Surface coating decorative film, decorated molded article, and composition for film coating

Abstract

To provide a surface-coated decorative film that achieves improved excoriation resistance without impairing the design of a decorative film, a decorative molding including the surface-coated decorative film, and a composition for film coating usable for forming a surface coating layer of the surface-coated decorative film.SOLUTION: A surface-coated decorative film has a decorative film, and a colorless, transparent surface coating layer that covers the surface of the decorative film, the surface coating layer formed by curing a composition for film coating containing an acrylic polyol and an aliphatic isocyanate.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a surface coating decorative film, a decorated molded article, and a film coating composition.

Background Art

[0002] As a method of imparting design properties to a base material (adherend), a method of attaching a decorative film to the base material has been conventionally used. A coating may be applied to the surface of the decorative film in order to improve scratch resistance and impart gloss. For example, Patent Document 1 discloses an exterior film having a surface layer formed on a base film made of a polyolefin resin, wherein the surface layer is made of a urethane-modified acrylic resin having a glass transition temperature (Tg) of 60 to 100°C. Further, Patent Document 2 discloses a decorative film having a polyvinyl chloride resin and a colorless transparent coating layer, wherein the coating layer is made of a cured product of an ultraviolet curable resin composition containing a polymerization initiator having an acylphosphine oxide group.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] In recent years, in order to enable application to various base materials, decorative films are required to be attachable to the curved surface portions of base materials having a three-dimensional shape, and in some cases, they may be attached to the base materials of decorative films by methods such as vacuum pressure forming. In such cases, since the decorative film is formed using a relatively flexible material, it has been strongly demanded to improve the scratch resistance of the film surface without impairing the design of the decorative film.

[0005] The present invention has been made in view of the above situation, and aims to provide a surface-coated decorative film with improved scratch resistance without impairing the design of the decorative film, a decorated molded article obtained using the surface-coated decorative film, and a film coating composition that can be used for forming the surface coating layer provided on the surface-coated decorative film.

Means for Solving the Problems

[0006] The surface-coated decorative film of the present invention includes a decorative film and a colorless and transparent surface coating layer that covers the surface of the decorative film, and the surface coating layer is composed of an acrylic urethane resin formed by curing a film coating composition containing an acrylic polyol and an aliphatic isocyanate.

[0007] The aliphatic isocyanate preferably contains pentamethylene diisocyanate or a derivative thereof.

[0008] The film coating composition preferably contains polyolefin particles.

[0009] The decorative film is a laminate including a resin film and an adhesive layer, and the surface coating layer preferably covers the resin film.

[0010] The resin film preferably contains polyvinyl chloride.

[0011] The above resin film preferably contains a plasticizer.

[0012] The decorated molded article of the present invention comprises the surface coating decorative film of the present invention and a base material, and is characterized in that the adhesive layer of the above decorative film is attached to the above base material.

[0013] The above base material has a three-dimensional curved surface, and it is preferable that the surface coating decorative film is attached to the three-dimensional curved surface.

[0014] The composition for film coating of the present invention is characterized by containing an acrylic polyol and an aliphatic isocyanate.

Advantages of the Invention

[0015] According to the surface coating decorative film of the present invention, since it is composed of an acrylic urethane resin having a specific composition and a colorless and transparent surface coating layer covers the surface of the decorative film, the scratch resistance can be improved without impairing the design of the decorative film. Further, according to the decorated molded article of the present invention, a base material (adherend) can be decorated using a decorative film excellent in scratch resistance and design. Furthermore, according to the composition for film coating of the present invention, a colorless and transparent surface coating layer capable of improving the scratch resistance without impairing the appearance can be formed on the surface of the film.

Brief Description of the Drawings

[0016]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0017] <Surface Coating Decorative Film> The surface coating decorative film of the present invention comprises a decorative film and a colorless and transparent surface coating layer covering the surface of the decorative film, and the surface coating layer is composed of an acrylic urethane resin formed by curing a film coating composition containing an acrylic polyol and an aliphatic isocyanate. In this specification, "film" is synonymous with "sheet", and the two are not distinguished by thickness.

[0018] FIG. 1 is a schematic cross-sectional view showing an example of the surface coating decorative film of the present invention. As shown in FIG. 1, the surface coating decorative film comprises a decorative film 20, a surface coating layer 10 covering one surface of the decorative film 20, and a separator 30 detachably attached to the other surface of the decorative film 20. The decorative film 20 is a laminate composed of a resin film (a surface layer 21, a printing layer 23a, and a base film 23b) and an adhesive layer 25. The surface on the surface layer 21 side is covered by the surface coating layer 10, and the separator 30 is attached to the surface on the adhesive layer 25 side. Note that the decorative film 20 may have another layer between the surface layer 21 and the adhesive layer 25. Further, when attaching to a substrate with an adhesive, the adhesive layer 25 and the separator 30 may not be provided, and instead, an adhesive layer may be provided.

[0019] The surface coating layer 10 is colorless and transparent and improves scratch resistance without impairing the design of the decorative film 20. Note that "colorless and transparent" in this specification means that the light transmittance in the visible light region is 50% or more, preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more. Further, the surface coating layer 10 may have a matting function.

[0020] The surface coating layer 10 is composed of an acrylic urethane resin formed by curing a film coating composition containing an acrylic polyol and an aliphatic isocyanate. According to such an acrylic urethane resin, a colorless and transparent surface coating layer 10 excellent in scratch resistance can be formed. Further, according to the acrylic urethane resin, a surface coating layer 10 excellent in elongation during molding (followability to the substrate) and weather resistance can be formed as compared with other resins such as acrylic resins. By using the acrylic polyol, high transparency can be obtained. By using the aliphatic isocyanate, it can be made excellent in weather resistance and less likely to yellow.

[0021] The above acrylic polyol is a polymer compound obtained by polymerizing a (meth)acrylic acid derivative monomer, or a polymer compound obtained by copolymerizing a (meth)acrylic acid derivative monomer and other monomers, etc., having a hydroxyl group at the terminal and reacting with the isocyanate group of an isocyanate compound.

[0022] Examples of the (meth)acrylic acid derivative monomer having a hydroxyl group at the terminal include hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, and the like.

[0023] In this specification, “(meth)acrylic acid” refers to both acrylic acid and methacrylic acid, and “(meth)acrylate” refers to both acrylate and methacrylate.

[0024] As the above acrylic polyol, commercially available products may be used. For example, Q828 (Tg: 135°C), Q555 (Tg: 100°C), Q628 (Tg: 84°C), Q199V (Tg: 67°C), Q631 (Tg: 66°C), Q563 (Tg: 54°C), Q193 (Tg: 46°C), Q641 (Tg: 38°C), Q519 (Tg: 32°C), Q155 (Tg: 30°C), etc., which are classified as non-styrene-based (not using styrene as a raw material) in the Orestar (registered trademark) series manufactured by Mitsui Chemicals, Inc., are preferably used.

[0025] Examples of the above aliphatic isocyanate include pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, and derivatives thereof. These may be used alone or in combination of two or more. Examples of the derivative include those modified with isocyanurate, allophanate, and / or urethane. As the above aliphatic isocyanate, those containing pentamethylene diisocyanate or the derivative are preferably used.

[0026] As the above aliphatic isocyanate, commercially available products may be used. For example, Takenate (registered trademark) series and Stabio (registered trademark) series D-370N (isocyanate: PDI, modification: isocyanurate, NCO%: 25.0), D-376N (isocyanate: PDI, modification: isocyanurate, NCO%: 24.0), D-160N (isocyanate: HDI, modification: TMP adduct, NCO%: 12.6), D-165N (isocyanate: HDI, modification: burette, NCO%: 23.3), D-170H (isocyanate: HDI, modification: isocyanurate, NCO%: 20.7), D-177N (isocyanate: HDI, modification: isocyanurate, NCO%: 20.0), D-178NL (isocyanate: HDI, modification: allophanate, NCO%: 19.2), etc. manufactured by Mitsui Chemicals, Inc. can be used.

[0027] The blending amounts of the acrylic polyol and the aliphatic isocyanate in the above composition for film coating are not particularly limited, but the NCO index (mole number of isocyanate groups in the aliphatic isocyanate / mole number of hydroxyl groups in the acrylic polyol) is preferably 1 to 2. If the NCO index is less than 1, the hardness of the surface coating layer 10 may be low, and there is a risk that the scratch resistance cannot be sufficiently improved. If the NCO index exceeds 2, the surface coating layer 10 may become too hard, and there is a risk that the flexibility required for the surface coating decorative film cannot be ensured.

[0028] The above composition for film coating may contain polyolefin particles. By containing polyolefin particles, the surface slipperiness can be improved and the scratch resistance can be enhanced without impairing the transparency of the surface coating layer 10. Also, by containing polyolefin particles, a matting function may be imparted to the surface coating layer 10. Examples of the material of the polyolefin particles include polyethylene, polypropylene, etc.

[0029] The average particle size of the polyolefin particles is preferably 0.01 to 500 μm. If the average particle size is less than 0.01 μm, the effect of improving the surface slipperiness may not be sufficiently obtained. If the average particle size exceeds 500 μm, it may affect the design of the surface coating decorative film, and in particular, when the polyolefin particles are detached from the surface of the surface coating decorative film, the design property may be greatly reduced.

[0030] The compounding amount of the polyolefin particles is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the acrylic polyol. If the compounding amount is less than 5 parts by weight, the effect of improving the surface slipperiness may not be sufficiently obtained. If the compounding amount exceeds 20 parts by weight, it may affect the design of the surface coating decorative film, and in particular, when the polyolefin particles are detached from the surface of the surface coating decorative film, the design property may be greatly reduced.

[0031] The thickness of the surface coating layer 10 is preferably 0.5 to 30 μm, more preferably 1 to 20 μm, and still more preferably 2 to 10 μm. When the thickness of the surface coating layer 10 is less than 0.5 μm, the effect of improving the scratch resistance may not be sufficiently obtained. When the thickness of the surface coating layer 10 is greater than 30 μm, the transparency and processability of the surface coating decorative film may be reduced.

[0032] The surface layer 21 may be a resin film (top film) or a resin layer composed of a coating film. The composition of the resin constituting the surface layer 21 is not particularly limited, but it is preferably contains polyvinyl chloride. According to polyvinyl chloride, the surface layer 21 is easy to stretch and difficult to break, so when pasted on the base material, the surface coating decorative film is easy to follow the surface shape of the base material. Also, according to polyvinyl chloride, compared with other resins such as polyethylene terephthalate, it can be molded at a low temperature (for example, a temperature of 130 ° C or lower (about 80 ° C)), so good moldability can be obtained.

[0033] Examples of the polyvinyl chloride include a homopolymer of vinyl chloride, a copolymer of vinyl chloride and another monomer, etc. Among them, from the viewpoint of dimensional stability, a homopolymer of vinyl chloride is preferable.

[0034] When the polyvinyl chloride is a copolymer of vinyl chloride and another monomer, examples of the other monomer include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene, and styrene; (meth)acrylate esters such as methyl acrylate, ethyl acrylate, and methyl methacrylate; maleic acid diesters such as dibutyl maleate and diethyl maleate; fumaric acid diesters such as dibutyl fumarate and diethyl fumarate; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl halides such as vinylidene chloride and vinyl bromide; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, etc. These monomers may be used alone or in combination of two or more.

[0035] When the polyvinyl chloride is a copolymer of vinyl chloride and another monomer, the content of the other monomer in the copolymer is usually 50% by weight or less, preferably 10% by weight or less. When the content of the other monomer is more than 50% by weight, the flex resistance of the surface layer 21 may decrease.

[0036] The average degree of polymerization of the polyvinyl chloride is appropriately adjusted according to the desired hardness of the surface layer 21, the amount of the plasticizer used for adjusting the hardness, etc., but from the viewpoint of processability, it is preferably 800 to 1300. In the present specification, the "average degree of polymerization of the polyvinyl chloride" means the average degree of polymerization measured in accordance with JIS K6721 "Test Methods for Vinyl Chloride Resins".

[0037] The resin constituting the surface layer 21 preferably contains a plasticizer. Examples of the plasticizer include epoxy-based plasticizers such as epoxidized soybean oil and epoxy resin; high molecular weight polyester plasticizers; phthalic acid diesters such as octyl phthalate (di-2-ethylhexyl phthalate), dibutyl phthalate, dinonyl phthalate, and diisononyl phthalate; aliphatic dibasic acid diesters such as dioctyl adipate and dioctyl sebacate; and triester phosphates such as tricresyl phosphate and trioctyl phosphate. These plasticizers may be used alone or in combination of two or more.

[0038] Examples of the high molecular weight polyester plasticizers include polyalkylene glycol diesters of phthalic acid such as polyethylene glycol diester, polypropylene glycol diester, and polyethylene glycol polypropylene glycol diester; and polyalkylene glycol diesters of aliphatic dibasic acids such as adipic acid and sebacic acid, such as polyethylene glycol diester, polypropylene glycol diester, and polyethylene glycol polypropylene glycol diester. These high molecular weight polyester plasticizers may be used alone or in combination of two or more.

[0039] The plasticizer preferably contains epoxidized soybean oil. Thereby, the heat resistance can be improved, and even when the top film is formed by calendar molding, sufficient heat resistance can be ensured.

[0040] The number average molecular weight of the plasticizer is preferably 350 to 3000. When the number average molecular weight of the plasticizer is less than 350, the plasticizer tends to bleed to the surface of the surface layer 21. When the number average molecular weight of the plasticizer is greater than 3000, sufficient flexibility is not imparted by the plasticizer, and the surface layer 21 becomes too hard, which may reduce the processability.

[0041] The plasticizer is preferably blended in an amount of 10 parts by weight or less, more preferably 8 parts by weight or less, based on 100 parts by weight of polyvinyl chloride. When the blending amount of the plasticizer is more than 10 parts by weight, the heat resistance of the surface coating decorative film may not be sufficiently increased. On the other hand, when the blending amount of the plasticizer is too small, for example, the processability when forming the top film by calendering may decrease. From such a viewpoint, the plasticizer is preferably blended in an amount of more than 5 parts by weight based on 100 parts by weight of polyvinyl chloride.

[0042] The resin constituting the surface layer 21 may further contain additives such as a heat shrinkage inhibitor, a stabilizer, an ultraviolet absorber, a colorant (pigment), a foaming agent, a lubricant, a modifier, a filler, a diluent, etc. As these additives, those generally blended with polyvinyl chloride can be used.

[0043] The thickness of the surface layer 21 is preferably 60 to 200 μm. When the thickness of the surface layer 21 is less than 60 μm, the surface layer 21 may become too flexible and the processability of the surface coating decorative film may decrease. When the thickness of the surface layer 21 is greater than 200 μm, the surface layer 21 may become too hard and the processability of the surface coating decorative film may decrease.

[0044] Surface processing such as embossing may be performed on the surface of the surface layer 21 on the surface coating layer 10 side. By performing embossing to impart an embossed shape (concave-convex shape), it is possible to enhance the design property of the decorative film 20.

[0045] The printing layer 23a is a layer on which patterns or the like for imparting design properties to the decorative film 20 are printed, and it may be a resin film or a resin layer composed of a coating film. The composition of the resin constituting the printing layer 23a is not particularly limited, and it may be the same as or different from the resin constituting the surface layer 21 or the base film 23b. The resin constituting the printing layer 23a preferably contains polyvinyl chloride and preferably contains a plasticizer. The resin constituting the printing layer 23a may further contain additives such as an anti-thermal shrinkage agent, a stabilizer, an ultraviolet absorber, a coloring agent (pigment), a foaming agent, a lubricant, a modifier, a filler, and a diluent. As these additives, those generally blended with polyvinyl chloride can be used. Examples of the printing method for forming the printing layer 23a include an inkjet printing method, a screen printing method, and a gravure printing method.

[0046] The thickness of the printing layer 23a is preferably 100 to 200 μm. When the thickness of the printing layer 23a is less than 100 μm, the color of the base material to which the surface coating decorative film is to be attached may be easily seen through, and it may be difficult to obtain the desired design properties. When the thickness of the printing layer 23a is greater than 200 μm, the surface coating decorative film may become too hard and the processability may decrease.

[0047] The base film 23b is a resin film that serves as a base for the printing layer 23a and the surface layer 21 in the decorative film 20. The composition of the resin constituting the base film 23b is not particularly limited, and it may be the same as or different from the resin constituting the surface layer 21 or the printing layer 23a. The resin constituting the base film 23b preferably contains polyvinyl chloride and preferably contains a plasticizer. The resin constituting the base film 23b may further contain additives such as an anti-thermal shrinkage agent, a stabilizer, an ultraviolet absorber, a coloring agent (pigment), a foaming agent, a lubricant, a modifier, a filler, and a diluent. As these additives, those generally blended with polyvinyl chloride can be used.

[0048] The thickness of the base film 23b is preferably 100 to 200 μm. When the thickness of the base film 23b is less than 100 μm, the color of the base material to which the surface coating decorative film is to be attached may be easily seen through, and it may be difficult to obtain the desired design property. Also, the base film 23b may become too flexible, resulting in a decrease in processability. When the thickness of the base film 23b is greater than 200 μm, the surface coating decorative film may become too hard, resulting in a decrease in processability.

[0049] The adhesive layer 25 is not particularly limited as long as it has an adhesive function (pressure-sensitive adhesiveness). Examples of the material of the adhesive layer 25 include acrylic adhesives, rubber adhesives, and silicone adhesives. Among them, acrylic adhesives are preferred because they are excellent in adhesiveness, processability, heat aging resistance, moisture aging resistance, and weather resistance, and are relatively inexpensive.

[0050] The thickness of the adhesive layer 25 is preferably 10 to 60 μm, more preferably 20 to 50 μm. When the thickness of the adhesive layer 25 is less than 10 μm, sufficient adhesiveness may not be obtained. When the thickness of the adhesive layer 25 is greater than 60 μm, the flexibility of the surface coating decorative film may be excessively reduced, resulting in a decrease in processability.

[0051] As the separator 30, those commonly used in the film field can be used, and examples include release films and release papers. The separator 30 can prevent the adhesive layer 25 from being exposed during the production, transportation, and storage of the surface coating decorative film, thereby preventing the deterioration of the adhesive layer 25 and improving the handleability of the surface coating decorative film. The separator 30 may be peeled off immediately before attaching the surface coating decorative film to the base material.

[0052] Examples of the release film include those obtained by subjecting the surface on the side to be attached to the adhesive layer 25 of a resin film such as a polyethylene terephthalate film to a release treatment by coating with a silicone-based release agent, an alkyd-based release agent, a fluorine-based release agent, or the like. Examples of the release paper include those obtained by subjecting the surface on the side to be attached to the adhesive layer 25 of a high-quality paper to a release treatment by coating with a silicone-based release agent, an alkyd-based release agent, a fluorine-based release agent, or the like.

[0053] The application target of the surface coating decorative film of the present invention is not particularly limited, and it can be applied, for example, to decorative uses in vehicle fields such as automobiles including motorcycles; building fields such as kitchen facing materials and bathroom vanities, furniture, etc.; and electronic terminal fields such as tablet PCs and covers of mobile phones. Among them, the surface coating decorative film of the present invention is preferably used for vehicle interiors.

[0054] The surface coating decorative film of the present invention can be attached to a substrate through the adhesive layer 25 by laminate molding such as vacuum pressure-air molding or membrane press molding. Vacuum pressure-air molding is performed as follows, for example, using a TOM molding machine. First, the surface coating decorative film and the substrate are set in a molding chamber in an atmospheric pressure state. Next, after making the molding chamber airtight, it is sucked with a vacuum tank to make the inside of the molding chamber a vacuum state. Subsequently, while maintaining the vacuum state, it is heated to a desired molding temperature using a heater to soften the surface coating decorative film. Then, after pressing the substrate against the softened surface coating decorative film, the inside of the molding chamber is returned to the atmospheric pressure state, and further, compressed air is supplied into the molding chamber from a pressure-air tank. As a result, the surface coating decorative film is pressed against the substrate and attached along the surface shape of the substrate through the adhesive layer 25. Thereafter, if necessary, the surplus portion of the surface coating decorative film protruding from the substrate is trimmed.

[0055] <Decorative molded product> The decorated molded article of the present invention comprises the surface coating decorative film of the present invention and a base material, and is characterized in that the adhesive layer of the decorative film is attached to the base material.

[0056] FIG. 2 is a schematic cross-sectional view showing an example of the decorated molded article of the present invention. As shown in FIG. 2, the decorated molded article comprises a surface coating layer 10, a decorative film 20, and a base material 50. That is, for the decorative film 20, the separator 30 that had been attached to the adhesive layer 25 is peeled off, and the decorative film 20 is attached to the base material 50 via the adhesive layer 25.

[0057] Examples of the base material 50 include vehicles such as bicycles, motorcycles, automobiles, buses, and trains; ships; aircraft such as airplanes and helicopters; helmets; household goods such as furniture and home appliances; buildings such as wall surfaces, floor surfaces, ceilings, roofs, columns, signboards, doors, and gates; electronic terminals such as smartphones and tablets; office supplies such as cabinets, desks, and personal computers; building materials at construction sites; and components thereof.

[0058] Examples of the material of the base material 50 include resins such as polycarbonate resin, acrylic resin, styrene resin, and acrylonitrile-butadiene-styrene copolymer (ABS resin); metals such as iron, copper, and aluminum, or alloys thereof.

[0059] The base material 50 has a three-dimensional curved surface, and it is preferable that the surface coating decorative film of the present invention is attached to the three-dimensional curved surface. The surface coating decorative film of the present invention can impart a three-dimensional design even on the surface of the base material 50 having a three-dimensional curved surface portion by a method such as vacuum pressure forming. Further, since the surface coating layer 10 is provided and has excellent scratch resistance, it is possible to improve the durability of the corner portion of the three-dimensional curved surface where the film is likely to be damaged.

[0060] One aspect of the present invention is also a film coating composition containing an acrylic polyol and an aliphatic isocyanate. According to the film coating composition of the present invention, a colorless and transparent surface coating layer can be formed on the surface of the film to improve scratch resistance without impairing the appearance of the film. The film coating composition of the present invention is suitably used in the field of decorative molding and can be used for both interior and exterior applications.

Examples

[0061] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples only.

[0062] <Example 1> To 100 parts by weight of polyvinyl chloride with an average degree of polymerization of 800, 6 parts by weight of epoxidized soybean oil (“Epoxysizer (registered trademark) W-100-EL” manufactured by DIC Corporation), 2 parts by weight of diisononyl phthalate, and 10 parts by weight of a methyl methacrylate-alkyl acrylate copolymer (“Metablen (registered trademark) H-602” manufactured by Mitsubishi Chemical Corporation) were added, and after melt-kneading with a Banbury mixer, calender molding was performed to produce a top film with a thickness of 90 μm.

[0063] To 100 parts by weight of polyvinyl chloride with an average degree of polymerization of 800, 6 parts by weight of epoxidized soybean oil (“Epoxysizer W-100-EL” manufactured by DIC Corporation), 2 parts by weight of diisononyl phthalate, and 10 parts by weight of a methyl methacrylate-alkyl acrylate copolymer (“Metablen H-602” manufactured by Mitsubishi Chemical Corporation) were added, and after melt-kneading with a Banbury mixer, calender molding was performed to produce a film for forming a printing layer with a thickness of 110 μm. The obtained film for forming a printing layer was printed with a design using a vinyl chloride-vinyl acetate copolymer·acrylic ink by an inkjet printer to obtain a printing layer.

[0064] To 100 parts by weight of polyvinyl chloride with an average degree of overlap of 800, 6 parts by weight of epoxidized soybean oil ("Epoxysizer W-100-EL" manufactured by DIC Corporation), 2 parts by weight of diisononyl phthalate, and 10 parts by weight of a methyl methacrylate-alkyl acrylate copolymer ("Metablen H-602" manufactured by Mitsubishi Chemical Corporation) were added, and after melt-kneading with a Banbury mixer, calender molding was performed to produce a base film with a thickness of 120 μm.

[0065] Next, by thermal lamination, a printed layer (a printed film for forming a printed layer) was bonded to the base film, and further, a top film was bonded to the printed layer to produce a laminated film.

[0066] Next, to 100 parts by weight (solid content) of an acrylic adhesive ("SK1506A" manufactured by Soken Chemical & Engineering Co., Ltd.) with a weight average molecular weight of 640,000 as the main agent, 0.04 parts by weight (solid content) of an epoxy-based curing agent ("E-5C" manufactured by Soken Chemical & Engineering Co., Ltd.), 3.2 parts by weight of a hindered amine-based light stabilizer ("LA-52" manufactured by Soken Chemical & Engineering Co., Ltd.), and 2.1 parts by weight of a benzophenone-based ultraviolet absorber ("Adekastab 1413" manufactured by ADEKA Corporation) were added to prepare an adhesive composition. As a separator, release paper with polyethylene laminated on both sides of high-quality paper and further coated with a silicone-based release agent was prepared. The adhesive composition was coated on this separator with a comma coater and dried to form an adhesive layer with a thickness of 40 μm. Then, the adhesive layer formed on the separator was bonded to the base film of the above laminated film. As a result, a decorative film having a structure in which a top film, a printed layer, a base film, an adhesive layer, and a separator were laminated in this order was obtained.

[0067] Next, 100 parts by weight of a non-styrene acrylic polyol (Orestar (registered trademark) Q555 manufactured by Mitsui Chemicals, Inc.) as the main agent (solid content 40%, solvents: butyl acetate and ethyl acetate) and 75 parts by weight of ethyl acetate as the solvent (diluent for viscosity adjustment) were mixed and stirred. After that, 7.2 parts by weight (solid content 100%) of a nurate-modified pentamethylene diisocyanate (Stabio (registered trademark) D-370N manufactured by Mitsui Chemicals, Inc., NCO group content: 25.0 mol%) as the curing agent was added and stirred again to prepare a composition for film coating. The blending amount of the curing agent was adjusted so that the NCO index of the composition for film coating became 1.

[0068] The obtained composition for film coating was applied onto the top film of the above decorative film, dried at 80°C for 2 minutes, and then cured at 40°C for 72 hours to form a colorless and transparent surface coating layer with a thickness of 5 μm. As a result, a surface coating decorative film having a structure in which the surface coating layer, top film, printing layer, base film, adhesive layer, and separator were laminated in this order was obtained.

[0069] <Example 2> When preparing the composition for film coating, a surface coating decorative film was produced in the same manner as in Example 1 except that the amount of the aliphatic isocyanate used as the curing agent was changed to 14.4 parts by weight, which was twice the amount. The blending amount of the curing agent was adjusted so that the NCO index of the composition for film coating became 2.

[0070] <Example 3> When preparing the composition for film coating, 100 parts by weight (solid content: 40%) of an acrylic polyol (“Orester (registered trademark) Q555” manufactured by Mitsui Chemicals, Inc.) as the main agent, 16.1 parts by weight (solid content: 15%, solvent: ethyl acetate) of solvent-dispersed polyethylene particles (“X-7019” manufactured by Gifu Ceramics Manufacturing Co., average particle diameter: 12 μm) as the additive, and 75 parts by weight of ethyl acetate as the solvent were mixed and stirred. Then, 14.4 parts by weight of an aliphatic isocyanate (“Stabio (registered trademark) D-370N” manufactured by Mitsui Chemicals, Inc.) as the curing agent was added and stirred again to prepare the composition for film coating. A surface-coated decorative film was produced in the same manner as in Example 1 except for the above. The blending amount of the curing agent was adjusted so that the NCO index of the composition for film coating was 2.

[0071] <Example 4> When preparing the composition for film coating, a surface-coated decorative film was produced in the same manner as in Example 3 except that the amount of the solvent-dispersed polyethylene particles used as the additive was changed to 48.3 parts by weight, which is three times the original amount. The blending amount of the curing agent was adjusted so that the NCO index of the composition for film coating was 2.

[0072] <Example 5> When preparing the composition for film coating, 100 parts by weight of “Orester (registered trademark) Q563” (solid content: 50%, solvents: butyl acetate and ethyl acetate) manufactured by Mitsui Chemicals, Inc. was used instead of 100 parts by weight of “Orester (registered trademark) Q555” as the acrylic polyol as the main agent, and a surface-coated decorative film was produced in the same manner as in Example 1 except that the blending amount of the curing agent was changed from 7.2 parts by weight to 8.7 parts by weight. The blending amount of the curing agent was adjusted so that the NCO index of the composition for film coating was 1.

[0073] <Example 6> When preparing the composition for film coating, a surface-coated decorative film was produced in the same manner as in Example 5, except that the amount of the aliphatic isocyanate used as a curing agent was changed to 17.4 parts by weight, which is twice the original amount. The blending amount of the curing agent was adjusted so that the NCO index of the composition for film coating was 2.

[0074] <Example 7> 100 parts by weight (solid content 50%) of an acrylic polyol (Orestar (registered trademark) Q563 manufactured by Mitsui Chemicals, Inc.) as the main agent, 20 parts by weight of solvent-dispersed polyethylene particles (X-7019 manufactured by Gifu Ceramics Co., Ltd.) as an additive, and 75 parts by weight of ethyl acetate as a solvent were mixed and stirred. Then, 17.4 parts by weight of an aliphatic isocyanate (Stabio (registered trademark) D-370N manufactured by Mitsui Chemicals, Inc.) as a curing agent was added and stirred again. A surface-coated decorative film was produced in the same manner as in Example 5, except for the preparation of the composition for film coating. The blending amount of the curing agent was adjusted so that the NCO index of the composition for film coating was 2.

[0075] <Example 8> When preparing the composition for film coating, a surface-coated decorative film was produced in the same manner as in Example 7, except that the amount of the solvent-dispersed polyethylene particles used as an additive was changed to 60 parts by weight, which is three times the original amount. The blending amount of the curing agent was adjusted so that the NCO index of the composition for film coating was 2.

[0076] <Comparative Example 1> 100 parts by weight (solid content 19.5%) of a silicone copolymer urethane resin (Resaloid LU-504SP manufactured by Dainichi Seika Kogyo Co., Ltd.) as the main agent and 4 parts by weight (solid content 100%) of a curing agent (Seikabond C-83 manufactured by Dainichi Seika Kogyo Co., Ltd.) were mixed and stirred. A surface-coated decorative film was produced in the same manner as in Example 1, except for the preparation of the composition for film coating. The main agent, "Resaloid LU-504SP", contains silica fine particles with a particle size of 0.1 to 0.8 μm.

[0077] <Comparative Example 2> A decorative film without a surface coating layer was produced in the same manner as in Example 1, except that no surface coating layer was formed.

[0078] <Evaluation> The following evaluations were performed on the surface coating decorative films of Examples 1 to 8 and Comparative Example 1, and the decorative film without a surface coating layer of Comparative Example 2. The results are shown in Table 1 below.

[0079] (1) Abrasion resistance test (steel wool scratching test) The surface on the surface coating layer side of the surface coating decorative film (Examples 1 to 8 and Comparative Example 1) or the surface on the top film side of the decorative film (Comparative Example 2) was rubbed 50 times back and forth with a load of 200 g using steel wool of grade #0000, and then the surface state was visually evaluated according to the following criteria. 0: The appearance did not change. 1: The appearance changed slightly. 2: The appearance changed significantly.

[0080] (2) Transparency The design of the printing layer was visually evaluated according to the following criteria by viewing from the surface on the surface coating layer side of the surface coating decorative film (Examples 1 to 8 and Comparative Example 1) or the surface on the top film side of the decorative film (Comparative Example 2). 〇: The upper layer was transparent and the design of the printing layer was clear. ×: The upper layer was cloudy and the design of the printing layer was unclear.

[0081]

Table 1

Explanation of symbols

[0082] 10: Surface coating layer 20: Decorative film 21: Surface layer 23a: Printing layer 23b: Base film 25: Adhesive layer 30: Separator 50: Substrate

Claims

1. A decorative film having a surface layer, and a colorless and transparent surface coating layer covering the surface on the surface layer side of the decorative film, wherein the surface layer contains a plasticizer having a number average molecular weight of 350 or more and 3000 or less, the surface coating layer is composed of an acrylic urethane resin formed by curing a film coating composition containing an acrylic polyol and an aliphatic isocyanate, and the aliphatic isocyanate includes pentamethylene diisocyanate or a derivative thereof. A surface coating decorative film characterized by this.

2. The surface coating decorative film according to claim 1, wherein the film coating composition contains polyolefin particles.

3. The surface coating decorative film according to claim 1 or 2, wherein the surface on the surface coating layer side of the surface layer is embossed.

4. The surface coating decorative film according to any one of claims 1 to 3, wherein the thickness of the surface layer is 60 μm or more and 200 μm or less.

5. The surface coating decorative film according to any one of claims 1 to 4, wherein the decorative film is a laminate including the surface layer, a printing layer, and a base film in this order.

6. The surface coating decorative film according to claim 5, wherein the surface layer and the base film contain polyvinyl chloride.

7. The surface coating decorative film according to claim 6, wherein the base film contains a plasticizer.

8. The surface coating decorative film according to claim 7, wherein the number average molecular weight of the plasticizer contained in the base film is 350 or more and 3000 or less.

9. The surface coating decorative film according to any one of claims 1 to 8, wherein the decorative film further includes an adhesive layer.

10. A decorative molded article comprising the surface coating decorative film according to claim 9 and a base material, wherein the adhesive layer of the decorative film is attached to the base material.

11. The base material has a three-dimensional curved surface, and the surface coating decorative film is attached to the three-dimensional curved surface. The decorative molded article according to claim 10, characterized by this.

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