestyrene copolymers (ABS), acrylonitrile-styrene copolymers (AS), or norbomene resins; inorganic substrates such as glass, ceramics, metals (e.g., carbon steel, stainless steel, and aluminum); or combinations of any of the above described materials. Preferable substrates include those having at least one resin layer selected from the group consisting of polyvinyl chloride, polyurethane, polyethylene, polypropylene, a vinyl chloride-vinyl acetate resin, an acrylic resin, a cellulose resin, an ionomer resin, a silicone resin, a fluororesin, or combinations thereof can be used. In an embodiment, the substrate layer includes a transparent polyvinyl chloride resin layer and a colored polyvinyl chloride resin layer. In some embodiments, the substrate may be stretchable, enabling the articles of the present disclosure to be applied onto nonplanar surfaces. In some embodiments, the substrate has a tensile stretching rate of greater than or equal to 30%, and approximately less than or equal to 400, 350, or even 300%. A sample having a width of 25 mm and a length of 150 mm is prepared and the tensile stretching rate of the transparent resin base film i s a value calculated by [Chuck distance at the time of breaking (min) - Chuck distance before stretching (mm) (= 100 mm)] / Chuck distance before stretching (mm) (= 100 mm) x 100 (%) when the sample is stretched by using a tensile tester at a temperature of 20° C., a tensile speed of 300 mm / min, and a chuck distance of 100 mm until the sample breaks.

[0049] In some embodiments, the substrate may be a peelable liner. When a peelable liner is used as the substrate, the liner can be removed after the above-described steps to obtain a film only including the surface layer.

[0050] A thickness of the substrate layer can be, for example, at least 25, 40, 50, 60, or even 80 pm; and at most 5, 4, 3, 2, 1, or even 0.5 mm. When the substrate layer is formed of two or more layers, the abovedescribed thickness means the total thickness of the substrate layer.

[0051] The substrate layer may include an adhesive layer opposite to the surface layer. A generally used adhesive such as a solvent-type, emulsion-type, pressure-sensitive type, heat-sensitive type, a heat-curable or ultraviolet-curable type adhesive, including acrylics, polyolefins, polyurethanes, polyesters, rubbers, or the like can be used as the adhesive layer. The thickness of the adhesive layer can typically be at least 5, 10, 15, or even 20 pm; and at most 100, 80, 60, 50, or even 40 pm.

[0052] Pressure sensitive adhesives that may be useful in embodiments of the present disclosure and their preparation are described, for example, in U. S. Pat. No. 4,994,322 (Delgado et al.), U. S. Pat. No. 4,968,562 (Delgado), EP 0570515, and EP 0617708, U. S. Pat. Nos. 5,296,277 and 5,362,516 (both Wilson et al.), 5,141,790 (Calhoun et al.), and WO 96 / 1687 (Keller et al.) Other examples of PSAs are described in U. S. Pat. No. Re 24,906 (Ulrich), U. S. Pat. No. 4,833,179 (Young et al.), U. S. Pat. No. 5,209,971 (Babu et al..), U. S. Pat. No. 2,736,721 (Dester), and U. S. Pat. No. 5,461,134 (Leir et al.). Acrylate-based PSAs include those described in U. S. Pat. No. 4,181,752 (Clemens et al.) and U. S. Pat. No. 4,418,120 (Kealy et al.), WO 95 / 13331.

[0053] A liner may be imparted to a surface of the adhesive layer. Examples of the liner include paper; a plastic material such as polyethylene, polypropylene, polyester, or cellulose acetate; or paper coated with such a plastic material. These liners may have a surface subjected to peeling treatment with silicone or thelike. The thickness of the liner is typically at least 5, 10, 15, or even 20 pm; and at most 500, 400, 300, 250, or even 200 pm.

[0054] In some embodiments, a colored layer is disposed between surface layer 110 and substrate layer 140, or between substrate layer 140 and adhesive layer 150, or on adhesive layer 150, opposite the substrate layer 140. For example, the substrate layer may include a printed layer on either one or both of surfaces. The printed layer imparts designability to the film. The printed layer can be formed by using a printing technique such as inkjet printing, gravure printing, electrostatic printing, screen printing, or offset printing. As printing ink, solvent-based ink, water-based ink, or UV curable ink can be used. The printing ink may be transparent, translucent, or opaque, and may be colorless or colored.[0055 The thicknesses of tire printed layer may vary. and when solvent-based ink is used, tire thickness can typically be at least 0.1, 0.2, 0.3, or even 0.5 gm; and at most 10, 5, 3, 2, or even 1 gm. When UV curable ink is used, the thickness can be approximately at least 1, 2, 4, or even 5,um; and at most 50, 40, 30, 20, or even 10 gm. In the present disclosure, the thickness of the printed layer refers to the thickness of the thickest portion, that is, the maximum thickness.

[0056] The printed layer may be continuous or discontinuous. The printed layer may be disposed to correspond to the entire surface of the substrate layer or may be disposed to correspond to a portion or a plurality of portions of the surface. The printed layer may cover the entire surface of the substrate layer. In an embodiment, the printed layer includes a printed region and an unprinted region. Examples of a design of the primed layer include woodgrain, stone, a logo, a picture, text, a symbol, or combinations thereof.

[0057] The design of the printed layer may or may not he synchronized with the embossed pattern of the surface layer. In a ease where the design of the printed layer is synchronized with the surface layer embossed pattern, a design closer io an actual object is easi ly reproduced, and thus this ease is preferable.

[0058] The embossed surface layer imparts a tactile texture to the film. The surface layer of embossed articles of the present disclosure forms a printed pattern having a pattern such as woodgrain, sand, cloth texture, leather (such as cow or pig), stone, concrete, or rust (a pattern like an oxidized film formed in a metal surface).

[0059] In some embodiments, the thickness of the embossing, measured from the top surface of the article comprising the surface layer 110 to the deepest embossed feature (i.e., depression) can be. for example, at least 3, 4, 5, 8, 9, or even 10 um; and at most 50, 40, 30, 25, 20, or even 15 µm. Ideally, the surface layer comprises an embossed structure (e.g., a depression) having a depth of at least 9 or even 10 µm. Embossing can be performed deeper than the thickness of the (meth)acrylate-based surface layer, and, for example, another layer such as the substrate layer (e.g., PVC) located below the (meth)acrylate- based film disclosed herein may be embossed together with the (meth)acrylate-based film. In these instances, it is believed that during embossing, the softened (meth)acrylate-based film of the surface layer backfills into the embossed substrate layer, thereby coating (and protecting) any embossed surfaces.

[0060] In some embodiments, the articles of the present disclosure may be a graphic film or may be an over-laminate film to be applied to a decorative surface.[0061 J Although not wanting to be limited by theory, it is believed that the hindered urea enables the cured film to soften when heated due to the decrosslinking of the (meth)acrylate-based resin which enables embossing of deep features. Then, when the embossed resin is returned to room temperature, the (meth)acrylate -based resin re-crosslinks enabling surface layers that have good scratch resistance.

[0062] Articles according to the present disclosure have good scratch resistance. In some embodiments, the surface layer has a scratch resistance of at least 1, 2, or even 3 N (Newtons) with a MCT3 scratch tester with 24 hour recovery time. In some embodiments, the surface layer passes the squeegee test method.

[0063] The surface layer should have good adhesion to the underlying layers of the article. In some embodiments, when tested for adhesion performance by the cross-cut adhesion test, the surface layer of the article has no topcoat pieces fall off.

[0064] In some preferred embodiments, it is desirable for the embossed surface layer to have a matte finish. In some embodiments, the embossed surface layer has an initial 60 degree gloss less than 25, 20, 15, or even 10 gloss units. In some embodiments, the embossed surface layer after heating at 85°C for 24h has a 60 degree gloss less than 25, 20, 15, or even 10 gloss units. In some embodiments, the embossed surface layer has a gloss retention, which should be the 60 degree gloss show less than 5, 4, 3, or even 2 gloss unit increase after heating at 85°C for 24h.

[0065] In some preferred embodiments, it is desirable for the embossed decorative film to be able to be stretched enabling its application to nonplanar surfaces. In some embodiments, the articles of the present disclosure have an elongation at room temperature of at least 15, 20, 25, or even 30%. Typically, the article would have a maximum elongation of no more than 200 or even 100%.EXAMPLES

[0066] Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, and all reagents used in the examples were obtained, or are available, from general chemical suppliers such as, for example, Sigma-Aldrich Company, Saint Louis, Missouri, or may be synthesized by conventional methods.

[0067] The following abbreviations were used: cm = centimeter, g = gram, h = hour, mol = mole, mm = millimeter, mol = mole, pm = micrometer, min = min, N = Newton, and s = second.Table 1. Materials tableAbbreviation DescriptionDesmodur I Isophorone diisocyanate (3-isocyanatomethyl-3,5,5- trimethylcyclohexylisocyanate) available under the trade designation DESMODUR I, obtained from Covestro LLC, Newark, OH.Desmodur N3300A Isophorone diisocyanate (3-isocyanatomethyl-3,5,5- trimethylcyclohexylisocyanate) available under the trade designation DESMODUR N3300A, obtained from Covestro LLC, Newark, OH.HEMA (Hydroxyethyl)methacrylate obtained from Fisher Scientific Chemicals,Hampton, NH.HEA Hydroxyethyl acrylate obtained from Fisher Scientific Chemicals, Hampton,NH.CPL Caprolactone obtained from Sigma-aldrich, St. Louis, MO.DTBEDA N, N'-Di-tert-butylethylenediamine obtained from Sigma-aldrich.DMEDA N, N'-Dimethylethylenediamine obtained from Sigma-aldrich.BTMPS Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate obtained from Sigma-aldrich. SR495B Caprolactone acrylate available under the trade designation SR495 B,obtained from Sartomer, Warrington, PA.SR285 Tetrahydrofurfuryl acrylate available under the trade designation SR285, obtained from Sartomer.SR268 Tetraethylene glycol diacrylate available under the trade designation SR268, obtained from Sartomer.SR217 Tertiobutyl cyclohexyl acrylate available under the trade designation SR217, obtained from Sartomer.SR238 1,6-Hexanediol diacrylate available under the trade designation SR2388, obtained from Sartomer.CN991 Aliphatic urethane diacrylate available under the trade designation CN991, obtained from Sartomer.CN9066 Aliphatic Urethane Acrylate available under the trade designation CN9066, obtained from Sartomer.CN9600 Aliphatic Urethane Acrylate available under the trade designation CN9600, obtained from Sartomer.TBAEMA 2-(tert-Butylamino)ethyl methacrylate obtained from Sigma-aldrich.IPA Isopropyl alcohol obtained from Sigma-aldrich.MEK Methyl ethyl ketone obtained from Sigma-aldrich.MPOH 2-Methoxypropanol obtained from Sigma-aldrich.BYK 3710 Polyether-modified, acryl- functional polydimethylsiloxane available under the trade designation BYK-SILCLEAN 3710, obtained from BYK, Chester, NY.TegoRad 2250 Silicon containing acrylates available under the trade designation TEGO Rad 25500, obtained from Evonik, Atlanta, GA.TegoRad 2300 Silicon containing acrylates available under the trade designation TEGO Rad 2300, obtained from Evonik, Atlanta, GA.Omnirad 4265 A liquid photoinitiator blend of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide mixed with 2 -hydroxy-2 -methylpropiophenone (50%-50%) available under the trade designation OMNIRAD 4265, obtained from IGM Resins, Charlotte, NC.Omnirad 1173 2 -Hydroxy-2 -methyl- 1 -phenylpropanone, available under the trade designation OMNIRAD 1173, obtained from IGM Resins.Omnirad 819 Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide available under the trade designation OMNIRAD 819 photoinitiator, obtained from IGM Resins. Photomer 4006 Trimethylolpropane triacrylate available under the trade designation PHOTOMER 4006 monomer, obtained from IGM Resins.Photomer 4184 2-[[Butylamino)carbonyl]oxy]ethyl acrylate available under the trade designation PHOTOMER 4184 monomer, obtained from IGM Resins. Photomer 6891 Aliphatic 2F urethane acrylate available under the trade designation PHOTOMER 6891 monomer, obtained from IGM Resins.Irgacure 184 1-Hydroxy-cyclohexyl-phenyl-ketone available under the trade desination Irgacure 184, obtained from Ciba.TPO 2,4,6-Trimethylbenzoyl-diphenyl phosphine oxide available under the trade designation OMNIRAD TPO, obtained from IGM Resins.Tinuvin 477 l-Methoxy-2-propylacetate available under the trade designation TINUVIN477 UV absorber, obtained from BASF, Charlotte, NC.Tinuvin 479 Hydroxyphenyltriazine available under the trade designation TINUVIN 479UV absorber, obtained from BASF.Tinuvin 123 Sterically hindered amine light stabilizer available under the trade designation TINUVIN 123, obtained from BASF.Kcat-672 A zinc catalyst for urethane production available under the trade designation K-KAT XK-672, obtained from King industries specialty chemicals, Norwalk, CT.BHT 2,6-Di-t-butyl-4-methylphenol obtained from Alfa Aesar.PVC-A Clear PVC, 80um, 72 parts Polyvinyl chloride / 12 parts Polyester plasticizer / 16 parts Additives (Acrylic resin, Zinc stearate, Benzotriazole UV absorber, etc.)PVC-B Clear PVC, 80um, 72 parts Polyvinyl chloride / 12 parts Polyester plasticizer / 16 parts Additives (Acrylic resin, Zinc stearate, Benzophenone UV absorber, etc.)PVC-Black Black PVC, 80um, 79 parts Polyvinyl chloride / 16 parts Ester typeplasticizer / 5 parts Additives (Acrylic resin, Zinc stearate, etc.)

[0068] Synthesis of HUB 1 and HUB2Where for HUB1: R= methyl, and HUB2: R=t-butyl

[0069] Synthesis of HUB 3SR495B (20.64g, 0.06 mol), Desmodur I (13.32g, 0.06 mol), BHT (0.01g), and KKat-672 (0.01g) were mixed in a round bottom flask equipped with a stir bar and heated at 80 °C. The reaction was monitored for the NCO peak at 2200cm-1via infrared (IR) every 30 min. After 2 h, the NCO peak intensity stay unchanged, and the resulting solution was cooled to room temperature. To initiate the coupling reaction, the designated diamine was then added to the flask. Again, the reaction progress was monitored by examination of the NCO peak by IR. After 30 min, the NCO peak completely disappeared, suggested the competition of the reaction and formation of the respective HUB-based diacrylates. The products were used without further purification.

[0070] For HUB1, the diamine used was DMEDA (2.64g). For HUB2, the diamine used was DTBEDA (5.16g).

[0071] Synthesis of HUB4 and HUB5Where for HUB4: R= methyl and HUB5: R=t-butyl.

[0072] Synthesis of HUB6

[0073] Using HEMA to ring open CPL generates a hydroxyl terminated caprolactone methacrylate. HEMA (11.43g) and CPL (20.00g) were charged into a round bottom flask, 0.01g of BHT was added and dry air was bubbled into the solution while the solution was heated at 160°C for 120 min.

[0074] The same procedure as described above for the synthesis of HUB 1-2 then was followed except that the resulting hydroxyl terminated caprolactone methacrylate (21.48 g) was used in place of SR495B.

[0075] For HUB4, the diamine used was DMEDA (2.64g). For HUB5, the diamine used was DTBEDA (5.16g). For HUB6, the diamine used was BTMPS (14.40g).

[0076] Synthesis of HUB 7

[0077] IEM (15.52g) was added to stirring TBAEMA (18.53g) in a round bottom flask. The flask was kept in a room temperature water bath for 30 min. The reaction released heat and the viscosity increased as the reaction progressed. After 30 min, IR of the products exhibited no NCO peak around 2200 cm-1, indicating the successful synthesis of HUB7.

[0078] Synthesis of HUB 8

[0079] TBAEMA (9.61g) was added to N33OOA (10.00g N33OOA in 9.61g MEK) with stirring in a round bottom flask. The flask was kept in a room temperature water bath for 30 min. The reaction released heat and the viscosity increased as the reaction progressed. After 30 min, IR of the products exhibited no NCO peak around 2200 cm-1, indicating the successful synthesis of HUB8.

[0080] HUB1-8 were tested for their decrosslinking temperature by dynamic mechanical thermal analysis (DMTA).

[0081] To create samples for DMTA testing, the formulated resin mixture was then poured into a silicone rectangle mold (1 mm thickness, trimmed to 20 mm× 6 mm ×1 mm before use). The filled mold was placed between two glass plates and cured in post-curing device (Asiga Pico Flash, Asga, Ann Arbor, MI) for 120 s. The sample was demolded and cured on the backside for another 120 s in the same device. The sample was then cured in a controlled-atmosphere cure chamber (CA3200, Clearstone Technologies, Hopkins, MN) equipped with 365, 385, and 405 nm LEDs, with nitrogen passing through the chamber.

[0082] The decrosslinking temperatures (or remelt temperatures) of the HUBs are defined as the onset temperatures of the second drop in their storage modulus (E’) was measured using a DMTA instrument (DMA 850, TA Instruments, New Castle, DE). The samples were mounted onto a dual screw clamp. An oscillation temperature ramp was performed on the material 'with 0.1% strain and 1.0 Hz frequency, ramping from -50°C to 180°C with a rate of 3.0 °C / min. The results are reported in Table 2.Table 2HUB decrosslinkingtemperature(°C)1 1752 1203 904 1785 1286 957 1208 120

[0083] Examples 1-7 (E1-E7) and Comparative Examples 1-14 (CE1-CE11)

[0084] Samples were prepared by weighing the components (indicated in tables 3 and 4) in an amber jar, followed by rolling on a roller (available under the trade designation OLDE MIDWAY PRO 18, Olde Midway, Savannah, GA) at room temperature until fully mixed.Table 3El E2 E3 E4 E5 E6 E7Materials: Weight percentages of the materials listed for each sampleHUB2 31.6 27.7 15.8HUB7 31.6 15.8HUB8 22.7 17.6CN991 15.8 15.8SR285 18.0 18.0 5.0 10.1 18.0 18.0Tegorad 2250 0.1 0.1 0.1Omnirad 0.8 0.8 0.8 0.84265Irgacure 184 0.8 0.8 0.8Tinuvin 477 0.6 0.6 0.6Tinuvin 479 0.6 0.6 0.6Tinuvin 123 0.3 0.3 0.3IPA 49.6 49.6 49.6 49.6MEK 24.0 13.5 13.5 24.0 13.5MPOH 45.9 56.4 56.4 45.9 56.4Table 4Example CE1 CE2 CE3 CE4 CE5 CE6 CE7 CE8 CE9 CE10 CE11 Materials Weight percentages of the materials listed for each sampleCN991 31.6 31.0 31.6 35.4 35.4 31.2 28.9CN9066 31.2CN9600 28.9 SR285 18.0 17.7 17.8 17.8 18.3 18.3 SR268 13.3SR217 18.0SR238 13.3Photomer 34.0 35.64006Photomer 10.0 10.54184Photomer 50.0 52.46891BYK3710 0.5 0.5 0.5 0.5 0.5IPA 49.6 50.0 49.6 50.0 50.0 50.1 50.2 51.5 51.5TPO 0.37Omnirad 0.8 0.8 0.8 0.8 0.8 1.5 0.8 0.8 0.84265Omnirad 5.0 0.371173Omnirad 819 1.0TegoRad230 0.160 ~

[0085] Coating and UV-curing method

[0086] Selected resins in tables 3 and 4 were coated on PVC-A or PVC-B by bar coaters (Meyer rods). If the resins contained solvents, the coated films were dried in the oven at 60°C for 2min. Then, the dried top layer was cured by H bulb under nitrogen atmosphere resulting in cured film.

[0087] Embossing method

[0088] The cured film was laminated to PVC -Black on the PVC-A or PVC-B side of the sample and the cured resin was embossed using a wave patterned emboss cylinder having feature depths of 32 micrometers with a speed of 7 m / min. The surface of the films was heated up to 170 °C during the embossing, resulting in an embossed film.

[0089] Scratch resistance testing method

[0090] The cured and embossed films were applied to an aluminum panel with the cured resin or embossed resin facing outward.

[0091] The cured resin was scratched by a micro Combi tester (MCT3, Anto Paar USA Inc., Vernon Hills, IL) scratch tester equipped with an 800μm diamond tip with a load of 0.1-1 ON. The scratch speed was set to 600 mm / min and the distance was set to 15 mm.

[0092] The embossed resin was scratched by a micro Combi tester equipped with an 800 pm diamond tip that is varied with an increasing load from 0.03 to 30 N. With each different load a new area was tested. The scratch speed was set to 600 mm / min and the distance was set to 20 mm. A hammer scratch test was also used on selected embossed samples by dragging the hammer (50g) across the surface with a speed of 150 mm / s. The samples after being scratched were left to sit at room temperature conditions for 24 h.

[0093] The initial number reported indicates the load amount on the tester that, when visually observed right after the tip scratched the surface, left no marks or scratches. The After 24 h number reported is the load amount on the tester that, when visually observed 24 h after the tip initially scratched the surface, left no marks or scratches.

[0094] Squeegee scratch resistance testing method

[0095] The embossed films were also tested for squeegee scratch resistance. The films were applied on an aluminum panel with the embossed resin facing outward. The embossed film was scratched by the edge of a felt covered squeegee. The load on the squeegee was about 2 kg and the felt was a black felt with a thickness of 1.2 mm. A pass indicated that no visual marks or scratches were left on the embossed film where a failure means a visible mark or scratch was left on the embossed film.

[0096] Adhesion testing method

[0097] The cured films were applied on an aluminum panel with the cured resin facing outward. A crosscut grid pattern of 100 squares (about 1mm2) was made by cutting the cured resin layer (surface of the cured films) with a utility knife.

[0098] A tape (No.405 made by Nichiban co., Ltd., Japan) was applied to the grid pattern by squeegeeing and left on for 15 seconds before peeling it off. The adhesion performance was evaluated based on the number of topcoat pieces in the scratched are that fall off from the film.

[0099] 100 / 100 indicates no topcoat was peeled off from the film by the tape. Fail indicates some or all cured HUB topcoat were peeled off from the sample by the tape.

[0100] Emboss depth measurement method

[0101] Emboss depth measurement was performed by using a microscope (available under the trade designation OPTELICS HYBRID, Lasertec Corp., Japan) microscope. The sample was applied on an aluminum panel and placed on the measurement stage. Measurements were taken using a 50x objective lens and White confocal mode. The measurements were performed twice, and the average value was taken as the emboss height.

[0102] Elongation measurement method

[0103] The % elongation in the machine direction was determined by uniaxial extension at a displacement rate of 300 mm / min using a tester (TENSILON RTC-1210A, A& D Company LTD, Tokyo, Japan). The measurement was performed three times at 20 °C, and the average value was reported.

[0104] Surface Gloss measurement method

[0105] The 60-degree surface glossiness of the embossed sample was measured using a portable glossmeter (GMX-203, Murakami Color Research Laboratory, Tokyo, Japan).

[0106] The initial number indicates the 60-degree surface glossiness of samples. The 85C number indicates the 60-degree surface glossiness of the sample surface left at 85°C for one day and then allowed to return to room temperature before measuring the surface glossiness.

[0107] Comparative Examples 12 and 13 (CE 12 and CE 13)

[0108] CE12 was PVC-A on PVC -black and CE13 was PVC-B on PVC-black. No cured resin was present. Each sample was tested for emboss depth, scratch resistance, elongation, and gloss. For CE 13 multiple depths were taken and the range is reported in Table 5. The results are shown in Table 5 below.Table 5Sample CE12 CE13NameEmboss 20.2 17.0 to 20.0Depth [urn]scratch resistance testInitial 0.6N 0.2NAfter 24h 0.6N 0.2N%ElongationMD 186% 213%Surface Gloss (60°)Initial 5.5 31.985Cxlday 5.4 30.8

[0109] The results in Table 5 show that PVC films exhibit excellent emboss height after the embossing process as well as high elongation (e.g. >150%) at room temperature. However, the PVC films show initial poor scratch resistance, which were non-recoverable and persisted after 24 h.

[0110] CE1-CE11 were coated onto PVCA / PVC-B laminated to PVC-black. The samples were tested for emboss depth, Scratch Resistance Test, Squeegee scratch resistance testing method, Adhesion Test, % Elongation, and Surface Gloss. The results are shown in Table 6.Table 6Coating CE1 CE2 CE3 CE4 CE5 CE6 CE7 CE8 CE9 CE10 CE11 Emboss 9.6 7.9 6.0 4.0 3.0 2.2 1.8 7.0 5.0 7.0 5.9 Depth[um]Scratch resistance testInitial 3N 3N 5N 3N 3N 3N 3N 3N 2N 3N 1.5N After 24h 5N 6N 5N 6N 5N 4N 3N 3N 2N 3N 1.5N Squeegee Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass resistancetestAdhesion 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 TestElongation 7% 61% 17% 42% 26%, 7% 12% 98% 49%, 46%. 11% Surface Gloss (60°)Initial 9.6 9.6 10 5 14.2 21.5 37.5 45.4 10.4 10.9 8 3 11.7 85Cxlday 22.4 17.7 25 3 40.5 71.0 73.3 85.3 23.4 26.2 16.9 30.5

[0111] E1-E7 were coated on PVC-A / PVC-B and laminated on PVC-Black then embossed with patterns and tested for emboss depth, scratch resistance, adhesion, elongation and surface gloss. The results are shown in Table 7.Table 7Sample El E2 E3 E4 E5 E6 E7NameEmboss 15.0 11.0 10.6 10.5 10.0 9.0 9.0Depth [uni]scratch resistance testInitial 0.6N 2N IN 2N 3N 3N 2NAfter 24h 3N 2N IN 2N 3N 3N 2NAdhesion 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 testElongation 65% 29% 127% 61% 23% 61% 50%Surface Gloss (60°)Initial 6.6 9.2 7.4 24.3 23.2 9.2 9.1 85Cxlday 8.3 9.8 11.9 18.3 16.7 12.2 11.4

[0112] Foreseeable modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention. This invention should not be restricted to the embodiments that are set forth in this application for illustrative purposes. To the extent that there is any conflict or discrepancy between this specification as written and the disclosure in any document mentioned or incorporated by reference herein, this specification as written will prevail.

Claims

What is claimed is:

1. A method of making a decorative film, the method comprising:(a) providing a cured film, wherein the cured film is derived from:(i) a first (meth)acrylate-based compound comprising at least one hindered urea;and(ii) an initiator, wherein the cured film has a decrosslinking temperature;(b) heating the cured film near the decrosslinking temperature to provide a softened film; (c) contacting the softened film with a patterned substrate to form an imprinted film; (d) releasing the imprinted film from the patterned substrate; and(e) cooling the imprinted film to form the decorative film.

2. The method of claim 1, wherein the first (meth)acrylate-based compound comprises:O O O0 0 0 0Jk JLXL,, A. xY:>A z- 'y o N N N N O yR1XH HX R2(IIA)0 0 0 0AA A,. L. JL xYy O N N N N2O Y I H1 1H1R1X X R2(IIB)0 o o oK, _, RO' N N N N N N 'O2XHj... L,Hvo " N ' '0O;3NHCT^NXL30O YR3(III)or combinations thereof,where R1, R2, and R3are independently selected from H or CH3; Y1, Y2, and Y3are independently selected from a divalent linking group selected from alkylene, alkenylene ester, cycloalkene, or aromatic alkylenylene group, optionally comprising at least one carbamate group, at least one urea group, or combinations thereof; each X is independently a bulky hydrocarbon group, optionally comprising one or more ether linkages: and L1, L2, and L3are independently selected from a divalent linking groups.

3. The method of any one of the previous claims, wherein the first (meth)acrylate-based compoundcompriseor combinations thereof, where R is methyl or t-butyl.

4. The method of any one of the previous claims, wherein the cured film is derived from 30 wt % to 100 wt% of the first (meth)acry late-based compound.

5. The method of any one of the previous claims, wherein the cured film is further derived from (iii) a second (meth)acrylate monomer or an oligomer thereof, wherein the oligomer has at least one (meth)acrylate moiety.

6. The method of claim 5, wherein the second (meth)acrylate monomer comprises 2 -methyl butyl acrylate, isobornyl (meth)acrylate, 2-ethyl hexyl acrylate, butyl acrylate, iso-octyl acrylate, tetrahydrofurfuryl acrylate, or combinations thereof.

7. The method of any one of claims 5-6, wherein the cured film is derived at least 10 wt % to at most 70 wt % of the second (meth)acrylate monomer or an oligomer thereof.

8. The method of any one of the previous claims, wherein the cured film is further derived from a polar (meth)acrylate monomer.

9. The method of claim 8, wherein the polar (meth)acrylate monomer comprises acrylic acid, methacrylic acid, 4-hydroxybutyl (meth)acrylate, hydroxy ethyl (meth)acrylate, tert- octylacrylamide, or combinations thereof.

10. The method of any one of the previous claims, wherein the initiator is a photoinitiator or a thermal initiator.

11. The method of any one of the previous claims, wherein the decrosslinking temperature is at least 70° C.

12. The method of any one of the previous claims, wherein the decrosslinking temperature is at least 90°C.

13. The method of any one of the previous claims, wherein the decrosslinking temperature is at most 200°C.

14. The method of any one of the previous claims, wherein the decorative film comprises a plurality of structures having a depth of at least 9 microns.

15. The method of any one of the previous claims, wherein the cured film is substantially free of a crosslinking agent that does not comprise a hindered urea.

16. An embossed film comprising a surface layer having a plurality of features, wherein the surface layer is derived from a first (meth)acrylate-based compound comprising at least one hindered urea; and an initiator, wherein at least a portion of the plurality of features has a depth of at least 9 micrometers.

17. The embossed film according to claim 16, wherein the embossed film has a scratch resistance of at least IN with a MCT3 scratch tester with 24h recovery time.

18. The embossed film according to any one of claims 16-17, wherein the embossed film has an initial 60 degree gloss less than 25 gloss units.

19. The embossed film according to any one of claims 16-18, wherein the embossed film has after heating at 85°C for 24h has a 60 degree gloss less than 25 gloss units.

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