Decorative film with cover film, and method for manufacturing and installing the same

Abstract

A decorated film with a cover film of one embodiment includes: (a) a polyurethane layer having a first surface and a second surface opposite the first surface and comprising an at least partially crosslinked polyurethane, wherein the at least partially crosslinked polyurethane comprises at least one of a polyester-based polyurethane or a polycarbonate-based polyurethane; (b) a removable cover film having a post-corona treated or post-plasma treated surface, wherein the post-corona treated or post-plasma treated surface of the removable cover film is in contact with the first surface of the polyurethane layer; (c) a base layer having a first surface and a second surface opposite the first surface, wherein the first surface of the base layer is in contact with the second surface of the polyurethane layer; and (d) an adhesive layer in contact with the second surface of the base layer.

Description

[0001] This disclosure relates to a decorative film with a covering film, a method for manufacturing the decorative film, and a method for installing the decorative film. Background Technology

[0002] As is well known, the decoration of a car's body, parts, and other exterior surfaces is achieved by attaching decorative film to the exterior rather than by painting.

[0003] Patent document 1 (JP 2013-039724A) discloses "a vehicle paint replacement film comprising a transparent material layer and a colored adhesive layer, the colored adhesive layer comprising: (i) a colorant premix comprising (a) an acrylic polyol and (b) a colorant dispersed in the acrylic polyol, the colorant being selected from the group consisting of: combinations of organic and inorganic pigments, combinations of organic and alumina photoluminescent materials, combinations of organic and mica photoluminescent materials, combinations of inorganic and alumina photoluminescent materials, combinations of inorganic and mica photoluminescent materials, combinations of alumina and mica photoluminescent materials, and combinations thereof; and (ii) an adhesive polymer; wherein the solid content mass ratio expressed as (adhesive polymer) / (adhesive polymer + acrylic polyol) is 25% or higher."

[0004] Patent document 2 (JP 2007-297569 A) discloses "a film forming a decorative layer, the film forming a decorative layer comprising: a top coating comprising a polyurethane resin; and a carrier film disposed on the surface side of the top coating, wherein the polyurethane resin comprises a polyurethane resin composition comprising: (1) a polyisocyanate, based on total polyisocyanate, the polyisocyanate comprising 0.5 equivalents or higher equivalents of isocyanurate resin, or an adduct of isophorone diisocyanate, or both; and (2) a polyol comprising caprolactone diol, polycarbonate diol, or a mixture thereof, and based on total polyol comprising 0.4 equivalents or higher equivalents of a polyester polyol having an average molecular weight of 1000 or less, and the equivalent ratio between the polyisocyanate and the polyol being 0.7 to 2.0." Summary of the Invention

[0005] The cured products of reactive polyurethane compositions exhibit excellent durability and are therefore advantageously used as the surface layer (top layer) of decorative films for external applications. However, when a surface layer is formed using a reactive polyurethane composition, problems such as pitting defects (indentations) may occur in the appearance of the decorative film. During the step of forming the surface layer of the decorative film, the reactive polyurethane composition typically does not fully cure by heat treatment alone; the curing reaction of the polyurethane continues and proceeds gradually after heat treatment. When the decorative film or intermediate component with the surface layer is wound into a roll after heat treatment, air may become trapped between the layers of the wound decorative film or the intermediate component. The incompletely cured soft surface layer is considered to be compressed by the trapped air, resulting in pitting defects on the surface layer.

[0006] refer to Figures 3A to 3D This describes the mechanism by which pit defects occur during the manufacturing of decorative films. A schematic cross-sectional view of the intermediate component of the decorative film is shown in... Figure 3A As shown in the figure, the intermediate component 30a is a laminate having a cover film 12a, a polyurethane layer 14a serving as the surface layer of the decorative film, a base layer 16a, and a process film 32a supporting the base layer 16a. The cover film 12a is laminated to protect the incompletely cured polyurethane layer 14a with a soft surface.

[0007] Intermediate component 30a is temporarily wound into a roll and stored until subsequent steps. Figure 3B A schematic cross-sectional view of an intermediate component wound into a roll and stacked is shown. When the intermediate component is wound into a roll, air 40 is trapped between the process film 32b of the upper intermediate component 30b and the cover film 12a of the lower intermediate component 30a. The incompletely cured polyurethane layer 14a with a soft surface is compressed and deformed by the air 40 through the cover film 12a, and pits 42 are formed on the polyurethane layer 14a.

[0008] After forming the adhesive layer in another step, the intermediate component is unwound from the roll, the process film is removed, and the adhesive layer is laminated onto the base layer. Figure 3C A schematic cross-sectional view of a decorative film with a cover film, in which an adhesive layer is laminated, is shown. In the decorative film 10a with the cover film, the adhesive layer 18a is laminated on the lower surface of the base film 16a of the intermediate member. The adhesive layer 18a is protected by a gasket 20a. In the decorative film 10a with the cover film, the cover film 12a returns to its initial shape due to its rigidity, but the polyurethane layer 14a is fully cured in the deformed state, while the pit 42 remains intact.

[0009] Then, the covering film is removed from the decorative film during installation. Figure 3DA schematic cross-sectional view of the decorative film is shown with the cover film removed. The pit 42 formed on the polyurethane layer 14a of the decorative film is visually identified as a defect on the surface of the decorative film.

[0010] Examples of methods for preventing or suppressing pitting include allowing the curing reaction of the reactive polyurethane composition to proceed further during heat treatment to increase the hardness of the polyurethane layer. Examples of ways to allow the curing reaction of the reactive polyurethane composition to proceed include increasing the temperature used for the heat treatment, increasing the duration of the heat treatment (e.g., decreasing the linear speed of the continuous oven), and increasing the amount of catalyst to be used.

[0011] However, as the hardness of the polyurethane layer increases, the adhesion of the polyurethane layer surface may decrease before the cover film is pressed onto it, and the cover film may not adhere well to the surface of the polyurethane layer. If the cover film has poor adhesion, it may separate from the decorative film during manufacturing, transportation, or use.

[0012] This disclosure provides a decorative film with a covering film, the decorative film comprising a polyurethane layer as a surface layer, having virtually no defects (such as pits) and high surface quality.

[0013] Summary of Implementation Plan

[0014] According to an embodiment of this disclosure, a decorative film with a covering film is provided, the decorative film comprising:

[0015] (a) A polyurethane layer having a first surface and a second surface opposite to the first surface and comprising at least partially crosslinked polyurethane, wherein the at least partially crosslinked polyurethane comprises at least one of polyester-based polyurethane or polycarbonate-based polyurethane.

[0016] (b) A removable cover film having a corona-treated or plasma-treated surface, wherein the corona-treated or plasma-treated surface of the removable cover film is in contact with the first surface of the polyurethane layer.

[0017] (c) a base layer having a first surface and a second surface opposite to the first surface, wherein the first surface of the base layer is in contact with the second surface of the polyurethane layer; and

[0018] (d) An adhesive layer that contacts the second surface of the substrate.

[0019] According to another embodiment of this disclosure, a method for manufacturing a decorative film with a covering film is provided, the method comprising:

[0020] (a) A base layer is provided, the base layer having a first surface and a second surface opposite to the first surface;

[0021] (b) A polyurethane layer is formed on the first surface of the substrate layer, the polyurethane layer having a first surface and a second surface opposite to the first surface and comprising at least partially crosslinked polyurethane, wherein the at least partially crosslinked polyurethane comprises at least one of polyester-based polyurethane or polycarbonate-based polyurethane, and the first surface of the substrate layer is in contact with the second surface of the polyurethane layer.

[0022] (c) Configure a removable cover film;

[0023] (d) Treat the surface of the removable cover film with corona or plasma;

[0024] (e) Laminating the removable cover film onto the polyurethane layer such that the corona-treated or plasma-treated surface of the removable cover film contacts the first surface of the polyurethane layer; and

[0025] (f) An adhesive layer is formed on the second surface of the base layer to obtain a decorative film with a covering film.

[0026] According to another embodiment of this disclosure, a method for manufacturing a decorative film is provided, the method comprising:

[0027] (a) A base layer is provided, the base layer having a first surface and a second surface opposite to the first surface;

[0028] (b) A polyurethane layer is formed on the first surface of the substrate layer, the polyurethane layer having a first surface and a second surface opposite to the first surface and comprising at least partially crosslinked polyurethane, wherein the at least partially crosslinked polyurethane comprises at least one of polyester-based polyurethane or polycarbonate-based polyurethane, and the first surface of the substrate layer is in contact with the second surface of the polyurethane layer.

[0029] (c) Configure a removable cover film;

[0030] (d) Treat the surface of the removable cover film with corona or plasma;

[0031] (e) The removable cover film is laminated on the polyurethane layer such that the corona-treated or plasma-treated surface of the removable cover film contacts the first surface of the polyurethane layer.

[0032] (f) forming an adhesive layer on the second surface of the substrate; and

[0033] (h) Remove the removable cover film from the first surface of the polyurethane layer.

[0034] According to another embodiment of this disclosure, a method for installing a decorative film is provided, the method comprising: applying the decorative film with a cover film to a substrate; and then removing the removable cover film from the first surface of the polyurethane layer.

[0035] According to another embodiment of the present disclosure, a method for installing a decorative film is provided, the method comprising: removing the removable cover film of the decorative film with the cover film from the first surface of the polyurethane layer to obtain the decorative film; and applying the decorative film to a substrate.

[0036] Beneficial effects of the invention

[0037] This disclosure provides a decorative film with a covering film, the decorative film comprising a polyurethane layer as a surface layer, having virtually no defects (such as pits) and high surface quality.

[0038] The above description should not be construed as disclosing all embodiments of the invention or all advantages associated with the invention. Attached Figure Description

[0039] Figure 1 This is a schematic cross-sectional view of a decorative film with a covering film in one embodiment.

[0040] Figure 2 This is a schematic cross-sectional view of a decorative film with a covering film in another embodiment.

[0041] Figure 3A This is an illustration of the mechanism by which pit defects occur during the manufacturing of decorative films.

[0042] Figure 3B This is an illustration of the mechanism by which pit defects occur during the manufacturing of decorative films.

[0043] Figure 3C This is an illustration of the mechanism by which pit defects occur during the manufacturing of decorative films.

[0044] Figure 3D This is an illustration of the mechanism by which pit defects occur during the manufacturing of decorative films. Detailed Implementation

[0045] In the following description, representative embodiments of the invention will be described in more detail with reference to the accompanying drawings for purposes of illustration, but the invention is not limited to these embodiments.

[0046] In this disclosure, the term "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, and the term "(meth)acrylate" refers to acrylate or methacrylate.

[0047] In this disclosure, “curing” also encompasses the concept commonly referred to as “crosslinking”.

[0048] In this disclosure, the term "film" covers articles referred to as "sheets".

[0049] In this disclosure, the term "transparent" refers to an average transmittance of about 80%, preferably about 85%, or about 90%, or higher in the visible light range (wavelengths from 400 nm to 700 nm), as measured according to JIS K 7375:2008. The upper limit of the average transmittance is not particularly limited and can be, for example, less than about 100%, about 99%, or about 98%, or lower.

[0050] In this disclosure, the term "semi-transparent" means an average transmittance of about 40% or more and less than about 80%, preferably about 75% or less, in the visible light range (wavelengths from 400 nm to 700 nm) as measured according to JIS K 7375.

[0051] According to one embodiment, the decorative film with a covering film includes:

[0052] (a) A polyurethane layer having a first surface and a second surface opposite to the first surface and comprising at least partially crosslinked polyurethane, wherein the at least partially crosslinked polyurethane comprises at least one of polyester-based polyurethane or polycarbonate-based polyurethane.

[0053] (b) A removable cover film having a corona-treated or plasma-treated surface, wherein the corona-treated or plasma-treated surface of the removable cover film is in contact with the first surface of the polyurethane layer.

[0054] (c) a base layer having a first surface and a second surface opposite to the first surface, wherein the first surface of the base layer is in contact with the second surface of the polyurethane layer; and

[0055] (d) An adhesive layer that contacts the second surface of the substrate.

[0056] Figure 1 A schematic cross-sectional view of a decorative film with a cover film is illustrated in one embodiment. The decorative film 10 with a cover film includes a removable cover film 12, a polyurethane layer 14, a base layer 16, and an adhesive layer 18. The corona-treated or plasma-treated surface 122 of the removable cover film 12 is adjacent to the first surface of the polyurethane layer 14. Figure 1 The upper surface of the substrate 16 is in contact with the substrate layer 16. Figure 1 The upper surface of the middle layer) and the second surface of the polyurethane layer 14 ( Figure 1The adhesive layer 18 contacts the lower surface of the substrate layer 16. Figure 1 (The lower surface of the film) contacts the decorative film 10. The decorative film 10 with the covering film may also include a pad 20 as an optional element.

[0057] The polyurethane layer comprises at least partially crosslinked polyurethane. The at least partially crosslinked polyurethane includes at least one of polyester-based polyurethane or polycarbonate-based polyurethane. In this disclosure, "partially crosslinked" means that some reaction sites (reaction sites participating in the crosslinking reaction) of the polyol and the crosslinking agent react to form crosslinks, but both the polyol and the crosslinking agent retain reaction sites capable of undergoing the crosslinking reaction. On the other hand, "fully crosslinked" means that at least one of the reaction sites of the polyol or the crosslinking agent (reaction sites participating in the crosslinking reaction) is completely consumed by the crosslinking reaction, or that the crosslinking of the polyurethane has progressed to a higher degree, and therefore the reaction sites can no longer participate in the crosslinking reaction. For example, in a reactive polyurethane composition in which the equivalence ratio (NCO / OH) between the polyol and the isocyanate crosslinking agent is less than 1, even if the hydroxyl groups of the polyol are retained, the polyurethane is fully crosslinked as long as the isocyanate groups of the isocyanate crosslinking agent are completely consumed.

[0058] The polyurethane layer composition (such as a reactive polyurethane composition) can be applied to the first surface of the substrate or the pad, for example, by means of blade coating, bar coating, blade coating, scraping, roller coating, casting coating, etc., and the composition can be heated if necessary to form the polyurethane layer. The polyurethane layer formed on the pad can be thermally laminated or transferred and laminated (where the first surface of the substrate has adhesion to the polyurethane layer) on the substrate, such that the second surface of the polyurethane layer contacts the first surface of the substrate. The heating temperature can be, for example, about 40°C or higher, about 50°C or higher, or about 60°C or higher, and about 140°C or lower, about 120°C or lower, or about 100°C or lower. The heating time can be, for example, about 1 minute or longer, about 2 minutes or longer, or about 5 minutes or longer, and about 1 hour or less, about 30 minutes or less, or about 20 minutes or less.

[0059] The reactive polyurethane composition can be a one-component curable type (moisture-curing type, isocyanate-terminated type, etc.) or a two-component curable type. In one embodiment, the reactive polyurethane composition is a two-component curable composition comprising a polyol and an isocyanate crosslinking agent.

[0060] Examples of such polyols include polyester polyols, such as polycaprolactone diol, polycaprolactone triol, or condensates of low molecular weight polyols having 2 to 20 carbon atoms with aliphatic or aromatic polyvalent carboxylic acids (e.g., polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, and polybutylene sebacate); and polycarbonate polyols, such as polybutylene carbonate, polyhexamethylene carbonate, poly(3-methyl-1,5-pentylene) carbonate, poly(1,4-dimethylcyclohexylene) carbonate, polyethylene diethylene carbonate, polytetraethylene diethylene carbonate, and polypropylene diethylene carbonate. Polyester-based polyurethanes are formed from polyester polyols. Polycarbonate-based polyurethanes are formed from polycarbonate polyols.

[0061] Examples of low-molecular-weight polyols having 2 to 20 carbon atoms that constitute the polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, glycerol, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexanediol, and methylpentanediol adipate.

[0062] The polyol may also include, as an optional component, the aforementioned low molecular weight polyols having 2 to 20 carbon atoms; (meth)acrylate polyols, which are copolymers of hydroxy-free (meth)acrylates such as methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and ethylene glycol diester with (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and ethylene glycol monomethacrylate; and polyether polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, their propylene oxide adducts, propylene oxide adducts of glycerol, propylene oxide adducts of sugars such as sorbitol and sucrose, and propylene oxide adducts of compounds having active hydrogen, such as ethylenediamine.

[0063] Polyols can be used alone, or in combination of two or more types of polyols.

[0064] Examples of such isocyanate crosslinking agents include aliphatic polyisocyanates, such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate; alicyclic polyisocyanates, such as isophorone diisocyanate, trans- and / or cis-1,4-cyclohexane diisocyanate, norbornene diisocyanate, and 4,4′-methylene dicyclohexyl diisocyanate (also known as hydrogenated MDI, H12MDI, etc.); aromatic polyisocyanates, such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, methylene bis(4-phenylisocyanate), 2,4′-diphenylmethane diisocyanate, and 2,2′-diphenylmethane diisocyanate; and their burette-modified, isocyanurate-modified, carbodiimide-modified, or adduct-modified products. The isocyanate crosslinking agent can be used alone, or a combination of two or more types of isocyanate crosslinking agents can be used.

[0065] The equivalent ratio (NCO / OH) between the polyol and the isocyanate crosslinking agent can be about 0.5 or greater, about 0.7 or greater, or about 0.9 or greater, or about 2.5 or less, about 2.0 or less, or about 1.5 or less.

[0066] The reactive polyurethane composition may contain a catalyst. Examples of such catalysts include dibutyltin dilaurate (DBTDL), zinc naphthenate, zinc octanoate, and triethylenediamine. The amount of such catalyst to be used is typically about 0.005 parts by weight or more and about 0.5 parts by weight or less per 100 parts by weight of total polyol and isocyanate crosslinking agent.

[0067] The reactive polyurethane composition can be aqueous or organic solvent-based. When the reactive polyurethane composition is aqueous, it can also be crosslinked with polycarbodiimide, aziridine, oxazoline, etc. The aqueous reactive polyurethane composition preferably comprises a combination of polycarbonate polyol with polycarbodiimide, 4,4′-methylenebis(cyclohexyl diisocyanate), and / or aziridine. The organic solvent-based reactive polyurethane composition preferably comprises a combination of polycaprolactone diol and polycarbonate diol with isophorone diisocyanate trimer (isocyanurate).

[0068] The polyurethane layer may contain additives, such as UV absorbers like benzotriazole, Tinuvin 99-2 (BASF Japan Ltd., Chuo-ku, Tokyo, Japan) and Tinuvin 1130 (BASF Japan Ltd.), and hindered amine light stabilizers (HALS) like Tinuvin 292 (BASF Japan Ltd.). When the base layer includes a decorative layer or colorant, the use of UV absorbers or hindered amine light stabilizers effectively prevents discoloration, fading, and degradation. The polyurethane layer may contain hard coating materials, gloss imparters, etc. To provide the desired appearance, the polyurethane layer may be transparent or translucent. Advantageously, the polyurethane layer is transparent.

[0069] The polyurethane layer can have various thicknesses, but typically includes thicknesses of about 1 μm or greater, about 5 μm or greater, or about 10 μm or greater, and about 100 μm or less, about 80 μm or less, or about 60 μm or less. When the decorative film is applied to articles with complex shapes, a thinner polyurethane layer is advantageous from a shape-fitting perspective. For example, the ideal thickness is about 80 μm or less, or about 60 μm or less. Alternatively, a thicker polyurethane layer is advantageous when imparting high lightfastness or weather resistance to the article. Ideally, for example, the thickness is about 5 μm or greater, or about 10 μm or greater.

[0070] The decorative film with a cover needs to have a good balance between the adhesion of the removable cover to the polyurethane layer (i.e., the cover does not fall off during the manufacture, transport, or operation of the decorative film with the cover) and the peelability of the removable cover (i.e., the cover can be easily removed during or after the installation of the decorative film with the cover). In this disclosure, as a way to achieve this balance, the surface of the removable cover is subjected to corona treatment or plasma treatment.

[0071] The removable cover film protects the surface of the polyurethane layer for a period of time before the polyurethane contained in the polyurethane layer is fully cross-linked and during the manufacture, transport, or use of the decorative film, or transfers the smooth surface of the removable cover film to such a polyurethane layer, and thus helps to improve the surface quality of the polyurethane layer. The removable cover film can also be used as a support during the manufacture, transport, or use of the decorative film.

[0072] Resin films of polyvinyl chloride, polyolefins (such as polyethylene and polypropylene), acrylic resins, polyesters (such as polyethylene terephthalate and polybutylene terephthalate), or fluoropolymers can be used as the removable cover film.

[0073] The removable cover film is preferably a polyethylene terephthalate (PET) film. This PET film effectively prevents damage to the polyurethane layer and maintains or improves the surface quality of the polyurethane layer.

[0074] Advantageously, the polyethylene terephthalate film is a biaxially stretched polyethylene terephthalate film. This biaxially stretched polyethylene terephthalate film has high elongation at break and tensile strength, and therefore can effectively prevent damage to the polyurethane layer and maintain or improve the surface quality of the polyurethane layer.

[0075] The surface of the removable cover film that contacts the first surface of the polyurethane layer is subjected to corona treatment or plasma treatment. This corona treatment and plasma treatment impart adhesiveness to the removable cover film, preventing it from detaching from the polyurethane layer (which has been relatively cross-linked during the formation of the polyurethane layer) during the manufacture, transport, and use of the decorative film with the cover film, and allowing the cover film to be removed from the polyurethane layer during installation of the decorative film with the cover film.

[0076] In one embodiment, the corona treatment and plasma treatment clean the surface of the removable cover film. This reduces or removes foreign matter trapped between the removable cover film and the polyurethane layer, and thus further enhances the surface quality of the polyurethane layer.

[0077] In one embodiment, the corona treatment and plasma treatment remove static electricity (caused by the removable cover film unwinding from the roll) from the surface of the removable cover film and prevent dust and other foreign matter from adhering to the surface of the removable cover film. Therefore, foreign matter remaining between the removable cover film and the polyurethane layer can be reduced or removed, and thus the surface quality of the polyurethane layer can be further enhanced.

[0078] The corona treatment can be performed using a corona treatment apparatus typically used for surface modification of resin films. Examples of such apparatus include the GXR50 (Sherman Treaters Ltd., Tim, Oxfordshire, England) and the TEG-4AX (KASUGA DENKI, INC., Kawasaki, Kanagawa, Japan). The conditions for this corona treatment are not particularly limited. For example, the applied power can be from 1 kW to 5 kW, the corona treatment time can be from 0.05 seconds to 5 seconds, and the frequency can be from 10 kHz to 20 kHz. The discharge during the corona treatment can be continuous or intermittent.

[0079] The plasma treatment can be performed using plasma treatment apparatuses commonly used for surface modification of resin films. Examples of such plasma treatment apparatuses include atmospheric pressure plasma treatment apparatuses and vacuum plasma apparatuses. The conditions for this plasma treatment are not particularly limited. For example, the plasma gas can be nitrogen or an inert gas (such as helium or argon), the power can be from 0.5 kW to 4 kW, the supply rate of the plasma gas can be from 50 liters per minute to 150 liters per minute, the pressure in the plasma treatment apparatus can be atmospheric pressure, and the plasma treatment time can be from 0.05 seconds to 5 seconds.

[0080] The surface tension of the removable cover film after corona treatment or plasma treatment is preferably about 40 mN / m or greater. More preferably, it is about 44 mN / m or greater, or about 46 mN / m or greater. Generally, the surface tension of the removable cover film after corona treatment or plasma treatment is preferably about 60 mN / m or less. More preferably, it is about 58 mN / m or less, or about 56 mN / m or less.

[0081] The surface of the removable cover film opposite to the corona-treated or plasma-treated surface may not undergo corona treatment or plasma treatment. In one embodiment, the surface tension of the surface of the removable cover film opposite to the corona-treated or plasma-treated surface is less than about 40 mN / m, about 39 mN / m or less, or about 38 mN / m or less.

[0082] The surface of the removable cover film after corona treatment or plasma treatment can be surface-treated to transfer the shape onto the surface of the polyurethane layer. Examples of such surface treatments include matte finishing, embossing, and sandblasting. The surface of the removable cover film opposite to the corona-treated or plasma-treated surface can be surface-treated to impart properties such as gliding and peelability.

[0083] The thickness of the removable cover film can be, for example, about 5 μm or more, about 10 μm or more, or about 25 μm or more, and can be 150 μm or less, 100 μm or less, or 80 μm or less.

[0084] A resin film of polyurethane, polyvinyl chloride, polyolefins (such as polyethylene and polypropylene), acrylic resins, polyesters (such as polyethylene terephthalate and polybutylene terephthalate), or fluoropolymers can be used as the base layer. The base layer preferably comprises at least one thermoplastic resin selected from the group consisting of polyurethane, polyvinyl chloride, polyolefins, acrylic resins, and polyesters. In this embodiment, the decorative film can be manually applied to an article with curved surfaces using a vacuum / pneumatic molding (dual vacuum thermoforming [DVT]) method or a vacuum molding (vacuum thermoforming [VT]) method with excellent shape conformability.

[0085] The base layer can be colored. Examples of colorants include organic pigments, inorganic pigments, aluminosiluminescent materials, and mica photoluminescent materials, as well as blends of two or more types thereof. The colorant is preferably selected from the group consisting of: combinations of organic and inorganic pigments; combinations of organic and aluminosiluminescent materials; combinations of organic and mica photoluminescent materials; combinations of inorganic and aluminosiluminescent materials; combinations of inorganic and mica photoluminescent materials; and combinations of aluminosiluminescent and mica photoluminescent materials; and combinations thereof. The use of the above colorant combinations allows for the acquisition of decorative films with a wide variety of hues, thereby allowing for the fulfillment of high design requirements.

[0086] Examples of organic pigments include phthalocyanine pigments (such as phthalocyanine blue and phthalocyanine green), azo lake pigments, indigo pigments, violet ketone pigments, perylene pigments, quinacridone pigments, dioxazine pigments, and quinacridone pigments (such as quinacridone red). Examples of inorganic pigments include titanium dioxide, lead yellow, iron oxide yellow, iron oxide red, and carbon black. Examples of aluminum photoluminescent materials include aluminum flakes, vapor-deposited aluminum flakes, metal oxide-coated aluminum flakes, and colored aluminum flakes. Examples of mica photoluminescent materials include flake-like mica coated with metal oxides (such as titanium dioxide or iron oxide) and synthetic mica.

[0087] The content of the colorant may be about 1% or more by mass, about 2% or more by mass, or about 5% or more by mass, and about 80% or less by mass, about 75% or less by mass, or about 66% or less by mass, based on the mass of the base layer.

[0088] In one embodiment, the base layer has a multi-layer structure, which includes a decorative layer. Figure 2 In another embodiment illustrated, the decorative film 10 with a covering film has a base layer 16 having a multilayer structure including a base film 162 and a decorative layer 164.

[0089] The resin film used for the substrate layer described above can be used as the base film. The thickness of the base film is preferably about 10 μm or more and about 500 μm or less, more preferably about 30 μm or more and about 300 μm or less, and even more preferably about 80 μm or more and about 200 μm or less.

[0090] Examples of such decorative layers include coloring layers (colored layers), patterned films (design films), and metallic layers. Specifically, the decorative layer can be a layer, coating, film, or metallic vapor-deposited film that imparts a metallic appearance (such as metal or silver metal), automotive exterior paint color (such as metallic, white pearl, pearl mica, or solid paint color), pattern, logo, or image to the decorative film.

[0091] In one embodiment, the decorative layer is a coloring layer. The coloring layer typically comprises an adhesive resin and a colorant.

[0092] Examples of adhesive resins include acrylic resins, polyurethanes, polyvinyl chloride, and polyesters. The adhesive resin preferably comprises a thermoplastic resin, and more preferably a thermoplastic acrylic resin. In this embodiment, the decorative film can be manually applied to an article with a curved surface using a vacuum / pneumatic molding (dual vacuum thermoforming [DVT]) method or a vacuum molding (vacuum thermoforming [VT]) method with excellent shape conformability.

[0093] The colorant is the same as that described for the base layer to be colored. The content of the colorant may be about 1% by mass or more, about 2% by mass or more, or about 5% by mass or more, and about 80% by mass or less, about 75% by mass or less, or about 67% by mass or less, based on the mass of the colored layer.

[0094] For example, a coloring layer composition comprising a binder resin, a colorant, and optionally a solvent can be applied to the base film via blade coating, bar coating, scalpel coating, scraping coating, roller coating, casting coating, gravure coating, etc., and the composition can be heated if necessary to form the coloring layer.

[0095] The coloring layer can have various thicknesses, but typically includes thicknesses of about 1 μm or greater, about 10 μm or greater, or about 20 μm or greater, and about 100 μm or less, about 80 μm or less, or about 60 μm or less. Adjusting the thickness of the coloring layer to about 10 μm or greater helps to mask the base color and provide the desired decorative appearance. When good shape conformability is required for the paint substitute film, the coloring layer is advantageously thinner, and ideally, for example, about 80 μm or less, or about 60 μm or less.

[0096] The thickness of the base layer is preferably about 10 μm or more and about 500 μm or less, more preferably about 30 μm or more and about 300 μm or less, and even more preferably about 80 μm or more and about 200 μm or less. When the decorative film is used on the underside of a vehicle side surface or the front surface of the vehicle, the thickness of the base layer is preferably about 80 μm or more, considering resistance to incoming debris. Except when the decorative film is temporarily provided as a protective strip on the surface of the attachment, the thickness of the base layer is preferably about 30 μm or more, because the film is less likely to wrinkle when attached to curved surfaces. When the decorative film is too thick, it may lose its conformability to curved surfaces, and from an economic point of view, the thickness of the base layer is preferably about 300 μm or less. In the case where the base layer has a multi-layer structure, the thickness of the base layer refers to the total thickness of all layers.

[0097] This adhesive layer comprises commonly used acrylic, polyolefin, polyurethane, polyester, rubber, silicone, or vinyl acetate-based adhesives. Generally, solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, thermosetting, or UV-curing adhesive compositions can be used to form this adhesive layer. This adhesive layer can be a pressure-sensitive adhesive layer.

[0098] The adhesive layer may contain colorless pigments (such as white pigments, black pigments, or mixtures thereof), colored pigments (such as yellow pigments, red pigments, green pigments, blue pigments, or orange pigments, or combinations thereof). The adhesive layer containing white pigment also serves as a masking layer to cover the surface (substrate) of the adherend. Titanium dioxide is preferably used as the white pigment due to its high whiteness.

[0099] The adhesive composition can be used to form the adhesive layer. Specifically, the adhesive composition can be applied to the second surface of the substrate and heated if necessary to form the adhesive layer. Alternatively, the adhesive composition can be applied to another pad and heated if necessary to form the adhesive layer, and the adhesive layer can be transferred and laminated onto the second surface of the substrate. For example, the adhesive composition can be applied to the substrate or the pad via blade coating, bar coating, blade coating, doctor blade coating, roller coating, casting coating, etc., and the composition can be heated if necessary to form the adhesive layer. The pad may have a surface treated with a release pad using silicone or the like.

[0100] The adhesive layer can have various thicknesses, but typically has a thickness of about 5 μm or more, about 10 μm or more, or about 20 μm or more, and a thickness of about 100 μm or less, about 80 μm or less, or about 50 μm or less. To adapt the adhesive layer to the shape of the grooves and protrusions on the surface of the substrate and achieve high adhesion that is unlikely to cause peeling, the thickness of the adhesive layer is preferably about 20 μm or more. To mitigate the phenomenon of adhesive bulging at the ends of the decorative film due to film shrinkage under high-temperature conditions after the decorative film has been stretched and attached, the thickness of the adhesive layer is preferably about 50 μm or less.

[0101] The decorative film may have a liner to protect the adhesive layer. Examples of such liner include paper, plastic materials (such as polyethylene, polypropylene, polyester, and cellulose acetate), and paper coated with such plastic materials. These liners may have a surface treated with a release liner, such as silicone. The thickness of the liner is typically about 5 μm or more, about 15 μm or more, or about 25 μm or more, and about 300 μm or less, about 200 μm or less, or about 150 μm or less.

[0102] The adhesive layer typically forms a flat adhesive surface, but it can also form an adhesive surface with grooves and protrusions. This grooved and protruding adhesive surface includes the adhesive surface of the adhesive layer (in which protrusions containing the adhesive are formed and grooves surrounding the protrusions), and when the adhesive surface is attached to an attachment, a communicating channel is formed between the attachment surface and the adhesive surface, the communicating channel being defined by the grooves and communicating with external space. An example of a method for forming this grooved and protruding adhesive surface will be described below.

[0103] A liner with a release surface is prepared, the release surface including predetermined grooves and protrusions. The adhesive composition is applied to the release surface of the liner, and heated if necessary to form an adhesive layer. Thereby, the grooves and protrusions (negative structure) of the liner are transferred to the surface of the liner in contact with the adhesive layer (which serves as the adhesive surface in the decorative film), and an adhesive surface with grooves and protrusions having a predetermined structure (positive structure) is formed on the adhesive surface. As described above, the grooves and protrusions of the adhesive surface are pre-designed to include grooves that allow the formation of communicating channels when the protrusions are attached to the substrate.

[0104] For the grooves in the adhesive layer, as long as air bubbles are prevented from remaining when the decorative film is attached to the article, grooves with a consistent shape can be arranged on the adhesive surface according to a regular pattern to form grooves with a regular pattern, or grooves with an indeterminate shape can be arranged to form grooves with an irregular pattern. When multiple grooves are formed to be substantially parallel to each other, the spacing between the grooves is preferably 10 μm to 2000 μm. The depth of the groove (the distance from the adhesive surface to the bottom of the groove, measured in the direction toward the substrate layer) is typically about 10 μm or more and about 100 μm or less. The shape of the groove is not particularly limited, as long as it does not impair the effect of the invention. For example, in the cross-section of the groove in the direction perpendicular to the adhesive surface, the shape of the groove can be generally rectangular (including trapezoidal), generally semi-circular, or generally semi-elliptical.

[0105] The decorative film with a covering film can be manufactured, for example, by a method including the following steps:

[0106] (a) A base layer is provided, the base layer having a first surface and a second surface opposite to the first surface;

[0107] (b) A polyurethane layer is formed on the first surface of the substrate layer, the polyurethane layer having a first surface and a second surface opposite to the first surface and comprising at least partially crosslinked polyurethane, wherein the at least partially crosslinked polyurethane comprises at least one of polyester-based polyurethane or polycarbonate-based polyurethane, and the first surface of the substrate layer is in contact with the second surface of the polyurethane layer.

[0108] (c) Configure a removable cover film;

[0109] (d) Treat the surface of the removable cover film with corona or plasma;

[0110] (e) Laminating the removable cover film onto the polyurethane layer such that the corona-treated or plasma-treated surface of the removable cover film contacts the first surface of the polyurethane layer; and

[0111] (f) An adhesive layer is formed on the second surface of the base layer to obtain a decorative film with a covering film.

[0112] The aforementioned material can be used as the substrate layer provided in step (a). The substrate layer may have a process film disposed on its second surface as a support.

[0113] The formation of the polyurethane layer in step (b) can be performed as described above. The polyurethane contained in the polyurethane layer is at least partially crosslinked. At the completion of step (b), the polyurethane is preferably not fully crosslinked. In this embodiment, in step (e), the removable cover film can be firmly attached to the polyurethane layer.

[0114] The above material can be used as a removable cover film in step (c).

[0115] The corona treatment or plasma treatment in step (d) can be performed as described above. In one embodiment, the corona treatment or plasma treatment is performed such that the surface tension of the removable cover film is about 40 mN / m or greater. After the corona treatment or plasma treatment is completed, step (e) is preferably performed within 1 hour, more preferably within 10 minutes. More preferably, steps (d) and (e) are performed as consecutive processes.

[0116] The lamination of the removable cover film in step (e) is preferably performed before the polyurethane is fully crosslinked. By laminating the removable cover film in a state where the polyurethane is partially crosslinked, the removable cover film can be firmly attached to the polyurethane layer.

[0117] In one embodiment, when the removable cover film is stored at 23°C for 48 hours after step (e) and then peeled off from the polyurethane layer, the peel strength of the removable cover film is from about 0.15 N / 50 mm to about 2.0 N / 50 mm. This peel strength is determined under the same conditions as those used in the method described in the embodiments for measuring the peel strength of the decorative film with the cover film.

[0118] The peel strength measured after storage at 23°C for 48 hours following step (e) can be used as an indicator of the degree of crosslinking reaction of the polyurethane contained in the polyurethane layer formed in step (b) at the completion of step (e). Specifically, when the crosslinking reaction of the polyurethane is in its initial stage, the low cohesive force within the polyurethane layer causes cohesive failure of the polyurethane layer rather than interfacial peeling between the polyurethane layer and the removable cover film. This results in a low measured apparent peel strength. As the crosslinking reaction of the polyurethane proceeds, the cohesive force within the polyurethane layer exceeds the interfacial peel strength between the polyurethane layer and the removable cover film, thereby causing interfacial peeling between the polyurethane layer and the removable cover film. However, the interior and surface of the polyurethane layer remain soft and the surface of the polyurethane layer is sticky, thus the measured peel strength is high. As the crosslinking reaction of the polyurethane proceeds further, the peel strength decreases as the adhesiveness of the polyurethane layer surface decreases. At this point, the surface of the polyurethane layer has sufficient adhesion to allow the cover film to adhere well after corona treatment or plasma treatment, and the hardness of the polyurethane layer increases to a level that suppresses surface defects (such as pits). As the polyurethane approaches a fully cross-linked state, the peel strength further decreases, and the removable cover film cannot adhere to the surface of the polyurethane layer with sufficient force.

[0119] The materials and formulation of the polyurethane layer composition, the conditions for forming the polyurethane layer in step (b), and the conditions for the corona treatment or plasma treatment in step (d) are selected such that the peel strength is in the range of about 0.15 N / 50 mm to about 2.0 N / 50 mm, thereby ensuring the adhesion of the removable cover film to the polyurethane layer while appropriately increasing the hardness of the polyurethane layer. Therefore, surface defects (such as pits) in the polyurethane layer can be suppressed, and the removable cover film can be prevented from peeling off during the manufacture, transport, and use of the decorative film with the cover film.

[0120] The formation of the adhesive layer in step (f) can be performed as described above. A decorative film with a cover film is obtained, wherein the decorative film has a release liner covering the adhesive layer.

[0121] The method for manufacturing a decorative film with a covering film may optionally include the following step (g):

[0122] (g) After the adhesive layer is formed, the decorative film with the covering film is wound into a roll.

[0123] In step (g), the decorative film with a cover film can be wound around the core using a winding device commonly used in film manufacturing. In this embodiment, the decorative film with a cover film can be stored and transported in rolls without deteriorating the surface quality of the decorative film.

[0124] In one implementation, the decorative film is manufactured by combining step (f) with step (h):

[0125] (h) Remove the removable cover film from the first surface of the polyurethane layer.

[0126] Step (h) involves peeling the cover film continuously using a winding device or manually peeling the cover film from the cut decorative film.

[0127] The total thickness of the decorative film (excluding the thickness of the cover film and the liner) can be about 25 μm or greater, about 80 μm or greater, or about 150 μm or greater, or about 600 μm or less, about 400 μm or less, or about 350 μm or less.

[0128] In one embodiment, the peel strength of the removable cover film in the decorative film with the cover film is about 0.15 N / 50 mm or greater, about 0.2 N / 50 mm or greater, about 0.25 N / 50 mm or greater, about 1.0 N / 50 mm or less, about 0.8 N / 50 mm or less, or about 0.5 N / 50 mm or less. This peel strength is determined by the method described in the examples.

[0129] The decorative film with a covering film can be in the form of a rolled-up object. In this embodiment, the surface quality of the decorative film can be maintained even when air is trapped between two overlapping decorative films due to the rolling.

[0130] One embodiment of a method for installing a decorative film includes: applying the decorative film with a cover film to a substrate; and then removing the removable cover film from the first surface of the polyurethane layer. In this embodiment, because the polyurethane layer is protected by the removable cover film, the decorative film can be firmly attached to the substrate by pressing it from above the removable cover film using a crimping clamp or the like, while maintaining the surface quality of the decorative film.

[0131] Another embodiment of the method for installing a decorative film includes: removing the removable cover film of the decorative film with a cover film from the first surface of the polyurethane layer to obtain the decorative film, and applying the decorative film to a substrate. In this embodiment, by removing the removable cover film before applying the decorative film, the decorative film can exhibit the shape-conforming ability inherent in the decorative film. Therefore, the decorative film can be applied to a substrate with a three-dimensional surface (such as corner portions, curved surfaces, or uneven shapes) with excellent shape-conforming ability.

[0132] The decorative film disclosed herein can be suitably used as a paint substitute. For example, the decorative film according to this disclosure can be applied to the body of a vehicle (including the roof, doors, hood, etc.) or parts of the body, or to components of the vehicle (e.g., bumpers, roof moldings, side moldings, pillars, etc.). Examples of such vehicles include: automobiles, such as trucks, buses, and cars; two-wheeled vehicles, such as motorcycles and scooters; bicycles; trains; and vessels, such as yachts, boats, and motorboats.

[0133] Example

[0134] The following embodiments illustrate specific implementations of this disclosure, but the invention is not limited to these embodiments. Unless otherwise specified, all 'parts' and 'percentages' are by mass. Numerical values ​​substantially include errors arising from the measurement principle and measuring equipment. Numerical values ​​are typically indicated by rounded significant figures.

[0135] The raw materials used in the polyurethane layer compositions of the examples are shown in Table 1 below.

[0136] Table 1

[0137]

[0138] Comparative Example 1

[0139] The decorative film with a cover film of Comparative Example 1 is generated by the following process.

[0140] (1) A base layer having a multilayer structure including a coloring layer and a base film is generated by coating an acrylic composition containing black pigment having the composition shown in Table 2 onto a thermoplastic polyurethane film with a thickness of 150 μm supported by a polypropylene film with a thickness of 80 μm as a process film, and heating the composition in a continuous oven at 80°C for 5 minutes to form a coloring layer with a dry thickness of 23 μm on the thermoplastic polyurethane film.

[0141] Table 2

[0142] acrylic resins 27.45 carbon black 1.00 Cellulose acetate butyrate 4.95 Isophorone diisocyanate 4.26 Propylene glycol monomethyl ether acetate 8.36 xylene 12.21 Ethylbenzene 7.23 Isobutyl acetate 8.17 Butyl acetate 15.57 Ethyl acetate 5.45 Methyl isobutyl ketone 535

[0143] (2) The polyurethane layer composition with a solid content of 76.5% by mass prepared according to the composition shown in Table 3 is applied to the colored layer side of the substrate layer formed in (1) and heated in a continuous oven at 80°C for 3 minutes and 20 seconds to form a polyurethane layer with a dry thickness of 25 μm comprising at least partially crosslinked polyester-based polyurethane and polycarbonate-based polyurethane.

[0144] Table 3

[0145] PLACCEL 205H 100 19.8 Nippolan 983 100 19.8 Tinuvin (trade name) 292 100 1.0 Tinuvin (trade name) 99-2 95 2.0 ACAC - 3.0 DBTDL 100 0.02 Butyl acetate - 4.6 Acrit UA702 51 4.6 VEATANAT (trade name) T1890E 70 45.3

[0146] (3) Immediately after the polyurethane layer is formed, a polyethylene terephthalate cover film with a thickness of 50 μm is pressed onto the surface of the polyurethane layer.

[0147] (4) An acrylic pressure-sensitive adhesive containing 2-ethylhexyl acrylate and acrylic acid is applied to a silicone-coated polyethylene terephthalate release liner and heated in a continuous oven at 80°C for 5 minutes to form a pressure-sensitive adhesive layer with a dry thickness of 35 μm.

[0148] (5) Remove the process film from the laminate formed in (3) and laminate the base film side of the base layer and the pressure-sensitive adhesive layer formed in (4) to make them in contact with each other, thereby generating a decorative film with a cover film.

[0149] Comparative Example 2

[0150] The decorative film with a cover was generated using the same process as in Comparative Example 1, except that the heating time in the continuous oven was changed to 8 minutes to 20 seconds when forming the polyurethane layer.

[0151] Example 1

[0152] The decorative film with a cover was generated using the same process as in Comparative Example 2, except that the polyethylene terephthalate cover was subjected to plasma treatment under the following conditions immediately before lamination.

[0153] Plasma processing equipment: AP-T04-R1400 (Sekisui Chemicals Co., Ltd., Osaka City, Osaka Prefecture, Japan)

[0154] N2 flow rate: 100 L / min

[0155] Voltage: 360V

[0156] Current: 3.5A

[0157] Example 2

[0158] The decorative film with a cover was generated using the same process as in Comparative Example 2, except that the polyethylene terephthalate cover was subjected to corona treatment under the following conditions immediately before lamination.

[0159] Corona treatment device: GX50R (Sherman Treaters Ltd., Tim, Oxfordshire, England)

[0160] Output power: 2kW

[0161] Example 3

[0162] The decorative film with a covering film of Example 3 is produced using the same process as in Example 2.

[0163] Example 4

[0164] The decorative film with a covering film was generated using the same process as in Example 2, except that the output power of the corona treatment was changed to 3kW.

[0165] Surface quality (pit defects)

[0166] After removing the covering film from each of the decorative films with a covering film in Examples 1 to 4 and Comparative Examples 1 and 2, the visual count showed a thickness of 0.3 mm. 2 The number of pits, or larger ones, is compared with a dirt comparison chart (manufactured by the National Printing Bureau and sold by Asahi-kai Co., Ltd. in Soka City, Saitama Prefecture, Japan).

[0167] Peel strength

[0168] Samples were prepared by cutting the decorative film with the cover film into pieces 50 mm wide and 200 mm long. The cover film was peeled 180 degrees at room temperature (23°C) using an Autograph AGS-X 500N (Shimadzu Corporation, Kyoto City, Kyoto Prefecture, Japan) at a peeling speed of 200 mm / min. The average of the two measurements was taken as the peel strength (N / 50 mm).

[0169] Surface tension

[0170] Surface tension was assessed using EnerDyne (trade name) Pen (Enercon Industries Corp., Menomoni Falls, Wisconsin, USA), an aqueous surface tension agent.

[0171] Details and evaluation results of the decorative films with cover films in Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 4. "Days after lamination" in Table 4 refers to the number of days after the cover film lamination for measuring surface tension and peel strength.

[0172] Table 4

[0173]

[0174] (Continued from Table 4)

[0175]

[0176] Various modifications and variations of the above-described embodiments and examples will be readily apparent to those skilled in the art without departing from the fundamental principles of the invention. Furthermore, various modifications and variations to the invention will be readily apparent to those skilled in the art without departing from its spirit and scope.

[0177] List of reference numerals

[0178] 10, 10a: Decorative film with a covering film

[0179] 12, 12a, 12b: Removable cover film

[0180] 122: Surface after corona treatment or plasma treatment

[0181] 14, 14a, 14b: Polyurethane layer

[0182] 16, 16a, 16b: Basal layer

[0183] 162: Base membrane

[0184] 164: Decorative layer

[0185] 18, 18a: Adhesive layer

[0186] 20, 20a: Padding

[0187] 30a, 30b: Intermediate components

[0188] 32a, 32b: Process membranes

[0189] 40: Air

[0190] 42: Pit

Claims

1. A decorative film with a covering film, the decorative film comprising: (a) A polyurethane layer having a first surface and a second surface opposite to the first surface and comprising at least partially crosslinked polyurethane, wherein the at least partially crosslinked polyurethane comprises at least one of polyester-based polyurethane or polycarbonate-based polyurethane. (b) A removable cover film having a corona-treated or plasma-treated surface, wherein the corona-treated or plasma-treated surface of the removable cover film is in contact with the first surface of the polyurethane layer. (c) A base layer having a first surface and a second surface opposite to the first surface, wherein the first surface of the base layer is in contact with the second surface of the polyurethane layer; and (d) An adhesive layer that contacts the second surface of the substrate layer, wherein: The surface tension of the corona-treated or plasma-treated surface of the removable cover film is 40 mN / m or greater, and the peel strength of the removable cover film is from 0.15 N / 50 mm to 1.0 N / 50 mm.

2. The decorative film with a cover film according to claim 1, wherein the surface tension of the surface of the removable cover film opposite to the corona-treated or plasma-treated surface is less than 40 mN / m.

3. The decorative film with a cover film according to claim 1, wherein the removable cover film is a polyethylene terephthalate film.

4. The decorative film with a covering film according to claim 1, wherein the base layer comprises at least one thermoplastic resin selected from the group consisting of polyurethane, polyvinyl chloride, polyolefin, acrylic resin and polyester.

5. The decorative film with a covering film according to claim 1, wherein the base layer has a multilayer structure, the multilayer structure including a decorative layer.

6. A roll comprising a decorative film with a covering film as described in claim 1, which has been wound up.

7. A method for manufacturing a decorative film with a covering film, the method comprising: (a) A base layer is provided, the base layer having a first surface and a second surface opposite to the first surface; (b) A polyurethane layer is formed on the first surface of the substrate layer, the polyurethane layer having a first surface and a second surface opposite to the first surface and comprising at least partially crosslinked polyurethane, wherein the at least partially crosslinked polyurethane comprises at least one of polyester-based polyurethane or polycarbonate-based polyurethane, and the first surface of the substrate layer is in contact with the second surface of the polyurethane layer. (c) Configure a removable cover film; (d) Treat the surface of the removable cover film with corona or plasma so that the surface tension of the surface of the removable cover film is 40 mN / m or greater; (e) The removable cover film is laminated onto the polyurethane layer such that the corona-treated or plasma-treated surface of the removable cover film contacts the first surface of the polyurethane layer. as well as (f) An adhesive layer is formed on the second surface of the base layer to obtain a decorative film with a covering film, wherein: When the removable cover film is stored at 23°C for 48 hours after step (e) and then peeled off from the polyurethane layer, the peel strength of the removable cover film is from 0.15 N / 50 mm to 2.0 N / 50 mm.

8. The method of claim 7, wherein the removable cover film is a polyethylene terephthalate film.

9. The method according to claim 7, further comprising: (g) After forming the adhesive layer, the decorative film with the covering film is wound into a roll.

10. A method for manufacturing a decorative film, the method comprising: (a) A base layer is provided, the base layer having a first surface and a second surface opposite to the first surface; (b) A polyurethane layer is formed on the first surface of the substrate layer, the polyurethane layer having a first surface and a second surface opposite to the first surface and comprising at least partially crosslinked polyurethane, wherein the at least partially crosslinked polyurethane comprises at least one of polyester-based polyurethane or polycarbonate-based polyurethane, and the first surface of the substrate layer is in contact with the second surface of the polyurethane layer. (c) Configure a removable cover film; (d) Treat the surface of the removable cover film with corona or plasma so that the surface tension of the surface of the removable cover film is 40 mN / m or greater; (e) The removable cover film is laminated onto the polyurethane layer such that the corona-treated or plasma-treated surface of the removable cover film contacts the first surface of the polyurethane layer. (f) An adhesive layer is formed on the second surface of the substrate layer; as well as (h) Remove the removable cover film from the first surface of the polyurethane layer, wherein: When the removable cover film is stored at 23°C for 48 hours after step (e) and then peeled off from the polyurethane layer, the peel strength of the removable cover film is from 0.15 N / 50 mm to 2.0 N / 50 mm.

11. A method for installing decorative film, the method comprising: The decorative film with a covering film as described in claim 1 is applied to a substrate; as well as Then, the removable cover film is removed from the first surface of the polyurethane layer.

12. A method for installing decorative film, the method comprising: The removable cover film of the decorative film with a cover film according to claim 1 is removed from the first surface of the polyurethane layer to obtain the decorative film; as well as The decorative film is applied to the substrate.

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