Interior trim film

Abstract

Multi-layer films include a transparent top layer article with at least 2 layers, an outermost film and a support film. The outermost film is a polyolefin-based layer and the bottom film is a support film that is transparent and has a pencil hardness of at least B. The outermost surface of the top layer article has a pencil hardness of at least 2B and is a structured surface with a plurality of protrusions. For increased scratch resistance, the polyolefin-based layer includes a nucleating agent. The top layer article may include a second polyolefin-based layer disposed on the support film. The multi-layer film may include additional layers. These layers include a heat-activated first adhesive layer in contact with the top layer article, a color layer in contact with the first adhesive layer, a thermally adherable thermoplastic resin layer in contact with the color layer, a second adhesive layer in contact with the thermally adherable thermoplastic resin layer, the second adhesive layer and a release liner on the second adhesive layer.

Description

[0001] INTERIOR TRIM FILM

[0002] Summary

[0003] Disclosed herein are multi-layer film articles that are suitable for use as interior trim films. Also disclosed herein are methods for prepare the multi-layer film articles.

[0004] In some embodiments, the multi-layer film comprises a top layer article with a first major surface and a second major surface comprising a transparent multi-layer film comprising at least 2 layers, an outermost film and a bottom film. The outermost film comprises a first polyolefin-based layer and the bottom film comprises a support film that is a transparent film layer with a pencil hardness of at least B. The first major surface of the top layer article is a structured surface comprising a plurality of protrusions arising from a base surface wherein the protrusions have a height of at least 5 micrometers, and the top layer article has a pencil hardness of at least 2B. In some embodiments, the first polyolefin-based layer further comprises a nucleating agent. The nucleating agent enhances the scratch resistance of the first polyolefin-based layer. In some embodiments, the top layer article further comprises a second polyolefin-based layer disposed on the support film, wherein the second polyolefin-based layer and the first polyolefin-based layer are the same composition or different.

[0005] The multi-layer film may comprise additional layers. In some embodiments, the multi-layer film further comprises a first adhesive layer in contact with the second major surface of the top layer article, comprising a heat-activated adhesive, a color layer in contact with the first adhesive layer, where the color layer comprises a pigment dispersed in a binder, a thermally adherable thermoplastic resin layer in contact with the color layer, a second adhesive layer in contact with the thermally adherable thermoplastic resin layer, the second adhesive layer comprising a (meth)acrylate-based adhesive layer, and a release liner in contact with the second adhesive layer.

[0006] Also disclosed are methods for making multi-layer film articles. In some embodiments, the method comprises preparing a top layer article with a first major surface and a second major surface comprising a transparent multi-layer film comprising at least 2 layers, an outermost layer and a bottom layer. The outermost layer comprises a polyolefin-based layer and the bottom layer comprises a support film that is a transparent film layer with a pencil hardness of at least B. The method further comprises preparing a TGP (Transfer Gravure Printing) sheet, comprising providing a carrier film and depositing a thermally adherable thermoplastic resin layer composition on the carrier film and drying the thermally adherable thermoplastic resin layer composition to form a thermally adherable thermoplastic resin layer, depositing a color solution on the thermally adherable thermoplastic resin layer to form a color layer comprising a pigment dispersed in a binder, and depositing a first adhesive comprising a heat activated adhesive on the color layer to form the first adhesive layer. The top layer article is heat laminated to the TGP sheet by contacting the bottom film of the top layer article to the first adhesive layer of the TGP sheet and applying heat and pressure to form an intermediate article. The carrier film is removed from the intermediate article to expose the thermally adherable thermoplastic resin layer. The method further comprises providing an adhesive article with a second adhesive layer disposed on a release liner, and heat laminating the second adhesive layer to the intermediate article such that the thermally adherable thermoplastic resin layer contacts the second adhesive layer and applying heat and pressure to form a secondary article. The polypropylene-based film surface of the secondary article is heated and contacted to an embossing tool to impart a structured surface to the first major surface of the top layer article.

[0007] Brief Description of the Drawings

[0008] The present application may be more completely understood in consideration of the following detailed description of various embodiments of the disclosure in connection with the accompanying drawings.

[0009] Figure 1A is a cross sectional view of a top layer article of this disclosure.

[0010] Figure IB is a cross sectional view of another top layer article of this disclosure. Figure 2 is a cross sectional view of a decorative article of this disclosure.

[0011] Figure 3 is a cross sectional view of another decorative article of this disclosure.

[0012] The figures are not necessarily to scale. Like numbers used in the figures refer to like components. Detailed Description

[0013] Decorative films such as those for interior decorative articles are used to decorate the interior parts of automobiles. The use of these materials is effective in improving the work environment because installing decorative panels requires no volatile organic compounds (VOC) or any spray mist. The decorative films generally have an outermost layer which protects the decorative article. Generally, the decorative article has an adhesive layer to mount the decorative article in a vehicle. Between the outermost layer and an adhesive layer, the article includes a variety of layers. Among these layers are aesthetic layers such as one or more colored layers and / or one or more metal layers. The layers may also include adhesive layers to bond together these layers.

[0014] The outermost layer has a number of requirements. These requirements include chemical resistance, thermal resistance, desirable hardness, stain resistance, scratch resistance, and the like. In some articles, the outermost layer of the interior trim articles is a fluorocarbon-based film layer, as fluorocarbon films fulfill these requirements. However, these films also have undesirable features such as high cost. Additionally, as the forward trend is to eliminate the use of fluorocarbon- based films, it is desirable to develop interior trim articles with outermost layers that do not have fluorocarbon films.

[0015] Replacement of outermost layer fluorocarbon films is difficult, since, as described above, the outermost layers have a variety of needed properties including hardness. Polyolefin-based films are potential candidates as replacement films since polyolefin-based films have desirable thermal resistance and stain resistance properties and are relatively inexpensive. However, it was discovered that polyolefin-based films did not have the required hardness and also were not scratch resistant.

[0016] In this disclosure, top layer articles for interior trim articles that do not contain fluorocarbon films are described. In some embodiments, the top layer articles comprise at least 2 film layers an outermost film and a support film, wherein the outermost film comprises a polyolefin-based layer and the support film comprises a transparent film layer with a pencil hardness of at least B, where the first major surface of the top layer article is a structured surface comprising a plurality of protrusions arising from a base surface. In some embodiments, the top layer articles further comprise a second polyolefin-based layer disposed on the support layer. In some embodiments, the polyolefin-based layer further comprises a nucleating agent to improve the scratch resistance of the layer.

[0017] Also disclosed are interior trim articles that contain the above-described top layer articles and methods of preparing the interior trim articles.

[0018] The term “adhesive” as used herein refers to polymeric compositions useful to adhere together two adherends. Examples of adhesives are heat activated adhesives.

[0019] Heat activated adhesives are non-tacky at room temperature but become tacky and capable of bonding to a substrate at elevated temperatures. These adhesives usually have a Tg(glass transition temperature) or melting point (Tm) above room temperature. When the temperature is elevated above the Tgor Tm, the storage modulus usually decreases and the adhesive becomes tacky.

[0020] The term “(meth)acrylate” refers to monomeric acrylic or methacrylic esters of alcohols. Acrylate and methacrylate monomers or oligomers are referred to collectively herein as "(meth)acrylates”. Materials referred to as “(meth)acrylate functional” are materials that contain one or more (meth)acrylate groups. The term “(meth)acrylic” as used herein refers to both acrylic and methacrylic compounds, where acrylic and methacrylic compounds are of the general structure: CH2=CR1-(C0)-, where R1is an H or a methyl group. When this group is linked to an -OR group where R is an alkyl or other substituted alkyl group, the compound is a (meth)acrylate as described above, when it is linked to an amino group -NR2 where each R group is independently an H or an alkyl group, the compound is a (meth)acrylamide.

[0021] The terms "room temperature" and "ambient temperature" are used interchangeably to mean temperatures in the range of 20°C to 25°C.

[0022] The terms “Tg” and “glass transition temperature” are used interchangeably. If measured, Tg values are determined by Differential Scanning Calorimetry (DSC) at a scan rate of 10°C / minute, unless otherwise indicated. Typically, Tg values for copolymers are not measured but are calculated using the well-known Fox Equation, using the homopolymer Tg values provided by the monomer supplier, as is understood by one of skill in the art. The term “adjacent” as used herein when referring to two layers means that the two layers are in proximity with one another with no intervening open space between them. They may be in direct contact with one another (e.g. laminated together) or there may be intervening layers.

[0023] The terms “polymer” and “macromolecule” are used herein consistent with their common usage in chemistry. Polymers and macromolecules are composed of many repeated subunits. As used herein, the term “macromolecule” is used to describe a group attached to a monomer that has multiple repeating units. The term “polymer” is used to describe the resultant material formed from a polymerization reaction.

[0024] Unless otherwise indicated, the terms “transparent”, and “visible light transmissive” are used interchangeably, and refer to an article, fdm or adhesive that has a high light transmittance over at least a portion of the visible light spectrum (about 400 to about 700 nm). Typically, transparent articles have a visible light transmittance of at least 50%. The term "transparent fdm" refers to a fdm having a thickness and when the fdm is disposed on a substrate, an image (disposed on or adjacent to the substrate) is visible through the thickness of the transparent fdm. In many embodiments, a transparent fdm allows the image to be seen through the thickness of the fdm without substantial loss of image clarity. In some embodiments, the transparent fdm has a matte or glossy finish.

[0025] The terms “EVOH” and “poly-EVOH” are used interchangeably and refer to poly(ethylene-vinyl alcohol).

[0026] Disclosed herein are multi-layer interior trim fdm articles that do not contain fluorocarbon films. The articles include a top layer article, as well as a variety of additional layers to form the interior trim fdm articles.

[0027] Disclosed herein are multi-layer films that are top layer articles. The top layer articles have a first major surface and a second major surface and comprise a transparent multi-layer fdm with at least 2 layers. The 2 layers are an outermost layer and a bottom layer. The outermost layer comprises a first polyolefin-based layer and the bottom layer is a support fdm that is a transparent fdm layer with a pencil hardness of at least B. The first major surface of the top layer article is a structured surface comprising a plurality of protrusions arising from a base surface where the protrusions have a height of at least 5 micrometers, and the top layer article has a pencil hardness of at least 2B. In some embodiments, the top layer article further comprises a second polyolefin-based layer disposed on the support film, where the second polyolefin-based layer is the bottom layer and the support film is disposed between the two polyolefin-based layers. Typically, the polyolefin-based layer and the support layer comprise crystalline materials, and the thermoforming operations described below tend to increase the pencil hardness of these layers. However, even after thermoforming, the polyolefin-based layer, without the support layer, did not have sufficient pencil hardness.

[0028] As described above, even though the combination of the support layer and the polyolefin-based layer provides a desirable pencil hardness, the resultant top layer articles may not have the desired scratch resistance. In order to increase the scratch resistance, in some embodiments, the polyolefin-based layer further comprises at least one nucleating agent. Nucleating agents are well-known polymer additives that promote the formation of crystals within semicrystalline polymers and therefore promote crystallization at lower temperatures as polymer melts cool. A subset or nucleating agents are called “clarifiers” and have a smaller particle size so as to not scatter light and enhance the clarity upon crystallization.

[0029] While nucleating agents have been found to improve the processing of semicrystalline polymers such as polypropylene, it was discovered that the addition of such nucleating agents also provides enhanced scratch resistance to the polyolefin-based layer.

[0030] A variety of materials are suitable for use as the first polyolefin-based layer of the top layer article. In many embodiments, the polyolefin-based layer comprises a polypropylene-based layer. A particularly suitable polypropylene material is MODIC P555 from Mitsubishi Chemical Corporation.

[0031] Besides the polypropylene material, the first polyolefin-based layer and the second polyolefin-based layer can also comprise a variety of optional additives. Among the suitable additives are UV stabilizers and anti-oxidants. Suitable UV stabilizers include HALS (Hindered Amine Light Stabilizers) such as ADK stab LA 63P from Adeka Corporation. Suitable anti-oxidants include IRGANOX 1098 from BASF Japan Co., Ltd. and ADK stab 2112 from Adeka Corporation, as well as combinations of these materials. Combinations of additives can also be used. Also, while not required, an ultraviolet absorbing agent can be used if desired. As mentioned above, in some embodiments the first polyolefin-based layer further comprises at least one nucleating agent. This is particularly true when the first polyolefin layer comprises polypropylene. Examples of suitable nucleating agents include CLEARMASTER PP-RM-SKZ H8020 a clarifying nucleating agent for polypropylene available from Dainichiseika Color & Engineering Mfg. Co., Ltd. As mentioned above, some embodiments comprise top layer articles with 3 layers: a polyolefin-based layer / a support film / a polyolefin-based layer. In many of these embodiments, the polyolefin- based layers comprise a polypropylene-based layer as described above. In some embodiments, the two polyolefin-based layers comprise the same materials.

[0032] A variety of materials are suitable for use in the support film of the top layer articles. The support film comprises a transparent film layer with a pencil hardness of at least B. Suitable materials include poly(ethylene-vinyl alcohol) often abbreviated as EVOH, and a cured poly(meth)acrylate layer. Examples of suitable materials include EVOH AT4403B from Mitsubishi Chemical Corporation and EVOH E105B from Kuraray Co. Ltd. Particularly suitable materials are EVOH AT4403B from Mitsubishi Chemical Corporation.

[0033] The top layer articles can have a range of thicknesses. In some embodiments, the top layer article has a thickness of at least 30 micrometers. Each of the layers can also have a variety of thicknesses. In some embodiments, the first polyolefin-based layer has a thickness of from 1-30 micrometers and the support layer has a thickness of at least 1 times the thickness of the first polyolefin-based layer. In embodiments where the top layer article comprises 3 layers, the first polyolefin-based layer has a thickness of from 1-30 micrometers, the support layer has a thickness of at least 1 times the thickness of the first polyolefin-based layer, and the second polyolefin-based layer has a thickness of from 1-30 micrometers. In some embodiments, the support layer has a thickness of at least 3 times the thickness of the first polyolefin-based layer.

[0034] The top layer article may further comprise optional layers. One particularly suitable layer is a bonding layer to facilitate the bonding of the polyolefin-based layer or layers to EVOH, when EVOH is used as the support film. Therefore, in some embodiments, the top layer article further comprises a bonding layer between the polyolefin-based layer and the support film, between the support film and the second polyolefin-based layer, or both, where the bonding layer comprises a thermoplastic modified polyolefin. A particularly suitable material for use in the bonding layer is ADMER ADHESIVE RESIN from Mitsui Chemicals.

[0035] Also disclosed herein are interior trim articles that include the top layer articles described above as well as a variety of additional layers. The additional layers can include a wide variety of different layers. In some embodiments, the additional layers can be grouped together as a TGP (Transfer Gravure Printing) sheet. The TGP sheet may or may not be assembled as a unit or the additional layers can be disposed on the top layer article or on each other in a variety of ways. However, assembled, the interior trim articles of this disclosure can be viewed as combinations of top layer articles and TGP sheets.

[0036] In some embodiments, the TGP sheet comprises: a first adhesive layer; a colored layer; a thermally adherable thermoplastic resin layer; a second adhesive layer; and a release liner. The TGP sheet can also contain additional optional layers. Each of these layers is described in detail below.

[0037] In some embodiments, the first adhesive layer of the TGP sheets is in contact with the second major surface of the top layer article. The second major surface of the top layer article may be the support film or the second polyolefin-based layer. The first adhesive layer comprises a heat-activated adhesive. In some embodiments, the first adhesive layer comprises: a) a chlorinated thermoplastic resin; b) a carboxylic acid-functional halogen-free polyolefin-based resin; c) an acrylic resin with a Tg less than or equal to -30°C; and d) at least one crosslinker.

[0038] In some embodiments, the adhesive composition further comprises up to 1.0 part by weight of at least one epoxy-functional crosslinker. As with the isocyanate-functional crosslinker, the epoxy-functional crosslinker is typically at least difunctional. A suitable epoxy-functional crosslinker is the tetrafunctional E-5XM from Soken Chemical and Engineering Co., Ltd.

[0039] The adhesive layer can also comprise a variety of optional additives. Among the suitable additives are UV stabilizers and anti-oxidants. Suitable UV stabilizers include HALS (Hindered Amine Light Stabilizers) such as ADK stab LA 63P from Adeka Corporation. Suitable anti-oxidants include IRGANOX 1098 from BASF Japan Co., Ltd. and ADK stab 2112 from Adeka Corporation, as well as combinations of these materials. Combinations of additives can also be used. Additionally, while not required, an ultraviolet absorbing agent can be used if desired.

[0040] Examples of suitable heat-activated adhesives are described in the co-pending application Attorney Docket Number PA102477US01.

[0041] The TGP sheets also comprise a color layer in contact with the first adhesive layer. Examples of suitable color layers include a color layer that exhibits a paint color, metallic color or the like, a pattern layer that imparts a logo, an image, or a pattern such as a wood grain pattern, stone grain pattern, geometric pattern or leather pattern to the structure, a relief (embossed pattern) layer in which recesses and protrusions are provided on the surface, and combinations thereof.

[0042] Pigments that may be used for the color layer by dispersion in a binder resin such as acrylic resin, polyurethane resin or the like are exemplified by inorganic pigments such as titanium oxide, carbon black, chrome yellow, yellow iron oxide, colcothar, red iron oxide, or the like; organic pigments such as phthalocyanine pigments (phthalocyanine blue, phthalocyanine green, or the like), azo lake pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments (quinacridone red, or the like), or the like; aluminum brightening agents such as aluminum flake, vapor-deposited aluminum flake, metal oxide-coated aluminum flake, colored aluminum flake, or the like; and pearlescent brightening materials such as flake- like mica and synthetic mica coated with a metal oxide such as titanium oxide or iron oxide, or the like. The colored layer can be formed by printing such as gravure direct printing, gravure offset printing, inkjet printing, laser printing, or screen printing, coating such as gravure coating, roll coating, die coating, bar coating, or knife coating. Examples of suitable colored layers are described in US Patent No. 10,774,242 (Y asuda et al.).

[0043] The color layer may be a single layer or a multi-layer construction comprising multiple color layers. If the color layer is a multi-layer construction, the multiple layers generally contain different pigments. In embodiments in which the color layer is a multi- layer construction, one or more of the layers may be a patterned layer. The multi-layer color layer may contain different colors, different patterns, or both.

[0044] The color layer may have a variety of thicknesses, and it is generally not less than approximately 0.01 micrometers, not less than approximately 0.1 micrometers, or not less than approximately 0.8 micrometers, and not more than approximately 100 micrometers, not more than approximately 50 micrometers, or not more than approximately 10 micrometers.

[0045] The TGP sheets also comprise a thermally adherable thermoplastic resin layer in contact with the color layer. A number of suitable thermally adherable thermoplastic resin layer materials are suitable. Particularly suitable are phenoxy resins, or combinations of phenoxy resins and polyurethanes. In the present disclosure, “phenoxy resin” means a thermoplastic polyhydroxy polyether synthesized using a bisphenol and epichlorohydrin and encompasses those having an epoxy group derived from a tiny amount of epichlorohydrin in the molecule (for example, at the terminal). For example, the epoxy equivalent amount of phenoxy resin is higher than that of epoxy resin, for example, not less than 5,000, not less than 7,000 or not less than 10,000. Particularly suitable thermally adherable thermoplastic resin layer materials are phenoxy resin and polyurethane. Examples of suitable phenoxy resin and polyurethanes are described in US Patent No. 10,774,242 (Yasuda et al.).

[0046] The articles also comprise a second adhesive layer in contact with the thermally adherable thermoplastic resin layer. It is desirable that the second adhesive layer not be tacky at room temperature. The second adhesive layer may be a heat activated adhesive such as the heat activated adhesive described above or it may a different heat activated adhesive . In some embodiments, the second adhesive layer comprises a (methacrylate- based adhesive layer comprising a cured layer prepared from a reaction mixture comprising: at least one alkyl (meth)acrylate; at least one (meth)acrylic monomer with a basic-functional group; at least one (meth)acrylate copolymer with a Tg of at least 55°C; at least one crosslinking monomer; and at least one initiator.

[0047] The reaction mixture comprises at least one alkyl (meth)acrylate of general formula I:

[0048] CH2=CR1-(CO)-OR2

[0049] Formula I wherein R1is hydrogen or a methyl group, and R2is an alkyl, with 4-22 carbon atoms. Suitable alkyl (meth)acrylate monomers include, but are not limited to, those selected from the group consisting of the esters of acrylic acid or methacrylic acid with non-tertiary alkyl alcohols such as 1 -butanol, isobutanol, 1 -pentanol, 2-pentanol, 3- pentanol, 2 -methyl- 1 -butanol, 1 -methyl- 1 -butanol, 1 -methyl- 1 -pentanol, 2-methyl-l- pentanol, 3 -methyl- 1 -pentanol, 2-ethyl-l -butanol, 2-ethyl-l -hexanol, 3,5,5-trimethyl-l- hexanol, 3 -heptanol, 2-octanol, 1 -decanol, 1 -dodecanol, and the like, and mixtures thereof. Such monomeric acrylic or methacrylic esters are known in the art and are commercially available.

[0050] In some embodiments, the alkyl(meth)acrylate monomer with alkyl groups comprising 8-18 carbon atoms or even 8-10 carbon atoms. Examples of particularly suitable alkyl acrylate monomers are isooctyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isobutyl acrylate, dodecyl acrylate and mixtures thereof.

[0051] The reaction mixture also comprises at least one (meth)acrylic monomer with a basic -functional group of general Formula II or general Formula III:

[0052] CH2=CR1-(CO)-OR3

[0053] Formula II wherein the compound is a (meth)acrylate where R1is hydrogen or a methyl group, and R3is an alkyl group containing 1-10 carbon atoms and a basic group. Basic groups include amino groups (-NH2).

[0054] CH2=CR1-(CO)-NR4R5

[0055] Formula III wherein the compound is a (meth)acrylamide where R1is hydrogen or a methyl group, and R4and R5are each independently a hydrogen atom or an alkyl group with 1-3 carbon atoms.

[0056] Examples of suitable (meth)acrylic monomers with basic -functional groups include ones of Formula II where R3is a -CH2-NH2, -CH2-CH2-NH2, -CH2-CH2-CH2-NH2, and ones of Formula III where R4and R5are each methyl groups, ethyl groups or propyl groups. Particularly suitable is DMAA (N,N-dimethyl acrylamide). The reaction mixture also comprises at least one (meth)acrylate copolymer with a Tg of at least 55°C. The (meth)acrylate copolymer comprises at least two monomers. Typically, at least one of the monomers is an alkyl (meth)acrylate monomer and at least one of the monomers is a (meth)acrylate monomer polar group. Examples of suitable alkyl (meth)acrylate monomers include those described by Formula I above. Examples of (meth)acrylate monomers with polar groups include (meth)acrylic acid. In some embodiments, methacrylate monomers are particularly suitable because they have higher homopolymer Tg values than their corresponding acrylate monomers.

[0057] The reaction mixture also comprises at least one crosslinking monomer. Particularly suitable crosslinking monomers are multi-functional (meth)acrylates. Examples of a useful multi-functional (meth)acrylates include, but are not limited to, a di(meth)acrylate, tri(meth)acrylate, and tetra(meth)acrylate, such as 1,6-hexanediol di(meth)acrylate, a polyethylene glycol) di(meth)acrylate, polybutadiene di(meth)acrylate, a polyurethane di(meth)acrylate, propoxylated glycerin tri(meth)acrylate, and mixtures thereof. Particularly suitable crosslinking monomers include HDDA (1,6- hexanediol di(meth)acrylate).

[0058] The reaction mixture also comprises at least one initiator. Typically, the initiator is a photoinitiator, meaning that the initiator is activated by light, typically ultraviolet (UV) light. Photoinitiators are well understood by one of skill in the art of (meth)acrylate polymerization. Examples of suitable free radical photoinitiators include DAROCURE 1173, DAROCURE 4265, IRGACURE 184, IRGACURE 651, IRGACURE 1173, IRGACURE 819, LUCIRIN TPO, LUCIRIN TPO-L, commercially available from BASF Japan Co., Ltd. The photoinitiator LUCIRIN TPO-L is particularly suitable.

[0059] Examples of suitable second adhesives are described in the co-pending application Attorney Docket Number PA 102510US01.

[0060] The articles also comprise a release liner in contact with the second adhesive layer. Release liners are well known in the adhesive arts. Exemplary release liners include those prepared from paper (e.g., Kraft paper) or polymeric material (e.g., polyolefins such as polyethylene or polypropylene, ethylene vinyl acetate, polyurethanes, polyesters such as polyethylene terephthalate, and the like, and combinations thereof). At least some release liners are coated with a layer of a release agent such as a silicone, a fluorosilicone- containing material or a fluorocarbon-containing material. The articles may also include additional layers. One particularly suitable additional layer is a vapor-deposited metal layer between the second adhesive layer and the thermally adherable thermoplastic resin layer. This vapor-deposited metal layer can aid in enhancing the visual appearance of the trim article. Light contacting the metal layer is reflected back through the color layer giving the trim article a metallic-like appearance. A variety of metals can be used, especially suitable metals are aluminum, tin, and indium or their oxidation products. A method for vapor-depositing metal onto the second adhesive layer is described in the co-pending application Attorney Docket Number PA102510US01.

[0061] Also disclosed herein are methods for making multi-layer films that are useful as decorative film articles. In some embodiments, the method comprises preparing a top layer article with a first major surface and a second major surface, preparing a TGP (Transfer Gravure Printing) sheet, heat laminating the top layer article to the TGP sheet by applying heat and pressure to form an intermediate article, removing the carrier film from the intermediate article, providing an adhesive article with a second adhesive layer disposed on a release liner, heat laminating the second adhesive layer to the intermediate article by applying heat and pressure to form a secondary article, and heating and contacting the outermost surface of the top layer article of the secondary article to an embossing tool to impart a structured surface to the first major surface of the top layer article.

[0062] In some embodiments, the top layer article comprises a transparent multi-layer film comprising at least 2 layers, an outermost layer and a bottom layer, where the outermost layer comprises a first polyolefin-based layer and the bottom layer comprising a support film that is a transparent film layer with a pencil hardness of at least B. In some embodiments, the top layer article further comprises a second polyolefin-based layer disposed on the support film. The top layer articles and their materials are described in detail above. In some embodiments, the top layer article is formed by co-extrusion. The components of the top layer articles are described in detail above. As mentioned above, the first polyolefin layer may further comprise a nucleating agent to enhance the scratch resistance of the top layer article.

[0063] In some embodiments, preparing the TGP (Transfer Gravure Printing) sheet, comprises providing a carrier film, depositing a thermally adherable thermoplastic resin layer composition on the carrier film and drying the thermally adherable thermoplastic resin layer composition, if necessary, to form a thermally adherable thermoplastic resin layer, depositing a color solution on the thermally adherable thermoplastic resin layer to form a color layer comprising a pigment dispersed in a binder, and depositing a first adhesive comprising a heat activated adhesive on the color layer to form the first adhesive layer. Each of these components and layers are described briefly below and in detail above.

[0064] A variety of films are suitable for the carrier film. Suitable carrier films include release liners as described above. Also suitable are polymeric films that do not have a release coating. Particularly suitable films include polyester films such as PET (polyethylene terephthalate) films.

[0065] In some embodiments, a thermally adherable thermoplastic resin layer composition is deposited on the carrier film and drying the thermally adherable thermoplastic resin layer composition, if necessary, to form a thermally adherable thermoplastic resin layer. A number of suitable thermally adherable thermoplastic resin layer materials are suitable. Particularly suitable are phenoxy resins, or combinations of phenoxy resins and polyurethanes. Examples of suitable phenoxy resin and polyurethanes are described above and in US Patent No. 10,774,242 (Yasuda et al.).

[0066] In some embodiments, a color solution is deposited on the thermally adherable thermoplastic resin layer to form a color layer comprising a pigment dispersed in a binder. As mentioned above, the color layer may comprise multiple colored layers or patterned layers. Suitable color layers are described above.

[0067] In some embodiments, a first adhesive comprising a heat activated adhesive is deposited on the color layer to form the first adhesive layer. Heat activated adhesives suitable for use as the first adhesive layer are described in detail above.

[0068] The method also comprises heat laminating the top layer article to the TGP sheet. In some embodiments, the support film or the second polyolefin-based layer disposed on the support film of the top layer article is heat laminated to the first adhesive layer of the TGP sheet and applying heat and pressure to form an intermediate article. In some embodiments, the applying of heat and pressure comprises passing the top layer article / TGP sheet laminate through a heated nip roller. The method also comprises providing an adhesive article with a second adhesive layer disposed on a release liner. Release liners are well understood in the art and are described above. As mentioned above, the second adhesive layer may be a heat activated adhesive. In some embodiments, the second adhesive layer comprises a (methacrylate- based adhesive layer comprising a cured layer prepared from a reaction mixture comprising: at least one alkyl (meth)acrylate; at least one (meth)acrylic monomer with a basic-functional group; at least one (meth)acrylate copolymer with a Tg of at least 55°C; at least one crosslinking monomer; and at least one initiator.

[0069] Examples of suitable second adhesives are described in the co-pending application Attorney Docket Number PA 102510US01.

[0070] In some embodiments, the adhesive article further comprises an optional layer that is a vapor-deposited metal layer disposed on the second adhesive layer. This vapor- deposited metal layer can aid in enhancing the visual appearance of the trim article by increasing the light passing through the colored layer. A variety of metals can be used, especially suitable metals are aluminum, tin, and indium, or their oxidation products. A method for vapor-depositing metal onto the second adhesive layer is described in the co- pending application Attorney Docket Number PA102510US01.

[0071] The method further comprises removing the carrier fdm from the intermediate article to expose the thermally adherable thermoplastic resin layer and heat laminating the second adhesive layer or the vapor-deposited metal layer disposed on the second adhesive layer to the intermediate article such that the thermally adherable thermoplastic resin layer contacts the second adhesive layer or the vapor-deposited metal layer disposed on the second adhesive layer and applying heat and pressure to form a secondary article. In some embodiments, heat laminating the second adhesive layer to the intermediate article by applying heat and pressure to form a secondary article comprises passing the adhesive article / intermediate article laminate through a heated nip roller.

[0072] The method further comprises heating and contacting the polyolefin-based film surface of the secondary article to an embossing tool to impart a structured surface to the first major surface of the top layer article. Embossing tools are well understood in the art has being tools that have structured surface, where the structured surface is the opposite of the pattern desired to be formed in the polyolefin-based film surface of the secondary article. For example, if one wishes to impart a series of protrusions in the polyolefin- based film surface of the secondary article, the tool has a series of depressions in its surface. Typically, the pattern embossed into the polyolefin-based film surface comprises a plurality of protrusions arising from a base surface wherein the protrusions have a height of at least 5 micrometers.

[0073] The articles of this disclosure may be more fully understood by reference to the figures. Figure 1A shows article 100A. Article 100A comprises top layer 160 comprising polyolefin-based layer 161 and support layer 162.

[0074] Figure IB shows article 100B. Article 100B comprises top layer 160 comprising polyolefin-based layer 161 and support layer 162, and polyolefin-based layer 163.

[0075] Figure 2 shows article 200. Article 200 comprises adhesive article 250 comprising release liner 251 and (meth)acrylate-based adhesive layer 252, and optional metal layer 253. Disposed on adhesive article 250 is thermally adherable resin thermoplastic resin layer 220, color layer 230 with optional color sublayers 231, 232, 233, and heat activated adhesive layer 240. Disposed on heat activated adhesive layer 240 is top layer 260 comprising polyolefin-based layer 261, support layer 262, and optional polyolefin-based layer 263.

[0076] Figure 3 shows article 300. Article 300 is article 200 that has had a structured surface imparted into the top layer 260. Article 300 comprises adhesive article 350 comprising release liner 351 and (meth)acrylate-based adhesive layer 352, and optional metal layer 353. Disposed on adhesive article 350 is thermally adherable resin thermoplastic resin layer 220, color layer 330 with optional color sublayers 331, 332, 333, and heat activated adhesive layer 340. Disposed on heat activated adhesive layer 340 is top layer 360 comprising polyolefin-based layer 361, support layer 362, and optional polyolefin-based layer 363. While layer 363 is shown as flat, in some embodiments the layer may not be flat but may have a pattern that mimics the pattern of the layers above (361 and 362). Additionally, the layers below layer 363, namely 340, 330, 320, 352, and 353, are also shown as flat but likewise may have a pattern that mimics the pattern of the layers above. Examples

[0077] These examples are merely for illustrative purposes only and are not meant to be limiting on the scope of the appended claims. All parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, unless noted otherwise.

[0078] Table of Abbreviations

[0079] Test Methods

[0080] Pencil Hardness

[0081] Pencil Hardness was measured by applying the sample to be tested to a PC / ABS Plate and vacuum forming by TOM (Three-dimensional Overlay Method) by passing through a thermoforming machine (from Fu-se Vacuum Forming, Ltd., model number NGF-0709) and measuring the pencil hardness with a TRIBOSTATION Type 32 from SHINTO Scientific Co., Ltd. The loading was 750 grams, the pencil angle was 45°, the moving speed was 60 millimeters per minute, and the stroke distance was 10 millimeters.

[0082] Chemical Durability The sample to be tested was applied to a PC / ABS Plate and vacuum formed by TOM (Three-dimensional Overlay Method) by passing through a thermoforming machine (from Fu-se Vacuum Forming, Ltd., model number NGF-0709). A plastic ring was applied to the sample with a sealing agent. 5 milliliters of 50% ethanol was placed in the ring and a glass plate was put over the ring. The sample was placed in a 55 °C oven for 4 hours. The sample was rinsed with water and the surface of the sample was observed for detectable differences in appearance. No detectable difference is reported as “Pass” and detectable difference is reported as “Fail”.

[0083] Texture Depth

[0084] The sample to be tested was applied to a PC / ABS Plate and vacuum formed by TOM (Three-dimensional Overlay Method) by passing through a thermoforming machine (from Fu-se Vacuum Forming, Ltd., model number NGF-0709). The texture depth was measured using a 3 -dimensional laser microscope LEXT OLS4100 from Olympus Corporation.

[0085] Transparency

[0086] The sample to be tested was applied to a PC / ABS Plate and vacuum formed by TOM (Three-dimensional Overlay Method) by passing through a thermoforming machine (from Fu-se Vacuum Forming, Ltd., model number NGF-0709). The transparency was determined visually by looking at the article and determining if the printed color design is observable through the top layer article. The result is reported as “Yes” if the printed color design is observable through the top layer article or “No” if not observable.

[0087] Formability

[0088] The sample to be tested was applied to a PC / ABS Plate and vacuum formed by TOM (Three-dimensional Overlay Method) by passing through a thermoforming machine (from Fu-se Vacuum Forming, Ltd., model number NGF-0709). The drawdown and stretchability are reported. Thermal Stability

[0089] The samples were tested by aging in a 110°C oven for 500 hours followed by visual inspection to determine if there is color change in the article. No detectable difference is reported as “Pass” and detectable difference is reported as “Fail”.

[0090] Scratch resistance test

[0091] Scratch resistance was tested by applying the sample to be tested to a PC / ABS Plate and vacuum forming by TOM (Three-dimensional Overlay Method) by passing through a thermoforming machine (from Fu-se Vacuum Forming, Ltd., model number NGF-0709) and scrabbing the sample surface by nail of first finger. The scratch resistance was determined visually by looking at the article and determining if the scratch is observable through the top layer article. The result is reported as “Yes” if the scratch is observable through the top layer article or “No” if not observable.

[0092] Examples E1-E5 and Comparative Examples CE1-CE3

[0093] Preparation of Example E1-E5 and Comparative Examples CE1-CE3:

[0094] Multi-layer constructions were prepared using the same general process described below, except for CE1 which was prepared by a process described below.

[0095] Preparation of Comparative Example CE1:

[0096] Comparative Example CE1 was prepared in a multi-step process. Step 1 is the Formation of a polyurethane layer on a PET carrier film, Step 2 is vapor coating of tin on the polyurethane layer, Step 3 is the preparation of a TGP sheet, Step 4 is heat lamination of the TGP sheet to the tin-coated polyurethane layer. Step 5 is the preparation of an ATT article and lamination to the article of Step 4, Step 6 is the formation of the Top Layer on the article of Step 5, Step 7 is embossing of the article of Step 6, and Step 8 is vacuum forming of the article of Step 7.

[0097] Step 1 : Formation of Polyurethane Layer:

[0098] On a layer of PET carrier film was coated a waterborne polyurethane and the coating was dried in a 140°C oven to form a 20-micrometer thick polyurethane layer.

[0099] Step 2: Vapor Coating of Polyurethane Layer To the polyurethane layer of Step 1, metal vapor of tin deposited using a vapor coater to give a metal thickness 30-60 nanometers.

[0100] Step 3: Formation ofTGP (T ransfer Gravure Printing) Sheet:

[0101] The TGP sheet was formed in sequence with a carrier fdm of PET on which was deposited by a gravure print roller a Phenoxy Adhesive layer (the components of the Phenoxy Adhesive are shown in Table 3) and the layer was dried in an 80°C oven to form a layer of 0.1 micrometer. A Color layer solution of a pigment in a binder was gravure printed with a gravure print roller on the Phenoxy Adhesive layer and dried in an 80°C oven to form a layer of 0.1 micrometer. A second Phenoxy Adhesive layer (the components of the Phenoxy Adhesive are shown in Table 3) was coated on the Color layer and the layer was dried in an 80°C oven to form a layer of 0.1 micrometer.

[0102] Step 4: Heat lamination of the TGP sheet to the tin-coated polyurethane layer

[0103] The second Phenoxy Adhesive layer of the TGP sheet was heat laminated at 120°C to the tin-coated layer of the polyurethane layer. The PET carrier film was removed from the polyurethane layer after heat lamination.

[0104] Step 5: Preparation of an ATT article and lamination

[0105] To the release surface of a Liner a solvent borne acrylic adhesive was coated and dried in a 120°C oven to form a 40 micrometers thick adhesive coating. The solvent borne adhesive is prepared by mixing 94 parts by weight of butyl acrylate and 6 parts by weight acrylic acid in 100 parts by weight of toluene and 100 parts by weight of ethyl acetate. To this solution was added 0.2 parts by weight of initiator (2,2'-Azobis(2,4- dimethylvaleronitrile) available as V-65 from FUJIFILM Wako Pure Chemical to 50°C for 24 hours to form mixture- 1. In a separate vessel, 60 parts by weight of methyl methacrylate (MMA) and 34 parts by weight of n-butyl methacrylate (BMA) and 6 parts by weight of dimethyl amino ethyl methacrylate (DMAEMA) were dissolved in 150 parts by weight of ethyl acetate after adding 0.6 parts by weight of polymerization initiator (Dimethyl 2.2‘-Azobis(2-methylpropionate) available as V-601 from FUJIFILM Wako Pure Chemical Corporation) the mixture was sealed and placed under a nitrogen atmosphere and heated to 65°C for 24 hours to form mixture-2. The adhesive formed by mixing 49.16 parts by weight of mixture-1, 17.85 parts by weight of mixture-2, 0.23 parts by weight of antioxidant available as SONGNOX 1010 from Songwon Industrial Co., Ltd., 1.08 parts by weight of titanium oxide pigment available as Ti-Pure R-960 from DuPont Kabushiki Kaisha, 0.46 parts of epoxy cross linker E-5XM from Soken Chemical & Engineering Co., Ltd., and 31.22 parts by weight of MIBK.

[0106] Step 6: Formation and Attachment of the Top Layer:

[0107] A 75 -micrometer thick PMMA layer was heat laminated at 120°C to the Phenoxy adhesive layer. A 30-micrometer thick layer of PVDF / PMMA alloy was heat laminated to the PMMA layer at 120°C to form a PVDF / PMMA -PMMA top layer on the article formed in Step 6.

[0108] Step 7: Embossing of the Top Layer

[0109] The article formed in Step 6 was heated to 250°C and passed under an embossing roll to form an embossed pattern (25 micrometer depth pattern) in the Top Layer.

[0110] Step 8: Vacuum Forming of the Embossed Article

[0111] The release liner was removed from the article of Step 7 and the exposed adhesive layer was contacted to the surface of a PC / ABS panel and the resultant construction was vacuum formed by TOM (Three-dimensional Overlay Method) by passing through a thermoforming machine (from Fu-se Vacuum Forming, Ltd., model number NGF-0709) at a temperature of 142°C. The embossed structures had a depth of 18 micrometers after Vacuum Forming.

[0112] Preparation of Example E1-E5 and Comparative Examples CE2-CE3:

[0113] Formation of Top Layer Articles

[0114] The Top layer Articles for Examples E1-E5 were prepared by co-extrusion of the materials shown in Table 1. The Top Layer Articles for Comparative Examples CE1-CE3 were either prepared fdms or monolayer PP fdms. The components and thickness of the formed layers are shown. In Table 1, the composition of the PP layer is shown in Table 2. The EVOH is EVOH-1 for E1-E4 and EVOH-2 in E5. Table 1 : Top Layer Article Compositions Table 2: Components of PP layer

[0115] Preparation of Additional Components

[0116] Formation of TGP (Transfer Gravure Printing) Sheets

[0117] The TGP sheet was formed in sequence with a carrier film of PET on which was deposited by a gravure print roller a Phenoxy Adhesive layer (the components of the Phenoxy Adhesive are shown in Table 3), and the layer was dried in an 80°C oven to form a layer of 0.1 micrometer. A Color layer solution of a pigment in a binder was gravure printed with a gravure print roller on the Phenoxy Adhesive layer and dried in an 80°C oven to form a layer of 0. 1 micrometer. An Adhesive Solution was gravure printed with a gravure print roller on the Color layer and dried in an 80°C oven to form an Adhesive Layer of 0.1 micrometer. The Adhesive Solution composition is shown in Table 4. Table 3 : Phenoxy Adhesive

[0118] Table 4: Adhesive Solution Formation of ATT (Adhesive Transfer Tape) Articles

[0119] To form the ATT, the adhesive mixture shown in Table 5 was disposed on the release surface of a Liner and cured with UV light to form an adhesive layer of 40 micrometer thickness. For Example El, this ATT was used (ATT-1), for Examples E2-E5 and Comparative Examples CE2-CE3 the adhesive surface had metal vapor deposited using a vapor coater to give a metal thickness 30-60 nanometers (ATT-2). The coatings used in each Example are shown in Table 6. Table 5

[0120] Table 6 Lamination of Top Layer Article to TGP Sheet to Form Intermediate Article

[0121] The Top Layer Article was laminated to the TGP sheet by contacting the bottom most layer of the Top Layer Article to the Adhesive Layer of the TGP and passing the construction through 120°C nip rolls. The resultant article is an Intermediate Article.

[0122] Lamination of Intermediate Article to ATT Article to Form Secondary Article

[0123] The PET carrier film was removed from the laminated construction prepared above, and the Intermediate Article with the PET carrier film removed was laminated to ATT sheet by contacting the Phenoxy Adhesive layer of the Intermediate Article to the Adhesive Layer or the metal layer of the ATT article and passing the construction through 120°C nip rolls. The resultant article is a Secondary Article.

[0124] Embossing of the Secondary Article

[0125] The secondary article was heated to 180°C and passed under an embossing roll to form an embossed pattern in the topmost polypropylene-based layer of the Secondary Article. For Examples CE3 and E4 a 25-micrometer depth embossing roll was used, for the other examples a 100-micrometer depth embossing roll was used.

[0126] Vacuum Forming of the Embossed Article

[0127] The release liner was removed from the Embossed Article and the exposed adhesive layer was contacted to the surface of a PC / ABS panel and the resultant construction was vacuum formed by TOM (Three-dimensional Overlay Method) by passing through a thermoforming machine (from Fu-se Vacuum Forming, Ltd., model number NGF-0709) at the temperature shown in Table 6.

[0128] Property Testing

[0129] Property testing of vacuum-formed samples was carried out as described in the test methods above. The results are shown in Table 7. In Table 6 PH = Pencil Hardness; CD = Chemical Durability; TD = Texture Depth; T = Transparency; F = Formability; and TS = Thermal Stability. The Formability results are presented as DD (drawdown distance in millimeters); FT (forming temperature in °C); and S (stretchability in %).

[0130] Table 7

[0131] NM = Not Measured

[0132] Examples E6-E9 and Comparative Examples CE4-CE5

[0133] These Examples are very similar to the above examples, but the outer polypropylene layer contains nucleating agent.

[0134] Preparation of Example E6-E9 and Comparative Examples CE4-CE5:

[0135] Formation of Top Layer Articles The Top layer Articles for Examples E6-E9 and CE4 and CE5 were prepared by co-extrusion of the materials shown in Table 8. The components and thickness of the formed layers are shown. In Table 8, the composition of the Layer 1 PP layer is shown in Table 9 and the Layer 2 PP layer is shown in Table 10. The EVOH is EVOH-1 for E6-E9 and CE4 and CE5. Table 8: Top Layer Article Compositions

[0136] Table 9: Components of PP layer 1

[0137] Table 10: Components of PP layer 2

[0138] Preparation of Additional Components

[0139] For the remaining components of the articles, the same procedure described above for Example E5 above were followed.

[0140] Property Testing

[0141] Property testing of vacuum-formed samples was carried out as described in the test methods above. The results are shown in Table 11. In Table 11 PH = Pencil Hardness; CD = Chemical Durability; TD = Texture Depth; SR = Scratch Resistance.

[0142] Table 11

Claims

What is claimed is:

1. A multi-layer film comprising: a top layer article with a first major surface and a second major surface comprising a transparent multi-layer film comprising at least 2 layers, an outermost film and a bottom film, wherein the outermost film comprises a first polyolefin-based layer and the bottom film comprises a support film that is a transparent film layer with a pencil hardness of at least B, wherein the first major surface of the top layer article is a structured surface comprising a plurality of protrusions arising from a base surface wherein the protrusions have a height of at least 5 micrometers, and wherein the top layer article has a pencil hardness of at least 2B.

2. The multi-layer film of claim 1, wherein the top layer article further comprises a second polyolefin-based layer disposed on the support film, wherein the second polyolefin-based layer and the first polyolefin-based layer are the same composition or different.

3. The multi-layer film of claim 1, wherein the first polyolefin-based layer of the top layer article comprises a polypropylene-based layer comprising a nucleating agent.

4. The multi-layer film of claim 3, wherein the polypropylene-based layer is scratch resistant.

5. The multi-layer film of claim 1, wherein the first polyolefin-based layer of the top layer article comprises a polypropylene-based layer comprising at least one additive selected from UV stabilizer and antioxidants.

6. The multi-layer film of claim 1, wherein the top layer article has a thickness of at least 30 micrometers.

7. The multi-layer film of claim 6, wherein the first polyolefin-based layer has a thickness of from 1-30 micrometers and the support film has a thickness that is at least 1 times greater than the thickness of the polyolefin-based layer.

8. The multi-layer film of claim 2, wherein the first polyolefin-based layer has a thickness of from 1-30 micrometers, the support film has a thickness that is at least 1 times greater than the thickness of the polyolefin-based layer and the second polypropylene-based layer has a thickness of from 1-30 micrometers.

9. The multi-layer film of claim 1, wherein the support film comprises EVOH (poly(ethylene-vinyl alcohol)) or polyacrylate.

10. The multi-layer film of claim 2, wherein the top layer article further comprises a bonding layer between the polyolefin-based layer and the support film, between the support film and the second polyolefin-based layer, or both, wherein the bonding layer comprises a thermoplastic modified polyolefin.

11. The multi-layer film of claim 1 further comprising: a first adhesive layer in contact with the second major surface of the top layer article, comprising a heat-activated adhesive; a colored layer in contact with the first adhesive layer, wherein the colored layer comprises a pigment dispersed in a binder; a thermally adherable thermoplastic resin layer in contact with the colored layer; a second adhesive layer in contact with the thermally adherable thermoplastic resin layer, the second adhesive layer comprising a (meth)acrylate-based adhesive layer; and a release liner in contact with the second adhesive layer.

12. The multi-layer film of claim 11, further comprising a vapor-deposited metal layer between the second adhesive layer and the thermally adherable thermoplastic resin layer, wherein the vapor-deposited metal layer comprises aluminum, tin, indium, or their oxidation products.

13. The multi-layer film of claim 11, wherein the first adhesive layer comprises: a) a chlorinated thermoplastic resin; b) a carboxylic acid-functional halogen-free polyolefin-based resin; c) an acrylic resin with a Tg less than or equal to -30°C; andd) at least one crosslinker.

14. The multi-layer film of claim 11, wherein the thermally adherable thermoplastic resin layer comprises phenoxy and polyurethane.

15. The multi-layer film of claim 11, wherein the second adhesive layer comprises a (meth)acrylate-based adhesive layer comprising a cured layer prepared from a reaction mixture comprising: at least one alkyl (meth)acrylate; at least one (meth)acrylic monomer with a basic-functional group; at least one (meth)acrylate polymer with a Tg of at least 55°C; at least one crosslinking monomer; and at least one initiator.

16. The multi-layer film of claim 11, wherein the color layer comprises multiple colored layers.

17. The method of making a multi-layer film comprising: preparing a top layer article with a first major surface and a second major surfacer comprising a transparent multi-layer film comprising at least 2 layers, an outermost layer and a bottom layer, wherein the outermost layer comprises a polyolefin-based layer and the bottom layer comprises a support film that is a transparent film layer with a pencil hardness of at least B; preparing a TGP (Transfer Gravure Printing) sheet, comprising: providing a carrier film; and depositing a thermally adherable thermoplastic resin layer composition on the carrier film and drying the thermally adherable thermoplastic resin layer composition to form a thermally adherable thermoplastic resin layer; depositing a color solution on the thermally adherable thermoplastic resin layer to form a color layer comprising a pigment dispersed in a binder; anddepositing a first adhesive comprising a heat activated adhesive on the color layer to form the first adhesive layer; heat laminating the top layer article to the TGP sheet by contacting the bottom film of the top layer article to the first adhesive layer of the TGP sheet and applying heat and pressure to form an intermediate article; removing the carrier film from the intermediate article to expose the thermally adherable thermoplastic resin layer; providing an adhesive article with a second adhesive layer disposed on a release liner; heat laminating the second adhesive layer to the intermediate article such that the thermally adherable thermoplastic resin layer contacts the second adhesive layer and applying heat and pressure to form a secondary article; and heating and contacting the polypropylene-based film surface of the secondary article to an embossing tool to impart a structured surface to the first major surface of the top layer article.

18. The method of claim 17, wherein the top layer article further comprises a second polyolefin-based layer disposed on the support film that is the bottom film.

19. The method of claim 17, wherein the polyolefin-based layer of the top layer article comprises a polypropylene-based layer comprising a nucleating agent.

20. The method of claim 17, wherein the top layer article is formed by coextrusion.

21. The method of claim 17, wherein heat laminating the top layer article to the TGP sheet by applying heat and pressure comprises passing the top layer article / TGP sheet laminate through a heated nip roller.

22. The method of claim 17, wherein heat laminating the second adhesive layer to the intermediate article by applying heat and pressure to form a secondary article comprises passing the adhesive article / intermediate article laminate through a heated nip roller.

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