Decorative film, and manufacturing method of decorative film

Abstract

To provide a decorative film exhibiting excellent external appearance, which is capable of enhancing productivity when attaching the decorative film to a substrate by heating with near-infrared radiation, or molding the decorative film by heating with the near-infrared radiation.SOLUTION: A decorative film comprises a substrate film layer 1 and a colored layer 2. The decorative film is characterized in that the colored layer 2 comprises at least a binder resin, and a coloring pigment and / or a brilliant pigment, and a mean value of transmittance at a wavelength of 780 to 2000 nm of the colored layer 2 is 1.0 to 90%.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a decorative film and a method for manufacturing a decorative film, and in particular to a decorative film that can increase productivity when the decorative film is heated with near-infrared rays and attached to a substrate, or when the decorative film is heated with near-infrared rays and molded, and that also has an excellent appearance. [Background technology]

[0002] Paints containing coloring pigments and luster pigments are widely used to protect and decorate the surfaces of automobiles and automobile parts, electrical appliances, building material parts, buildings and structures, etc. When imparting such effects with paints, the painting process often requires multiple steps to form a multilayer film including multiple coating layers such as a colored layer, a primer layer, and a clear layer, which poses issues such as securing a large-scale painting site, complicated process management, and increased CO2 emissions in each baking process. For this reason, in recent years, various methods have been considered to impart design to substrates using decorative films instead of paints.

[0003] JP 2004-299220 A (Patent Document 1) discloses an invention of a metallic laminate film having a guard film layer (A), a clear coating layer (B), a glittering material (C3) containing aluminum flakes, and a colored coating layer (C) containing an orientation control material (C4). Patent Document 1 describes that by adding an orientation control material (C4) and controlling the orientation of the aluminum flakes so as to achieve a high SV value and a high IV value, it is possible to provide a metallic laminate film that has excellent processability when decorating molded products and can impart design properties to the decorated molded products that are equal to or better than those achieved by conventional coating methods.

[0004] JP 2011-079156 A (Patent Document 2) discloses an invention of a decorative film in which an active energy ray-curable clear coating layer (B) and a colored coating layer (C) are laminated in this order on a polyglycolic acid sheet layer (A). Patent Document 2 describes that by laminating an active energy ray-curable clear coating layer on a polyglycolic acid sheet layer that has excellent processability and solvent resistance, a decorative film that has excellent processability, appearance, and surface curing properties of the clear layer can be provided.

[0005] Japanese Patent Publication WO2016 / 080423 (Patent Document 3) discloses an invention of a laminated film for decorating three-dimensional molded products, which has an adhesive layer (A), a metallic design layer (B), a clear coating layer (C) made of an energy ray-curable coating film, and a base film layer (D). Patent Document 3 describes that it is possible to provide a film that improves problems such as cracking and whitening and has excellent properties such as scratch resistance, hardness, and chemical resistance on the surface after decoration. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2004-299220 A [Patent Document 2] JP 2011-079156 A [Patent Document 3] Special publication WO2016 / 080423 Summary of the Invention [Problem to be solved by the invention]

[0007] Patent Documents 1 to 3 describe useful inventions relating to a method for decorating a substrate using a decorative film including a colored layer. On the other hand, in order to mold the decorative film in a short time or to attach it to the substrate efficiently, the decorative film may be heated with near infrared rays. However, in the case of a decorative film having a colored layer including a color pigment or a glittering pigment, the decorative film is difficult to heat up, and it takes time to heat up to a specific temperature, resulting in a decrease in productivity. In particular, glittering pigments having a specific shape such as a scale shape are arranged parallel to the coating surface, so that they are difficult to transmit near infrared rays (wavelength range 700 to 2500 μm) when heated, and it takes time to transmit heat to the substrate film layer, resulting in a more significant decrease in productivity when attaching or molding the decorative film.

[0008] Therefore, an object of the present invention is to provide a decorative film that can increase productivity when heating a decorative film with near-infrared rays and attaching it to a substrate or when heating a decorative film with near-infrared rays and molding it, and that also has an excellent appearance. [Means for solving the problem]

[0009] As a result of intensive research into achieving the above-mentioned object, the inventors have discovered that, in a decorative film having at least a base film layer and a colored layer, by adjusting the average transmittance of the colored layer at wavelengths of 780 to 2000 nm to be 1.0 to 90%, it is possible to increase the productivity when the decorative film is heated with near-infrared rays and attached to a base material, or when the decorative film is heated with near-infrared rays and molded, and it is also possible to provide a decorative film with excellent appearance, which has led to the completion of the present invention.

[0010] Therefore, the decorative film of the present invention has at least (A) a base film layer and (B) a colored layer, The (B) colored layer contains at least a binder resin and a color pigment and / or a luster pigment, The decorative film is also characterized in that the average transmittance in the wavelength range of 780 to 2000 nm is 1.0 to 90%.

[0011] In another preferred embodiment of the decorative film of the present invention, the (B) colored layer contains a glittering pigment, The solid content mass ratio of the bright pigment to the binder resin is 5:100 to 50:100.

[0012] In another preferable embodiment of the decorative film of the present invention, the luster pigment includes a vapor-deposited aluminum pigment and / or a resin-coated metal pigment.

[0013] Another embodiment of the decorative film of the present invention is a decorative film having at least (A) a base film layer, (B) a colored layer, and (D) a clear layer, The multilayer coating film including the (B) colored layer and the (D) clear layer is a decorative film characterized in that the average transmittance at wavelengths of 780 to 2000 nm is 1.0 to 90%.

[0014] The present invention also provides a method for producing a decorative film having at least (A) a base film layer and (B) a colored layer, The process includes providing a colored layer (B) on a base film layer (A), The (B) colored layer contains at least a binder resin and a color pigment and / or a luster pigment, The method for producing a decorative film is also characterized in that the average transmittance in the wavelength range of 780 to 2000 nm is 1.0 to 90%.

[0015] Another embodiment of the method for producing a decorative film of the present invention is a method for producing a decorative film having at least (A) a base film layer, (B) a colored layer, and (D) a clear layer, A step of providing a colored layer (B) on a base film layer (A); (B) a step of providing a clear layer (D) on the colored layer, The (B) colored layer contains at least a binder resin and a color pigment and / or a luster pigment, The method for producing a decorative film is characterized in that the multilayer coating film including the (B) colored layer and the (D) clear layer has an average transmittance of 1.0 to 90% at wavelengths of 780 to 2000 nm. Effect of the Invention

[0016] According to the present invention, it is possible to increase the productivity when a decorative film is heated with near-infrared rays and attached to a substrate or when a decorative film is heated with near-infrared rays and molded, and it is also possible to provide a decorative film that has excellent appearance. [Brief description of the drawings]

[0017] [Figure 1] 1 is a schematic diagram showing one embodiment of a decorative film of the present invention. [Diagram 2] 1 is a schematic diagram showing one embodiment of a decorative film of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention relates to a decorative film and a method for producing the decorative film.

[0019] The decorative film of the present invention can be used to decorate a substrate by attaching it thereto, or to mold the decorative film itself to obtain a decorated article. Here, "decoration" means to provide a design to a substrate or to impart a texture different from that of the substrate. The design means a shape, a pattern, a color, or a combination of these.

[0020] In the present invention, the substrate means an object to which the decorative film is applied. Substrates include various articles, such as automobiles and automobile parts, electrical appliances, building material parts, architecture and structures, small items, interior goods, etc. In addition, the materials of the substrate are also diverse, such as metal substrates such as iron, stainless steel, aluminum, copper, titanium and their alloys, inorganic substrates other than metals such as cement, concrete, gypsum, calcium silicate, calcium carbonate, marble, artificial marble, glass, and ceramics, wood substrates, plastic substrates such as epoxy resin, ABS resin, polycarbonate, polyvinyl chloride, polystyrene, acrylic resin, particularly polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), and polypropylene (PP), as well as composite substrates combining two or more of these substrates.

[0021] The shape of the substrate is also diverse, and includes, for example, two-dimensional substrates such as film, sheet, and plate, and three-dimensional substrates that are complex three-dimensional objects, etc. The surface of the substrate may be smooth or may have irregularities.

[0022] The decorative film of the present invention has a multi-layer structure and includes at least a base film layer and a colored layer. In this specification, the base film layer may be referred to as (A) base film layer, and the colored layer may be referred to as (B) colored layer.

[0023] In the present invention, the base film layer means a film layer that supports a colored layer and the like among the layers that constitute the decorative film.

[0024] The base film layer is preferably composed of a resin film. The resin used in the film is preferably a thermoplastic resin, such as acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-styrene-acrylic acid ester resin, acrylic resin, polyolefin resin such as polypropylene and polyethylene, polycarbonate resin, vinyl chloride resin such as polyvinyl chloride (PVC), polyethylene terephthalate (PET) resin, polyphenylene ether (PPE) resin, etc. Among these, acrylic resin, ABS resin, and PVC resin are particularly preferable. The resin may be used alone or in combination of two or more kinds.

[0025] The glass transition point of the base film layer is preferably −20° C. to 140° C., more preferably 20° C. to 130° C., and particularly preferably 50° C. to 120° C. By setting the glass transition point of the base film layer to 140° C. or lower, the formability of the decorative sheet is excellent, particularly when a base material having a complex shape is decorated with the decorative sheet by heating in vacuum forming or the like, and by setting the glass transition point of the base film layer to −20° C. or higher, particularly 50° C. or higher, the blocking resistance and durability of the decorative film are improved.

[0026] In this specification, the glass transition point (Tg) of the base film layer is the spectrum peak in a temperature change curve of loss tangent (tan δ) measured at a measurement frequency of 1 Hz using a solid viscoelasticity measuring device based on JIS K7244-4.

[0027] Specifically, the loss modulus and storage modulus of the base film layer are measured at each temperature under the following measurement conditions using a solid viscoelasticity measuring device (e.g., RSA-GII (manufactured by TA Instruments)), the loss tangent is calculated from the loss modulus and storage modulus, a temperature change curve of the loss tangent is created, and the spectrum peak value of the loss tangent is read. <Measurement conditions> Temperature range: -50℃~200℃ Heating rate: 5℃ / min Measurement length: 20.0 mm Measurement width: 5.0mm Frequency: 1Hz Distortion: 0.05%

[0028] The base film layer may be one layer or two or more layers.

[0029] The thickness of the base film layer is preferably 10 to 2000 μm. When the decorative film is attached to a substrate, the thickness of the base film layer is more preferably 10 to 250 μm, and when the decorative film itself is molded to obtain a decorated article, the thickness of the base film layer is more preferably 500 to 2000 μm. When the base film layer is made up of multiple layers, the numerical range described here refers to the total thickness of the base film layers.

[0030] Examples of molding methods that can be used to produce the film include injection molding, blow molding, extrusion molding, vacuum molding, pressure molding, and TOM (Three Dimension Overlay Method) molding.

[0031] In the present invention, the colored layer is a layer that is necessary to impart a design to the substrate, among the layers that constitute the decorative film.

[0032] The colored layer contains at least a binder resin and a color pigment or / and a luster pigment, and the average value of the transmittance at wavelengths of 780 to 2000 nm is in the range of 1.0 to 90%, more preferably in the range of 3.0 to 50%. If the average value of the transmittance at wavelengths of 780 to 2000 nm is below 1.0%, for example, when the decorative film is heated with near infrared rays by an IR heater and attached to a substrate or heated with near infrared rays to form the decorative film, it is difficult for a sufficient amount of near infrared rays to reach the substrate film layer for heating, and it takes time to heat the decorative film to a specific temperature, resulting in reduced productivity. In addition, when forming a colored layer with excellent appearance using a color pigment or a luster pigment, taking into consideration the near infrared transmittance of the color pigment or the luster pigment, the average value of the transmittance at wavelengths of 780 to 2000 nm is 90% or less, more preferably 50% or less. Furthermore, when the colored layer has a metallic design containing a glittering pigment, the average transmittance at wavelengths of 780 to 2000 nm is preferably 50% or less, and more preferably 30% or less, in terms of having a good appearance.

[0033] Here, the average value of the transmittance in the wavelength range of 780 to 2000 nm means the near-infrared transmittance, which can be measured using an ultraviolet-visible-near-infrared spectrophotometer (for example, V-700 manufactured by JASCO Corporation).

[0034] Examples of the binder resin include acrylic resin, silicone resin, acrylic silicone resin, styrene-acrylic copolymer resin, polyester resin, fluororesin, rosin resin, petroleum resin, coumarone resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid resin, fumaric acid resin, vinyl resin such as vinyl chloride resin, amine resin, and ketimine resin.

[0035] The binder resin preferably contains an acrylic resin and / or a cellulose resin. By using an acrylic resin as the binder resin, the chemical resistance and weather resistance of the coating film can be improved. In addition, by using a cellulose resin as the binder resin, the drying property of the coating film is improved, and in particular, when a glittering pigment is contained, the orientation of the glittering pigment in the colored layer is easily controlled, so that a glittering layer without color unevenness or decorative unevenness can be easily formed.

[0036] The acrylic resin is preferably a polymer or copolymer containing an acrylic acid ester and / or a methacrylic acid ester as a main component, where the main component means a component contained in an amount of 50 mol % or more.

[0037] The acrylic resin preferably has a small amount of hydroxyl groups, and preferably has a hydroxyl value of less than 40 mgKOH / g. In particular, in the case of a one-component paint, it is more preferable that the paint contains an acrylic resin having a hydroxyl value of 5 mgKOH / g or less. In addition, in the case where the colored layer contains a plurality of acrylic resins, the amount of the acrylic resin having a hydroxyl value of less than 40 mgKOH / g is preferably 90 mass% or more of the total acrylic resin.

[0038] In this specification, the hydroxyl value of an acrylic resin is the number of milligrams of potassium hydroxide required to completely acetylate the free hydroxyl groups in 1 g of a sample with acetic anhydride and then neutralize them.

[0039] The weight average molecular weight of the acrylic resin is preferably from 3,000 to 300,000, and more preferably from 4,000 to 200,000.

[0040] In this specification, the weight average molecular weight of a resin is a value measured by gel permeation chromatography, and polystyrene is used as the standard substance.

[0041] The amount of the acrylic resin in the colored layer is preferably 5 to 95% by mass, and more preferably 10 to 90% by mass. The acrylic resin may be used alone or in combination with two or more other resins.

[0042] Examples of cellulose resins include cellulose ether, cellulose ester, nitrocellulose, cellulose sulfate, cellulose phosphate, and cellulose acetate nitrate. Examples of cellulose ethers include methyl cellulose, ethyl cellulose, benzyl cellulose, trityl cellulose, cyanoethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, aminoethyl cellulose, and oxyethyl cellulose (also called hydroxyethyl cellulose). Examples of cellulose esters include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose propionate, and cellulose butyrate.

[0043] In addition, examples of cellulose resins include acrylic modified cellulose derivatives, polyester modified cellulose derivatives, and polyurethane modified cellulose derivatives. The acrylic modified cellulose derivatives are compounds obtained by graft polymerizing acrylic components such as (meth)acrylates to cellulose derivatives such as cellulose ethers and cellulose esters. The polyester modified cellulose derivatives are compounds obtained by binding polyester components (i.e., components having multiple ester bonds in the main chain) such as polytrimethylene terephthalate, polyethylene terephthalate, and polybutylene terephthalate to cellulose derivatives such as cellulose ethers and cellulose esters. The polyurethane modified cellulose derivatives are compounds obtained by reacting hydroxyl groups of cellulose derivatives such as cellulose ethers and cellulose esters with, for example, isocyanate prepolymers.

[0044] As the cellulose resin, nitrocellulose is particularly preferable. The nitrocellulose preferably has a nitrogen content of 10% by mass or more.

[0045] The weight-average molecular weight of the cellulose resin is preferably 20,000 to 150,000, and more preferably 30,000 to 140,000. The cellulose resin may also include a cellulose resin having a weight-average molecular weight of 20,000 or more and less than 80,000, and preferably 30,000 to 70,000, and a cellulose resin having a weight-average molecular weight of 80,000 or more and 150,000 or less, and preferably 80,000 to 130,000.

[0046] The amount of the cellulose resin in the colored layer is preferably 1 to 80% by mass, more preferably 2 to 70% by mass. The cellulose resin may be used alone or in combination with two or more other resins.

[0047] Examples of color pigments include titanium oxide, iron oxide, carbon black, yellow lead, molybdate orange, ultramarine blue, Prussian blue, phthalocyanine blue, phthalocyanine green, quinacridone red, naphthol red, benzimidazolone yellow, Hansa yellow, benzimidazolone orange, dioxazine violet, etc. In the color layer of the present invention, the amount of the color pigment is, for example, preferably 1 to 30% by mass, and more preferably 1 to 10% by mass.

[0048] Examples of the luster pigment include metal pigments such as aluminum, indium, nickel, chromium, tin, copper, silver, platinum, gold and stainless steel, and glass flakes.

[0049] The luster pigment is preferably scaly, and more preferably a scaly aluminum pigment.

[0050] The scaly luster pigment preferably has an average particle size of 5 to 35 μm and an average aspect ratio of 10 to 1000. The average particle size of the scaly luster pigment is more preferably 7 to 25 μm. The average aspect ratio of the scaly luster pigment is more preferably 20 to 1000. The average thickness of the scaly luster pigment is, for example, 5 to 3000 nm.

[0051] The particle size of the scaly luster pigment in this specification is the average value of the major axis diameter (the maximum length of a straight line connecting two points on the periphery) and the minor axis diameter (the minimum length of a straight line connecting two points on the periphery) of the particle plane in an image observed by SEM (scanning electron microscope). Here, when the particle plane is circular, the diameter of the circle is the particle size. The average particle size of the scaly luster pigment is the average particle size of the scaly luster pigment contained in the luster layer. In addition, in the present invention, the average aspect ratio of the scaly luster pigment is the ratio (D / T) of the average particle size (D) to the average thickness (T). The average thickness (T) can be adjusted during the production of the scaly luster pigment. In the present invention, the particle size of the luster pigment was measured using SEM (scanning electron microscope), and the average particle size was obtained for 100 or more particles.

[0052] More preferably, the luster pigment comprises a vapor-deposited aluminum pigment and / or a resin-coated metal pigment.

[0053] Vapor-deposited aluminum pigments are scaly glittering pigments prepared by crushing and adjusting the particle size of a thin aluminum film obtained by uniformly depositing aluminum. Vapor-deposited aluminum pigments having a coated surface can also be used. For example, silica-coated vapor-deposited aluminum pigments are vapor-deposited aluminum pigments whose surface is coated with a silica film. The amount of silica coating is preferably 0.1 to 25 g per 100 g of vapor-deposited aluminum pigment.

[0054] The resin-coated metal pigment is a metal pigment whose surface is coated with a resin. Here, the resin-coated metal pigment is preferably scaly, more preferably aluminum flake. Examples of the resin include acrylic resin, polyester resin, and urethane resin, and acrylic resin is preferable. The amount of resin coating is preferably 0.1 to 25 g per 100 g of the metal pigment, and particularly preferably 5 to 20 g.

[0055] When the colored layer contains a luster pigment, the solid content mass ratio of the luster pigment to the binder resin is preferably 5:100 to 50:100, more preferably 5:100 to 40:100. If the solid content mass ratio of the luster pigment to the binder resin is in the range of 5:100 to 50:100, when the decorative film is heated and attached or molded to a substrate, a sufficient amount of near infrared rays for heating can easily reach the substrate film layer, and the time required to heat the decorative film to a specific temperature is shortened, thereby improving productivity. In addition, a metallic appearance sufficient for a decorative film can be obtained. The luster pigment may be used alone or in combination of two or more kinds.

[0056] The colored layer may contain, as other components, as necessary, appropriately selected from the following: a pigment that does not fall under the category of a color pigment or a luster pigment, a dispersant, an antioxidant, an anti-settling agent, an antifoaming agent, a silane coupling agent, an adhesion imparting agent, an anti-algae agent, an anti-fungal agent, a preservative, an insecticide, an antibacterial agent, an antiviral agent, an ultraviolet absorbing agent, a radical scavenger, an antistatic agent, an electrical conductivity imparting agent, and the like.

[0057] The glass transition point of the colored layer is preferably from 40°C to 120°C.

[0058] In this specification, the glass transition point (Tg) of the colored layer is a spectrum peak in a temperature change curve of loss tangent (tan δ) measured at a measurement frequency of 1 Hz using a solid viscoelasticity measuring device based on JIS K7244-4.

[0059] Specifically, the loss modulus and storage modulus of the colored layer are measured at each temperature under the following measurement conditions using a solid viscoelasticity measuring device (e.g., RSA-GII (manufactured by TA Instruments)), the loss tangent is calculated from the loss modulus and storage modulus, a temperature change curve of the loss tangent is created, and the spectral peak value of the loss tangent is read. <Measurement conditions> Temperature range: -50℃~200℃ Heating rate: 5℃ / min Measurement length: 20.0 mm Measurement width: 5.0mm Frequency: 1Hz Distortion: 0.05%

[0060] The colored layer may be one layer or two or more layers.

[0061] The colored layer has a thickness of preferably 0.1 to 40 μm, more preferably 0.5 to 30 μm. When the colored layer is made up of a plurality of layers, the numerical range described here refers to the total thickness of the colored layers.

[0062] The thickness of the colored layer can be appropriately adjusted depending on the application of the decorative film and the type and concentration of the pigment contained in the colored layer. For example, when the colored layer contains a high concentration of a glittering pigment, it is preferable to make the thickness of the colored layer thin so that the average transmittance at a wavelength of 780 to 2000 nm does not fall below 1.0%.

[0063] Examples of coating methods that can be used to produce the colored layer include brush coating, roller coating, trowel coating, spatula coating, flow coater coating, spray coating (e.g., air spray coating, airless spray coating), shower coater coating, and dipping coating.

[0064] When the decorative film of the present invention is composed of a base film layer and a colored layer, an example of the configuration of the decorative film of the present invention is a base film layer / colored layer. In this specification, when the multilayer structure is expressed as, for example, a base film layer / colored layer, it means that the decorative film of the present invention has a multilayer structure in which the base film layer and the colored layer are arranged in this order.

[0065] FIG. 1 is a schematic diagram showing one embodiment of the decorative film of the present invention. The decorative film shown in FIG. 1 includes a base film layer 1 and a colored layer 2 arranged on the base film layer 1. The decorative film in FIG. 1 is a decorative film having a base film layer / colored layer configuration, and can be suitably used to obtain a decorated article by molding the decorative film itself. In addition, although not shown, a primer layer described later may be present between the base film layer 1 and the colored layer 2, and a clear layer described later may be arranged on the colored layer 2.

[0066] The decorative film of the present invention may further include an adhesive layer. In this specification, the adhesive layer may be referred to as (C) adhesive layer. In the present invention, the adhesive layer is a layer composed of an adhesive, and is preferably used when attaching a decorative film to decorate a substrate. The adhesive layer and the adhesive may be referred to as a pressure-sensitive adhesive layer and a pressure-sensitive adhesive, respectively. Examples of the adhesive include a urethane adhesive, an acrylic adhesive, an epoxy adhesive, and a rubber adhesive, and among these, an acrylic adhesive is preferred.

[0067] The thickness of the adhesive layer is preferably 20 to 200 μm.

[0068] The adhesive layer can be formed by applying an adhesive to the surface of the substrate. Since the decorative film of the present invention is applied to the substrate via the adhesive layer, the adhesive layer is located on at least one surface of the decorative film of the present invention.

[0069] When the decorative film of the present invention is composed of a base film layer, a colored layer, and an adhesive layer, examples of the configuration of the decorative film of the present invention include adhesive layer / base film layer / colored layer, base film layer / colored layer / adhesive layer, etc.

[0070] The decorative film of the present invention may further include a clear layer. In this specification, the clear layer may be referred to as a (D) clear layer. From the viewpoint of protecting the colored layer, the clear layer is preferably located on the colored layer in the decorative film of the present invention, and is preferably located on the side of the colored layer where the base film layer is not located, and is also preferably located on the surface of the decorative film.

[0071] When the clear layer is located on the colored layer or the colored layer is located on the clear layer, the multilayer coating film including the colored layer and the clear layer preferably has an average transmittance of 1.0 to 90% at wavelengths of 780 to 2000 nm, more preferably 3.0 to 50%. If the average transmittance at wavelengths of 780 to 2000 nm is below 1.0%, for example, when the decorative film is heated with near infrared rays by an IR heater and attached to a substrate or heated with near infrared rays to form the decorative film, it is difficult for a sufficient amount of near infrared rays to reach the substrate film layer for heating, and it takes time to heat the decorative film to a specific temperature, resulting in reduced productivity. In addition, when forming a colored layer with excellent appearance using a color pigment or a glittering pigment, taking into consideration the near infrared transmittance of the color pigment or the glittering pigment, the average transmittance at wavelengths of 780 to 2000 nm is 90% or less, more preferably 50% or less. Furthermore, when the colored layer has a metallic design containing a glittering pigment, in order to have a good appearance, the average transmittance at wavelengths of 780 to 2000 nm is preferably 50% or less, and more preferably 30% or less.

[0072] In the present invention, the clear layer means a layer having a visible light transmittance of 30% or more, preferably 40% or more, and more preferably 50% or more.

[0073] In this specification, the visible light transmittance means the total light transmittance in the visible region (360 nm to 750 nm), and can be measured in accordance with JIS K 7375:2008.

[0074] The clear layer preferably has an ultraviolet ray transmittance of 30% or less, more preferably 25% or less.

[0075] In this specification, the ultraviolet transmittance means the transmittance of light in the wavelength range of 280 nm to 400 nm, and can be measured using a spectrophotometer (for example, UV-2450 manufactured by Shimadzu Corporation).

[0076] The clear layer usually contains a resin. The amount of resin in the clear layer is preferably 40 to 99.5% by mass, more preferably 50 to 99% by mass. When the clear layer is composed of multiple layers, the numerical range described here refers to the amount of resin in each clear layer.

[0077] Examples of resins that can be used in the clear layer include acrylic resins, silicone resins, acrylic silicone resins, styrene-acrylic copolymer resins, polyester resins, fluororesins, rosin resins, petroleum resins, coumarone resins, phenolic resins, urethane resins, melamine resins, urea resins, epoxy resins, cellulose resins, xylene resins, alkyd resins, aliphatic hydrocarbon resins, butyral resins, maleic acid resins, fumaric acid resins, vinyl resins (vinyl chloride resins, etc.), amine resins, ketimine resins, etc. The resins may be used alone or in combination of two or more.

[0078] The clear layer may contain, as other components, appropriately as necessary, a pigment, a dispersant, an antioxidant, an antisettling agent, an antifoaming agent, a silane coupling agent, an adhesion imparting agent, an anti-algae agent, an anti-fungal agent, a preservative, an insecticide, an antibacterial agent, an antiviral agent, an ultraviolet absorbing agent, a radical scavenger, an antistatic agent, a conductivity imparting agent, and the like.

[0079] The glass transition point of the clear layer is preferably 40° C. to 120° C., and more preferably 50° C. to 110° C. When the glass transition point is 40° C. or higher, the durability of the coating film, such as chemical resistance, and blocking resistance are improved. In addition, when the glass transition point is higher than 120° C., problems may occur in terms of followability when applying the decorative film to a substrate having a complex shape by vacuum forming or the like.

[0080] In this specification, the glass transition point (Tg) of the clear layer is a spectrum peak in a temperature change curve of loss tangent (tan δ) measured at a measurement frequency of 1 Hz using a solid viscoelasticity measuring device based on JIS K7244-4.

[0081] Specifically, the loss modulus and storage modulus of the clear layer are measured at each temperature under the following measurement conditions using a solid viscoelasticity measuring device (e.g., RSA-GII (manufactured by TA Instruments)), the loss tangent is calculated from the loss modulus and storage modulus, a temperature change curve of the loss tangent is created, and the spectral peak value of the loss tangent is read. <Measurement conditions> Temperature range: -50℃~200℃ Heating rate: 5℃ / min Measurement length: 20.0 mm Measurement width: 5.0mm Frequency: 1Hz Distortion: 0.05%

[0082] The clear layer may be one layer or two or more layers.

[0083] The clear layer has a thickness of preferably 5 to 40 μm, more preferably 10 to 30 μm. When the clear layer is made up of a plurality of layers, the numerical range described here refers to the total thickness of the clear layers.

[0084] Examples of coating methods that can be used to produce the clear layer include brush coating, roller coating, trowel coating, spatula coating, flow coater coating, spray coating (e.g., air spray coating, airless spray coating), shower coater coating, and dipping coating.

[0085] When the decorative film of the present invention is composed of a base film layer, a colored layer, and a clear layer, examples of the configuration of the decorative film of the present invention include base film layer / colored layer / clear layer, colored layer / clear layer / base film layer, etc.

[0086] When the decorative film of the present invention is composed of a base film layer, a colored layer, an adhesive layer and a clear layer, examples of the configuration of the decorative film of the present invention include adhesive layer / base film layer / colored layer / clear layer, adhesive layer / colored layer / clear layer / base film layer, clear layer / base film layer / colored layer / adhesive layer, etc.

[0087] FIG. 2 is a schematic diagram showing one embodiment of the decorative film of the present invention. The decorative film shown in FIG. 2 includes a base film layer 1, a colored layer 2 arranged on the base film layer 1, and a clear layer 3 arranged on the colored layer 2, and has an adhesive layer 4 on the surface of the base film layer 1 on which the colored layer 2 is not arranged. The decorative film in FIG. 2 is a decorative film having a structure of an adhesive layer / base film layer / colored layer / clear layer. Here, the clear layer 3 and the adhesive layer 4 do not necessarily have to be present. In addition, although not shown, a primer layer described later may be present between the base film layer 1 and the colored layer 2.

[0088] The decorative film of the present invention may further include a primer layer. In this specification, the primer layer may be referred to as a (E) primer layer.

[0089] In the present invention, the primer layer means a layer that is first provided on the base film layer and does not correspond to a colored layer, an adhesive layer, or a clear layer. From the viewpoint of improving the adhesion between the base film layer and the colored layer, it is preferable that the primer layer is located between the base film layer and the colored layer in the decorative film of the present invention.

[0090] The primer layer preferably has a gel fraction of 80% or more, more preferably 82 to 100%, particularly when the colored layer is a glittering layer containing a glittering pigment. The gel fraction is an index of the degree of resistance of the primer layer to organic solvents. If a glittering layer is formed on a primer layer with a low gel fraction, the paint for forming the glittering layer may be soaked into the primer layer more than expected, which may disturb the orientation of the glittering pigment and make it difficult to impart a desired glittering design. According to a preferred embodiment of the decorative film of the present invention, by using a primer layer with a gel fraction of 80% or more, it is possible to easily achieve both adhesion between the substrate or substrate film layer and the glittering layer and a desired glittering design.

[0091] In this specification, the gel fraction of the primer layer refers to the mass proportion of the primer layer that remains without dissolving when the primer layer in a completely dried and cured state is immersed in an organic solvent. Specifically, when the mass of the primer layer before immersion is M1 and the mass of the primer layer after immersion is M2, the gel fraction of the primer layer can be calculated from the following formula. Gel fraction (%) = M2 / M1 × 100 Here, immersion refers to immersing the primer layer in a mixed solution of toluene and acetone (mass ratio 1:1) in an amount of 100 g per 1 g of primer layer under reflux for 5 hours. The mass of the primer layer after immersion is the mass of the primer layer after drying at 105°C for 30 minutes after immersion.

[0092] The gel fraction of the primer layer can be adjusted by appropriately adjusting the glass transition point (Tg) or hydroxyl value of the resin used in the paint for forming the primer layer and the functional group content of the curing agent, or by using a curing accelerator or a reaction catalyst in the paint for forming the primer layer. For example, a primer layer having a gel fraction of 80% or more can be obtained by using a resin having a Tg of 40 to 120°C, preferably 50 to 100°C, a resin having a hydroxyl value of 25 to 250 mgKOH / g, preferably 50 to 200 mgKOH / g, or a functional group content of the curing agent (e.g., isocyanate group, epoxy group, aziridine group, etc.) of 2 to 10 mass% of the solid content of the paint, preferably 3 to 8 mass%, etc. Regarding the paint for forming the primer layer, the glass transition point (Tg) of the resin means the glass transition temperature calculated by the FOX formula, and the hydroxyl value of the resin is the number of mg of potassium hydroxide required to neutralize the free hydroxyl groups in 1 g of the sample after completely acetylating them with acetic anhydride.

[0093] The primer layer usually contains a resin. The amount of the resin in the primer layer is preferably 30 to 99% by mass, and more preferably 50 to 95% by mass. When the primer layer is composed of multiple layers, the numerical range described here refers to the amount of the resin in each primer layer.

[0094] Examples of resins that can be used in the primer layer include acrylic resins, silicone resins, acrylic silicone resins, styrene-acrylic copolymer resins, polyester resins, fluororesins, rosin resins, petroleum resins, coumarone resins, phenolic resins, urethane resins, melamine resins, urea resins, epoxy resins, cellulose resins, xylene resins, alkyd resins, aliphatic hydrocarbon resins, butyral resins, maleic acid resins, fumaric acid resins, vinyl resins, amine resins, ketimine resins, etc. The resins may be used alone or in combination of two or more.

[0095] The primer layer may contain, as other components, appropriately as necessary, a pigment, a dispersant, an antioxidant, an antisettling agent, an antifoaming agent, a silane coupling agent, an adhesion imparting agent, an anti-algae agent, an anti-fungal agent, a preservative, an insecticide, an antibacterial agent, an antiviral agent, an ultraviolet absorbing agent, a radical scavenger, an antistatic agent, a conductivity imparting agent, and the like.

[0096] The primer layer may be one layer or two or more layers.

[0097] The primer layer preferably has a thickness of 3 to 15 μm. When the primer layer is made up of multiple layers, the numerical range described here refers to the total thickness of the primer layers.

[0098] Examples of coating methods that can be used to produce the primer layer include brush coating, roller coating, trowel coating, spatula coating, flow coater coating, spray coating (e.g., air spray coating, airless spray coating), shower coater coating, and dipping coating.

[0099] When the decorative film of the present invention is composed of a base film layer, a colored layer, and a primer layer, an example of the configuration of the decorative film of the present invention is base film layer / primer layer / colored layer, etc.

[0100] When the decorative film of the present invention is composed of a base film layer, a colored layer, an adhesive layer and a primer layer, examples of the configuration of the decorative film of the present invention include adhesive layer / base film layer / primer layer / colored layer, base film layer / primer layer / colored layer / adhesive layer, etc.

[0101] When the decorative film of the present invention is composed of a base film layer, a colored layer, a clear layer and a primer layer, examples of the configuration of the decorative film of the present invention include base film layer / primer layer / colored layer / clear layer, clear layer / base film layer / primer layer / colored layer, etc.

[0102] When the decorative film of the present invention is composed of a base film layer, a colored layer, an adhesive layer, a clear layer and a primer layer, examples of the configuration of the decorative film of the present invention include adhesive layer / base film layer / primer layer / colored layer / clear layer, clear layer / base film layer / primer layer / colored layer / adhesive layer, etc.

[0103] The decorative film of the present invention has an elongation rate of 30% or more at the temperature when applied to the substrate, more preferably 80% or more, and even more preferably 90% or more. In particular, when the colored layer is a glittering layer containing a glittering pigment, the elongation rate of the decorative film of the present invention is adjusted in this way, and the mass ratio of the glittering pigment to the binder resin is set within the range of 5:100 to 50:100 as described above, so that the occurrence of color unevenness and decoration unevenness can be suppressed even when decorating the substrate or forming the decorative film by vacuum forming or the like. Furthermore, by ensuring the elongation rate of the decorative film of the present invention, it is also possible to suppress the occurrence of cracks and peeling during the molding of the decorative film when applying the decorative film to the substrate. Similarly, it is also possible to suppress the occurrence of cracks and peeling during the molding of the decorative film itself. From these points of view, the appearance after the decorative film is applied to or formed on the substrate is also excellent. In addition, although there is no particular limit on the upper limit of the elongation rate of the decorative film of the present invention, for example, the elongation rate at the temperature when applied to or formed on the substrate is 400% or less.

[0104] When the decorative film of the present invention is applied to or formed on a substrate (more specifically, when the decorative film of the present invention is attached to a substrate or when the decorative film itself is formed), the temperature is, for example, 80° C. to 120° C. Here, if the average value of the transmittance at wavelengths of 780 to 2000 nm of the colored layer or the multilayer coating film including the colored layer and the clear layer is 1.0% or more, a sufficient amount of near infrared rays for heating can easily reach the substrate film layer, and the time required to heat the decorative film to 80° C. to 120° C. is shortened, thereby improving the productivity when attaching the decorative film to a substrate or forming the decorative film. More preferably, the average value of the transmittance at wavelengths of 780 to 2000 nm is 3.0% or more, and even more preferably, the transmittance at a wavelength of 1000 nm is 3.0% or more.

[0105] The means for applying or forming the decorative film of the present invention to a substrate (more specifically, the means for attaching the decorative film of the present invention to a substrate or forming the decorative film itself) is not particularly limited, and examples thereof include vacuum forming, overlay vacuum forming, hand application, blow molding, insert molding, in-mold molding, etc.

[0106] In this specification, the elongation percentage (%) of the decorative film is the elongation percentage of the sample at the yield point when a tensile test is performed on the sample using a tensile tester (e.g., AGS-X (manufactured by SHIMADZU)) under the measurement conditions described below, or, in the case where defects such as cracks or cracks occur on the surface of the decorative film before the yield point is reached, the maximum elongation percentage of the sample at which no defects such as cracks or cracks are visually observed on the surface of the decorative film. <Measurement conditions> Pulling speed: 5mm / min Test temperature: The temperature at which the decorative film is applied or molded onto the substrate (molding temperature) Sample size: 10mm x 30mm (thickness is the thickness of the decorative film applied to the substrate.)

[0107] The elongation of the decorative film can be adjusted by changing the molecular weight, Tg, etc. of the resin contained in each layer constituting the decorative film. For example, if the elongation at the temperature when the decorative film is applied or molded to the substrate is less than 30%, the elongation can be increased by increasing the molecular weight of the resin or decreasing the Tg.

[0108] The base film layer has an elongation rate of 30% or more, and preferably 80% or more, at the temperature when the decorative film is applied to the base material or when the decorative film is molded; the colored layer has an elongation rate of 20% or more, and preferably 80% or more, at the temperature when the decorative film is applied to the base material; and the clear layer has an elongation rate of 20% or more, and preferably 80% or more, at the temperature when the decorative film is applied to the base material or when the decorative film is molded.

[0109] In this specification, the elongation percentage (%) of the base film layer, the colored layer and the clear layer refers to the elongation percentage of the sample at break when a tensile test is performed on the sample using a tensile tester (e.g., AGS-X (manufactured by SHIMADZU)) under the measurement conditions described below. For each layer, prepare a sample of 10 mm x 30 mm (the thickness is the thickness of the layer that constitutes the decorative film). For example, a colored layer can be formed on a polypropylene (PP) substrate, which is a poor adherend, and then peeled off from the PP substrate to prepare a single film. <Measurement conditions> Tensile speed: 5mm / min Test temperature: The temperature at which the decorative film is applied to the substrate (molding temperature)

[0110] Next, a method for producing the decorative film of the present invention will be described.

[0111] The method for producing a decorative film of the present invention includes a step of providing a colored layer on a base film layer.

[0112] One embodiment of the method for producing a decorative film of the present invention includes a method for producing a decorative film that includes a step of applying a paint to a base film layer to produce a colored layer.

[0113] The method for producing the decorative film of the present invention may also include a step of providing a colored layer and an adhesive layer on the base film layer. The order in which the colored layer and the adhesive layer are provided on the base film layer may be arbitrary, but it is preferable to provide the adhesive layer on the surface of the base film layer on which the colored layer is not provided after providing the colored layer on the base film layer.

[0114] In this case, one embodiment of the manufacturing method for the decorative film of the present invention includes a manufacturing method that includes a step of applying paint to the base film layer to prepare a colored layer, and a step of applying adhesive to the surface of the base film layer on the side on which the colored layer is not disposed to prepare an adhesive layer.

[0115] The method for producing the decorative film of the present invention may also include a step of providing a colored layer and a clear layer on the base film layer. The order in which the colored layer and the clear layer are provided on the base film layer may be arbitrary, but it is preferable to arrange the colored layer and the clear layer on the base film layer in this order.

[0116] In this case, one embodiment of the method for manufacturing a decorative film of the present invention includes a step of applying paint to a base film layer to produce a colored layer, and a step of applying paint to the colored layer to produce a clear layer.

[0117] The method for producing the decorative film of the present invention may also include a step of providing a colored layer, a clear layer, and an adhesive layer on the base film layer. The order in which the colored layer, the clear layer, and the adhesive layer are provided on the base film layer may be arbitrary, but it is preferable to provide an adhesive layer on the surface of the base film layer on which the colored layer is not provided after the colored layer and the clear layer are provided on the base film layer in this order.

[0118] In this case, one embodiment of the method for manufacturing a decorative film of the present invention includes a step of applying paint to a base film layer to prepare a colored layer, a step of applying paint to the colored layer to prepare a clear layer, and a step of applying an adhesive to the surface of the base film layer on the side on which the colored layer is not disposed to prepare an adhesive layer.

[0119] The method for producing the decorative film of the present invention may also include a step of providing a colored layer and a primer layer on the base film layer. Here, the order in which the colored layer and the primer layer are provided on the base film layer may be arbitrary, but it is preferable to arrange the primer layer and the colored layer on the base film layer in this order.

[0120] In this case, one embodiment of the method for manufacturing a decorative film of the present invention includes a step of applying paint to a base film layer to produce a primer layer, and a step of applying paint to the primer layer to produce a colored layer.

[0121] The method for producing the decorative film of the present invention may also include a step of providing a colored layer, a primer layer, and an adhesive layer on the base film layer. The order in which the colored layer, primer layer, and adhesive layer are provided on the base film layer may be arbitrary, but it is preferable to provide an adhesive layer on the surface of the base film layer on which the colored layer is not provided after the primer layer and the colored layer are provided in this order on the base film layer.

[0122] In this case, one embodiment of the method for manufacturing a decorative film of the present invention includes a step of applying paint to a base film layer to prepare a primer layer, a step of applying paint to the primer layer to prepare a colored layer, and a step of applying an adhesive to the surface of the base film layer on the side where the primer layer is not located to prepare an adhesive layer.

[0123] The method for producing the decorative film of the present invention may also include a step of providing a colored layer, a primer layer, and a clear layer on the base film layer. The order in which the colored layer, the primer layer, and the clear layer are provided on the base film layer may be arbitrary, but it is preferable to arrange the primer layer, the colored layer, and the clear layer on the base film layer in this order.

[0124] In this case, one embodiment of the method for manufacturing a decorative film of the present invention includes a method for manufacturing a decorative film including a step of applying paint to a base film layer to prepare a primer layer, a step of applying paint to the primer layer to prepare a colored layer, and a step of applying paint to the colored layer to prepare a clear layer.

[0125] The method for producing the decorative film of the present invention may also include a step of providing a colored layer, a primer layer, a clear layer, and an adhesive layer on the base film layer. The order in which the colored layer, primer layer, clear layer, and adhesive layer are provided on the base film layer may be arbitrary, but it is preferable to provide an adhesive layer on the surface of the base film layer on which the colored layer is not provided after the primer layer, colored layer, and clear layer are provided in this order on the base film layer.

[0126] In this case, one embodiment of the method for manufacturing a decorative film of the present invention includes a step of applying paint to a base film layer to prepare a primer layer, a step of applying paint to the primer layer to prepare a colored layer, a step of applying paint to the colored layer to prepare a clear layer, and a step of applying an adhesive to the surface of the base film layer on the side where the primer layer is not located to prepare an adhesive layer. EXAMPLES

[0127] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way.

[0128] [Example of decorative film manufacturing] <Preparation of colored paint> Various aluminum flakes were dispersed in the paint No. 1 described below in the blending ratios shown in Table 1 by a known method to prepare colored coating compositions 1 to 10 for the colored layer of Examples 1 to 11 and Comparative Examples 1 to 7. Similarly, colored coating compositions 11 to 17 for the colored layer of Examples 12 to 16 and Comparative Examples 8 to 12 were prepared using paint No. 2. Similarly, colored coating compositions 18 to 19 for the colored layer of Example 17 and Comparative Example 13 were prepared using paint No. 3.

[0129] <Paint No.1> Cellulose resin A, acrylic resin A, and acrylic resin B were mixed in a solid content mass ratio of cellulose resin A / acrylic resin A / acrylic resin B = 28 / 36 / 36, and an organic solvent was added appropriately and dispersed by a known method to prepare paint No. 1 (solid content: 27.65 mass%). The materials used are as follows. Cellulose resin A (product name: CAB-381-01, Tg: 123°C, weight average molecular weight: 50,000, solid content: 100% by mass, manufactured by Eastman Chemical Japan Co., Ltd.) Acrylic resin solution A (Tg: 80°C, weight average molecular weight: 67,600, solid content: 43% by mass, hydroxyl value: 0 mgKOH / g) Acrylic resin solution B (Tg: 62°C, weight average molecular weight: 48,000, solid content: 45% by mass, hydroxyl value: 3.7 mgKOH / g) <Paint No. 2> An appropriate amount of organic solvent was added to the cellulose resin B and the resin was dissolved by a known method to prepare paint No. 2 (solid content: 0.72% by mass). The materials used are as follows. Cellulose resin solution B (product name: industrial nitrocellulose TR7, solid content: 70% by mass, manufactured by TNC INDUSTRIAL) <Paint No.3> The cellulose resin solution B and the silane coupling agent were mixed in a solid content mass ratio of cellulose resin B / silane coupling agent = 4.7 / 95.3, and an organic solvent was appropriately added to dissolve the mixture by a known method to prepare paint No. 3 (solid content: 1.02 mass%). The materials used are as follows. Cellulose resin solution B (product name: industrial nitrocellulose TR7, solid content: 70% by mass, manufactured by TNC INDUSTRIAL) Silane coupling agent (product name: KBM403, solid content: 97% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0130] Aluminum pigment dispersion A (solid content: 70% by mass, average particle size: 14.2 μm, average aspect ratio: 71, resin-coated aluminum flakes, manufactured by Toyo Aluminum Co., Ltd.) Aluminum pigment dispersion B (solid content: 64% by mass, average particle size: 9 μm, average aspect ratio: 60, resin-coated aluminum flakes, manufactured by Toyo Aluminum Co., Ltd.) Aluminum pigment dispersion C (solid content: 55% by mass, average particle size: 22 μm, average aspect ratio: 50, resin-coated aluminum flakes, manufactured by Toyo Aluminum Co., Ltd.) Aluminum pigment dispersion D (solid content: 10% by mass, average particle size: 11.5 μm, aspect ratio: 300 to 450, evaporated aluminum pigment, Asahi Kasei Chemicals Corporation) Aluminum pigment dispersion E (solid content: 10% by mass, average particle size: 10.5 μm, average aspect ratio: 250, silica-coated vapor-deposited aluminum pigment, manufactured by BYK Japan Co., Ltd.) Aluminum pigment dispersion F (solid content: 10% by mass, average particle size: 7 μm, aspect ratio: 450 to 700, evaporated aluminum pigment, manufactured by Toyo Aluminum Co., Ltd.)

[0131] [Table 1]

[0132] <Preparation of clear paint> Paint No. 4 described below was used as the paint for the clear layer in Examples 10-17 and Comparative Examples 6-13.

[0133] <Paint No.4> Cellulose resin C, acrylic resin C, and acrylic resin D were mixed in a solid content mass ratio of cellulose resin B / acrylic resin C / acrylic resin D = 2 / 49 / 49, and an organic solvent was added appropriately and dispersed by a known method to prepare a paint before mixing with a hardener. Isocyanate hardener A was added to the paint so that the equivalent ratio was 1.0 and mixed to prepare paint No. 4 (solid content: 54.0 mass%). The materials used are as follows. Cellulose resin C (product name: CAB-321-01, Tg: 127°C, weight average molecular weight: 12,000, solid content: 100% by mass, manufactured by Eastman Chemical Japan Co., Ltd.) Acrylic resin solution C (Tg: 88°C, weight average molecular weight: 33,000, solid content: 43% by mass, hydroxyl value: 34 mgKOH / g) Acrylic resin solution D (Tg: 33°C, weight average molecular weight: 80,000, solid content: 49% by mass, hydroxyl value: 0 mgKOH / g) Isocyanate curing agent A (product name: Sumidur N3300, solid content: 100% by mass, NCO group content: 21.8% by mass, manufactured by Sumika Covestro Urethane Co., Ltd.)

[0134] <Preparation of decorative film> The above-mentioned colored paint was applied using an air spray onto the (A) base film layer so as to obtain a (B) colored layer having a thickness when dried (hereinafter referred to as "dry film thickness") shown in Table 2, and then the layer was dried at 80°C for 30 minutes to form the (B) colored layer and produce a decorative film. The decorative film thus produced has a two-layer structure of a base film layer / a colored layer.

[0135] For Examples 10 to 17 and Comparative Examples 6 to 13, the above-mentioned clear paint was applied onto the (B) colored layer using an air spray so as to obtain a (D) clear layer having a dry film thickness shown in Table 2, and then the layer was dried at 80°C for 30 minutes to form the (D) clear layer and form a decorative film. The decorative film produced here has a three-layer structure of a base film layer / a colored layer / a clear layer.

[0136] In addition, for Examples 18 to 19 and Comparative Examples 14 to 15, the (A) base film layer on which the (B) colored layer was formed and the (A) base film layer on which the (B) colored layer and the (D) clear layer were formed were then bonded with Nitto Denko's "No. 5015" as an adhesive layer to the surface of the (A) base film layer on the side on which the (B) colored layer was not formed, to form a decorative film. The decorative films produced here were a decorative film having a three-layer structure of adhesive layer / base film layer / colored layer and a decorative film having a four-layer structure of adhesive layer / base film layer / colored layer / clear layer.

[0137] [Examples of manufacturing a decorated article obtained by molding a decorative film or a decorated article decorated with a decorative film] The pressure was reduced using a vacuum molding device (product name NGF, manufactured by Fuse Vacuum), the decorative film was heated using a near-infrared lamp, and the decorative film was molded and pressed onto a thermoplastic resin molded substrate to obtain a decorative article. Here, the obtained decorative article refers to the molded decorative film itself in Examples 1 to 17 and Comparative Examples 1 to 13, and the decorative film attached to a substrate in Examples 18 to 19 and Comparative Examples 14 to 15.

[0138] The resulting decorative films and decorated articles were evaluated according to the following test methods.

[0139] ●Near infrared transmittance: The spectrum of each coating film was measured using an ultraviolet-visible-near infrared spectrophotometer (for example, V-700 manufactured by JASCO Corporation). Table 2 shows the average transmittance at wavelengths of 780 to 2000 nm and the transmittance at a wavelength of 1000 nm. In Examples 1 to 9 and Comparative Examples 1 to 5, each colored coating composition was applied to a PP substrate so as to have a dry film thickness as shown in Table 2, (B) a colored layer was formed, and the spectrum of the coating film obtained by peeling it off from the PP substrate was measured. In Examples 10 to 17 and Comparative Examples 6 to 13, each colored coating composition was applied to a PP substrate so as to have a dry film thickness as shown in Table 2, (B) a colored layer was formed, (B) a clear coating was applied to the colored layer so as to have a dry film thickness as shown in Table 2, (D) a clear layer was formed, and the spectrum of the multilayer coating film obtained by peeling it off from the PP substrate was measured.

[0140] ● Formability of decorative film The formability of the decorative film means the property that each layer can follow the surface shape of the substrate when the decorative film is applied to the substrate or when the decorative film is molded. If near-infrared rays do not sufficiently reach the substrate film layer, the formability of the decorative film decreases, and defects such as cracks and fractures occur on the surface. The formability of the decorative film was visually evaluated according to the following criteria. The decorative films rated as ⊚ and ◯ had no defects such as cracks or fractures on the surface and had excellent appearance. The substrate used was a curved molded substrate measuring 200 mm in length, 100 mm in width, and 2 mm in thickness. (standard) ◎: When the heating time during molding is 90 seconds, the near-infrared rays reach the base film layer sufficiently and can follow the molded substrate. ○: When the heating time during molding is 140 seconds, the near-infrared rays reach the base film layer sufficiently and can follow the molded substrate. ×: When the heating time during molding was 140 seconds, near-infrared rays did not sufficiently reach the base film layer, and defects such as cracks and cracks were observed on the surface of the decorative film after molding.

[0141] Appearance of the decorated item (curved part after molding) The appearance of the entire surface of the decorated article was visually evaluated according to the following criteria: The base material used was a curved molded substrate measuring 200 mm in length, 100 mm in width, and 2 mm in thickness. (standard) ⊚: The resulting decorated article has a high sense of design. In addition, no unevenness in color or decoration is observed on the decorated article. ◯: The resulting decorated article had no uneven color or decoration, but the design was slightly deteriorated. ×: Color unevenness or decoration unevenness was observed in the resulting decorated article.

[0142] Comparative Example 1 (A) ABS film (acrylonitrile-butadiene-styrene copolymer resin film) was used as the base film layer. From paint No. 1, a colored paint composition 1 was prepared. A decorative film was produced according to the above <Production of Decorative Film>. (B) The dry thickness of the colored layer was 15 μm, and the thickness of the decorative film was 1015 μm. Also, a decorated article was produced according to the above-mentioned "Production example of a decorated article obtained by molding a decorative film, or a decorated article decorated with a decorative film". The heating temperature condition of the decorative film was 140°C. The above evaluations were carried out, and the results are shown in Table 1.

[0143] (Examples 1 to 5, Comparative Examples 2 to 3) Colored coating compositions 2 to 8 were prepared by mixing aluminum pigment A with coating No. 1 in the ratios shown in Table 1. Except for the above, the same procedure as in Comparative Example 1 was followed to obtain decorated articles. The above evaluations were carried out, and the results are shown in Table 2.

[0144] (Examples 6 to 7) Colored coating compositions 9 and 10 were prepared by changing the aluminum pigment A in colored coating composition 5 to aluminum pigment B or aluminum pigment C. Otherwise, the same procedure as in Comparative Example 1 was repeated to obtain decorated articles. The above evaluations were carried out, and the results are shown in Table 2.

[0145] (Example 8, Comparative Example 4) Colored coating compositions 7 and 8 were prepared, and decorative films were produced so that the dry thickness of the (B) colored layer was 10 μm. Otherwise, the same procedure as in Comparative Example 1 was repeated to obtain decorated articles. The above evaluations were carried out, and the results are shown in Table 2.

[0146] (Example 9, Comparative Example 5) A colored coating composition 5 was prepared, and a decorative film was produced so that the dry thickness of the (B) colored layer was 30 μm or 50 μm. Otherwise, a decorated article was obtained in the same manner as in Comparative Example 1. The above evaluations were carried out, and the results are shown in Table 2.

[0147] (Examples 10 to 11, Comparative Examples 6 to 7) Colored coating compositions 1, 2, 5, and 7 were prepared, and (B) colored layer was prepared so that the dry film thickness was 15 μm. In addition, paint No. 4 was used as a paint for the clear layer, and (D) clear layer was provided as a protective layer on the (B) colored layer of the above-mentioned decorated article so that the dry film thickness was 20 μm. Otherwise, a decorated article was obtained in the same manner as in Example 1. The above evaluations were carried out, and the results are shown in Table 2.

[0148] (Examples 12 to 13, Comparative Examples 8 to 10) Paint No. 2 was mixed with aluminum pigment D in the ratios shown in Table 1 to prepare colored paint compositions 11 to 15, and (B) colored layer was prepared so that the dry film thickness was 5 μm. In addition, paint No. 4 was used as a paint for the clear layer, and (D) clear layer was provided as a protective layer on the (B) colored layer of the above-mentioned decorated article so that the dry film thickness was 30 μm. Otherwise, a decorated article was obtained in the same manner as in Comparative Example 1. The above evaluations were carried out, and the results are shown in Table 2.

[0149] (Examples 14 to 15, Comparative Example 11) Colored coating compositions 13 to 15 were prepared, and (B) colored layer was produced so that the dry film thickness was 1 μm. In addition, paint No. 4 was used as a paint for the clear layer, and (D) clear layer was provided as a protective layer on the (B) colored layer of the above-mentioned decorated article so that the dry film thickness was 30 μm. Otherwise, a decorated article was obtained in the same manner as in Comparative Example 1. The above evaluations were carried out, and the results are shown in Table 2.

[0150] (Example 16, Comparative Example 12) Paint No. 2 was mixed with aluminum pigment E in the ratios shown in Table 1 to prepare colored paint compositions 16 and 17, and (B) colored layer was prepared so that the dry film thickness was 1 μm. In addition, paint No. 4 was used as a paint for the clear layer, and (D) clear layer was provided as a protective layer on the (B) colored layer of the above decorated article so that the dry film thickness was 30 μm. Otherwise, a decorated article was obtained in the same manner as in Comparative Example 1. The above evaluations were carried out, and the results are shown in Table 2.

[0151] (Example 17, Comparative Example 13) Paint No. 3 was mixed with aluminum pigment F in the ratios shown in Table 1 to prepare colored paint compositions 18 and 19, and (B) colored layer was prepared so that the dry film thickness was 0.2 μm. In addition, paint No. 4 was used as a paint for the clear layer, and (D) clear layer was provided as a protective layer on the (B) colored layer of the above decorated article so that the dry film thickness was 30 μm. Otherwise, a decorated article was obtained in the same manner as in Comparative Example 1. The above evaluations were carried out, and the results are shown in Table 2.

[0152] [Table 2]

[0153] (Example 18) For the decorative film produced in Example 4, an acrylic film (manufactured by Mitsubishi Chemical Corporation, film thickness 50 μm) was used instead of the ABS film as the (A) base film layer, and further, Nitto Denko's "No. 5015" was attached as an adhesive layer to the surface of the (A) base film layer on the side on which the (B) colored layer was not arranged, to produce a decorative film. The thickness of the decorative film was 185 μm. In addition, a decorative article was produced according to the above [Manufacturing example of a decorated article decorated with a decorative film or obtained by molding a decorative film]. The heating temperature condition of the decorative film was 140 ° C. As a result of carrying out the above-mentioned evaluations, the same results as those in Example 4 were obtained.

[0154] Comparative Example 14 For the decorative film produced in Comparative Example 1, an acrylic film (manufactured by Mitsubishi Chemical Corporation, film thickness 50 μm) was used instead of the ABS film as the (A) base film layer, and further, Nitto Denko's "No. 5015" was attached as an adhesive layer to the surface of the (A) base film layer on the side on which the (B) colored layer was not arranged, to produce a decorative film. The thickness of the decorative film was 185 μm. In addition, a decorative article was produced according to the above [Manufacturing example of a decorated article decorated with a decorative film or obtained by molding a decorative film]. The heating temperature condition of the decorative film was 140 ° C. As a result of carrying out the above-mentioned evaluations, the same results as those in Comparative Example 1 were obtained.

[0155] (Example 19) For the decorative film produced in Example 11, an acrylic film (manufactured by Mitsubishi Chemical Corporation, film thickness 50 μm) was used instead of the ABS film as the (A) base film layer, and further, Nitto Denko's "No. 5015" was attached as an adhesive layer to the surface of the (A) base film layer on the side where the (B) colored layer and (D) clear layer were not arranged, to produce a decorative film. The thickness of the decorative film was 205 μm. In addition, a decorative article was produced according to the above [Manufacturing example of a decorated article decorated with a decorative film or obtained by molding a decorative film]. The heating temperature condition of the decorative film was 140 ° C. As a result of carrying out the above-mentioned evaluations, the same results as those in Example 11 were obtained.

[0156] Comparative Example 15 For the decorative film produced in Comparative Example 7, an acrylic film (manufactured by Mitsubishi Chemical Corporation, film thickness 50 μm) was used instead of the ABS film as the (A) base film layer, and further, Nitto Denko's "No. 5015" was attached as an adhesive layer to the surface of the (A) base film layer on the side where the (B) colored layer and (D) clear layer were not arranged, to produce a decorative film. The thickness of the decorative film was 205 μm. In addition, a decorative article was produced according to the above [Manufacturing example of a decorated article decorated with a decorative film or obtained by molding a decorative film]. The heating temperature condition of the decorative film was 140 ° C. As a result of carrying out the above-mentioned evaluations, the same results as those of Comparative Example 7 were obtained.

Claims

1. A decorative film having at least (A) a base film layer and (B) a colored layer, The (B) colored layer contains at least a binder resin and a color pigment and / or a luster pigment, The decorative film is also characterized in that the average transmittance in the wavelength range of 780 to 2000 nm is 1.0 to 90%.

2. The (B) colored layer contains a glittering pigment, 2. The decorative film according to claim 1, wherein a solid content mass ratio of the glittering pigment to the binder resin is 5:100 to 50:

100.

3. 3. The decorative film according to claim 2, wherein the luster pigment comprises a vapor-deposited aluminum pigment and / or a resin-coated metal pigment.

4. A decorative film having at least (A) a base film layer, (B) a colored layer, and (D) a clear layer, A decorative film characterized in that the multilayer coating film including the (B) colored layer and the (D) clear layer has an average transmittance of 1.0 to 90% at wavelengths of 780 to 2000 nm.

5. A method for producing a decorative film having at least (A) a base film layer and (B) a colored layer, The method includes the step of providing a colored layer (B) on a base film layer (A), The (B) colored layer contains at least a binder resin and a color pigment and / or a luster pigment, The method for producing a decorative film is characterized in that the average transmittance at wavelengths of 780 to 2000 nm is 1.0 to 90%.

6. A method for producing a decorative film having at least (A) a base film layer, (B) a colored layer, and (D) a clear layer, A step of providing a colored layer (B) on a base film layer (A); (D) providing a clear layer on (B) the colored layer; The (B) colored layer contains at least a binder resin and a color pigment and / or a luster pigment, A method for producing a decorative film, characterized in that the multilayer coating film including the (B) colored layer and the (D) clear layer has an average transmittance of 1.0 to 90% at wavelengths of 780 to 2000 nm.

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