Photoluminescent resin layer, metallic decorative laminate, metallic article, and method for producing metallic decorative laminate

Abstract

The present invention provides: a photoluminescent resin layer which is used in the field of imparting a metallic design to an article, has a metallic design by containing one or more hydrophilic photoluminescent materials and a resin component that contains one or more polyurethane resins, reduces environmental load, and is easy to produce; a metallic decorative laminate which comprises the photoluminescent resin layer; a metallic article which comprises the photoluminescent resin layer; and a method for producing a metallic decorative laminate.

Description

Glossy resin layer, metallic decorative laminate, metallic article, and method for producing metallic decorative laminate

[0001] The present invention relates to a glossy resin layer, a metallic decorative laminate, a metallic article, and a method for producing a metallic decorative laminate.

[0002] In order to improve the designability of a molded body, a metallic luster (hereinafter also referred to as a metallic design) has been imparted to the surface of the molded body. In order to impart a metallic luster, metal plating has been performed for a long time (Patent Document 1).

[0003] As a method of imparting a metallic design to an article, a method using a metallic decorative film having a metal vapor deposition layer is also known (Patent Document 2). Since the metallic decorative film having a metal vapor deposition layer has a metal layer in its structure, external light is reflected by the metal layer (hereinafter referred to as metal layer reflected light) and is recognized as a metallic design by an observer.

[0004] As another method, an electromagnetic wave transmissive glossy coating resin product having a glossy coating film using a flat glossy material made of aluminum is also known (Patent Document 3).

[0005] JP-A-2002-241948 JP-A-2008-055688 JP-A-2010-030075

[0006] An object of the present invention is to provide a glossy resin layer, a metallic decorative laminate, a metallic article, and a method for producing a metallic decorative laminate that exhibit an excellent metallic design, reduce environmental load, and are easy to manufacture.

[0007] The present inventors have conducted diligent studies to solve the above problems and have provided the following [1] to [5]: [1] A glossy resin layer containing a resin component containing one or more polyurethane resins and one or more hydrophilic glossy materials. [2] A metallic decorative laminate comprising the glossy resin layer described in [1]. [3] A metallic article comprising the glossy resin layer described in [1]. [4] A metallic article comprising the metallic decorative laminate described in [2]. [5] A method for producing the metallic decorative laminate described in [2], comprising, in this order, applying a coating liquid containing a resin component containing one or more polyurethane resins and one or more hydrophilic glossy materials to a release layer, and heating it.

[0008] According to the present invention, it is possible to provide a glossy resin layer, a metallic decorative laminate, a metallic article, and a method for manufacturing a metallic decorative laminate that exhibits an excellent metallic design, reduces environmental impact, and is easy to manufacture.

[0009] This is a schematic diagram showing an example of a cross-section of a metallic decorative laminate containing a glossy resin layer of this embodiment. This is a schematic diagram showing the relationship between the glossy resin layer of this embodiment and ambient light and irradiated light. This is a schematic diagram of the hydrophilic glossy material in the glossy resin layer. This is a schematic diagram to explain the behavior of the hydrophilic glossy material that causes matting.

[0010] Patent Document 1 describes an invention relating to a plated synthetic resin component for vehicles that exhibits a metallic luster when plated. However, metal plating has problems such as a complex process and high manufacturing costs, as well as the generation of wastewater which puts a burden on the environment. In addition, it was difficult to apply a uniform and beautiful plating film when the surface of the molded body had an uneven shape.

[0011] Furthermore, when used in areas such as the front grille of an automobile, it may be necessary to install a light source on the vehicle body side of the front grille and allow the illuminated light to pass through to create an aesthetically pleasing design. Since metal plating does not transmit visible light, it cannot be used in applications that require such transmitted light.

[0012] Furthermore, sensors such as millimeter-wave radar are used to detect obstacles around vehicles such as automobiles. Millimeter-wave radar is a device that measures the distance to an obstacle by irradiating it with radio waves with a wavelength of 1 to 10 mm, measuring the time it takes for the waves to reflect back from the obstacle, and so on. Millimeter-wave radar is less affected by weather conditions such as rain and fog, and can detect obstacles at a distance, so it has been introduced by many automobile manufacturers. For this automobile millimeter-wave radar, the millimeter-wave band in the 76 to 77 GHz range is used. The main unit of this millimeter-wave radar is mounted, for example, behind the bumpers or emblems at the front and rear of the automobile body, and the millimeter waves are emitted from the main unit, pass through the bumpers or emblems, and are reflected by the obstacles. Typically, car bumpers and emblems are manufactured by molding resins such as polypropylene or polycarbonate and then painting them. However, in the case of cars with metallic-looking paint on the body, a metallic appearance is required for the bumper to maintain design consistency, and furthermore, millimeter-wave transmittance (hereinafter referred to as "millimeter-wave transmittance") is also required.

[0013] In the case of metal plating, millimeter waves cannot be transmitted, so it cannot be used for the metallic decorative components of bumpers and emblems as described above.

[0014] For this reason, decorative films having a metal vapor deposition layer (Patent Document 2) and decorative films having a glossy coating using a flat, glossy material made of aluminum (Patent Document 3) have been developed, but there is a need for improvement in their moldability and other properties. Furthermore, there has been a strong demand for the development of a metallic-looking decorative laminate that satisfies the requirements for scratch resistance.

[0015] In contrast, the glossy resin layer and metallic decorative laminate of the present disclosure exhibit an excellent metallic design, reduce environmental impact compared to plating used for similar metallic decorations, are easy to manufacture, have excellent moldability, and exhibit excellent visible light transmittance, millimeter wave transmittance, and scratch resistance.

[0016] The term "easy to manufacture" can be evaluated by the ease with which a coating solution containing one or more polyurethane-based resin components and one or more hydrophilic glossy materials can be prepared when manufacturing the glossy resin layer and the metallic decorative laminate, and by the shelf life of the obtained coating solution. These evaluations can be performed, for example, by the method described in the examples.

[0017] The following describes the glossy resin layer, metallic decorative laminate, metallic article, and method for manufacturing the metallic decorative laminate according to the present invention. However, the present invention is not limited to the following examples.

[0018] In this disclosure, the thickness direction 100 refers to the stacking direction of the metallic decorative laminate, as shown in Figure 1, and the width direction 110 refers to a direction different from the thickness direction, and is perpendicular to the longitudinal direction 120 of the metallic decorative laminate. For example, when the metallic decorative laminate described later is manufactured by roll-to-roll, the longitudinal direction 120 corresponds to the flow direction (MD: machine direction), and the width direction 110 corresponds to the TD (transverse direction) perpendicular to the MD.

[0019] The embodiments of this disclosure (hereinafter sometimes referred to as "these embodiments") will be described below. In this disclosure, the numerical values ​​related to "greater than or equal to," "less than or equal to," "~," etc., in the description of numerical ranges can be any combination of values.

[0020] Furthermore, any provision deemed preferable can be adopted at will. That is, one provision deemed preferable can be adopted in combination with one or more other provisions deemed preferable. A combination of preferred provisions is considered even more preferable.

[0021] [Glossy Resin Layer] The glossy resin layer of this embodiment is a layer that gives metallic luster to the metallic decorative laminate, and is required to be a glossy resin layer containing a resin component containing one or more polyurethane resins and one or more hydrophilic glossy materials.

[0022] The glossy resin layer may contain only the polyurethane resin as the resin component, but may also contain one or more of the thermoplastic resins described later, or other components described later.

[0023] In other words, the glossy resin layer may contain only two types of resin components: the polyurethane resin and the hydrophilic glossy material; it may contain only three types of resin components: the polyurethane resin, the hydrophilic glossy material and the other components described later; it may contain only three types of resin components: the urethane resin, the thermoplastic resin and the hydrophilic glossy material; or it may contain the polyurethane resin, the hydrophilic glossy material, the thermoplastic resin and the other components described later.

[0024] As will be described in detail later, it is preferable that the metallic-looking article is laminated in the order of article, base layer, adhesive layer, and glossy resin layer. In particular, it is preferable that the glossy resin layer be the outermost surface of the metallic-looking article, and since the glossy resin layer comes into contact with the atmosphere, solvents, chemicals, etc., its scratch resistance, chemical resistance, and weather resistance play a major role in improving the scratch resistance, chemical resistance, and weather resistance of the metallic-looking article.

[0025] The glossy resin layer contains a polyurethane resin and a hydrophilic glossy material, which allows the hydrophilic glossy material to be dispersed uniformly or nearly uniformly, resulting in an excellent metallic appearance. In particular, as shown in Figure 3, the hydrophilic glossy material described later is such that the thickness direction 210 of the hydrophilic glossy material is perpendicular to or approximately perpendicular to the surface 21 on the side of the glossy resin layer opposite the article and the surface 22 on the article side of the glossy resin layer, and the particle diameter direction 220 of the hydrophilic glossy material is parallel to or approximately parallel. This is preferable because it increases the reflected light 6 from the glossy resin layer, resulting in an excellent metallic appearance. The aforementioned approximately horizontal and approximately vertical means that the deviation from horizontal or vertical is approximately 20° or less. If the deviation of the particle diameter direction 220 of the hydrophilic glossy material from the parallel becomes large, the matte appearance becomes stronger and the metallic appearance decreases.

[0026] Furthermore, as described above, when the hydrophilic glossy material is oriented, the scratch resistance of metallic articles is improved, and chemical resistance and weather resistance can be enhanced. Even those skilled in the art would not expect that combining polyurethane resin and hydrophilic glossy material would improve these properties. However, it has been found that the configuration in this embodiment significantly improves scratch resistance, chemical resistance, and weather resistance. The reason for this is not entirely clear, but it is thought that because the hydrophilic glossy material is hydrophilic, it disperses easily in the polyurethane resin, resulting in a uniform dispersion of the hydrophilic glossy material within the glossy resin layer.

[0027] The thickness of the glossy resin layer is preferably 5 μm or more, more preferably 8 μm or more, even more preferably 10 μm or more, and even more preferably 13 μm or more in order to improve the metallic appearance, scratch resistance, chemical resistance, and weather resistance. In order to improve moldability, visible light transmittance, and millimeter wave transmittance, the thickness is preferably 100 μm or less, more preferably 60 μm or less, even more preferably 40 μm or less, and even more preferably 35 μm or less.

[0028] In order to balance metallic appearance, scratch resistance, chemical resistance, weather resistance, millimeter-wave transmittance, and moldability, the particle size is preferably 5 μm to 100 μm, more preferably 8 μm to 60 μm, even more preferably 10 μm to 40 μm, and even more preferably 13 μm to 35 μm.

[0029] To improve metallic appearance, scratch resistance, chemical resistance, and weather resistance, the amount of the hydrophilic glossy material in the glossy resin layer is preferably 0.10 parts by mass or more, more preferably 0.30 parts by mass or more, even more preferably 0.50 parts by mass or more, and even more preferably 0.80 parts by mass or more, based on 100 parts by mass of the total resin components. To improve millimeter-wave transmittance and moldability, the amount is preferably 20.00 parts by mass or less, more preferably 10.00 parts by mass or less, even more preferably 5.00 parts by mass or less, and even more preferably 3.00 parts by mass or less.

[0030] In order to balance metallic appearance, scratch resistance, chemical resistance, weather resistance, millimeter-wave transmittance, and moldability, the hydrophilic glossy material in the glossy resin layer is preferably in an amount of 0.10 parts by mass or more and 20.00 parts by mass or less, more preferably 0.30 parts by mass or more and 10.00 parts by mass or less, even more preferably 0.50 parts by mass or more and 5.00 parts by mass or less, and even more preferably 0.80 parts by mass or more and 3.00 parts by mass or less, per 100 parts by mass of the total resin components.

[0031] In this embodiment, the total light transmittance of the luminous resin layer is preferably 10% or more for ambient light 5 in Figure 2, and the total light transmittance of the irradiated light 8 is preferably 10% or more for ambient light 5. The total light transmittance is preferably 1% to 60%, more preferably 5% to 50%, even more preferably 7% to 45%, even more preferably 8% to 40%, and particularly preferably 10% to 35%.

[0032] The millimeter-wave transmittance of the glossy resin layer in this embodiment can be evaluated by its millimeter-wave transmittance, and can be appropriately adjusted to match the millimeter-wave transmittance required for the metallic decorative laminate containing it.

[0033] The glossy resin layer may, if necessary, have various patterns applied to its surface by embossing or other processes, or a matte finish may be given by creating fine irregularities. Alternatively, a hairline finish may be applied to give it a hairline-like design.

[0034] <Resin Components> The glossy resin layer requires a resin component containing one or more polyurethane resins as described above, and the resin component may also contain other components as described below. These may be a mixture (polymer alloy) or reactants, but a mixture (polymer alloy) is more preferable in order to improve the dispersibility of the hydrophilic glossy material in the glossy resin layer.

[0035] Details of the polyurethane resin will be described later, but one type of polyurethane resin may be used, or two or more types may be used in combination. Using only one type is preferable because a uniform, glossy resin layer can be easily produced, while using two or more types is preferable because the physical properties of the resin components, such as the melting point, can be easily adjusted.

[0036] When the total amount of resin components contained in the glossy resin layer is 100 parts by mass, the total amount of polyurethane resin is preferably 80.00 parts by mass or more, more preferably 90.00 parts by mass or more, even more preferably 95.00 parts by mass or more, and even more preferably 97.00 parts by mass or more. The upper limit is not particularly limited, but it is preferably substantially 100 parts by mass. Substantially means excluding impurities that have been unintentionally included.

[0037] The resin component contained in the glossy resin layer may also contain other components besides the polyurethane resin. Details of the other components will be described later. In this disclosure, the resin component refers to any component other than the hydrophilic glossy material contained in the glossy resin layer.

[0038] When the total amount of the resin components contained in the glossy resin layer is 100 parts by mass, the content of the other components is preferably 1.00 parts by mass or more and 50.00 parts by mass or less, more preferably 3.00 parts by mass or more and 45.00 parts by mass or less, even more preferably 5.00 parts by mass or more and 25.00 parts by mass or less, and even more preferably 6.00 parts by mass or more and 20.00 parts by mass or less.

[0039] <Polyurethane resin>When used together with the hydrophilic brightening material, the polyurethane resin has excellent metallic design, scratch resistance, chemical resistance, weather resistance, millimeter-wave permeability, and moldability.

[0040] The brightening resin layer is preferably the outermost layer when the article has a metallic appearance. When the polyurethane resin is formed into a sheet by itself, the total light transmittance is preferably 85% or more, more preferably 88% or more, and the upper limit is not particularly limited, but is generally about 90% in order to exhibit metallic design.

[0041] The polyurethane resin is preferably a polycarbonate-based polyurethane resin and is preferably classified as so-called water-based urethane.

[0042] In order to improve metallic design, scratch resistance, chemical resistance, and weather resistance, the hydrophilic brightening material in the brightening resin layer is preferably 0.10 parts by mass or more, more preferably 0.30 parts by mass or more, further preferably for 100 parts by mass of the total polyurethane resin contained in the resin component. 0.50 parts by mass or more, even more preferably 0.80 parts by mass or more. In order to improve millimeter-wave permeability and moldability, it is preferably 20.00 parts by mass or less, more preferably 10.00 parts by mass or less, further preferably 5.00 parts by mass or less, and even more preferably 3.00 parts by mass or less.

[0043] In order to balance metallic design, scratch resistance, chemical resistance, weather resistance, millimeter-wave permeability, and moldability, the hydrophilic brightening material in the brightening resin layer is preferably 0.10 parts by mass or more and 20.00 parts by mass or less, more preferably 0.30 parts by mass or more and 10.00 parts by mass or less, and for 100 parts by mass of the total polyurethane resin contained in the resin component. Further preferably 0.50 parts by mass or more and 5.00 parts by mass or less, even more preferably 0.80 parts by mass or more and 3.00 parts by mass or less.

[0044] <<Polycarbonate-based polyurethane resin>>The polycarbonate-based polyurethane is a reaction product of a polycarbonate-based polyol and a polyisocyanate compound, and is a resin having a carbonate group as a main skeleton. The polycarbonate exhibits flame retardancy, and the polyurethane exhibits hardness.

[0045] The polycarbonate-based polyurethane resin is preferably a thermosetting polycarbonate-based polyurethane and a cured product containing carbodiimide, and more preferably further contains a silicone-based surfactant.

[0046] (Thermosetting polycarbonate-based polyurethane) It is a polyurethane that polymerizes and cures by heating. For example, a solvent of a thermosetting polycarbonate-based polyurethane dispersion volatilizes, and a dry cured product obtained by further polymerizing and curing by heating can be mentioned.

[0047] (Carbodiimide) It is preferable to contain carbodiimide in the polycarbonate-based polyurethane resin because the weather resistance of the polycarbonate-based polyurethane resin can be improved.

[0048] Further, by including carbodiimide, the chemical resistance of the polycarbonate-based polyurethane resin can be improved.

[0049] As the carbodiimide, it is preferable to adopt one that is compatible with the thermosetting polycarbonate-based polyurethane. By using a carbodiimide that is compatible with both resins, the total light transmittance of the metal-like decorative laminate is improved, which is preferable. As such a compatible carbodiimide, for example, a polycarbodiimide having a carbodiimide group in the molecule can be used.

[0050] When a mixture of a thermosetting polycarbonate-based polyurethane and carbodiimide dries and cures to form the surface layer, the metal-like decorative laminate will have at least two of designability, scratch resistance, weather resistance, millimeter wave transmittance, and moldability being excellent.

[0051] (Mass ratio of polyurethane to carbodiimide) If the amount of carbodiimide is too small, the effect of improving chemical resistance such as alkali resistance may not be achieved, and if the amount of carbodiimide is too large, it may inhibit the properties of polyurethane and reduce chemical resistance such as alkali resistance. From the above viewpoint, it is preferable that the amount of carbodiimide be 3.00 parts by mass or more and 9.50 parts by mass or less, and more preferably 4.00 parts by mass or more and 9.00 parts by mass or less, per 100 parts by mass of the total resin components of the thermosetting polycarbonate polyurethane.

[0052] <Hydrophilic Luminous Material> The hydrophilic luminous material is dispersed in the luminous resin layer to reflect ambient light (incident light) and impart a metallic luster to the luminous resin layer. For this reason, it is not particularly limited as long as it is included to bring out the design of the metallic decorative laminate, and may be an inorganic pigment or an organic pigment, and may be a natural material or a synthetic material, but an inorganic pigment is preferable in order to improve the reflection performance of ambient light.

[0053] The aforementioned hydrophilic glossy material refers to a glossy material that has undergone hydrophilic treatment, and its surface is coated. This coating may be made of an organic substance such as silicone, or an inorganic substance such as silica gel or alumina, but it must be hydrophilic. The hydrophilic treatment is preferably a silica film, and the silica film may be further modified with phosphorus atoms, molybdenum atoms, polysilicate, aryl group-containing silane compounds, silane coupling agents, or organosilica sol. By performing the hydrophilic treatment, the affinity for water and alcohol is improved, making it easier to disperse in the polyurethane resin. This differs from hydrophobic treatment, as it has polar groups such as hydroxyl groups and carbonyloxy groups on its surface.

[0054] The hydrophilic luminous material preferably contains one or more materials selected from flaky or flake metals, flaky or flake metal alloys, flaky or flake metal oxides, flaky or flake mica, glass flakes, and film pulverized materials.

[0055] The hydrophilic glossy material can be any material that exhibits glossiness when included in the resin composition, but to improve ease of availability and design, the hydrophilic glossy material preferably contains at least one material selected from flaky or flake metal, flaky or flake metal alloy, flaky or flake metal oxide, flaky or flake mica, glass flakes, and film pulverized material, more preferably flaky or flake metal, flaky or flake mica, and even more preferably flaky or flake metal.

[0056] The aforementioned flaky or scale-like metal is a particle formed by flaking metal powder. While any metal commonly used for flaky or scale-like metals is preferable, aluminum, iron, copper, nickel, zinc, gold, silver, oxides of these metals, and alloys containing these metals are more preferable. Examples of flaky or scale-like metals include aluminum flakes, stainless steel flakes, copper flakes, and nickel flakes. To obtain a metallic decorative laminate with excellent metallic design, the flaky or scale-like metal is preferably aluminum or an alloy flake, with aluminum flakes being more preferable.

[0057] Examples of flaky or scale-like mica include white pearl pigments, interference pearl pigments, and colored pearl pigments.

[0058] The aforementioned white pearl pigment is made by covering a flaky matrix such as mica, aluminum, or glass with a coating layer made of a colorless, high refractive index material such as titanium dioxide, and the thickness of the coating layer is preferably about 0.10 μm to 0.15 μm.

[0059] The interference pearl pigment has a coating layer made of a colorless, high refractive index material such as titanium dioxide, and the thickness of the coating layer is preferably greater than 0.15 μm.

[0060] Preferably, the hydrophilic luminous material is uniformly dispersed in the resin component within the luminous resin layer 20 in Figure 3, and oriented such that the thickness direction 210 of the hydrophilic luminous material is substantially parallel to the thickness direction 100. Although Figure 3 schematically depicts the hydrophilic luminous material as a disc, it is not limited to this. The longest length in the planar direction (particle diameter direction 220 of the hydrophilic luminous material) of the hydrophilic luminous material 200 is defined as the particle diameter 221 of the hydrophilic luminous material, and the average thickness in the thickness direction perpendicular to the planar direction is defined as the thickness 211 of the hydrophilic luminous material. These are average values ​​measured under an optical microscope after randomly sampling 20 pieces of the hydrophilic luminous material. The particle diameter 221 of the hydrophilic luminous material is the volume average particle diameter (D) as described in the examples. ５０ ) can be used as a substitute. Particle size 221 (D) of hydrophilic luminous material ５０ For ease of availability and to achieve a metallic appearance, the particle size (D) is preferably 1.0 μm or larger, more preferably 2.0 μm or larger, even more preferably 3.0 μm or larger, and even more preferably 4.0 μm or larger. To improve transmitted light, improve millimeter-wave transmittance, and improve chemical resistance and weather resistance, the particle size is preferably 50.0 μm or smaller, more preferably 30.0 μm or smaller, even more preferably 20.0 μm or smaller, and even more preferably 18.0 μm or smaller. To balance these properties, the particle size is preferably 1.0 μm or larger and 50.0 μm or smaller, more preferably 2.0 μm or larger and 30.0 μm or smaller, even more preferably 3.0 μm or larger and 20.0 μm or smaller, and even more preferably 4.0 μm or larger and 18.0 μm or smaller. ５０ ) can be measured by standard methods.

[0061] Particle size 221 (D) of hydrophilic luminous material ５０The ratio of the particle size to the thickness 211 of the hydrophilic glossy material (=particle size / thickness) is preferably 3 or more and 200 or less, more preferably 5 or more and 150 or less, even more preferably 8 or more and 120 or less, and even more preferably 10 or more and 100 or less.

[0062] <<Other Ingredients>> As other ingredients, if necessary, anti-settling agents, crosslinking agents for aqueous resins, nucleating agents, dyes, ultraviolet absorbers, antioxidants, antistatic agents, leveling agents, and defoaming agents may be used.

[0063] When the total amount of polyurethane resin contained in the resin component in the glossy resin layer is 100 parts by mass, the content of the other components is preferably 1.00 parts by mass or more and 50.00 parts by mass or less, more preferably 3.00 parts by mass or more and 45.00 parts by mass or less, even more preferably 5.00 parts by mass or more and 25.00 parts by mass or less, and even more preferably 6.00 parts by mass or more and 20.00 parts by mass or less.

[0064] Commonly used compounds can be used as UV absorbers, antioxidants, antistatic agents, leveling agents, and defoaming agents. Benzotriazole compounds are preferred as the UV absorbers. Silicone surfactants are preferred as the leveling agents.

[0065] (Settling inhibitor) The hydrophilic, glossy material has the property of being easily dispersed in the polyurethane resin, but further addition of a settling inhibitor is preferable as it allows for even more uniform dispersion.

[0066] The aforementioned settling inhibitor is preferably an acrylic-based settling inhibitor such as VISCOTEX46 manufactured by Arkema Corporation or Borchi Gen L75N manufactured by Matsuo Sangyo Co., Ltd., or a polyamide-based rheology control agent for water-based paints such as AQH-810 manufactured by Kusumoto Kasei Co., Ltd., and more preferably a polyamide-based rheology control agent for water-based paints. When the total amount of urethane resin contained in the glossy resin layer is 100 parts by mass, the total content of the settling inhibitor is preferably 1.00 parts by mass or more and 25.00 parts by mass or less, more preferably 2.00 parts by mass or more and 20.00 parts by mass or less, even more preferably 3.00 parts by mass or more and 18.00 parts by mass or less, and even more preferably 5.00 parts by mass or more and 17.00 parts by mass or less.

[0067] (Crosslinking agent for aqueous resins) The above-mentioned crosslinking agent for aqueous resins is used to crosslink polyurethane resins and preferably reacts with hydroxyl groups present in polyurethane. In order not to affect the properties when present in polyurethane resin, it is preferable that it has a carbodiimide group in its structure, and is preferably polycarbodilimide.

[0068] (Dyne) The dye is included in the resin composition to express color tones that could not be expressed by the hydrophilic glossy material alone, by being dispersed in the resin composition, and is excluded from the hydrophilic glossy material. Mainly particle size 221 (D ５０ ) differs in the ratio of the thickness of the hydrophilic glossy material to 211.

[0069] The aforementioned dye does not reflect ambient light (incident light), but rather absorbs light of a specific wavelength to adjust the hue of the lustrous resin layer.

[0070] The pigment contained in the glossy resin layer is one that is commonly used in the present art and is not particularly limited as long as the metallic decorative laminate exhibits the desired metallic design. It may be a dye or pigment, an inorganic compound or an organic compound, a natural pigment or a synthetic pigment, as long as it absorbs visible light. In particular, when used outdoors and weather resistance is required, a synthetic pigment is preferred, and an organic pigment is preferred to improve color development. The pigment preferably contains an inorganic pigment or an organic pigment, and is preferably an inorganic pigment or an organic pigment. More specifically, inorganic pigments such as titanium white (titanium dioxide), zinc oxide, iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, lead yellow, and carbon black; and organic pigments (including dyes) such as isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, induthlene blue RS, and aniline black are preferred.

[0071] It is preferable that the amount of the dye in the glossy resin layer is 0.05 parts by mass or more and 20.00 parts by mass or less per 100 parts by mass of the resin component. The amount of addition can be adjusted according to the desired design, but it is preferable that it is above the lower limit because the dye can be added to create a specific design, and it is preferable that it is below the upper limit because cracking during molding is less likely to occur. It is more preferable that it is 0.10 parts by mass or more and 10.00 parts by mass or less per 100 parts by mass of the total polyurethane resin contained in the resin component described later, even more preferable that it is 0.20 parts by mass or more and 8.00 parts by mass or less, even more preferable that it is 0.30 parts by mass or more and 5.00 parts by mass or less, even more preferable that it is 0.35 parts by mass or more and 3.00 parts by mass or less, and even more preferable that it is 0.40 parts by mass or more and 1.00 parts by mass or less.

[0072] (Thermoplastic resin) The resin component preferably further contains one or more thermoplastic resins.

[0073] The total content of thermoplastic resin in the aforementioned resin component is preferably 20.00 parts by mass or more and less than 70.00 parts by mass, more preferably 25.00 parts by mass or more and 60.00 parts by mass or less, even more preferably 30.00 parts by mass or more and 50.00 parts by mass or less, and even more preferably 35.00 parts by mass or more and 45.00 parts by mass or less.

[0074] Examples of the thermoplastic resin include polyolefin resins, polyester resins, and polystyrene resins, but polyolefin resins are preferred because they have good moldability.

[0075] The mass-average molecular weight (Mw) of the polyolefin resin is preferably 30,000 to 500,000, more preferably 50,000 to 300,000, even more preferably 70,000 to 200,000, and even more preferably 90,000 to 100,000 in order to improve impact resistance.

[0076] The polydispersity (Mw / Mn) of the polyolefin resin is preferably 1.5 or more and 5.0 or less, more preferably 1.6 or more and 4.0 or less, even more preferably 1.7 or more and 3.0 or less, and even more preferably 1.9 or more and 2.2 or less, in order to improve impact resistance.

[0077] [Metallic Decorative Laminate] The metallic decorative laminate of this embodiment must be a metallic decorative laminate that includes the above-mentioned glossy resin layer.

[0078] The metallic decorative laminate of this embodiment can be used, for example, to decorate resin parts and metal parts such as bumpers for automobiles (hereinafter also simply referred to as "articles") by film decoration methods such as insert molding or overlay molding using the metallic decorative laminate. The metallic decorative laminate can also be used to decorate the surface of articles via an adhesive layer or bonding layer, and can be used as a surface layer in automobile exteriors such as pillars, door moldings, roof moldings, entire door surfaces, and entire roof surfaces. Furthermore, the metallic decorative laminate of this embodiment exhibits an excellent metallic design, has excellent scratch resistance, weather resistance, moldability, millimeter-wave transmittance and moldability, and also has excellent chemical resistance, so it is preferable to use it for decorating four-wheeled vehicles, two-wheeled vehicles, pumps, etc., which use lubricating oil.

[0079] Furthermore, as will be described in detail later, the metallic decorative laminate of this embodiment is preferable because it is easy to manufacture and therefore highly suitable for mass production. It is also preferable because it can reduce the environmental impact compared to metal plating.

[0080] The aforementioned metallic decorative laminate can impart a metallic design to the surface of an article. Furthermore, by installing a light source, other designs can be imparted by light transmitted through the luminous resin layer.

[0081] For illustrative purposes, Figure 2 is shown. Figure 2 is a schematic diagram illustrating the role of the glossy resin layer 20, and the glossy resin layer included in a metallic decorative laminate can be considered similarly. As shown in Figure 2, the glossy resin layer 20 reflects ambient light 5, and the reflected light 6 from the glossy resin layer is visible to the observer 4, creating a metallic design. However, when there is no ambient light 5, such as at night, the reflected light 6 from the glossy resin layer does not reach the observer 4 sufficiently. As a result, the observer 4 may perceive that the metallic design is not being displayed.

[0082] In contrast, by positioning the light source 7 on the side of the lustrous resin layer 20 opposite to the observer 4, the irradiated light 8 passes through the metallic decorative laminate (including the lustrous resin layer) and reaches the observer 4 as light transmitted through the lustrous resin layer 9. By positioning the light source 7, the observer 4 can confirm the design using the light transmitted through the lustrous resin layer 9 even at night.

[0083] Furthermore, unlike plating, the aforementioned metallic decorative laminate has the ability to transmit radio waves classified as millimeter waves. For detecting obstacles around vehicles such as automobiles, sensors such as millimeter-wave radar are used. Millimeter-wave radar is a device that measures the distance to an obstacle by irradiating it with radio waves with a wavelength of 1 to 10 mm, measuring the time it takes for the waves to reflect back from the obstacle, and so on. Millimeter-wave radar is less affected by weather conditions such as rain and fog, and can detect obstacles at a distance, so it has been introduced by many automobile manufacturers. For automobiles, the millimeter-wave band in the 76 to 77 GHz range is used, and the main unit of the millimeter-wave radar device is mounted, for example, behind the bumpers on the front and rear of the automobile body, and the millimeter waves are irradiated from the main unit through the bumpers to the obstacle.

[0084] The millimeter-wave transmittance of the metallic decorative laminate of this embodiment can be evaluated by the attenuation of 76.5 GHz radio waves (hereinafter referred to as millimeter-wave transmission attenuation; the attenuation is described as an absolute value). When used with a millimeter-wave radar, and the metallic decorative laminate is placed on the irradiation and reflection path of millimeter waves, in order to maintain a high level of detection sensitivity of the millimeter-wave radar, it is preferable that the attenuation is 1.0 dB or less, and more preferably 0.5 dB or less. There is no particular limit to the lower limit, and 0.0 dB is preferred, but since attenuation also occurs due to resin components, etc., it is practically 0.1 dB or more.

[0085] Patent Document 2 discloses a method for manufacturing an aluminum-look bumper that transmits millimeter waves, which involves coating a resin substrate with a paint containing a flat, glossy material made of aluminum (aluminum flakes). In this method, where a metallic design is created using aluminum flakes, the aluminum flakes cause reflection of millimeter waves. To suppress this reflection and improve millimeter wave transmittance, a method of increasing the distance between the aluminum flakes was known (Patent Document 2). However, in the method described in Patent Document 2, if the thickness of the glossy resin layer that can be produced by coating the paint once exceeds 10 μm, the aluminum flakes settle in the paint film before the paint film hardens, making it impossible to secure a sufficient distance between the aluminum flakes, and thus the suppression of the reflection could not be sufficiently achieved.

[0086] Furthermore, in Patent Document 2, a sufficient amount of aluminum flakes is required for the glossy resin layer to exhibit a metallic design. However, if the amount of aluminum flakes in the glossy resin layer is increased to achieve this, the distance between the aluminum flakes decreases, resulting in a reduction in millimeter-wave transmittance.

[0087] While it is preferable to have a certain film thickness or higher to achieve a metallic appearance, in the method for manufacturing a glossy resin layer described in Patent Document 2, as mentioned above, sedimentation of aluminum flakes occurs in the coating film. Therefore, in order to ensure sufficient distance between aluminum flakes, it was necessary to form the film with a thickness of 10 μm or less. Due to this constraint, it was not possible to manufacture a glossy resin layer with a thickness of 20 μm or more in a single layer. To achieve a thickness of 20 μm or more, it was necessary to stack at least two glossy resin layers. Thus, in order to obtain a glossy resin layer with a thickness of 20 μm or more using the manufacturing method described in Patent Document 2, the coating film formation process had to be performed at least twice, resulting in a complicated process.

[0088] Furthermore, as described in Patent Document 2, when a glossy resin layer is manufactured using an acrylic urethane paint containing aluminum flakes, the aluminum flakes are insoluble in the acrylic urethane paint and have low dispersibility. As a result, the aluminum flakes, which have a higher specific gravity, settle during the manufacturing process due to the difference in specific gravity. Consequently, a distribution of aluminum flake content occurs within each glossy resin layer, with the content increasing from the upper surface to the lower surface in the thickness direction. When regions with high and low aluminum flake content exist in this way, millimeter-wave reflection occurs, resulting in a decrease in millimeter-wave transmittance.

[0089] In this embodiment, the layer thickness of the metallic decorative laminate is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, and even more preferably 20 μm or more, in order to improve aesthetic appeal and weather resistance. In order to improve moldability, it is preferably 200 μm or less, more preferably 100 μm or less, even more preferably 70 μm or less, and even more preferably 40 μm or less.

[0090] To achieve a balance between aesthetic appeal, weather resistance, and chemical resistance, the particle size is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm, even more preferably 15 μm to 70 μm, and even more preferably 20 μm to 40 μm.

[0091] In this disclosure, "coating liquid preparation properties" refers to the property of a coating liquid used to create a glossy resin layer (coating liquid for glossy resin layer) that is less prone to layer separation after preparation. The higher the coating liquid preparation properties, the easier it is to manufacture a glossy resin in which hydrophilic glossy materials are uniformly dispersed, thus facilitating the manufacture of the glossy resin layer. This can be evaluated, for example, by the method described in the examples.

[0092] In this disclosure, "coating liquid storage stability" refers to the property that hydrophilic glossy material is less likely to precipitate from the coating liquid for glossy resin layers even after a certain period of time has elapsed since the coating liquid for glossy resin layers was prepared. Higher coating liquid stability allows the coating liquid for glossy resin layers to be stored for a longer period of time, making it possible to prepare it in advance. Furthermore, it can be said that manufacturing is easier because precipitation is less likely to occur in the coating machine when applying the coating liquid for glossy resin layers to create the glossy resin layer. This can be evaluated, for example, by the method described in the examples.

[0093] In this disclosure, "design appeal" means the property that, when the metallic decorative laminate of this disclosure is used in an article, the article exhibits a metallic design and can express a required color tone, and furthermore, the property that the required color tone can be expressed by light transmitted through the lustrous resin layer. For example, it can be evaluated by the method described in the examples.

[0094] In this disclosure, "heat resistance" means that the properties of a material change little or no even when heated, and can be evaluated, for example, by the method described in the examples.

[0095] In this disclosure, "chemical resistance" refers to the property that prevents dissolution, swelling, and reaction of the glossy resin layer contained in the metallic decorative laminate of this disclosure even when organic solvents or lubricating oils come into contact with it, and includes oil resistance and solvent resistance. For example, this can be evaluated by immersing the metallic decorative laminate in an organic solvent such as pentane and observing its appearance.

[0096] In this disclosure, "weather resistance" means the property of being resistant to deformation, discoloration, deterioration, etc., when used outdoors, and can be evaluated, for example, by the method described in the examples.

[0097] In this disclosure, "moldability" refers to the ease of manufacturing a metallic-looking article using the metallic-looking decorative laminate of this disclosure. Moldability can be improved by increasing the layer thickness to suppress tearing during molding, or by decreasing the layer thickness to decorate even the fine details of the article. For example, it can be evaluated by the method described in the examples.

[0098] The total light transmittance of the metallic decorative laminate in this embodiment can be adjusted as needed. If the total light transmittance of the layers other than the glossy resin layer is sufficiently high, the total light transmittance of the metallic decorative laminate will be approximately the same as the total light transmittance of the glossy resin layer.

[0099] The metallic decorative laminate of this embodiment may further include one or more layers selected from a base layer, a protective layer, and an adhesive layer.

[0100] <Base layer> The base layer 40 is preferably located on the side opposite to the observer 4 of the glossy resin layer 20 in the metallic decorative laminate 1, as shown in Figures 1 and 2.

[0101] The base layer 40 is preferably transparent to the irradiation light 8 irradiated from the light source 7, and its total light transmittance is preferably 85% or more. The base layer is preferably made of a general-purpose resin such as polycarbonate resin, polyurethane resin, polyester resin, acrylic resin, acrylic urethane resin, or vinyl chloride-vinyl acetate copolymer resin, and may be a single layer or a laminate of multiple layers made of different resins.

[0102] The base layer may be in direct contact with the glossy resin layer, or it may be laminated via the design layer 30, or via the adhesive layer described later.

[0103] Furthermore, the thickness of the base layer may be any thickness typical for a metallic decorative laminate. In order to suppress the occurrence of defects such as wrinkles during film formation and to suppress the breakage of the metallic decorative laminate during the molding process of the metallic article, it is preferably 10 μm to 1000 μm, more preferably 50 μm to 700 μm, even more preferably 100 μm to 500 μm, and even more preferably 150 μm to 300 μm.

[0104] The base layer is preferably millimeter-wave transparent, and more preferably highly transparent. The total light transmittance, as an indicator of transparency, is preferably 85% or higher, more preferably 88% or higher. There is no particular upper limit as long as the design is aesthetically pleasing, but it is generally around 90%.

[0105] <Protective Layer (Release Layer)> The protective layer (release layer) is used when manufacturing a metallic decorative laminate, as described below, by applying a coating solution that forms a glossy resin layer to it. It is a layer that protects the outermost surface of the glossy resin layer when transporting or storing the metallic decorative laminate. It also serves as a release layer because it peels off at one of the stages of the manufacturing process of the metallic article.

[0106] The protective layer (release layer) can be any material used as a protective layer (release layer) in the relevant art, and can be appropriately selected from polyethylene-based substrates, polyester-based substrates (including polyethylene terephthalate (PET) substrates), polycarbonate-based substrates, etc. PET is more preferred due to requirements such as ease of handling during manufacturing and availability.

[0107] The thickness of the substrate can be as long as it does not interfere with the manufacturing process, but generally, a thickness of 10 μm to 150 μm can be used.

[0108] <Adhesive layer> The adhesive layer is a layer containing a resin component that exhibits adhesive properties.

[0109] The adhesive layer is preferably a layer located between the glossy resin layer and the base layer, and is used to bond them together. It may also be a primer layer that exhibits adhesive properties through thermal lamination.

[0110] The adhesive layer may contain the dye. By including the dye, the color shift that occurs when light from the light source 7 shown in Figure 2 passes through the metal layer can be corrected.

[0111] The adhesive resin component in the aforementioned adhesive layer preferably uses an adhesive that exhibits excellent adhesion to the luminous pigment layer and the base layer. Examples of such adhesives include one or more resins selected from polyurethane, polyvinyl acetate, ethylene vinyl acetate copolymer, polyvinyl alcohol, epoxy, and silicone resins. For example, considering aesthetics, weather resistance, transparency, adhesion, and heat resistance to withstand molding temperatures, a polyurethane adhesive can be used.

[0112] The polyurethane adhesive is a reaction product of a polyester diol, a polycarbonate diol, and an aliphatic isocyanate, and preferably contains a carbodiimide and a silane coupling agent having an epoxy group.

[0113] The method for forming the adhesive layer is not particularly limited. For example, the adhesive layer can be formed by applying an appropriate amount to the glossy pigment layer and / or base layer using a solvent as appropriate, or as an emulsion, by known means such as a gravure coater, reverse coater, knife coater, or roll coater, and drying as necessary.

[0114] The thickness of the adhesive layer can be a typical thickness for a metallic decorative laminate. For example, it is preferably 1 μm to 20 μm, more preferably 2 μm to 15 μm, and even more preferably 3 μm to 13 μm, considering aesthetics, weather resistance, adhesion, drying time, cost, etc.

[0115] <Design Layer> The metallic decorative laminate of this embodiment may have a design layer as needed. The design layer is a layer configuration for expressing designs that are difficult to express with the glossy resin layer alone, together with the glossy resin layer. The design layer is preferably a layer printed on the base layer, but the design may also be letters, figures, etc.

[0116] The ink composition (coating liquid) used to form the design layer is, for example, a mixture of a solvent and solid components such as a colorant and a binder resin. The ink composition may also contain other components such as stabilizers, plasticizers, catalysts, and curing agents. The explanation regarding the solvent is the same as above and will be omitted. Since the solvent eventually evaporates, the design layer is mainly formed by solid components such as a colorant and a binder resin. The aforementioned dyes can be used as the colorant, but black carbon is preferred when the design layer is a light-shielding layer. The binder resin is not particularly limited, but it is preferably a general-purpose resin such as polycarbonate resin, urethane resin, polyester resin, acrylic resin, acrylic urethane resin, or vinyl chloride-vinyl acetate copolymer resin.

[0117] The thickness of the design layer can be appropriately selected depending on the required properties, but it is preferably 0.1 μm or more and 100 μm or less, more preferably 0.5 μm or more and 50 μm or less, and even more preferably 1 μm or more and 30 μm or less.

[0118] <Laminated Structure of Metallic Decorative Laminates> Specific examples of the laminated structure of metallic decorative laminates include, for example, (1) to (6) below. (3) to (6) are preferred, (4) or (6) are preferred during transportation, etc., and (3) or (5) are preferred during use. Note that " / " indicates the boundary between each layer. Also, the right side of Figure 2 represents the observer 4 side, and the left side represents the light source 7 side (the item side described later). (1) Shiny resin layer (2) Shiny resin layer / protective layer (3) Base layer / Shiny resin layer (4) Base layer / Shiny resin layer / protective layer (5) Base layer / adhesive layer / Shiny resin layer (6) Base layer / adhesive layer / Shiny resin layer / protective layer (7) Base layer / adhesive layer / Shiny resin layer / adhesive layer / protective layer (8) Base layer / adhesive layer / Shiny resin layer / Base layer (9) Base layer (laminate of polycarbonate layer and acrylic layer) / adhesive layer (primer layer) / Shiny resin layer

[0119] [Metallic Articles] The metallic articles of this embodiment must include the glossy resin layer or the metallic decorative laminate.

[0120] The metallic articles of this embodiment are manufactured using the metallic decorative laminate by, for example, the manufacturing method described later, and are molded into a desired shape according to the purpose. For example, they can be used in the casings and decorative parts of personal computers, TVs, and home appliances, as well as in the casings and decorative parts of pachinko machines, pachislot machines, and game machines, or in general applications such as carry bags and suitcases, and can provide metallic decorative and design features in place of plating or metal materials.

[0121] In particular, the metallic decorative laminate of this embodiment not only imparts a metallic design to an article, but also imparts chemical resistance and weather resistance to the article. In this disclosure, "article" refers to a precursor of a metallic article, which becomes a metallic article by being decorated with the decorative laminate.

[0122] The metallic-looking article of this embodiment may have other configurations in addition to the above-described configuration. For example, in order to keep the surfaces of the glossy resin layer, adhesive layer (primer layer), and / or base layer clean and prevent dirt from adhering until the metallic-looking article of this embodiment is used, release paper, protective film, etc., can be provided on the surface of the glossy resin layer.

[0123] [Method for manufacturing metallic decorative laminate and metallic article] The glossy resin layer of this embodiment is formed during the process of manufacturing the metallic decorative laminate.

[0124] The method for manufacturing the metallic decorative laminate of this embodiment requires, in this order, applying a coating liquid containing one or more polyurethane resins and one or more hydrophilic glossy materials to the release layer, followed by heating.

[0125] Since the resin components containing polyurethane resins and hydrophilic glossy materials have already been explained, they will be omitted here.

[0126] (Coating liquid containing a resin component containing one or more polyurethane resins and one or more hydrophilic glossy materials) The coating liquid containing the resin component containing one or more polyurethane resins and one or more hydrophilic glossy materials is a coating liquid for forming a glossy resin layer and may further contain the other components.

[0127] The coating liquid may further contain a solvent, and may be a homogeneous solvent or a slurry.

[0128] (Solvent) The solvent can be any solvent that is generally used in the field in question. As a solvent, water, methanol, ethanol, isopropyl alcohol, and other alcohol-based solvents can be selected, but it is preferable to use a mixed solvent of water and an alcohol-based solvent in order to improve the reactivity of the polyurethane resin.

[0129] In the method for manufacturing the metallic decorative laminate of this embodiment, a solvent should be selected so that the hydrophilic glossy material is well dispersed, and a settling inhibitor may be added as one of the other components as needed.

[0130] When using the aforementioned solvent, in order to shorten the heating process time described later and improve the applicability of the coating liquid to the substrate, the total amount of the resin components is preferably 5.0 parts by mass or more and 100.0 parts by mass or less, more preferably 10.0 parts by mass or more and 50.0 parts by mass or less, and even more preferably 15.0 parts by mass or more and 30.0 parts by mass or less, per 100 parts by mass.

[0131] <Application> The application can be carried out by known means such as a die coater, knife coater, or roll coater on the protective layer (release layer) or a resin layer formed on the protective layer (release layer).

[0132] <Heating> The heating may be started before the coating is completed or after the coating is completely finished, but it is preferable to heat while the coating liquid is on the protective layer (release layer). The heating includes cases where the protective layer (release layer) is heated beforehand, the coating is applied, and then further heating is performed.

[0133] By heating, if the solvent is used in the coating liquid, the solvent is evaporated and solidified.

[0134] The heating temperature can be appropriately selected depending on the heating time, the resin components used, the hydrophilic glossy material, other components, solvent, and protective layer (release layer), but in order to obtain a metallic decorative laminate that achieves metallic appearance, scratch resistance, chemical resistance, weather resistance, millimeter wave transmittance, and moldability, a temperature of 130°C or higher is preferred, 140°C or higher is more preferred, 160°C or higher is even more preferred, 220°C or lower is preferred, 200°C or lower is more preferred, and 180°C or lower is even more preferred.

[0135] The heating method can be appropriately selected based on the shape, size, and other factors of the object to be heated, using a heating method appropriate for the field.

[0136] The heating time can be appropriately selected depending on the size of the laminate to be manufactured, the heating temperature, the thermoplastic resin used, the solvent, and the substrate, but in order to obtain a metallic decorative laminate with excellent design and millimeter-wave transmittance, a heating time of 30 seconds or more is preferable, 1 minute or more is more preferable, 5 minutes or less is preferable, and 3 minutes or less is even more preferable.

[0137] If necessary, a metallic decorative laminate can be obtained by applying an adhesive to the glossy resin layer formed on the protective layer (release layer) and then bonding the base layer.

[0138] <<Removing the protective layer (release layer)>> The method for manufacturing the metallic decorative laminate of this embodiment may include removing the protective layer (release layer), or the protective layer (release layer) may be removed after the metallic article described below has been produced.

[0139] The method of removal is not particularly limited, as long as it is a method commonly used in the field.

[0140] <Method for manufacturing metallic articles> The metallic articles of this embodiment can be manufactured, for example, by the following method.

[0141] The process includes a molding step in which the surface temperature of the decorative laminate is set to 150°C to 200°C, and if the glossy resin layer of the metallic decorative laminate has a base layer, the base layer is brought into close contact with the mold so that it faces the article, thereby forming it on the surface of the article to obtain a metallic article.

[0142] (Molding Process) In order to thermoform the metallic decorative laminate, the surface temperature of the metallic decorative laminate is set to 150°C to 180°C. This prevents the metallic decorative laminate from drawing down during molding and prevents whitening, etc., thus satisfying good moldability. A surface temperature of 150°C or higher prevents the metallic decorative laminate from softening sufficiently, and prevents the metallic decorative laminate from sagging and deforming due to the drawdown phenomenon, which would make processing and molding difficult. Furthermore, a surface temperature of 200°C or lower prevents the metallic decorative laminate from becoming too soft due to melting, making molding difficult, and also prevents whitening and matting (as shown in Figure 4, a state in which the thickness direction 210 of the hydrophilic glossy material has an inclination with respect to a plane consisting of the width direction 110 and the length direction 120, causing diffuse reflection of ambient light 5).

[0143] The shape of the mold used to press the metallic decorative laminate can be any shape that allows the metallic article to be molded into the desired shape. For example, molds such as male and female molds with a brass surface chrome-plated can be used. Furthermore, the mold temperature can be set to any temperature that takes into account the control of the surface temperature of the metallic decorative laminate and the control of the cooling conditions of the metallic article after the molding process.

[0144] As a method for adhering the metallic decorative laminate to a mold, any method can be adopted considering ease of molding and cost, such as straight molding using a female mold, drape molding using a male mold, or plug-assisted molding using a plug (auxiliary mold). In addition, vacuum forming, which sucks the metallic decorative laminate into the mold, or compressed air forming, which uses compressed air pressure to adhering the metallic decorative laminate to the mold, can be employed. For example, by adhering the metallic decorative laminate to the mold using vacuum and / or compressed air, the adhesion between the decorative laminate and the mold is improved, allowing for processing into more precise shapes.

[0145] (Clamping Process) The method for manufacturing the metallic-looking article may include a clamping process before the molding process in which the metallic-looking decorative laminate is clamped. This process allows the metallic-looking decorative laminate to be adjusted and fixed so that it does not sag during molding. Clamping can be performed, for example, by using multiple gripping means capable of gripping both sides of the metallic-looking decorative laminate, for example, by gripping both ends of the metallic-looking decorative laminate. Gripping of the metallic-looking decorative laminate is not limited to both ends, but any part of the metallic-looking decorative laminate can be gripped. Normally, when continuously producing metallic-looking articles, both ends in the width direction of the metallic-looking decorative laminate can be gripped. Also, when batch producing metallic-looking articles using rectangular pieces of metallic-looking decorative laminate cut to a predetermined length, the ends of all four sides can be gripped with upper and lower frames.

[0146] (Heating step) The method for manufacturing the metallic-looking article may also include a heating step after the clamping step in which the metallic-looking decorative laminate is heated. For example, after clamping the metallic-looking decorative laminate at room temperature and adjusting it so that it does not loosen, multiple heaters or the like can be used as heating means, with these heaters positioned above and below the metallic-looking decorative laminate to heat both sides of the metallic-looking decorative laminate simultaneously and uniformly. This heating step allows the surface temperature of the metallic-looking decorative laminate to be controlled to 150°C to 200°C.

[0147] (Other Processes) In addition to the above processes, the manufacturing method for metallic articles may include other processes. For example, a bonding process may be included in which a protective film or the like is attached to the surfaces of the glossy resin layer, adhesive layer (primer layer), and / or base layer to maintain the surfaces of the metallic article in a clean state and prevent contamination until the metallic article is processed in the next process. Furthermore, after inserting the metallic article into an injection molding die, insert injection molding is performed by injecting resin, and the surface of the injection-molded product can be decorated.

[0148] The following [1] to [9] are preferred for the manufacturing method of the glossy resin layer, metallic decorative laminate, metallic article, and metallic decorative laminate of this embodiment. [1] A glossy resin layer containing a resin component containing one or more polyurethane resins and one or more hydrophilic glossy materials. [2] The glossy resin layer according to [1], wherein the hydrophilic glossy material contains one or two materials selected from flaky or flake metals, flaky or flake metal alloys, flaky or flake metal oxides, flaky or flake mica, glass flakes, and film pulverized materials that have been hydrophilically treated. [3] The glossy resin layer according to [1] or [2], wherein the polyurethane resin contains a polycarbonate polyurethane resin. [4] The glossy resin layer according to any one of [1] to [3], wherein the hydrophilic glossy material in the glossy resin layer is 0.10 parts by mass or more and 20.00 parts by mass or less with respect to 100 parts by mass of the total resin components. [5] A metallic decorative laminate comprising the glossy resin layer according to any one of [1] to [4]. [6] The metallic decorative laminate according to [5], further comprising one or more layers selected from a base layer, a protective layer and an adhesive layer. [7] A metallic article comprising the glossy resin layer according to any one of [1] to [4]. [8] A metallic article comprising the metallic decorative laminate according to [5] or [6]. [9] A method for manufacturing a metallic decorative laminate according to [5] or [6], comprising, in this order, applying a coating liquid containing one or more polyurethane resin components and one or more hydrophilic glossy materials to a release layer, and then heating it.

[0149] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited in any way to the following examples.

[0150] (Evaluation Method) 1. Coating Solution Preparation Properties The coating solutions obtained by the preparation methods for the glossy resin layer described in the following examples and comparative examples were observed immediately after preparation and evaluated as follows (A to C). A: No clear layer separation (separation into a layer containing precipitated hydrophilic glossy material and a layer of solution mainly containing resin components) occurred even after stirring was stopped, or the interface of the separated layers could not be confirmed. B: The interface of the separated layers could be slightly confirmed. C: The hydrophilic glossy material separated and was present at the bottom of the container, and its interface could be confirmed. 2. Coating Solution Storage Properties The coating solutions obtained by the preparation methods for the glossy resin layer described in the following examples and comparative examples were observed after standing for 30 minutes and evaluated as follows (A to C). A: No clear layer separation (separation into a layer containing precipitated hydrophilic glossy material and a layer of solution mainly containing resin components) occurred, or the interface of the separated layers could not be confirmed. B: The interface of the separated layers could be slightly confirmed. C: The hydrophilic glossy material separates and is located at the bottom of the container, and its interface can be confirmed. 3. Design Evaluation The metallic decorative laminates obtained in the examples and comparative examples were visually observed from the glossy resin layer side and evaluated as follows: A: Exhibits a metallic design. B: Exhibits a metallic design, but has a matte finish. C: Does not exhibit a metallic design. 4. Weather Resistance (Humidity Resistance) Evaluation The metallic decorative laminates obtained in the examples and comparative examples were left standing for 24 hours in an atmosphere of temperature: 50°C and humidity: 95% RH (in accordance with JIS K5600-7-2). The metallic decorative laminates after standing were compared with those before the test, and the presence or absence of delamination between layers, changes in design, and changes in shape (such as undulation) were observed and evaluated as follows: A: No practical problems. B: Slight changes are observed, but at a practical level. C: Significant delamination or changes in design were observed. 5. Scratch Resistance Evaluation The glossy resin layer of the metallic decorative laminate obtained in the examples and comparative examples was used as the test surface. Based on the conditions of European automotive standard TL226, gauze wrapped around a 15 mm diameter terminal was pressed against the surface 21 with a load of 9 N, and the pressed gauze was moved back and forth for 60 minutes at a stroke of 10 cm and 60 reciprocations / minute. The glossy resin layer after the test was visually observed and evaluated as A to C. A: No scratches were observed. B: Slight scratches were observed, but at a usable level. C: Significant peeling or changes in appearance were observed.6. Heat Resistance Evaluation The decorative laminates obtained in the examples and comparative examples were left in a 100°C environment for 500 hours, and the color difference of the sample surface on the glossy resin layer side of the decorative laminate before and after the test was measured using a colorimeter CM-3600A (manufactured by Konica Minolta). 7. Millimeter Wave Transmittance Evaluation The millimeter wave transmission attenuation at a frequency of 76.5 GHz in the metallic decorative laminate was measured using a RAS (SM5899) manufactured by KEYCOM. The metallic decorative laminate was set in the apparatus so that millimeter waves were transmitted from the base layer side of the glossy resin layer. The measurement was performed 250 times, and the average of the absolute values ​​of the 250 measurements was taken as the transmission attenuation (dB). 8. For metallic-looking articles made using the metallic-looking decorative laminates obtained in the moldability evaluation examples and comparative examples, the presence or absence of clouding in the stretched portion of the laminate at the corner of the mold after the molding process (stretched to 200% of the original stretch) was visually observed. A: No clouding was observed. B: Slight clouding was observed. C: Significant clouding was observed.

[0151] (Materials used) (Polyurethane (1)) UW-5002E (manufactured by UBE Corporation) (Polyurethane (2)) UW-5502D-C1 (manufactured by UBE Corporation) (Glossy material (1)) EMR-D6390 (manufactured by Toyo Aluminum Co., Ltd., aluminum flake, emerald (corresponds to hydrophilic glossy material)) Volume average particle size (D ５０ ): 7.0 μm (Luminous material (2)) GX40A (manufactured by Asahi Kasei Corporation, resin-coated aluminum flake (not a hydrophilic luminous material), volume average particle size (D ５０ (19.0 μm) (Settling inhibitor (1)) AQH-810 (manufactured by Kusumoto Chemical Co., Ltd., polyamide-based rheology control agent for water-based paints) (Settling inhibitor (2)) VISCOTEX46 (manufactured by Arkema Co., Ltd., acrylic-based settling inhibitor) (Settling inhibitor (3)) Borchi Gen L75N (manufactured by Matsuo Sangyo Co., Ltd., acrylic-based settling inhibitor) (Crosslinking agent for water-based resins (1)) Carbodilite V-02 (manufactured by Nisshinbo Chemical Co., Ltd., polycarbodiimide) (Others) Contains a total of 1.0 part by mass of antioxidant, UV absorber, dye (black), and leveling agent per 100 parts by mass of polyurethane resin.

[0152] (Examples 1-6) <Manufacturing of metallic decorative laminates> (Formation of glossy resin layer) The glossy resin layer coating solution described below was applied to a protective layer (PET film (G2000 (manufactured by Toyobo Co., Ltd.))). The amount applied was adjusted so that the thickness of the glossy resin layer after heating was 20 μm.

[0153] Immediately after coating, the material was heated at 180°C for 2 minutes to form a glossy resin layer on the protective layer. The material was then cooled to room temperature to obtain a laminate.

[0154] ((Coating liquid for glossy resin layer)) The polyurethane resin, hydrophilic glossy material, and other materials shown in Table 1 were mixed with 16 parts by mass of water and 4 parts by mass of isopropyl alcohol (IPA) as diluents per 100 parts by mass of polyurethane resin to obtain a coating liquid for glossy resin layer containing resin components and hydrophilic glossy material. The amount (parts by mass) of each material used when the total amount of materials and polyurethane resin used is 100 parts by mass is listed in Table 1.

[0155] In the table, "-" indicates that the ingredient in question is not used.

[0156] (Lamination of Adhesive Layer and Base Layer) A urethane adhesive was prepared by mixing a main component consisting of a polyester diol (TM-K51, manufactured by Toyo Morton Co., Ltd.), a polycarbonate diol (Duranole T5652, manufactured by Asahi Kasei Corporation), a carbodiimide (Carbodilite V-07, manufactured by Nisshinbo Chemical Co., Ltd.), a silane coupling agent having an epoxy group (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), and a mixture of ethyl acetate, with a curing agent consisting of an aliphatic isocyanate (CAT-RT85, manufactured by Toyo Morton Co., Ltd.). This urethane adhesive was applied to the surface of the glossy resin layer of the laminate using a bar coater to a dry film thickness of approximately 10 μm, and the coated material was dried at 60°C for 1 minute. After that, a base layer (polycarbonate film, PC-11FU (manufactured by Waverock Advanced Technology Co., Ltd.)) was placed on the adhesive layer side and laminated. Furthermore, the protective layer was peeled off to produce a metallic-looking decorative laminate containing a glossy resin layer, an adhesive layer, and a base layer.

[0157] The coating properties and storage life of the obtained glossy resin layer coating liquid, as well as the design, weather resistance, and scratch resistance of the metallic decorative laminate, were evaluated, and the results are shown in Table 2.

[0158] <Manufacturing of Metallic-Look Articles> Using the obtained metallic-look decorative laminate, a compression molding machine was used to clamp the metallic-look decorative laminate to a test mold so that the base layer of the metallic-look decorative laminate would face the article side. Then, with a pre-forming temperature of 160°C and a compressed air pressure of 6 bar, the metallic-look decorative laminate was preformed to fit the mold for injection molding. Unnecessary parts that protruded from the mold were trimmed to obtain metallic-look articles.

[0159] In the table, "-" indicates that the corresponding evaluation was not conducted.

[0160] From the results of Examples 1 to 6 shown in Table 2, it was confirmed that the glossy resin layer and metallic decorative laminate of this embodiment exhibit an excellent metallic design, reduce environmental impact, and allow for easy preparation of the coating solution. Furthermore, from the results of Examples 1 to 4, it was confirmed that the coating solution has excellent storage properties, making it possible to store and transport the coating solution and accommodate larger product sizes, which is desirable. It was also confirmed that it has excellent weather resistance, scratch resistance, and moldability. Furthermore, it was confirmed that it has excellent chemical resistance, heat resistance, and millimeter-wave transmittance.

[0161] (Comparative Example 1) In Comparative Example 1, a coating solution for a glossy resin layer was prepared using glossy material (2) instead of glossy material (1), but it aggregated and separated. Lamination of a glossy resin layer was carried out using the supernatant liquid in the same manner as in Example 1, but because it did not contain enough hydrophilic glossy material, the metallic design did not appear. Furthermore, the glossy resin layer did not contain enough hydrophilic glossy material due to precipitation, and large granulated clumps of hydrophilic glossy material were also contained in the glossy resin layer, making it impossible to perform weather resistance evaluation and scratch resistance evaluation.

[0162] The glossy resin layer, metallic decorative laminate, and metallic articles of this embodiment exhibit excellent metallic design, reduce environmental impact during manufacturing, and are easy to manufacture. Furthermore, the metallic decorative laminate can provide metallic articles with excellent design, making it suitable for use in automobiles, home appliances, information terminals, and the like.

[0163] 1: Metallic decorative laminate 4: Observer 5: Ambient light 6: Reflected light from the glossy resin layer 7: Light source 8: Irradiated light 9: Transmitted light from the glossy resin layer 10: Protective layer (release layer) 20: Glossy resin layer 21: Surface of the glossy resin layer opposite the article 22: Surface of the glossy resin layer on the article side 30: Adhesive layer 40: Base layer 100: Thickness direction 110: Width direction 120: Longitudinal direction 200: Hydrophilic glossy material 210: Thickness direction of the hydrophilic glossy material 211: Thickness of the hydrophilic glossy material 220: Particle diameter direction of the hydrophilic glossy material 221: Particle diameter of the hydrophilic glossy material

Claims

1. A resin component containing one or more polyurethane resins and a glossy resin layer containing one or more hydrophilic glossy materials.

2. The glossy resin layer according to claim 1, wherein the hydrophilic glossy material contains one or more materials selected from flaky or flake metals, flaky or flake metal alloys, flaky or flake metal oxides, flaky or flake mica, glass flakes, and film pulverized materials.

3. The glossy resin layer according to claim 1 or 2, wherein the polyurethane resin contains a polycarbonate-based polyurethane resin.

4. The glossy resin layer according to any one of claims 1 to 3, wherein the hydrophilic glossy material in the glossy resin layer is 0.10 parts by mass or more and 20.00 parts by mass or less with respect to 100 parts by mass of the total resin components.

5. A metallic decorative laminate comprising a glossy resin layer according to any one of claims 1 to 4.

6. The metallic decorative laminate according to claim 5, further comprising one or more layers selected from a base layer, a protective layer, and an adhesive layer.

7. A metallic-looking article comprising a glossy resin layer according to any one of claims 1 to 4.

8. A metallic-looking article comprising a metallic-looking decorative laminate according to claim 5 or 6.

9. A method for producing a metallic decorative laminate according to claim 5 or 6, comprising, in this order, applying a coating liquid containing one or more polyurethane resins and one or more hydrophilic glossy materials to a release layer, and then heating it.

Images