Method for applying polymeric films to substrates and resulting articles

Abstract

To provide alternative methodology for application of polymeric films to surfaces of articles.SOLUTION: A polymeric film assembly comprising a first solidified interlayer on a polymeric film or a laminate comprising the polymeric film is contacted with at least a portion of a surface of an underlying article to provide, for example, desired surface characteristics. At least a portion of the first solidified interlayer becomes a softened interlayer positioned between the polymeric film and the surface of the article when contacted as such. The softened interlayer is then converted to a second solidified interlayer. Here, the second solidified interlayer may be in a different form or same form as the first solidified interlayer initially provided, for adherence of the polymeric film to at least the portion of the surface of the article. Ease of removal and / or repair of polymeric film and laminates comprising the polymeric film that are so applied is facilitated.SELECTED DRAWING: None

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 62 / 577,960, filed October 27, 2017, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a method for applying a polymeric film to a substrate and the resulting article. [Background technology]

[0003] Polymeric materials (also referred to herein simply as "polymers") are typically used in the form of films for many applications. A "film" is generally understood to be a relatively thin, continuous, single layer (layer of material). In contrast, many conventionally applied "coatings" do not form a continuous or uniform layer of material on the underlying substrate. Thus, unlike polymeric films, which can be used as a single layer or as one of multiple layers in other applications, coatings often cannot be physically separated from the supporting substrate on which they are formed. Thus, coating technology has limitations and is typically distinguished from polymeric film technology.

[0004] Polymeric films can often provide desired properties for intended applications without the need for coating multiple layers or laminating multiple films, and are widely used in many applications. The suitability of a polymeric film for an application depends, for example, on its physical properties (strength, elasticity, transparency, color, durability, etc.). However, even when the properties of a polymeric film are optimized, these benefits are often not fully realized because conventional methods for applying such films to a substrate often result in air being trapped between the polymeric film and the substrate, visible as defects. This problem and one solution to it are described in U.S. Patent Application Publication No. 2015 / 0183198 (Patent Document 1).

[0005] As described in U.S. Patent No. 5,999,623, painted surfaces are widely used in many different applications. Painted surfaces not only enhance aesthetic properties, but can additionally or alternatively enhance the functional properties of the underlying surface and help protect that surface. One such application is in the transportation industry, where exterior painted surfaces are typically exposed to a variety of environments, some of which can be extremely hostile to the surface. Examples of articles in the transportation industry having such painted surfaces include land, water, and air transportation vehicles. Such vehicles include aircraft and land motorized vehicles such as automobiles and trucks. The paint on such surfaces is less susceptible to damage from exposure. It can act as a surface protector, however the coating itself must be able to withstand repeated exposure to such damaging environments.

[0006] In recent years, film-form coatings have been developed for application to surfaces to replace traditional liquid-based coatings, which are typically applied to such surfaces in liquid form. Film-form coatings comprise at least one polymeric film, also referred to herein as a "polymeric film" or "polymeric paint film." An example of such a polymeric paint film is described in U.S. Patent Application Publication No. 2010 / 0059167, entitled "Paint Replacement Films, This is described in "Composites Therefrom, and Related Methods" (Patent Document 2).

[0007] However, when applying other polymeric films to surfaces, particularly those with complex irregularities, it has proven difficult to provide adequate adhesion at the interface and effectively remove trapped air between the polymeric film and the substrate. For example, in many cases, adhesives attached to polymeric films are applied to substrate surfaces (where the adhesion does not necessarily proceed along a uniform front surface), particularly when the substrate surface is irregular (e.g., with significant protrusions or The more complex the adhesive layer (e.g., with recesses), the more likely it is that air will be trapped at the adhesive interface between the polymer film and the substrate surface. The more the polymer film is bonded, the more difficult it becomes to completely remove the air trapped behind the adhesive. Therefore, research has been conducted into the mechanisms that promote the release of air from the adhesive surface (air bleeding).

[0008] Many conventional air bleed mechanisms use adhesive layer structures to remove trapped air. See, for example, U.S. Patent Application Publication No. 2011 / 0111157 and U.S. Patent No. 7,332,205. Other polymeric film-based structures known to promote air bleed between the structure and the underlying surface after application include microstructured surfaces, such as those described in U.S. Patent No. 5,897,930. While effective in many applications, such microstructures have been found to reduce optical clarity in certain applications. For example, structures from adhesive layers may still be visible (to the naked human eye) after application of the polymeric film to the underlying surface. The visibility is often even more pronounced as the polymeric film thickness decreases and / or the transparency of the polymeric film increases. As can be easily understood, such structures are not an ideal solution to the problem of trapped air removal. Furthermore, the constraints associated with the presence of such microstructured surfaces limit the types of polymeric films that can be effectively applied to the surface of an article.

[0009] The optical clarity of a polymeric material is an important consideration when selecting materials for optical and other applications where a particular surface aesthetic is desired relative to the appearance of the polymeric film applied to the article. Surface aesthetics may alternatively or additionally be related to maintaining or enhancing the properties of the underlying surface of the article to which the polymeric film is applied. When the surface beneath the applied polymeric film is made of a composite material, trapped air and other defects naturally present in the underlying surface are often more pronounced, and further, the underlying surface is more susceptible to damage when attempting to maintain or enhance the aesthetics of the underlying surface.

[0010] For composite materials (e.g., fiber-reinforced composites), achieving the desired surface aesthetics without affecting the physical properties of the composite surface is often difficult, but is becoming increasingly important in light of the increasing use of composites in applications where lightweight materials are desired and where the associated loss of material strength or stiffness is problematic. Additionally, composite materials often have superior corrosion resistance compared to alternative materials, making many composite materials useful in applications where corrosion resistance is desirable.

[0011] There are many types of composite materials known. In the case of fiber-reinforced composites, the composite is often formed by a polymer resin matrix and fiber reinforcement. A variety of materials can be used for each of the matrix and fiber reinforcement components. For example, useful materials for the fiber reinforcement include carbon fiber, boron fiber, and glass fiber. Furthermore, examples of useful materials for the polymeric resin matrix include thermoplastic materials (e.g., nylon) and thermosetting materials (e.g., epoxy and phenolic resins).

[0012] Due to their advantageous properties, composite materials are increasingly being formed into a variety of specialized sporting goods and other articles. For example, composite materials are used to form sporting goods with shafts (kicks, etc.). Composite materials are increasingly being used in sports equipment (generally sporting goods having a longitudinally extending portion, which may or may not be hollow throughout and may or may not be uniform in thickness and shape) and similar articles. Examples of such articles include golf clubs, bicycle frames, hockey sticks, lacrosse sticks, skis, ski poles, fishing rods, tennis rackets, arrows, polo mallets, and bats. Composite materials, for example, allow golf club manufacturers to produce shafts with a variety of strengths, flexibilities, and torsional stiffnesses.

[0013] Additionally, various articles in the transportation and energy industries are increasingly being formed from composite materials. For example, composite materials are often used to form various aerospace components, such as wing and blade components in helicopters and specialized military aircraft. Furthermore, composite materials are often used to form various interior and exterior automotive components, such as body panels, roofs, doors, gear shift knobs, seat frames, steering wheels, etc. In the energy industry, composite materials are used to form wind turbine blades; for example, the use of carbon fiber reinforced composites makes the blades of large wind turbines more efficient. Indeed, the number of current and future applications for composite materials is enormous.

[0014] Advantageously, composite materials offer improved strength, stiffness, corrosion resistance, and weight reduction. These advantageous properties are offset by the competing disadvantages of wear resistance and impact resistance. These factors are often balanced. Furthermore, because many composite articles are formed by stacking multiple individual composite layers to achieve desired properties, such composite articles are prone to delamination, especially upon impact. This is particularly common in carbon fiber reinforced composites (also known as "CFR composites"). Delamination can compromise the structural integrity of such articles and prevent the composite article from being used as intended. Furthermore, in extreme cases where a composite article does fail, sharp fracture surfaces (i.e., reinforcing fibers extending haphazardly from the affected area) can affect not only the usefulness of the article but also the safety of the user of the article and those around it. Therefore, preventing and suppressing failure is also an important design factor.

[0015] Gel coats and similar protective coatings have traditionally been used to enhance certain properties of composite articles. Gel coats often impart a glossy appearance and enhance other aesthetic properties of the article. Gel coats can also provide some, albeit limited, improvement in abrasion resistance. Gel coats and similar protective coatings have traditionally been applied to composite articles formed by molding, even if only for aesthetic purposes. However, the need for aesthetic enhancement arises, particularly because of the tendency for surface defects to occur when articles are molded from composite materials. One mechanism for the increased number of surface defects in molded composite articles is related to the formation of microscopic air bubbles at the mold interface when the polymer matrix of such composites does not flow sufficiently throughout the reinforcement (e.g., fibers) during molding. As a result, the surface of a composite article formed against the mold surface can have defects such as voids that detract from its glassy or other desired appearance. These defects can complicate the surface finishing process of the composite article.

[0016] There are two widely used methods for applying gel coat or similar outer protective coatings to composite articles. One method is to spray the gel coat onto the outer surface of the composite article after it has been formed (e.g., by molding). This method can be subject to defects that complicate the finishing process of the surface of the composite article. For example, when a coating is sprayed onto a surface, air can become trapped in voids on the surface. Where this air is trapped, there is no substrate for the coating to adhere to. This typically results in the coating either flowing into the voids or dissolving in that area of ​​the surface. In addition to the problems associated with trapped air, Conventional coatings that flow generally tend to conform to irregularities and imperfections in the underlying surface, subsequently replicating the texture of the underlying surface in the externally exposed surface of the cured coating.

[0017] A second method eliminates subsequent (e.g., post-molding) processing steps by pre-applying a gel coat to the interior surface of a mold, for example, which can be transferred to the exterior surface of the composite article formed within the mold. See, for example, U.S. Pat. No. 4,081,578; U.S. Pat. No. 4,748,192; and U.S. Pat. No. 5,849,168. This method is a variation of "in-mold processing," which may also be referred to as in-mold decoration or in-mold labeling, depending on the application and materials used. Another variation using in-mold processing to apply materials, although more complex and inefficient, is described in U.S. Pat. No. 5,768,285.

[0018] Compared to coatings, polymeric films still present problems when applied to surfaces. For example, the traditional application of polymeric films with a pressure-sensitive adhesive (PSA) on the backside The application process can be complicated by voids. Similar to the problems associated with applying conventional coatings, where air is trapped on the surface, the polymeric film and any adhesive on its backside have no substrate to adhere to. Because of this, and because the polymeric film is not a liquid coating, it will not flow into the voids or cause dewetting of the surface. As a result, the polymeric film will typically cover the voids with trapped air underneath. If pressure is applied to these areas and the polymeric film has sufficient stretchability, the polymeric film will typically close the voids. The trapped air often extends into the gap spaces, causing visible defects in the surface. If the trapped air is not removed, it often expands or contracts during use of the resulting article, resulting in irregularities in the surface of the polymeric film. In addition to the problems associated with trapped air, conventional polymeric films often have a constant thickness, which causes the film to conform to irregularities and imperfections in the underlying surface, replicating the texture of the underlying surface on the exposed surface of the film. [Prior art documents] [Patent documents]

[0019] [Patent Document 1] U.S. Patent Application Publication No. 2015 / 0183198 [Patent Document 2] U.S. Patent Application Publication No. 2010 / 0059167 [Patent Document 3] U.S. Patent Application Publication No. 2011 / 0111157 [Patent Document 4] U.S. Patent No. 7,332,205 [Patent Document 5] U.S. Patent No. 5,897,930 [Patent Document 6] U.S. Patent No. 4,081,578 [Patent Document 7] U.S. Patent No. 4,748,192 [Patent Document 8] U.S. Patent No. 5,849,168 [Patent Document 9] U.S. Patent No. 5,768,285 Summary of the Invention [Problem to be solved by the invention]

[0020] All things considered, an alternative method for applying a polymeric film to the surface of an article is desirable. This need is particularly evident when using conventional spray-applied clear coats, which typically require the application of several coating layers, often with sanding between each coat, to achieve a smooth surface with a desired gloss. Particularly when the underlying surface is a fiber composite, this method is not only time-consuming but can also damage the fiber composite surface during sanding. [Means for solving the problem]

[0021] According to the present invention, a polymeric film or a laminate comprising said polymeric film is applied to at least a portion of the surface of an underlying article, for example to impart a desired surface texture. To aid in this application, a first solidified interlayer is applied to the surface of said polymeric film or laminate comprising said polymeric film to form a polymeric film assembly in contact with said portion of the surface of said article. This polymeric film assembly comprises said first A solidified interlayer is applied to at least a portion of the surface of the article by contacting the surface of the article, and at least a portion of the first solidified interlayer becomes a softened interlayer disposed between the polymeric film and the surface of the article. The softened interlayer then transforms into a second solidified interlayer, which then holds the polymeric film in place in front of the surface of the article. This may be of a different or the same form as the first solidified intermediate layer initially applied to adhere to at least a portion of the substrate.

[0022] In polymeric films and laminates comprising such polymeric films, a substantial portion of the second solidified interlayer is attached to the underlying article. The polymeric film and layers adjacent to the second solidified interlayer can be efficiently and effectively separated from the article while leaving the polymeric film and layers adjacent to the second solidified interlayer intact, thereby facilitating removal and / or repair of the polymeric film and laminates including the polymeric film. Other polymeric films or laminates including polymeric films can be efficiently and effectively applied to the surface of the article by conventional methods without the use of additional solidified interlayer materials in related processes. DETAILED DESCRIPTION OF THE INVENTION

[0023] According to the present invention, a polymeric film assembly including a polymeric film is applied to at least a portion of an underlying surface of an article, wherein the polymeric film applied to the underlying surface of the article has a desired surface texture (e.g., smoothness, gloss, etc.).

[0024] To aid in the application of such polymeric films to substrate surfaces of articles, particularly surfaces of fiber-based composite materials (i.e., fiber composite surfaces), a room-temperature-setting interlayer (also referred to herein as a "setting interlayer") is present on the surface of the polymeric film assembly that contacts the surface of the article to which the polymeric film is to be applied. When the polymeric film assembly is applied to a heated article surface, only the heated portion of the setting interlayer softens, forming a "softened interlayer." This allows the softened interlayer to have a viscosity that allows it to flow over and into voids and imperfections commonly found in fiber composite surfaces when applied to the substrate. This flow results in a smoother surface for the resulting article, with fewer visible imperfections. Advantageously, according to this exemplary embodiment, movement of the softened interlayer away from the interface between the polymeric film assembly and the substrate with which it contacts is minimized because only the portion of the setting interlayer that contacts the heated surface is softened.

[0025] After the softened interlayer contacts the substrate surface, it optionally undergoes polymerization to return to a solidified interlayer. As used herein, terms such as "polymerization" may include the meaning of "curing" or the like used by those skilled in the art. These terms may be used interchangeably herein and by those skilled in the art. For example, the term "curing" is often used to describe the polymerization (also known as "hardening") of epoxy resins.

[0026] According to one embodiment, after being applied to the surface, the softened interlayer reverts to an essentially identical solidified interlayer (in terms of composition and material properties) upon cooling. After application to the surface, the softened interlayer of polymerizable composition is partially polymerized and then solidified upon cooling. Upon cooling, the previously softened interlayer can exhibit the properties of a viscoelastic fluid, a viscoelastic solid, or an elastic solid. In an exemplary embodiment, after the polymeric film is applied to the substrate surface and cooled to room temperature, the solidified interlayer has a Brookfield viscosity at room temperature of greater than about 20,000 cP.

[0027] Using the method of the present invention, the polymeric film of the present invention provides a desirable surface texture as an improvement over conventional techniques that use surface coatings such as spray painting. Thus, by using the method of the present invention, articles having improved surface texture can be obtained. In preferred embodiments, the resulting article has surface quality that is at least equivalent (and often superior) to that of conventionally sprayed clear coatings or polymeric films adhered to a substrate surface using conventional methods.

[0028] Another advantage of the present invention relates to the ease of removal and / or repair of polymeric films applied to substrate surfaces according to the improved methods. For example, in one embodiment, when the polymeric film is part of a laminate containing the polymeric film, the solidified interlayer adheres better to the substrate surface than the polymeric film and / or adjacent layers (e.g., any adhesive layers). The absence of covalent crosslinks between the solidified interlayer and the polymeric film and / or adjacent layers contributes to this characteristic adhesion. The absence of such covalent crosslinks allows a substantial portion of the solidified interlayer to be bonded to the underlying material. The polymeric film and adjacent layers can be efficiently and effectively separated from the underlying article while leaving the underlying article intact.

[0029] Without the use of additional interlayer material in the related methods, polymeric films or laminates including polymeric films can be efficiently and effectively reapplied to the surface of the article by conventional methods, and surface voids and imperfections (e.g., those commonly found on fiber composite surfaces) that were present on the underlying surface of the article prior to application of the polymeric film removed according to the methods of the present invention are substantially eliminated by the presence of the solidified interlayer deposited on the surface during application of the original polymeric film.

[0030] [Polymer films and laminates containing polymer films] A "polymeric film" of the present invention is a relatively thin, continuous single layer of polymeric material. The polymeric film of the present invention is not what one skilled in the polymer arts would normally think of as an adhesive.

[0031] In further embodiments, two or more layers of polymeric film or other material may be provided in the form of a "laminate" that is applied to the surface of an article. While greater thicknesses are possible, in one aspect of a polymeric film laminate, the laminate has a total thickness of less than about 400 microns. In a further embodiment, the total thickness of the laminate is less than about 200 microns. In yet another embodiment, the total thickness of the laminate is less than about 50 microns. In yet another embodiment, the total thickness of the laminate is about 10 microns. Generally, thicker laminates are more resistant to abrasion, although thinner laminates may be used when resistance to corrosion, etc., is a primary concern.

[0032] The properties of polymeric film laminates useful in the present invention may vary depending, for example, on whether the laminate is first applied to a surface of an article with a solidified interlayer in contact with the surface, or whether the laminate is applied to the same surface after removing the applied polymeric film with a solidified interlayer from the surface. For example, in one embodiment, the polymeric film laminate applied to the surface of an article to which a polymeric film assembly including a solidified interlayer has previously been applied has an adhesive (e.g., pressure-sensitive adhesive) layer. In an exemplary aspect of this embodiment, such a polymeric film laminate has an adhesive layer on the surface of the polymeric film opposite the solidified interlayer that contacts the substrate surface to which the laminate is applied.

[0033] Various types of polymeric films (sometimes called "protective sheets") are known and have been applied to a variety of substrate surfaces, including composite materials. See, for example, U.S. Pat. No. 8,545,959, incorporated herein by reference. However, as noted in the background section above, the application of polymeric films can be complicated, particularly given the problems associated with removing trapped air between the polymeric film and the substrate surface. Trapped air is one of the factors that often causes visible defects in the resulting surface.

[0034] The polymeric film may optionally be at least partially pigmented (i.e., colored) as a "polymeric paint film" and / or at least partially metallized. In exemplary embodiments, the polymeric film of the present invention is at least partially pigmented. The pigmented polymeric film of the present invention may be substantially translucent, depending on, among other things, the type of pigment and the thickness of the polymeric film. Or it may be substantially opaque.

[0035] In other exemplary embodiments, the polymeric films of the present invention are metallized. Typically, the metallized polymeric films of the present invention are substantially opaque, although the metallized polymeric films may be at least partially transparent depending on the degree of metallization.

[0036] In a further exemplary embodiment, the polymeric film of the present invention is both pigmented and metallized, but the polymeric film may not contain additives that alter the appearance of the underlying article to make the polymeric film applicable according to the method of the present invention.

[0037] In other exemplary embodiments, the polymeric film is substantially color-free and metallized. According to one aspect of this embodiment, the polymeric film is substantially transparent. According to another aspect of this embodiment, the polymeric film is substantially translucent. According to another aspect of this embodiment, the polymeric film is substantially opaque.

[0038] To enhance the adhesion of the polymeric film to surfaces with relatively complex topography, the polymeric film is preferably stretchable. The term "stretchable" refers to the ability of a material to be ductile and stretched (stretched). An exemplary stretchable polymeric film can be stretched to at least about 105% or more of its initial length without breaking. For example, a 100 cm long stretchable polymeric film can be stretched to at least 105 cm or more without breaking. In one embodiment, the stretchable polymeric film can be stretched to at least about 125% or more of its initial length without breaking. For example, a 100 cm long stretchable polymeric film can be stretched to at least 125 cm or more without breaking. In another embodiment, the stretchable polymeric film can be stretched to at least about 150% or more of its initial length without breaking. For example, a 100 cm long stretchable polymeric film can be stretched to at least 150 cm or more without breaking.

[0039] In one embodiment, the polymeric film does not fully recover once stretched. Exemplary polymeric films having such reduced recovery can be stretched to a length of at least about 110% of their initial length without breaking; According to one aspect of this embodiment, after being stretched to a length of at least about 110% of its initial length, the polymer film recovers only to about 105%, preferably about 110%, of its initial length.

[0040] In other embodiments, the polymeric film is not only extensible but also stretchable. Stretchability refers to the ductility of a material and its ability to be stretched and to essentially return to its original state after stretching. A stretchable polymeric film can recover to its original state when stretched to a length of about 125% or more of its initial length. That is, a stretchable polymeric film can recover to its original state when stretched to a length of about 125% or more of its initial length. For example, a polymeric film having an initial length of about 100 cm can recover to a length of about 100 cm after being stretched to a length of 125 cm or more if the film is stretchable. Preferably, a stretchable polymeric film can recover to its original state when stretched to a length of about 150% or more of its initial length.

[0041] In other preferred embodiments, the polymeric film exhibits essentially no plastic deformation when stretched to about 125% of its initial length (e.g., when the polymeric film is stretched from an initial length of 100 cm to a length of about 125 cm). In further preferred embodiments, the polymeric film exhibits essentially no plastic deformation when stretched to about 150% of its initial length (e.g., when the polymeric film is stretched from an initial length of 100 cm to a length of about 150 cm). Preferably, the force required to stretch the polymeric film to 150% of its initial length is less than about 40 N.

[0042] According to preferred embodiments of the present invention, the polymeric film can be stretched greater than 200% before breaking. In other preferred embodiments, the polymeric film exhibits an elongation at break of greater than about 210% when tested according to ASTM D638-95. In more preferred embodiments, the polymeric film exhibits an elongation at break of greater than about 260% when tested according to ASTM D638-95. In even more preferred embodiments, the polymeric film exhibits an elongation at break of greater than about 300% when tested according to ASTM D638-95. In yet another preferred embodiment, the polymeric film exhibits an elongation at break of greater than about 350% when tested according to ASTM D638-95.

[0043] Useful polymeric films may have any suitable composition, and although more than one polymeric material may be used in the polymeric film of the present invention, and more than one polymeric material may be used in other layers in the laminate, the following will generally refer to one type of polymeric material in such layers solely for the sake of brevity.

[0044] The polymeric film may comprise any suitable polymeric material. For example, the polymeric film may be based on polyurethane, polyacrylate, polyepoxide, or polyester elastomer. Although generally not preferred in certain embodiments due to their relatively low stretchability, the polymeric film may also be based on polyvinyls (such as polyvinyl chloride (PVC), polyvinyl acetate (PVA), polyvinylidene fluoride (PVDF), general-purpose polyvinyl fluoride (PVF) (e.g., polyvinyl fluoride sold by DuPont under the trade name TEDLAR)) or α-olefins in embodiments where full recovery of the polymeric film after stretching is not necessary or desired.

[0045] The polymeric film is preferably polyurethane-based and includes any suitable polyurethane material. For simplicity, the term "polyurethane" is used herein to refer to a polymeric film that contains urethane (also known as carbamate) linkages in combination with urea linkages [i.e., The term "poly(urethane-urea)" is sometimes used to refer to a polymeric material having at least a urethane bond and optionally a urea bond. Thus, the polyurethane of the present invention has at least a urethane bond and optionally a urea bond. Many commercially available polyurethanes are suitable for use as polyurethane-based polymeric films of the present invention. For example, polyurethanes manufactured by Entrotech, Inc. (Columbus, OH) Suitable polyurethanes (trade names: HT1331, HT2312, HT2313) are available from Polyurethanes.

[0046] In addition to the additives included in the exemplary embodiments that alter the appearance of the article, the polymeric film may optionally contain any suitable additives. For example, stabilizers (such as antioxidants, heat stabilizers, and UV stabilizers), crosslinkers (such as aluminum or melamine crosslinkers), binders, corrosion inhibitors, plasticizers, photocrosslinkers, fillers, and other conventional additives known to those skilled in the art may be added to the polymeric film. If desired, the polymeric film may also contain an adhesion promoter. However, in preferred embodiments, the materials included in the polymeric film are selected to be chemically compatible with any adjacent layers in a laminate of which the polymeric film is a part. Therefore, according to preferred embodiments of the present invention, an adhesion promoter is not required.

[0047] The polymeric film may be pigmented and / or metalized and may be substantially transparent, substantially translucent, or substantially opaque, depending on the application. If the polymeric film is substantially transparent or substantially translucent, but a pigmented and / or metalized aesthetic is desired, at least one pigmented and / or metalized layer may be provided within a laminate including the polymeric film (e.g., between the polymeric film and any adhesive layer or between the polymeric film and a solidified interlayer). Alternatively, in other embodiments, a pigmented and / or metalized layer may be provided on the opposite side of the polymeric film. Alternatively, in the laminate, in combination with at least one colored and / or metallized layer sandwiched between the polymeric film and the adhesive layer, the colored and / or metallized layer may be disposed on the opposite side of the polymeric film. In such embodiments, if the polymeric film is substantially opaque, the outer surface of the polymeric film, typically the side that is visible from the outside when the polymeric film is applied to a surface, may be pigmented and / or metallized. In this embodiment, the polymeric film may be impregnated with a material (e.g., titanium dioxide) that causes the polymeric film to act as a reflective background, thereby enhancing the color of the pigment superimposed thereon. Also, if the polymeric film is substantially transparent or substantially transparent, the color may be enhanced. In this case, the outer surface of the polymeric film may be colored and / or metallized, either on the polymeric film alone or in combination with a colored and / or metallized layer in a laminate that includes the polymeric film.

[0048] Those skilled in the art are familiar with materials and methods for forming color and metallized layers. In embodiments of the present invention in which the polymeric film is colored and / or metallized, any suitable materials and methods can be used. While more than one colored and / or metallized layer can be used in a laminate including a polymeric film of the present invention, the following description of such a layer will refer to it as a single layer solely for the sake of brevity. When multiple colored and / or metallized layers are used, each of the colored and / or metallized layers in such a laminate can be the same or different.

[0049] When a metallized layer is provided, the metallized layer may comprise any suitable material to provide a desired aesthetic appearance when a laminate including the polymeric film is adhered to a surface. The metallized layer may be continuous or discontinuous. It should be noted that the metallized layer may be essentially graphic. The layer may be a discontinuous layer and / or a non-planar layer, and may be formed of a block, pattern, or the like.

[0050] In one embodiment, the metallization layer is formed by chemical or physical vapor deposition of a thin layer of aluminum or a desired metal or alloy thereof. The thickness of the metallization layer can be any suitable thickness. In an exemplary embodiment, the maximum thickness of the metallization layer is about 1,000 Å, and preferably less than about 500 Å. In a further embodiment, the minimum thickness of the metallization layer is at least about 70 Å.

[0051] When a color layer is provided, the color layer may comprise any suitable material that provides a desired aesthetic appearance when the polymeric film-containing laminate is adhered to a surface. The color layer may be continuous or discontinuous. The color layer may essentially consist of graphics, patterns, etc., and may be discontinuous and / or non-planar.

[0052] The color layer typically includes at least one material that imparts a desired color to a laminate or portion thereof that includes the polymeric film. In one embodiment, the color layer includes a dye. In another embodiment, the color layer includes an ink. Any suitable commercially available ink can be used. Non-limiting examples of suitable inks include pigmented acrylic inks (including fast-drying pigmented acrylic inks), pigmented urethane inks, epoxy inks, and urethane enamel coatings (e.g., manufactured by PRC-Desoto International, Inc. (PPG Aerospace)). and urethane enamel coatings under the trade name DESOTHANE HS, manufactured by Epson Corporation, a division of Epson Corporation (Glendale, CA).

[0053] Any suitable additives may be optionally used in the color layer. For example, stabilizers (such as antioxidants, heat stabilizers, and UV stabilizers), crosslinkers (such as aluminum or melamine crosslinkers), corrosion inhibitors, plasticizers, photocrosslinkers, additional colorants, fillers, and other conventional additives known to those skilled in the art may be added to the color layer. If desired, the color layer may also contain an adhesion promoter. However, in preferred embodiments, the materials contained in the color layer are selected to be chemically compatible with any adjacent layers of the laminate, including the polymer film. Therefore, according to preferred embodiments of the present invention, an adhesion promoter is not required.

[0054] Preferably, the color layer is substantially free of components that may tend to migrate to the outer surface of the polymeric film, to laminates containing the polymeric film, or to interfaces therein, where such components may promote delamination or otherwise adversely affect the adhesion of the polymeric film to adjacent surfaces or layers. Also, the color layer is preferably resistant to chemicals to which the polymeric film may be exposed during use.

[0055] The color layer may have any suitable thickness. In an exemplary embodiment, the color layer has a maximum thickness of about 50 microns, more preferably less than about 25 microns, and preferably between about 5 microns and about 8 microns.

[0056] Preferably, the polymeric film is substantially free of components that may tend to migrate to the outer surface of the polymeric film or to interfaces in laminates containing the polymeric film. Such components may promote delamination or otherwise adversely affect the adhesion of the polymeric film to adjacent surfaces or layers. The polymeric film is also preferably resistant to chemicals to which it may be exposed during use. For example, the polymeric film is preferably resistant to degradation by water or hydraulic fluids. Furthermore, the polymeric film is preferably .... It is preferable that the film has heat resistance to temperatures that the film may be exposed to during use.

[0057] The thickness of the polymeric film may be any suitable thickness. In one embodiment, the thickness of the polymeric film is from about 10 microns to about 400 microns. In another embodiment, the thickness of the polymeric film is from about 10 microns to about 200 microns. In yet another embodiment, the thickness of the polymeric film is from about 10 microns to about 50 microns. In an exemplary embodiment, the thickness of the polymeric film is about 25 microns or less. It has been found that the use of relatively thin polymeric films results in greater extensibility of the polymeric film. This extensibility allows the polymeric films of the present invention to be effectively used to coat articles having curved or other non-planar surfaces.

[0058] If an adhesive layer is provided on the laminate containing the polymeric film, the adhesive layer may comprise any suitable material. In one embodiment, the adhesive layer typically comprises a base polymer containing one or more additives. The base polymer of the adhesive layer may be of any suitable composition, but (meth)acrylate (i.e., acrylate and methacrylate)-based compositions are preferred. In particular, the base polymer may be based on a polymer obtained by polymerizing 2-ethylhexyl acrylate, vinyl acetate, and acrylic acid monomers using methods known to those skilled in the art. However, other suitable chemicals are known to those skilled in the art, including those based on synthetic and natural rubbers, polybutadiene and its copolymers, polyisoprene and its copolymers, or silicones (such as polydimethylsiloxane and polymethylphenylsiloxane). In a preferred embodiment, the adhesive layer comprises a pressure-sensitive adhesive (PSA).

[0059] Any suitable additives may be optionally used in combination with the base polymer of the adhesive layer. For example, stabilizers (such as antioxidants, heat stabilizers, and UV stabilizers), crosslinkers (such as aluminum or melamine crosslinkers), corrosion inhibitors, tackifiers, plasticizers, photocrosslinkers, fillers, and other conventional adhesive additives known to those skilled in the art may be added to the adhesive layer. If desired, the adhesive layer may also contain an adhesion promoter. However, in a preferred embodiment, the materials contained in the adhesive layer are selected to be chemically compatible with the polymer film. Therefore, according to a preferred embodiment of the present invention, an adhesion promoter is not required.

[0060] Like the polymeric film, the adhesive layer may be pigmented and / or metalized and may be substantially transparent, substantially translucent, or substantially opaque, depending on the application and the properties of the polymeric film and any pigmented and / or metalized layers in the laminate containing the polymeric film. In one embodiment, when the polymeric film is substantially transparent or substantially translucent, the adhesive layer is pigmented and / or metalized at its interface with the polymeric film. In this embodiment, the adhesive layer may be impregnated with a material (e.g., titanium dioxide) that causes the adhesive layer to act as a reflective background, thereby capturing the color of the pigment layer overlaid thereon.

[0061] Preferably, the adhesive layer is substantially free of components that migrate to the outer surface of the polymeric film or to interfaces in laminates containing the polymeric film, where such components may promote delamination or otherwise adversely affect the adhesion of the polymeric film to adjacent surfaces or layers. The adhesive layer is also preferably resistant to chemicals to which the polymeric film may be exposed during use. For example, the adhesive layer is preferably resistant to degradation by water or hydraulic fluids.

[0062] The adhesive layer may have any suitable thickness. In one embodiment, the adhesive layer has a thickness of about 5 microns to about 150 microns. In a further embodiment, the adhesive layer has a thickness of about 30 microns to about 100 microns. In an exemplary embodiment, the adhesive The thickness of the layer is about 25 microns or less, however, the thickness of the adhesive layer can vary substantially without departing from the spirit and scope of the present invention.

[0063] In an exemplary embodiment, the laminate including the polymeric film is a stretchable multi-layer protective sheet such as that described in U.S. Patent Application Publication No. 2008 / 0286576 (entitled "Protective Sheets, Articles, and Methods"), which is incorporated herein by reference in its entirety. Other examples of such laminates are described in U.S. Patent Application Publication No. 2010 / 0059167 (entitled "Paint Replacement Films, Composites Therefrom, and Related Methods"), which is incorporated herein by reference in its entirety.

[0064] The polymeric film can be stored with an optional release liner, if provided, in contact with the adhesive layer until it is applied to a surface. The selection and use of such a liner is within the knowledge of one skilled in the art. Advantageously, when using the improved application method of the present invention, the texture of the release liner in contact with the adhesive layer does not need to be such as to provide air release channels in the adhesive layer. In a preferred embodiment, while some randomly oriented texture may be present on the surface of the adhesive layer when applied to an article, the adhesive layer does not need to have a regular texture, such as air release channels, when a laminate including the polymeric film is applied to a surface [e.g., a structured release liner (trade name "POLY SLIK Air") manufactured by Loparex LLC, Cary, NC]. Thus, according to such preferred embodiments, any release liner attached to the adhesive layer prior to application of the laminate is essentially smooth.

[0065] Preferably, an essentially smooth release liner has a profile roughness parameter (Ra) of less than about 50 nm, for example, as measured according to DIN 4768. More preferably, an essentially smooth release liner has a profile roughness parameter (Ra) of less than about 30 nm, for example, as measured according to DIN 4768. Even more preferably, an essentially smooth release liner has a profile roughness parameter (Ra) of less than about 10 nm, for example, as measured according to DIN 4768.

[0066] Those skilled in the art will be familiar with the wide variety of suitable smooth release liners, many of which are commercially available as "optically clear" release liners. Exemplary essentially smooth release liners include those sold by the NORTON films group of Saint-Gobain Performance Plastics Corp. (Aurora, OH) under the trade names OPTILINER and SUPRALINER.

[0067] The polymeric film can be applied to a variety of articles according to the methods of the present invention to form an assembly, such that when applied to an article, the polymeric film and at least one outer surface of the article are in contact with the polymerizable composition therebetween to form an assembly.

[0068] [Middle layer] By using the term "intermediate layer," it is to be understood that such layer is disposed between the polymeric film or laminate comprising a polymeric film and the substrate surface of the resulting article, the polymeric film being in the state after it has been applied in accordance with the method of the present invention, but before the polymeric film or laminate comprising a polymeric film is applied to the substrate surface, the term "intermediate layer" refers to the polymeric film in its free state without surrounding structure. It can also be used to refer to a layer of material, where the intermediate layer is exposed and sandwiched between the polymeric film and the underlying surface of the article with which the polymeric film assembly contacts. According to the present invention, any suitable material can be used for the intermediate layer.

[0069] It should be understood that the solidified interlayer may be fully polymerized, partially polymerized, or substantially unpolymerized prior to application to a substrate surface. Preferably, after heating, the resulting softened interlayer has a relatively low viscosity so that it can flow over and into voids and imperfections common in fiber composite surfaces. Such flow results in a smoother surface for the resulting article with fewer visible imperfections. The softened interlayer may develop a desired viscosity when measured at room temperature or upon heating. Viscosity measurements described herein are performed on the interlayer in its neat form (i.e., 100% nonvolatile), without the use of viscosity-reducing solvents. Viscosity can be measured by techniques well known to those skilled in the art, such as the Cole-Parmer viscosity test. The viscosity may also be measured using a Brookfield rotational viscometer manufactured by Brookfield Corporation (Vernon Hills, IL).

[0070] According to the present invention, the intermediate layer exhibits a desired viscosity only after being heated to form a softened intermediate layer. According to an exemplary aspect of this embodiment, the Brookfield viscosity of the intermediate layer is less than about 10,000 cP after being heated to form a softened intermediate layer. In another embodiment, the Brookfield viscosity of the intermediate layer is less than about 5,000 cP after being heated to form a softened intermediate layer. In yet another embodiment, the Brookfield viscosity of the intermediate layer is less than about 2,000 cP after being heated to form a softened intermediate layer. In yet another embodiment, the Brookfield viscosity of the intermediate layer is less than about 1,500 cP after being heated to form a softened intermediate layer. In an exemplary embodiment, the Brookfield viscosity of the intermediate layer is between about 50 cP and about 1,500 cP after being heated to form a softened intermediate layer. In another exemplary embodiment, the Brookfield viscosity of the intermediate layer is between about 400 cP and about 1,500 cP after being heated to form a softened intermediate layer.

[0071] According to the method of the present invention, the intermediate layer can be made of any suitable composition and method for solidifying the composition. The intermediate layer can comprise a thermoplastic or thermosetting polymer. Examples of thermoplastic resins include polyamide resins, saturated polyester resins, polycarbonate resins, ABS resins, polyvinyl chloride resins, polyacetal resins, polystyrene resins, polyethylene resins, polyvinyl acetate resins, AS resins, methacrylate resins, polypropylene resins, and fluororesins. While the composition can be varied, epoxy-based, (meth)acrylate-based, and urethane-based compositions are particularly suitable and are suitable for many applications.

[0072] In one embodiment, the softened intermediate layer can be polymerized using a free radical polymerization method or a similar polymerization method. According to this embodiment, the softened intermediate layer and the previously solidified intermediate layer (to obtain the softened intermediate layer) comprise at least one monomer (e.g., vinyl or (meth)acrylate). The at least one monomer can react with itself and, in some further embodiments, with other monomers present. Depending on the type of radiation used, the softened intermediate layer and the previously solidified intermediate layer (to obtain the softened intermediate layer) can also comprise at least one initiator along with the at least one monomer.

[0073] In yet another embodiment, the softened intermediate layer can be polymerized using a cationic or similar polymerization method. According to this embodiment, the softened intermediate layer and the previously solidified intermediate layer (to obtain the softened intermediate layer) comprise at least one monomer and at least one cationic initiator.

[0074] Polymerizable systems based on ultraviolet polymerization, electron beam polymerization, or thermal polymerization can be used. Such systems include, for example, one-component and two-component epoxy resins. Resins can be thermosetting and thermoplastic resins, either alone or in combination. The most common types of epoxy resins are diglycidyl ethers of bisphenol A and epoxy novolacs (also known as cresol novolacs, phenol novolacs, or In one embodiment, the present invention utilizes low viscosity epoxy resins, such as epoxy resins based on diglycidyl ethers of bisphenol F. Typical epoxy resins based on diglycidyl ethers of bisphenol A [Resolution Performance Products EPON 826 manufactured by Resolution Performance Products, Inc. (Houston, TX) compared to exemplary low viscosity epoxy resins of the present invention (EPON 862 and EPON 866 manufactured by Resolution Performance Products, Inc.). ON 863) is based on the diglycidyl ether of bisphenol F and has a viscosity when tested at 25°C that is higher than that of typical epoxy resins based on the diglycidyl ether of bisphenol A, which is 6.5-9.6 Pa·s (65-96 Pa·s). In contrast, epoxy resins based on diglycidyl ethers of bisphenol F have been reported to have viscosities of 2.5-4.5 Pa·s (25-45 Pa). Other examples of bisphenol F-based epoxy resins include those manufactured by CVC Specialty Chemicals, Inc. (Moorestown, VA). The epoxy resin is EPALLOY 8230 manufactured by Epson Corporation (Pennsylvania, NJ). The reported viscosity of EPALLOY 8230 epoxy resin is 2.5-4.7 Pa·s (2,500-4,700 cP).

[0075] Generally, when a thermosetting resin is used, a curing agent is required to finally cure the resin. Any suitable curing agent can be used. As known to those skilled in the art, different curing agents provide different benefits when used. For example, in epoxy systems, aliphatic amine curing agents allow curing at room temperature, while aromatic amine curing agents provide optimal chemical resistance and greater rigidity in the final part. As another example, anhydride curing agents can provide superior electrical properties. However, it should be understood that the curing agent is selected based on the desired curing conditions and application, among other well-known factors. In an exemplary embodiment, at least one curing agent is used that accelerates the cure of the resin composition in about 45 to about 60 minutes when heated to about 120°C (250°F).

[0076] An exemplary class of curing agents useful for curing epoxy resins are modified aliphatic amine curing agents, such as those available under the trade name ANCAMINE from Air Products and Chemicals, Inc. (Allentown, PA). Within this class, ANCAMINE 2441 curing agent is particularly useful with exemplary resins of the present invention.

[0077] Other curing agent classes include dicyandiamides, which may optionally be used with common accelerators. One useful combination, for example, includes OMICURE DDA 5, an ultramicronized grade of dicyandiamide, and OMICURE U-52, an aromatic-substituted urea used as an accelerator for the dicyandiamide cure of epoxies (both manufactured by CVC Specialty Chemicals, Inc., Moorestown, NJ). Another useful combination includes AMICURE CG-1400, a micronized grade of dicyandiamide, and AMICURE UR, a substituted urea accelerator (1-phenyl-3,3-dimethylurea) for dicyandiamide-cured epoxy resins (both manufactured by Air Products and Chemicals, Inc., Allentown, PA).

[0078] The amount of the curing agent used in the resin composition of the present invention can be any suitable amount. Generally, it is well known to those skilled in the art to select a particular type of curing agent and then calculate the amount to be used.

[0079] In another embodiment of the one-component system, the polymer film is in contact with the underlying fiber composite surface. After contact with the polymeric film assembly, polymerization of the softened interlayer is initiated using thermal radiation. According to one aspect of the invention, thermal radiation is applied by heating the underlying fiber composite surface. According to another aspect of the invention, thermal radiation is applied by heating both the polymeric film assembly and the underlying fiber composite surface. According to an exemplary aspect of this embodiment, initiating polymerization using thermal radiation activates latent curing agents or unblocks blocked reactive components (e.g., blocked isocyanates).

[0080] The type and amount of the intermediate layer are selected depending on the application method and the desired properties of the resulting article. In laminates containing the polymer film, where an adhesive layer is present on the surface that contacts the substrate surface, the amount of the intermediate layer applied can be limited to a level sufficient to compensate for defects and fill voids present on the substrate surface. For Class A surfaces (e.g., those used in the automotive industry), only a small amount of intermediate layer is required. In certain embodiments, the intermediate layer may be 1-5 g / m 2 A middle layer of (gsm) is sufficient.

[0081] In alternative embodiments in which an adhesive layer is not present, it is often desirable to maintain a minimum thickness of the interlayer (and resulting solidified interlayer) between the polymeric film or laminate containing the polymeric film and the underlying substrate. According to one aspect of this embodiment, the interlayer is selected so that the resulting solidified interlayer has a thickness of about 5 to about 100 microns, preferably about 25 to about 50 microns. If desired, an optional filler material may be used to assist in maintaining this minimum thickness. An exemplary filler is 25-50 micron polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER) manufactured by Sekisui Plastics Co., Ltd.

[0082] The length of time required for the softened interlayer to properly solidify can vary. Preferably, the interlayer will revert to a solidified interlayer (if desired, even if the entire composition is not fully polymerized, and has a viscosity high enough to provide adequate adhesion to the substrate surface) within about 10 minutes, more preferably within about 5 minutes, and even more preferably within about 1 minute of contacting the softened interlayer with the substrate surface. The interlayer will be suitable for application and processing. Depending on the application, the solidified intermediate layer may exhibit properties associated with a viscoelastic fluid, a viscoelastic solid, or an elastic solid. In an exemplary embodiment, the solidified intermediate layer has a Brookfield viscosity at room temperature of greater than about 20,000 cP.

[0083] According to another aspect of the exemplary embodiment, the solidified interlayer has a peak loss factor of less than about 1.0 when tested as a standalone film according to the Loss Factor Test Method described below. Loss Factor is often used interchangeably with the term "Tan Delta," which is also used herein. It should be understood that the "loss factor" described in the specification is essentially the same.

[0084] The test was performed in tension mode using a dynamic mechanical analyzer (trade name: TA Instruments DMA Q800) manufactured by TA Instruments (Newcastle, DE) in accordance with the loss factor test method. Nominal sample sizes of 5-12 mm in length, 4-8 mm in width, and 0.02-0.2 mm in thickness were used. A frequency of 1 Hz, a strain of 0.3%, and a ramp rate of 3°C / min were used to measure the loss factor of the sample. This loss factor corresponds to a storage modulus greater than the loss modulus of the composition. The storage modulus can be tested using the dynamic mechanical analyzer described in the Loss Factor Test Method above.

[0085] It will be apparent to those skilled in the art that various modifications and adaptations of the present invention can be made without departing from the spirit and scope of the present invention, as defined by the appended claims. It should be noted that the steps recited in the following method claims do not necessarily have to be performed in the order recited. Those skilled in the art will recognize variations in performing those steps other than the order recited. Furthermore, the failure to mention or describe a structure, step, or element provides a basis for a claim that excludes the unrecited structure or element by similar language in a condition or claim. Furthermore, throughout, ranges are used as shorthand for representing all values ​​within that range. Any value within the range can be selected as a boundary value for that range. Similarly, any individual value within the range can be selected as a minimum or maximum value described in describing the structure and defining the scope of the present invention. It should also be noted that, as discussed herein, the polymerizable compositions described herein may contain all of the components in one or more portions. Other variations will occur to those skilled in the art. The present invention includes the following embodiments. [Aspect 1] 1. A method for applying a polymeric film to at least a portion of a surface of an article, comprising: providing the polymeric film or a laminate including the polymeric film; applying a first solidified interlayer to a surface of the polymeric film or a surface of a laminate including the polymeric film to form a polymeric film assembly in contact with the portion of the surface of the article; applying the polymeric film assembly to at least a portion of the surface of the article by contacting the first solidified interlayer with the surface of the article, thereby causing at least a portion of the first solidified interlayer to become a softened interlayer disposed between the polymeric film and the surface of the article; converting the softened interlayer into a second solidified interlayer, the second solidified interlayer being of a different or the same form as the first solidified interlayer originally applied to adhere the polymeric film to the at least a portion of the surface of the article; A method comprising: [Aspect 2] 10. The method of claim 1, wherein the polymeric film is polyurethane-based. Aspect 3 10. The method of claim 1, wherein the portion of the surface of the article is a fiber composite surface. Aspect 4 10. The method of claim 1, wherein the softened intermediate layer has a Brookfield viscosity of less than about 10,000 cP. Aspect 5 10. The method of claim 1, wherein the softened intermediate layer has a Brookfield viscosity of less than about 5,000 cP. Aspect 6 10. The method of claim 1, wherein the softened intermediate layer has a Brookfield viscosity of less than about 2,000 cP. Aspect 7 10. The method of claim 1, wherein the softened intermediate layer has a Brookfield viscosity of less than about 1,500 cP. Aspect 8 2. The method of claim 1, wherein the softened intermediate layer has a Brookfield viscosity of from about 50 cP to about 1,500 cP. Aspect 9 10. The method of claim 1, wherein the first solidified intermediate layer has a Brookfield viscosity greater than about 20,000 P. Aspect 10 10. The method of claim 1, wherein the second solidified intermediate layer has a Brookfield viscosity greater than about 20,000 P. Aspect 11 10. The method of claim 1, wherein the polymeric film or a laminate comprising the polymeric film is at least partially pigmented and / or at least partially metallized. Aspect 12 The method of claim 1, further comprising the step of separating the polymeric film, and, if present, a laminate including the polymeric film, from the portion of the surface of the underlying article while leaving a substantial portion of the second solidified intermediate layer on the underlying article. Aspect 13 13. The method of claim 12, further comprising applying a second polymeric film or a second laminate comprising the second polymeric film to at least a portion of the surface of the underlying article. Aspect 14 10. The method of claim 1, wherein the article comprises a motorized vehicle. Aspect 15 10. An article prepared by the method of claim 1, comprising: the polymer film or a laminate including the polymer film exposed to the outside of the article; the second solidified intermediate layer; the underlying surface of the article; The items are arranged in this order. Aspect 16 16. The article of claim 15, wherein the second solidified intermediate layer has a Brookfield viscosity at room temperature of greater than about 20,000 cP. Aspect 17 16. The article of claim 15, wherein the polymeric film is exposed to the outside of the article. Aspect 18 16. The article of claim 15, wherein the second solidified interlayer has a peak loss factor of less than about 1.0. Aspect 19 16. The article of claim 15, wherein the article comprises a motorized vehicle. Aspect 20 14. An article prepared by the method of claim 13, comprising: the second polymeric film or a second laminate including the second polymeric film exposed to the outside of the article; the second solidified intermediate layer; the underlying surface of the article; The items are arranged in this order.

Claims

1. 1. A method for applying a polymeric film to at least a portion of a surface of an article, comprising: providing the polymeric film or a laminate including the polymeric film; applying a first solidified interlayer to a surface of the polymeric film or a surface of a laminate including the polymeric film to form a polymeric film assembly in contact with the portion of the surface of the article; heating a surface of at least a portion of the article to form a heated surface; applying the polymeric film assembly to the portion of the heated surface of the article by contacting the first solidified interlayer with the portion of the heated surface of the article, thereby causing at least a portion of the first solidified interlayer to become a softened interlayer disposed between the polymeric film and the portion of the heated surface of the article; cooling the heated surface of the article to transform the softened interlayer into a second solidified interlayer, the second solidified interlayer being of a different or the same form as the first solidified interlayer originally applied to adhere the polymeric film to the at least a portion of the surface of the article; A method comprising: the step of transforming the softened interlayer into a second solidified interlayer comprises at least partially polymerizing the softened interlayer; and The method, wherein the article comprises a vehicle.

2. 10. The method of claim 1, wherein the polymeric film is polyurethane-based.

3. 3. The method of claim 1 or 2, wherein the portion of the surface of the article is a fiber composite surface.

4. 4. The method according to any one of claims 1 to 3, wherein the polymeric film or the laminate comprising the polymeric film is at least partially pigmented and / or at least partially metallized.

5. 5. The method of claim 1, further comprising the step of separating the polymeric film, and, if present, a laminate including the polymeric film, from the portion of the surface of the underlying article while leaving a substantial portion of the second solidified intermediate layer on the underlying article.

6. 6. The method of claim 5, further comprising applying a second polymeric film or a second laminate comprising said second polymeric film to said at least a portion of said surface of said underlying article.

7. The method of any one of claims 1 to 6, wherein the article comprises a motorized vehicle.

8. The article, the polymer film or a laminate including the polymer film exposed to the outside of the article; the second solidified intermediate layer; the underlying surface of the article; The method according to any one of claims 1 to 7, wherein the articles are arranged in this order.

9. The method described in claim 8, wherein the polymer film is exposed to the outside of the article.

10. The method described in claim 8 or 9, wherein the peak loss coefficient of the second solidified intermediate layer is less than 1.

0.

11. A method as described in claim 9 or 10, wherein the item comprises a motorized vehicle.

12. The article, the second polymeric film or a second laminate including the second polymeric film exposed to the outside of the article; the second solidified intermediate layer; the underlying surface of the article; The method of claim 6, wherein the articles are arranged in this order.