Decorative laminated members and decorative molded products

Abstract

The present invention provides a decorative laminated member that provides high design aesthetics and excellent adhesion, and exhibits minimal change in design aesthetics before and after stretching, as well as a method for manufacturing the same, and a decorative molded product containing the decorative laminated member, and a method for manufacturing the same. [Solution] A decorative laminated member having a design layer (A) and an opaque heat-resistant film layer (B), A decorative laminated member characterized in that the difference ΔL* between the L* value measured from one side of the decorative laminated member and the L* value measured from the other side is between -30 and 30.

Description

[Technical Field]

[0001] The present invention relates to a decorative laminated member, a method for manufacturing a decorative laminated member, a decorative molded product, and a method for manufacturing a decorative molded product. [Background technology]

[0002] Conventionally, there is an insert molding method in which a decorative sheet is heated and pre-molded to fit the desired injection molding die, pre-shaped, placed in the injection molding die so that molten resin is injected into the backer layer, and then injection molding is performed to weld the molten resin to the backer layer, thereby integrating the decorative sheet and the molten resin, and the insert molded product is removed from the injection molding die. The backer layer protects the design layer from the heat and pressure during injection molding and improves adhesion with the molded body. It also plays a role in making the pre-molded decorative sheet easier to handle by providing it with thickness.

[0003] The decorative sheet described above provides aesthetic appeal and surface protection to a molded body by having a design layer, a clear coating layer, etc., and is applied not only to flat molded bodies but also to molded bodies with three-dimensional curved surfaces, such as vehicles. In other words, the decorative sheet is made to conform to the three-dimensional shape of the molded body and then applied to the surface of the molded body. In this case, the decorative sheet is usually stretched before being applied to the surface of the molded body. However, this stretching can cause the design layer to stretch, which can lead to a decrease in the aesthetic appeal of the decorative sheet, such as uneven coloring or uneven decoration.

[0004] In particular, when decorative sheets in white or other colors were stretched, the opacity of the design layer decreased due to the stretching, making them more susceptible to the influence of the underlying color and prone to changes in design. Similarly, when decorative sheets containing luminous pigments in the design layer were stretched, the spacing between the luminous pigments widened, making the decorative sheet more susceptible to the influence of the underlying color and prone to a decrease in design.

[0005] For example, Patent Document 1 discloses a decorative sheet in which the difference in L value (ΔL) measured by the SCE method from the transparent resin layer side before and after subjecting the decorative sheet to a tensile test is 1.5 or less. However, this is based on the assumption that a black layer with high opacity and less susceptibility to changes in design due to stretching is used as the design layer, and it is not disclosed whether it can be applied to decorative sheets of colors with low opacity such as white or metallic decorative sheets. Furthermore, in this patent, the L value is evaluated after the black decorative sheet is attached to a black ABS plate, so if the decorative sheet is attached to a material other than black, it is conceivable that the ΔL will be larger due to the influence of the color of the material to which it is attached. Furthermore, while Patent Documents 2 to 4 disclose decorative sheets having a metallic appearance, they limit the physical properties of the lustrous pigment used in the design layer, the resin composition, the layer structure, etc., and do not focus on the role of the backer layer.

[0006] [Patent Document 1] Japanese Patent Publication No. 2023-28516 [Patent Document 2] Japanese Patent Publication No. 2023-23358 [Patent Document 3] Japanese Patent Publication No. 2023-166845 [Patent Document 4] Japanese Patent Publication No. 2022-66786 [Overview of the project] [Problems that the invention aims to solve]

[0007] In view of the above, the present invention aims to provide a decorative laminated member that provides high design aesthetics and excellent adhesion, and exhibits little change in design aesthetics before and after stretching, as well as a method for manufacturing the same, and a decorative molded product including the decorative laminated member, and a method for manufacturing the same. [Means for solving the problem]

[0008] The present invention relates to a decorative laminated member having a design layer (A) and an opaque heat-resistant film layer (B), The difference ΔL* between the L* value measured from one side of the decorative laminated member and the L* value measured from the other side is -30 or more and 30 or less, and relates to a decorative laminated member. The decorative laminated member may further have at least one layer among an adhesive layer (C), a resin base material layer (D), and a clear coating film layer (E).

[0009] It is preferable that the difference ΔSz between the maximum surface roughness value Sz0 measured from the design layer (A) side of the decorative laminated member and the maximum surface roughness value Sz1 measured from the design layer (A) side of the decorative laminated member stretched by 40% is 40 μm or less. It is preferable that the maximum valley depth Sv of the surface on the design layer (A) side of the heat-resistant film layer (B) satisfies Sv ≤ 5 μm. It is preferable that the color difference ΔE(100) between the color measured from the design layer (A) side of the decorative laminated member and the color measured from the design layer (A) side of the decorative laminated member stretched by 100% is 1.5 or less. It is preferable that the color difference ΔE(200) between the color measured from the design layer (A) side of the decorative laminated member and the color measured from the design layer (A) side of the decorative laminated member stretched by 200% is 3 or less. It is preferable that the total light transmittance measured from the design layer (A) side of the decorative laminated member stretched by 200% is 20% or less. It is preferable that the 60° gloss measured from the design layer (A) side of the decorative laminated member is 60 or more. The decorative laminated member has an integrated light quantity of 2000 mJ / cm 2 After irradiating with active energy rays of, the outermost layer) surface on the design layer (A) side of the decorative laminated member is abraded 10 times while applying a vertical load of 4.9 N per 4 cm 2 with a gauze containing acetone, and it is preferable that the change amount of the 60° gloss of the outermost layer surface is 10 or less.

[0010] It is preferable that the heat-resistant film layer (B) has a thickness of 50 to 500 μm. The heat-resistant film layer (B) preferably contains at least one of the following: polypropylene resin, ABS resin, PC resin, PMMA resin, and PC-ABS resin. The above design layer (A) comprises an acrylic resin which is a binder component, and at least one of a glossing agent and a coloring pigment. It is preferable that the total solid content of the binder component, luminescent material, and coloring pigment is 0.5 to 60 parts by mass of the luminescent material and coloring pigment in 100 parts by mass of the total solid content of the binder component, luminescent material, and coloring pigment. The above-mentioned resin substrate layer (D) is preferably made of at least one of polymethyl methacrylate (PMMA), polycarbonate (PC), and PMMA / PC, and has a thickness of 50 to 300 μm. The clear coating layer (E) is preferably formed using an after-cure type radiation-curable clear coating layer forming composition or a thermosetting type urethane resin composition.

[0011] The present invention is also a decorative molded product characterized by being obtained by pressing the above-mentioned decorative laminated member onto the surface of a molded body.

[0012] The present invention relates to a method for manufacturing the above-described decorated molded product, This method for manufacturing a decorated molded product is characterized by comprising an injection molding process in which the main surface on the design layer (A) side is brought into contact with the mold, and molten resin is injected toward the main surface on the heat-resistant film layer (B) side. The method for manufacturing the above-described decorative molded product preferably includes a preforming step before the injection molding step in which a decorative laminated member is molded into a shape that conforms to the three-dimensional shape of the mold. [Effects of the Invention]

[0013] The present invention provides a decorative laminate that can reduce changes in design before and after stretching, and is particularly suitable for insert molding. Therefore, it can be suitably used to decorate molded products having three-dimensional shapes, such as automobile bodies, automobile exterior parts, and automobile interior parts. Note that automobiles also include motorcycles and the like. [Brief explanation of the drawing]

[0014] [Figure 1] This is a schematic diagram showing an example of the laminated structure of the decorative laminated member of the present invention. [Figure 2] This figure specifically illustrates the method for reading Tg from a chart in the Tg measurement method of the present invention. [Modes for carrying out the invention]

[0015] The present invention will be described in detail below. (Laminated material for decorative purposes) The decorative laminated member of the present invention has a laminated structure that includes a design layer (A) and a heat-resistant film layer (B) as essential components. Optionally, it may also have an adhesive layer (C), a resin substrate layer (D), a clear coating layer (E), etc., depending on the purpose. Specifically, for example, it may have the laminated structure shown in Figure 1. A film with this configuration is bonded to a molded product by a heat-resistant film layer (B) for decoration. Furthermore, the decorative laminated member of the present invention may optionally have a protective film layer (F) or the like. These layers can be arranged in various laminated configurations as needed.

[0016] The decorative laminated member of the present invention is characterized in that the difference ΔL* between the L* value measured from one side and the L* value measured from the other side is between -30 and 30. In other words, the difference ΔL* between the L* value measured from the side of the heat-resistant film layer opposite to the design layer and the L* value measured from the side of the design layer opposite to the heat-resistant film layer is between -30 and 30, meaning that the L* value of the heat-resistant film layer alone is close to the L* value of the design layer alone. The present invention has found that by providing a heat-resistant film layer in which the difference ΔL* can be within the above range, changes in the design when the decorative laminate is stretched can be suppressed.

[0017] In this regard, in the Lab color space, it is sufficient to keep the L value representing lightness within the above range, and the values ​​of a and b in the complementary color dimensions are not important. Therefore, for example, even if the design layer is a color design, the heat-resistant film layer (B) may be black and white or have a different hue, and only the L value may fall within the above range.

[0018] Such a heat-resistant film layer needs to be opaque, and for example, the desired heat-resistant film layer can be formed by incorporating a coloring pigment. Conventional backer layers usually do not contain coloring pigments, or if they do, they are intended to assist in opacity when unstretched, and do not participate in controlling the design when stretched. The present invention has found that by including a heat-resistant film layer in which a coloring pigment is appropriately incorporated so that ΔL* is within the above range, it is possible to suppress changes in the design when the decorative laminate is stretched. Furthermore, because the decorative laminated member of the present invention suppresses the deterioration of design quality through the above-mentioned action, there are no limitations on the physical properties and blending amount of pigments used in the design layer, nor on the composition and layer structure of the design layer. In addition, since a heat-resistant film layer with ΔL* within the above-mentioned range can be used in common for multiple design layers of different colors, the production efficiency of the decorative laminated member can be increased.

[0019] The above ΔL* can be determined by measuring the L* value using a colorimeter in accordance with the provisions of JIS K 5600-4, from the design layer side and the heat-resistant film layer side of the decorative laminated member. The above ΔL* is more preferably -25 for the lower limit and 25 for the upper limit. As the above-mentioned colorimeter, for example, a Konica Minolta CR-400 can be used.

[0020] The above ΔL* can be adjusted by any method. For example, it can be adjusted by adjusting the type and amount of coloring pigment contained in the heat-resistant film layer, the resin composition, manufacturing conditions, film thickness, etc. Among these, adjusting the type and amount of coloring pigment is simple and preferred.

[0021] The physical properties of the decorative laminated member in this invention are measured with any of the above-mentioned layers present. For example, in the case of the laminated structure shown in Figure 1, which includes an adhesive layer (C), a resin substrate layer (D), and a clear coating layer (E), the difference ΔL* between the L* value measured from the heat-resistant film layer side and the L* value measured from the clear coating layer side is used. The same applies to ΔSz, ΔE, and total light transmittance, which are explained below.

[0022] In the decorative laminated member of the present invention, it is preferable that the difference ΔSz between the maximum surface roughness Sz0 measured from the design layer (A) side of the decorative laminated member and the maximum surface roughness Sz1 measured from the design layer (A) side of the decorative laminated member stretched by 40% is 40 μm or less. When the above ΔSz is 40 μm or less, it is considered that changes in surface smoothness during the molding process are suppressed, and the design as intended can be obtained. The above ΔSz is more preferably 35 μm or less. The above ΔSz values ​​were measured using a VK-X3000 laser microscope (manufactured by Keyence Corporation) in accordance with ISO 25178. Specifically, the surface of the decorative laminated member on the design layer (A) side was magnified 60 times, and the maximum surface roughness Sz was measured at five points in a 3mm x 3mm area, and Sz0 was obtained from the average value. Similarly, the surface of the decorative laminated member on the design layer (A) side was magnified 60 times, and the maximum surface roughness Sz was measured at five points in a 3mm x 3mm area, and Sz1 was obtained from the average value. From these, ΔSz = Sz1 - Sz0 was calculated.

[0023] In the decorative laminated member of the present invention, it is preferable that the difference ΔE(100) between the color measured from the design layer (A) side of the decorative laminated member and the color measured from the design layer (A) side of the decorative laminated member after 100% stretching is 1.5 or less. When the above ΔE(100) is 1.5 or less, it is considered that the change in design due to stretching is suppressed, and uniformity of the design in molded products using this decorative laminated member is ensured, which is therefore preferable. The above ΔE(100) is more preferably 1.2 or less, and even more preferably 1 or less. In the decorative laminated member of the present invention, it is preferable that the difference ΔE(200) between the color measured from the design layer (A) side of the decorative laminated member and the color measured from the design layer (A) side of the decorative laminated member stretched by 200% is 3 or less. When the above ΔE(200) is 3 or less, it is considered that the change in design due to stretching is suppressed, and uniformity of the design in molded products using this decorative laminated member is ensured, which is preferable. The above ΔE(200) is more preferably 2 or less, and even more preferably 1 or less. Furthermore, the above ΔE can be determined by measuring the L*, a*, and b* values ​​using a colorimeter in accordance with the provisions of JIS K 5600-4.

[0024] Furthermore, it is preferable that the decorative laminated member of the present invention has a total light transmittance of 20% or less, measured from the design layer (A) side of the decorative laminated member stretched by 200%. It is even more preferable that the total light transmittance be 10% or less. The heat-resistant film layer is preferably opaque to such an extent that the total light transmittance is 20% or less, and by keeping it within the above range, it is possible to sufficiently suppress changes in design due to the influence of the color of the injection resin in the stretched portion. The above total light transmittance values ​​were measured using a haze meter NDH4000 (Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7361-1. A halogen lamp was used as the light source for the measurement.

[0025] Furthermore, it is preferable that the decorative laminated member of the present invention has a 60° gloss of 60 or higher, measured from the design layer (A) side. A 60° gloss of 60 or higher is preferable because it results in a good appearance suitable for automobile exteriors. A 60° gloss of 70 or higher is more preferable, and 80 or higher is even more preferable. The 60° gloss is a value measured using a gloss meter (BYK Corporation; product name: Microtrigloss) in accordance with JIS Z 8741 Specular gloss - Measurement method.

[0026] The decorative laminated member of the present invention has an integrated light intensity of 2000 mJ / cm². 2 After irradiating with the active energy rays, the outermost surface of the design layer (A) was wiped with acetone-soaked gauze for 4 cm.2 When subjected to 10 cycles of abrasion under a vertical load of 4.9 N, it is preferable that the change in the 60° gloss of the outermost layer surface is 10 or less. More preferably, the change in the 60° gloss is 5 or less. A change in the 60° gloss of 10 or less is preferable because it exhibits excellent chemical resistance.

[0027] The following describes each layer that makes up the decorative laminated material. (Design layer (A)) The decorative laminated member of the present invention comprises at least one design layer (A) to provide a decorative appearance. Such a layer may be a design layer (A-1) formed by a colored paint composition, a design layer (A-2) formed by printing, a metallic design layer (A-3), etc. The design layer (A) may consist of any one of the above-mentioned layers, or it may consist of multiple layers. A unique appearance can be obtained by combining these layers. The following describes each of the above design layers (A-1) to (A-3).

[0028] (Design layer (A-1) formed by a colored paint composition) The colored paint composition that can be used in forming the above-mentioned design layer (A-1) is not particularly limited, but it is preferable that it contains an acrylic resin and at least one of a glossing agent and a coloring pigment. In addition to the above components, the colored paint composition may also contain other components such as ultraviolet absorbers (UVA), light stabilizers (HALS), binder resins and crosslinking agents, pigments, orientation control agents, settling inhibitors, surface modifiers, defoaming agents, conductive fillers, and solvents. The colored paint composition may be cured by electromagnetic radiation, or it may be thermoplastic or thermosetting.

[0029] (Acrylic resin) The acrylic resin contained in the colored coating composition is not particularly limited, but it is preferably such that its weight-average molecular weight Mw is 10,000 or more and 300,000 or less, and more preferably 30,000 or more and 200,000 or less. If the weight-average molecular weight Mw is less than 10,000, the film strength of the design layer (C) decreases, and if the weight-average molecular weight Mw exceeds 300,000, it becomes difficult to manufacture the colored coating composition and apply it to the film.

[0030] The above acrylic resin preferably has a Tg of -30°C to 160°C. If the Tg is below -30℃, the tackiness of the coating film after coating and drying may increase, and the film strength may decrease. If it exceeds 160℃, molding defects may occur due to increased coating film hardness.

[0031] The binder component used in the design layer may include thermoplastic resins other than acrylic resin, such as cellulose resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyester resin, urethane resin, epoxy resin, and styrene resin.

[0032] In this specification, Tg refers to the value measured using a differential scanning calorimeter (DSC) (thermal analyzer SSC5200 (manufactured by Seiko Electronics)) through the following process: Step 1, where the temperature is raised from 20°C to 150°C at a heating rate of 10°C / min; Step 2, where the temperature is cooled from 150°C to -50°C at a cooling rate of 10°C / min; and Step 3, where the temperature is raised from -50°C to 150°C at a heating rate of 10°C / min. Tg is the value obtained from the chart during the heating phase of Step 3. Specifically, Tg is defined as the temperature indicated by the arrow in the chart shown in Figure 2.

[0033] (shining material) The above-mentioned luminous material is not particularly limited, but is preferably at least one selected from the group consisting of aluminum, glass, inorganic pigments, and organic pigments. More specifically, examples include metallic pigments using metallic luminous materials such as coated aluminum, aluminum flakes, copper, zinc, nickel, tin, aluminum oxide, and other metals or alloys; and mica pigments such as interference mica and white mica.

[0034] (Coloring pigments) Examples of coloring pigments include azo lake pigments, phthalocyanine pigments, indigo pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and metal complex pigments. Examples of inorganic pigments include yellow iron oxide, red iron oxide, titanium dioxide, and carbon black.

[0035] The above-mentioned colored paint composition preferably contains 0.5 to 60 parts by mass of the luminous agent and colored pigment in 100 parts by mass of the total solid content of the binder component, luminous agent, and colored pigment.

[0036] (Other ingredients) Other components included in the colored paint composition, such as binder resins and crosslinking agents, include, for example, modified acrylic resins, polyester resins, epoxy resins, olefin resins, modified olefin resins, melamine resins, polyisocyanate compounds, and blocked isocyanate compounds. Furthermore, the solvent included in the colored paint composition can be one or more organic solvents commonly used in paints, such as ester-based, ether-based, alcohol-based, amide-based, ketone-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, and aromatic hydrocarbon-based solvents. However, when using the above solvents, if volatile substances remain in the laminated film, they may volatilize during decoration of the molded article, causing pinholes or blistering. Therefore, it is preferable to sufficiently reduce the amount of volatile substances contained in the laminated film.

[0037] (Design layer formed by printing (A-2)) The decorative laminated member of the present invention may have a design layer (A-2) formed by printing. The printing method is not particularly limited and can be formed by known methods such as inkjet printing, screen printing, offset printing, or flexographic printing. In particular, inkjet printing is preferred because it can form various printed layers inexpensively. Furthermore, the printing may be performed using energy ray curing ink.

[0038] (Metallic design layer (A-3)) The present invention may involve forming a coating layer containing vapor-deposited aluminum (A-3a) or a vapor-deposited metal layer made of indium or tin (A-3b) in order to obtain an excellent metallic appearance as if it were made of metal. By forming a metallic design layer such as (A-3a) or (A-3b) above, not only is a good metallic appearance obtained, but decoration can be performed on a three-dimensional molded product without cracking or whitening due to stretching during decoration, and a good metallic appearance can be achieved.

[0039] Since such metallic-looking design layers consist of a coating layer containing vapor-deposited aluminum (A-3a) or a vapor-deposited metal layer made of indium or tin (A-3b), these will be described in detail below.

[0040] (Coating layer containing vapor-deposited aluminum (A-3a)) The first example of a coating layer for forming a metallic-looking design layer in the present invention is one formed by a paint containing vapor-deposited aluminum pigment.

[0041] Examples of coating layers containing such vapor-deposited aluminum pigment (A-3a) include those formed by a metallic base coating containing 30 to 85% by weight of vapor-deposited aluminum pigment relative to the amount of paint solids.

[0042] The above-mentioned vapor-deposited aluminum pigment is obtained by shredding a vapor-deposited aluminum film into flakes. Such non-leafing vapor-deposited aluminum pigments can be manufactured, for example, by using a plastic film such as oriented polypropylene, crystalline polypropylene, or polyethylene terephthalate as a base film, applying a release agent on it, and then vapor-depositing aluminum on top of the release agent.

[0043] Unlike conventional aluminum pigments such as aluminum flakes, the above-mentioned vapor-deposited aluminum pigment has less particle size, which makes it possible to provide a design layer with a mirror-like appearance similar to a metal surface.

[0044] The above-mentioned vapor-deposited aluminum pigment is more preferably a non-leafing vapor-deposited aluminum pigment. The non-leafing vapor-deposited aluminum pigment is preferably a particle size of 3 to 20 μm and a thickness of 0.01 to 0.1 μm. Having the above particle size makes it possible to obtain a new metallic design with less graininess. The above particle size is more preferably 5 to 15 μm. In this specification, the particle size is the value measured with a laser diffraction particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.). Examples of commercially available non-leafing vapor-deposited aluminum that can be used in the present invention include Metashen 11-0010, 41-0010, 71-0010, 91-0010, MS-750, MS-650 (manufactured by Ciba Specialty Co., Ltd.), and Silverline P1000, P4100, Metalure L, Metalure A21010BG (manufactured by Ekart Co., Ltd.).

[0045] Leafing treatment is a treatment applied to the surface of aluminum using hydrophobic and / or oleophobic agents. The non-leafing vapor-deposited aluminum pigment used in this invention is preferably a non-leafing vapor-deposited aluminum pigment that has not undergone such leafing treatment. When leafing vapor-deposited aluminum is used, the adhesion to adjacent coating layers decreases, resulting in adhesion problems. Therefore, in this invention, it is preferable to use non-leafing vapor-deposited aluminum.

[0046] The amount of the vapor-deposited aluminum pigment is 30 to 85% by weight relative to the total solid content of the coating layer (A-3a) containing the vapor-deposited aluminum. Below 30% by weight, a glossy coating film that satisfies the dense metallic luster cannot be obtained, and above 85% by weight, the physical properties of the coating film deteriorate. The content of the non-leafing vapor-deposited aluminum pigment is more preferably 40 to 80% by weight.

[0047] The coating layer (A-3a) containing the above-mentioned vapor-deposited aluminum further contains a binder resin in addition to the non-leafing vapor-deposited aluminum pigment. The binder resin is not particularly limited and can include vinyl chloride resin, acrylic resin, urethane resin, polyester resin, etc., and two or more of these may be mixed and used. Among these, vinyl chloride resin is particularly preferred.

[0048] The vinyl chloride resin can be one that is available on the market. The vinyl chloride resin may be a homopolymer of vinyl chloride, or a copolymer of vinyl chloride with other vinyl monomers that can copolymerize with vinyl chloride. More specifically, the copolymer can be a copolymer of vinyl chloride with vinyl acetate, maleic anhydride or its esters, vinyl ether, acrylic acid, acrylic hydroxyl group-containing monomers, etc.

[0049] The degree of polymerization of these polyvinyl chloride resins is typically 200 to 2000, preferably 300 to 1000. Easily available commercially produced polyvinyl chloride resins include Solvine C, CN, A, TA2, TAO, TAOL, and M5 from Nisshin Chemical Industry; Vinnol H11 / 59, E15 / 48A, LL4320, and E15 / 45M from Wacker; and VYHD, VAGD, VMCH, and VMCC from Dow UCAR. Two or more of these can also be used in mixture form.

[0050] The coating layer (A-3a) containing the above-mentioned vapor-deposited aluminum may also contain an aluminum anti-coagulation agent. This is preferable because the action of the aluminum anti-coagulation agent can suppress cohesive failure between the aluminum and the resin. Specifically, Diana RE360 (manufactured by Mitsubishi Rayon Co., Ltd.) can be used as the aluminum anti-coagulation agent.

[0051] The coating layer (A-3a) containing the above-mentioned vapor-deposited aluminum may contain other luminous pigments and / or coloring pigments in addition to the above-mentioned specific non-leafing vapor-deposited aluminum pigment. Other luminous pigments and coloring pigments are not limited to those mentioned above, but include the luminous materials and coloring pigments described above.

[0052] The metallic base paint for forming the coating layer (A-3a) containing the above-mentioned vapor-deposited aluminum may contain, in addition to the above-mentioned components, polyethylene wax, settling inhibitors, curing catalysts, ultraviolet absorbers, antioxidants, leveling agents, surface modifiers such as silicones and organic polymers, anti-sagging agents, thickeners, defoaming agents, crosslinkable polymer particles (microgels), etc., as appropriate. The metallic base paint may be in the form of a solvent-based paint, a water-based paint, etc.

[0053] The coating layer (A-3a) containing the above-mentioned vapor-deposited aluminum preferably has a thickness of 0.05 to 5 μm. If it is outside this range, it is undesirable as it is prone to problems such as whitening and cracking.

[0054] (A vapor-deposited metal layer consisting of indium or tin (A-3b)) First, let's explain the vapor-deposited metal layer. Vapor deposition is a method of forming a thin film by heating and vaporizing a deposition material in a vacuum container and depositing it onto the surface of a substrate placed at a distance. In this invention, the metals used for vapor deposition are tin and indium. -3 ~10 -4Because a vacuum of approximately Pa is required, the container must first be brought into a vacuum state. Therefore, deposition is a complete batch process, and continuous processing is not possible.

[0055] Furthermore, the deposition method for film generally involves (1) setting the film roll and target metal in a chamber, and (2) evacuating the chamber (10 -3 ~10 -4 The process consists of (1) heating the target and starting the film's movement, (2) heating the target and generating steam to deposit the film onto the surface, and (3) opening the chamber to the atmosphere upon completion of the deposition. Compared to direct deposition onto parts, this batch process allows for continuous processing of an entire roll of film, resulting in high economic efficiency. It also has the advantage of allowing for easy control of the thickness and quality of the deposited film. However, the film itself cannot be applied to three-dimensional objects.

[0056] The vapor-deposited metal layer (A-3b) made of indium or tin in the present invention can be formed by a conventional vapor deposition method using these metals. By using indium or tin, a metal layer with good elongation properties can be obtained, so cracking or whitening does not occur when forming into a three-dimensional shape, and there is no adverse effect on the appearance.

[0057] In this invention, by using indium or tin as the vapor-deposited metal layer, the discontinuous vapor deposition process has the advantage of making it less prone to cracking and whitening.

[0058] When forming such a vapor-deposited metal layer, its thickness is preferably 0.05 to 5 μm. This thickness allows for the successful achievement of the aforementioned objectives.

[0059] (Heat-resistant film layer (B)) The heat-resistant film layer protects the design layer from heat and pressure during insert molding and enhances adhesion to the molded body. Its thickness also facilitates handling of the pre-molded decorative sheet. The heat-resistant film layer is selected according to the resin being molded, but generally, polyolefin resins such as ABS resin and polypropylene resin, polymethyl methacrylate (PMMA) resin, styrene resin, acrylic resin, vinyl chloride resin, polycarbonate resin, and PC-ABS resin are preferred. Among these, it is preferable to include at least one of polypropylene resin, ABS resin, PC resin, PMMA resin, and PC-ABS resin.

[0060] The heat-resistant film layer described above is opaque. Specifically, it is preferable that it contains a coloring pigment, and the coloring pigment is not particularly limited; the coloring pigments listed for the design layer described above can be used. The content of the coloring pigment is not particularly limited, but it is preferable that it is contained in a proportion of 0.5 to 60% by mass relative to the weight of the heat-resistant film layer.

[0061] The method for manufacturing the heat-resistant film layer described above is not particularly limited. For example, a method can be used in which a colored pigment is kneaded into the resin described above and then formed into a film by extrusion molding, calendering, or the like. The thickness of the heat-resistant film layer described above is preferably 50 to 500 μm, and more preferably 100 to 500 μm. The thickness can be adjusted as appropriate, but it is desirable to adjust it to a thickness that provides sufficient opacity.

[0062] Preferably, the maximum valley depth Sv on the design layer side of the heat-resistant film layer satisfies Sv ≤ 5 μm. This range makes it easier to prevent the inclusion of fine voids between layers when forming the heat-resistant film layer on top of and adjacent to the heat-resistant film layer. This effect is preferable because it prevents the phenomenon where the surface smoothness changes due to thermal expansion of air in the fine voids between layers during pre-forming of decorative laminated members, thereby impairing the design. More preferably, the maximum valley depth Sv satisfies Sv ≤ 4 μm. The maximum valley depth Sv was determined by using a laser microscope to magnify the surface of the heat-resistant film layer on the design layer side at 480x magnification, measuring Sv at five points in a 300 μm × 300 μm area, and taking the average of these values ​​as the maximum valley depth Sv.

[0063] The heat-resistant film layer (B) is opaque, and more specifically, it is preferable that its total light transmittance be 10% or less. Having such opacity allows the above-mentioned objectives to be suitably achieved. This total light transmittance was measured using a haze meter NDH4000 (Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7361-1.

[0064] (Adhesive layer (C)) The decorative laminated member of the present invention may optionally have an adhesive layer (C). The adhesive layer is a layer that serves to bond adjacent layers together, and may be an adhesive layer or a primer layer. The adhesive layer (C) described above is composed of thermoplastic elastomer (TPE), acrylic resin (PMMA: Poly Methyl Methacrylate), polycarbonate resin (PC: Polycarbonate), polyester resin (PET: Polyethylene Terephthalate), silicone resin, urethane resin or epoxy resin, as well as tackifiers and softeners. Thermoplastic elastomers include thermoplastic polystyrene (styrene-based elastomer) (TPS: Thermoplastic Polystyrene), thermoplastic polyurethane (TPU: Thermoplastic Polyurethane), thermoplastic polyolefin (TPO: Thermoplastic Olefin), thermoplastic polyester (TPE: Thermoplastic Polyester), thermoplastic polyamide (TPA: Thermoplastic Polyamide), polyvinyl chloride (PVC: Polyvinyl Chloride), and polyvinyl butyral (PVB: Polyvinyl Butyral), etc. Among these, thermoplastic polystyrene and acrylic resin are preferred from the viewpoint of heat resistance and weather resistance. The thermoplastic polyolefin mentioned above may be a chlorinated polyolefin. The tackifier contains one or more resins selected from terpene resins, rosin resins, petroleum resins, coal resins, phenolic resins, xylene resins, etc. Examples of terpene resins include α-pinene terpene resins, β-pinene terpene resins, dipentene terpene resins, aromatically modified terpene resins, terpene phenolic resins, and hydrogenated terpene resins. Examples of rosin resins include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, and modified rosin. Examples of petroleum resins include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, copolymerized (C5 / C9) petroleum resins, alicyclic (hydrogenated, dicyclopentadiene (DCPD)) petroleum resins, and styrene (styrene, substituted styrene) petroleum resins. Examples of coal resins include coumarone-indene resin.The softening agent contains one or more process oils selected from paraffinic process oils, naphthenic process oils, aromatic process oils, liquid polybutene, or liquid polyisobutylene. Furthermore, the thickness of the adhesive layer (C) is preferably in the range of 5 μm to 200 μm.

[0065] The adhesive layer (C) may contain a curing agent. If a curing agent is included, it is preferable to use a polyisocyanate as the curing agent. The polyisocyanate that can be used is not particularly limited, and for example, those exemplified as usable in the formation of the clear coating layer (E) described later can be used. When using a curing agent, it is preferable to use an adhesive resin that has a reactive functional group with the curing agent. Specifically, it is preferable that it has a hydroxyl group. In this case, the hydroxyl value is preferably 0.5 to 100 mg KOH / g. The lower limit of the above is more preferably 1 mg KOH / g, and even more preferably 2 mg KOH / g. The upper limit of the above is more preferably 80 mg KOH / g, and even more preferably 50 mg KOH / g. If the hydroxyl value is too low, a sufficient crosslinked film cannot be obtained, and if the hydroxyl value is too high, the film after crosslinking may have poor stretchability, or the reaction with the isocyanate may be insufficient, leaving unreacted hydroxyl values, which may result in poor performance such as water resistance.

[0066] The amount of polyisocyanate used as a curing agent is appropriately determined by the OH equivalent of the resin in the adhesive layer (C) and the NCO equivalent of the polyisocyanate.

[0067] The adhesive layer (C) described above may contain components other than the adhesive resin, curing agent, and components for imparting aesthetic properties, as long as they do not impede the purpose of the invention. Examples of such components include ultraviolet absorbers (UVA), light stabilizers (HALS), curing catalysts, antioxidants, surface modifiers, leveling agents, anti-sagging agents, thickeners, defoaming agents, conductive fillers, and solvents.

[0068] Furthermore, solvents may be used to mix the components contained in the adhesive layer (C) and to adjust their viscosity. As the solvent, one or more conventionally known organic solvents used in paints, such as ester-based, ether-based, alcohol-based, amide-based, ketone-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, and aromatic hydrocarbon-based solvents, may be used. However, when using the above solvents, if volatile substances remain in the laminated film, these volatile substances may volatilize, causing pinholes or blistering during decoration of the molded article. Therefore, it is preferable to sufficiently reduce the amount of volatile substances contained in the laminated film.

[0069] (Resin base layer (D)) The decorative laminated member of the present invention may have a resin substrate layer (D) in order to obtain a homogeneous design layer (A) and / or a clear coating layer (E). When a metallic pigment is used in the design layer, the gloss may decrease after stretching due to the metallic pigment appearing on the surface of the design layer. For this reason, it is preferable to provide a resin substrate layer on the outer side of the design layer, for example, as shown in Figure 1, in order to suppress the aforementioned decrease in gloss.

[0070] Examples of resin substrate layers according to the present invention include polyester films such as polycarbonate films, polyethylene terephthalate, and polyethylene naphthalate; cellulosic films such as diacetylcellulose and triacetylcellulose; and acrylic films such as polymethyl methacrylate (PMMA), which are made of resin substrates and have high transparency. Furthermore, the above-mentioned resin substrate layer may consist of resin substrates such as polystyrene, styrene-based films such as acrylonitrile-styrene copolymer; olefin-based films such as polyvinyl chloride, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, ethylene-propylene copolymer; or amide-based films such as nylon and aromatic polyamide. Furthermore, the above-mentioned resin substrate layer may be made of a resin substrate such as polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinyl butyral, polyarylate, polyoxymethylene, epoxy resin, or a blend of the above polymers. Furthermore, the resin substrate layer may be a laminate of multiple resin substrates. For example, it may be a laminated member or sheet of a film made of acrylic resin and a film made of polycarbonate resin. As the above-mentioned resin substrate, at least one of polymethyl methacrylate (PMMA), polycarbonate (PC), and PMMA / PC is preferred due to its excellent weather resistance and shape stability, with PMMA being particularly preferred.

[0071] The above-mentioned resin substrate layer can be appropriately selected from among these resin substrates depending on the application, including those with low optical birefringence, those in which the phase difference is controlled to 1 / 4 (λ / 4) or 1 / 2 (λ / 2) of the wavelength (e.g., 550 nm), or those in which birefringence is not controlled at all.

[0072] The thickness of the resin substrate layer can be appropriately selected depending on the application of the decorative laminate and the processing method of the component. Generally, from the viewpoint of strength and workability such as handling, it is 50 μm to 400 μm, with 75 μm to 350 μm being particularly preferred, and 100 μm to 300 μm being more preferred.

[0073] (Clear coating layer (E)) The decorative laminated member of the present invention may have a clear coating layer (E) to provide a surface protection function. The clear coating layer (E) is not particularly limited, but is preferably formed by a thermosetting clear coating layer-forming composition or an active energy ray curing clear coating layer-forming composition, and its specific composition is not particularly limited as long as it does not impair the physical properties of the laminated film.

[0074] The clear coating layer (E) described above forms the outermost layer when an article is attached, and therefore requires properties such as weather resistance, water resistance, and impact resistance. For this reason, it is preferable to form the layer with a thermosetting clear coating layer-forming composition or an active energy ray curing clear coating layer-forming composition that is superior in these properties. The above-mentioned thermosetting clear coating layer forming composition and active energy ray curing clear coating layer forming composition are not particularly limited, and conventionally known compositions can be used. Furthermore, the composition may be aqueous or solvent-based, and may be one-component or two-component.

[0075] Among the clear coating layers (E) described above, those obtained using an after-cure type clear coating layer forming composition are preferred because they have excellent stretchability, abrasion resistance, chemical resistance, and high hardness, and those obtained using an after-cure type active energy ray curing type clear coating layer forming composition are particularly preferred. Having such a clear coating layer allows the material to have an appearance suitable for automobile exteriors and the like even after stretching.

[0076] (Composition for forming a thermosetting clear coating layer) Examples of the thermosetting clear coating layer forming composition mentioned above include a two-component clear coating layer forming composition comprising a main component containing a polyol and a curing catalyst, and a curing agent containing an isocyanurate compound. By mixing the main component and the curing agent, the polyol and the isocyanurate compound react to obtain a cured coating film. The main component and / or the curing agent may each be heated and / or degassed under vacuum before mixing. This reduces the amount of water contained in the two-component clear coating layer forming composition obtained by mixing the two, making it easier to improve the appearance of the resulting coating film.

[0077] (Main ingredient) Examples of resin components for the main agent include, but are not limited to, acrylic resins, alkyd resins, epoxy resins, urethane resins, fluororesins, polyether diols, polyester diols, polycarbonate diols, caprolactone diols, polyether polyols, polyester polyols, polycarbonate polyols, and caprolactone polyols.

[0078] Acrylic resin is preferred as the main resin component. Furthermore, it is preferable to use a mixture of the resin component and an isocyanate compound in the composition for forming the clear coating layer. With such a mixture, tackiness does not occur at room temperature, but heating the clear coating layer increases the plasticity of the resin component, making the resin component easily deformable and resulting in a certain degree of tackiness. The above acrylic resin is preferably included as an acrylic polyol. The following provides a detailed description of each component.

[0079] Polyols are film-forming resins. Polyols react with curing agents, for example, by heating, to form a cured coating. Each polyol molecule contains two or more hydroxyl groups. This tends to result in a coating with high hardness. Polyols can be used individually or in combination of two or more types.

[0080] The main component preferably contains a polyol (A1) having 3 or more hydroxyl groups per molecule and a polyol (A2) having 2 hydroxyl groups per molecule. The ratio of polyol (A1) to polyol (A2) is not particularly limited. The proportion of polyol (A2) may be 50% by mass or less, 40% by mass or less, or 30% by mass or less of the total of polyol (A1) and polyol (A2).

[0081] The hydroxyl value of the polyol is between 20 mg KOH / g and 1000 mg KOH / g. Having the hydroxyl value of the polyol within this range increases the reaction rate between the polyol and the isocyanate compound when the main agent and curing agent are mixed. Therefore, the curing time can be shortened, improving productivity. Furthermore, a certain amount of reaction heat is generated during the reaction, which particularly improves the adhesion of the coating film to the resin substrate.

[0082] If two or more polyols are included, the apparent hydroxyl value, calculated based on the hydroxyl value and mass ratio of each polyol, should be between 20 mg KOH / g and 1000 mg KOH / g. In other words, the main ingredient may contain a polyol with a hydroxyl value of less than 20 mg KOH / g and / or a polyol with a hydroxyl value exceeding 1000 mg KOH / g.

[0083] The hydroxyl value of the polyol (including the apparent hydroxyl value; the same applies hereinafter) is more preferably 30 mg KOH / g or more. The hydroxyl value of the polyol is more preferably 800 mg KOH / g or less, and even more preferably 700 mg KOH / g or less.

[0084] The type of polyol is not particularly limited. Examples of polyols include acrylic polyols, polyester polyols, polyether polyols, polycarbonate polyols, polyacrylate polyols, and polyhydric alcohols. These can be used individually or in combination of two or more. In particular, it is preferable that the polyol includes at least one selected from the group consisting of acrylic polyols, polyester polyols, polyether polyols, and polycarbonate polyols.

[0085] Polyester polyols are preferably made to have a branched structure. Polyester polyols having a branched structure can be prepared, for example, by reacting a trivalent or higher polyhydric alcohol compound with two or more polyhydric carboxylic acids, and repeating the above reaction as needed.

[0086] Examples of commercially available polyester polyols include desmofen VPLS2249 / 1 (manufactured by Sumika Covestro Urethane Co., Ltd.), desmofen 800 (manufactured by Sumika Covestro Urethane Co., Ltd.), desmofen XP2488 (manufactured by Sumika Covestro Urethane Co., Ltd.), Kuraray Polyol P-510 (manufactured by Kuraray Co., Ltd.), and Kuraray Polyol F-510 (manufactured by Kuraray Co., Ltd.).

[0087] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and their block forms. Polyether polyols may also be prepared by adding ethylene oxide and / or propylene oxide to a polyhydric alcohol compound. By the above procedure, polyether polyols having a divalent, trivalent, or higher number of OH functional groups per molecule can be prepared.

[0088] Examples of commercially available polyether polyols include the Sannix series manufactured by Sanyo Chemical Industries, Ltd. Specifically, these include Sannix GP-250, Sannix GP-400, Sannix PP-200, and Sannix GP-600.

[0089] Polycarbonate polyols can be prepared, for example, by reacting a polyhydric polyol with dimethyl carbonate. Examples of commercially available polycarbonate polyols include Duranol T5650E (manufactured by Asahi Kasei Corporation), C-590 (manufactured by Kuraray Co., Ltd.), and ETERNACOLL PH-50 (manufactured by Ube Industries, Ltd.).

[0090] Examples of polyhydric alcohols include ethylene glycol, glycerin, trimethylolpropane, propylene glycol, tetramethylene glycol, and pentaerythritol. The weight-average molecular weight (Mw) of a polyol is not particularly limited. The Mw of the polyol can be set appropriately according to the hydroxyl value, etc.

[0091] The main component may contain a polyol with an average number of hydroxyl groups less than 3. The main component may also contain other film-forming resins other than polyols. Examples of film-forming resins include acrylic resins, polyester resins, alkyd resins, polyether resins, polyolefin resins, polyurethane resins, polycarbonate resins, melamine resins, epoxy resins, and carbodiimide resins. Other film-forming resins may be used individually or in combination of two or more.

[0092] (curing catalyst) The curing catalyst promotes the curing reaction. The curing catalyst is not particularly limited. From the viewpoint of promoting effect, at least one organometallic catalyst containing a metal element selected from the group consisting of Bi, Zn, Al, Zr, and Sn is preferred as the curing catalyst. Among these, at least one organometallic catalyst containing a metal element selected from the group consisting of Bi, Zn, Al, and Zr is preferred.

[0093] Examples of organometallic catalysts containing Bi include bismuth carboxylic acid and its salts. Examples of organometallic catalysts containing Zn include zinc complex catalysts. Examples of organometallic catalysts containing Al include aluminum complex catalysts. Examples of organometallic catalysts containing Zr include zirconium chelate catalysts. Examples of organometallic catalysts containing Sn include dialkyltin dicarboxylates such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin diacetate; tin oxide compounds such as dibutyltin oxide; and tin carboxylate salts such as 2-ethylhexanoate tin.

[0094] Examples of commercially available organometallic catalysts containing Bi include K-KAT 348 (manufactured by Kusumoto Chemical Co., Ltd.) and K-KAT XK-640 (manufactured by Kusumoto Chemical Co., Ltd.). Examples of commercially available organometallic catalysts containing Zr include K-KAT 4205, K-KAT XC-9213, K-KAT XC-A209, and K-KAT 6212 (all manufactured by Kusumoto Chemical Co., Ltd.). Examples of commercially available organometallic catalysts containing Al include K-KAT 5218 (manufactured by Kusumoto Chemical Co., Ltd.). Examples of commercially available organometallic catalysts containing Zn include K-KAT XK-314, K-KAT XK-635, K-KAT XK-639, and K-KAT XK-620 (all manufactured by Kusumoto Chemical Co., Ltd.). A commercially available organometallic catalyst containing Sn is, for example, TVS TIN LAU (manufactured by Nitto Kasei Co., Ltd.).

[0095] The content of the curing catalyst is, for example, 0.25 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the coating-forming resin. This allows the curing reaction of the coating-forming resin to proceed rapidly. Therefore, a coating with excellent appearance and physical properties can be obtained by layer formation through coating. The content of the curing catalyst is more preferably 0.5 parts by mass or more per 100 parts by mass of the coating-forming resin. The content of the curing catalyst is more preferably 7 parts by mass or less per 100 parts by mass of the coating-forming resin.

[0096] (Hardening agent) The curing agent crosslinks the film-forming resin, such as acrylic resin or polyol, improving the corrosion resistance and durability of the resulting coating. The curing agent preferably contains an isocyanurate compound. The isocyanurate compound is a trimer of an isocyanate compound and has a ring structure.

[0097] The isocyanate compound is not particularly limited, and any known curing agent for two-component reactive compositions can be used. Examples of isocyanate compounds include aromatic diisocyanates such as tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), and metaxylylene diisocyanate (MXDI); hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and 2-methylpentane-1,5-diisocyanate. Examples include aliphatic diisocyanates such as 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, and trioxyethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate (IPDI), cyclohexyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate. These may be used individually or in combination of two or more.

[0098] Among these, aliphatic diisocyanates are preferred due to their relatively low viscosity, and HDI is more preferred. Trimers of these isocyanates exhibit particularly high reactivity with polyols. Therefore, they are more suitably used in methods for forming clear coating layers by coating.

[0099] The ratio of the isocyanate group equivalent of the isocyanate compound to the hydroxyl group equivalent of the polyol (NCO equivalent / OH equivalent) is preferably 0.3 / 1 to 2 / 1, and more preferably 0.35 / 1 to 1.5 / 1. When the equivalent ratio is within the above range, the curability is high, and it is particularly suitable for use in forming a clear coating layer by coating.

[0100] The curing agent may contain other curing agents besides isocyanurate compounds. Examples of other curing agents include amino resins, monomers or dimers of the above isocyanate compounds, biuret forms of the above isocyanate compounds, blocked forms of the above isocyanate compounds, epoxy compounds, aziridine compounds, carbodiimide compounds, and oxazoline compounds. These may be used individually or in combination of two or more. The curing agent may be a blocked isocyanate. When using a blocked isocyanate, it is preferable to appropriately adjust the conditions of the coating process, curing process, preforming process, injection molding process, etc., so that the blocking agent dissociates and the curing reaction proceeds.

[0101] The curing agent content is, for example, 5% by mass or more and 90% by mass or less of the resin solids content of the paint composition. The curing agent content is preferably 7% by mass or more, and more preferably 10% by mass or more. The curing agent content is preferably 85% by mass or less, and more preferably 70% by mass or less.

[0102] (solvent) The solvent content is 60% by mass or less. Preferably, the solvent content is 55% by mass or less, and more preferably 50% by mass or less.

[0103] The solvent is not particularly limited. The solvent is usually an organic solvent. Examples of organic solvents include ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ether solvents such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, methyl methoxybutanol, ethoxypropanol, ethylene glycol isopropyl ether, ethylene glycol-t-butyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methoxybutanol, and propylene glycol monobutyl ether; alcohol solvents such as methanol, ethanol, butanol, and propyl alcohol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as Swarzol, Shellzol, and mineral spirits; and aromatic solvents such as xylene, toluene, Solvesso-100 (S-100), and Solvesso-150 (S-150). These can be used individually or in combination of two or more.

[0104] (others) The two-component clear coating layer forming composition may contain other components as needed. Examples of other components include additives commonly used in the coating and paint fields. Specifically, these include light stabilizers, UV absorbers, various pigments, surface modifiers, viscosity modifiers, antioxidants, UV inhibitors, defoamers, catalyst aids, rust inhibitors, settling inhibitors, and dispersants. These additives may be added to the main component or to the curing agent. The amount of additives is not particularly limited and can be set as appropriate. The active energy ray curable clear coating layer forming composition is a monomer, oligomer, or polymer that can be crosslinked and cured by radiation. The active energy ray curable resin in this invention may include polyfunctional (meth)acrylate compounds such as polyfunctional (meth)acrylate monomers, polyfunctional (meth)acrylate oligomers, or polyfunctional (meth)acrylate polymers, from the viewpoint of achieving a high crosslink density after curing, a high surface hardness improvement effect, and a high transparency improvement effect. Here, "(meth)acrylate" refers to acrylate and / or methacrylate. In this specification, polyfunctional (meth)acrylate compounds refer to those that do not have a urethane structure and do not include the urethane acrylates described below. In addition to the above-mentioned polyfunctional (meth)acrylate compounds, the active energy ray curable resin may also contain monofunctional (meth)acrylate compounds.

[0105] (Composition for forming a clear coating layer that is curable by active energy rays) (Resin components) The active energy ray-curable clear coating layer formation composition contains a resin component that forms the clear coating layer. Preferably, this resin component contains an active energy ray-curable component. Active energy ray curable components are monomers, oligomers, or polymers (also called resins) that can be crosslinked and cured by active energy rays (e.g., ultraviolet light). Specific examples of such active energy ray curable components include monomers, oligomers, or polymers having at least one unsaturated double bond group, more specifically, (meth)acrylate monomers, (meth)acrylate oligomers, (meth)acrylate polymers, urethane (meth)acrylate monomers, urethane (meth)acrylate oligomers, urethane (meth)acrylate polymers, silicon (meth)acrylate, and modified monomers, oligomers, and polymers thereof, all having at least one unsaturated double bond group. These monomers, oligomers, and polymers may also be used in combination. Note that "(meth)acrylate" refers to acrylate and / or methacrylate. In one embodiment, the active energy ray curable clear coating layer forming composition contains an unsaturated double bond-containing acrylic resin (also called an unsaturated double bond-containing acrylic polymer). In one embodiment, the clear coating layer-forming composition may include a non-reactive acrylic resin. Furthermore, the clear coating layer-forming composition may include an unsaturated double-bond-containing acrylic resin and / or a non-reactive acrylic resin. The clear coating layer-forming composition may, for example, contain multiple types of unsaturated double bond-containing acrylic resins and / or non-reactive acrylic resins.

[0106] For example, an active energy ray curable component, such as a clear coating layer forming composition, includes an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin having a weight-average molecular weight (Mw) of 5,000 to 100,000. In one embodiment, the unsaturated double bond-containing acrylic resin and / or the non-reactive acrylic resin may have a weight-average molecular weight (Mw) of 5,000 to 100,000, for example, a weight-average molecular weight (Mw) of 6,000 to 95,000. The weight-average molecular weight (Mw) can be calculated by known methods.

[0107] In another embodiment, when the active energy ray curable component includes multiple types of polymers, one polymer may have a weight-average molecular weight (Mw) of 5,000 to 100,000, and another polymer may have a weight-average molecular weight (Mw) of 10,000 to 80,000. Furthermore, polymers having different ranges of weight-average molecular weight (Mw) may be included. By using polymers with various weight-average molecular weight ranges in combination, the clear coating layer can exhibit various properties such as high smoothness and high rigidity in the uncured state. Furthermore, the hard coat layer obtained by curing the clear coating layer can also have high smoothness and excellent hard coat performance, such as high hardness, abrasion resistance, and chemical resistance.

[0108] While it should not be interpreted in isolation from any particular theory, the inclusion of an unsaturated double-bond-containing acrylic resin and / or a non-reactive acrylic resin can increase the rigidity of the uncured clear coating layer. Furthermore, by including at least one selected from the group consisting of polyfunctional (meth)acrylates and polyfunctional urethane (meth)acrylates, the crosslinking density of the hard coat layer cured from the clear coating layer can be maintained, allowing the clear coating layer to have high viscosity at room temperature. Moreover, heating can lead to lower viscosity and excellent moldability. As a result, it becomes possible to mold even more complex shapes, further reduce the occurrence of defective products during molding, and the resulting molded articles can have superior hard coat performance, such as higher hardness, wear resistance, and chemical resistance.

[0109] In one embodiment, the clear coating layer-forming composition comprises an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin, and at least one selected from the group consisting of polyfunctional (meth)acrylates and polyfunctional urethane (meth)acrylates. For example, the clear coating layer-forming composition comprises an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin having a weight-average molecular weight (Mw) of 5,000 to 100,000, and at least one selected from the group consisting of polyfunctional (meth)acrylates with an acrylate equivalent of 50 to 500 and polyfunctional urethane (meth)acrylates with an acrylate equivalent of 50 to 500.

[0110] In this specification, a non-reactive acrylic resin is an acrylic resin that does not react or shows little to no reaction when irradiated with active energy rays, for example, an acrylic resin that does not react or shows little to no reaction when irradiated with ultraviolet light.

[0111] The acrylate equivalents of the above-mentioned polyfunctional (meth)acrylate and polyfunctional urethane (meth)acrylate are, for example, 50 to 500, for example, 60 to 400, in another embodiment, 70 to 350, and in yet another embodiment, 100 to 200. By including such a polyfunctional (meth)acrylate and / or polyfunctional urethane (meth)acrylate with the acrylic resin described above, it is possible to further suppress air entrapment and obtain a clear coating layer free from dust, scratches, etc. Furthermore, even with complex shapes, it is possible to obtain molded products with an excellent appearance without defects such as cracks. In addition, molded products can be obtained that have excellent wear resistance and chemical resistance, as well as high hardness.

[0112] In one embodiment, the composition for forming a clear coating layer comprises an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin, a polyfunctional silicone (meth)acrylate, a fluororesin, and inorganic oxidized fine particles. For example, a composition for forming a clear coating layer includes an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin, a polyfunctional silicon (meth)acrylate having a weight-average molecular weight (Mw) of 700 to 100,000, a fluororesin, and inorganic oxidized fine particles. While it should not be interpreted in isolation from any particular theory, the inclusion of polyfunctional silicon (meth)acrylate enables lower surface tension, excellent leveling properties, and reduced tack. Furthermore, the inclusion of fluororesin imparts slipperiness to the clear coating layer (coating). Additionally, the inclusion of inorganic oxidized fine particles provides excellent abrasion resistance and reduces tack.

[0113] The weight-average molecular weight (Mw) of the polyfunctional silicon (meth)acrylate is, for example, 700 to 100,000, in one embodiment it is 800 to 90,000, and in another embodiment it is 800 to 85,000.

[0114] In one embodiment, the fluorine content of the fluororesin is 5% by weight or more and 80% by weight or less, for example, 5% by weight or more and 75% by weight or less.

[0115] For example, a clear coating layer-forming composition contains, per 100 parts by mass of the solid content in the composition, an amount of unsaturated double bond-containing acrylic resin and / or non-reactive acrylic resin in an amount greater than 20 parts by mass and less than or equal to 70 parts by mass, for example, 30 parts by mass or more and less than or equal to 60 parts by mass, and in one embodiment, 35 parts by mass or more and less than or equal to 60 parts by mass of unsaturated double bond-containing acrylic resin and / or non-reactive acrylic resin. When a clear coating layer-forming composition contains multiple types of unsaturated double bond-containing acrylic resin and / or non-reactive acrylic resin, it is preferable that the total amount of multiple types of unsaturated double bond-containing acrylic resin and / or non-reactive acrylic resin is within the above range. In this invention, 100 parts by mass of solids contained in the composition means that the total of the resin solids, such as the unsaturated double bond-containing acrylic resin and / or non-reactive acrylic resin, polyfunctional (meth)acrylate, polyfunctional urethane (meth)acrylate, polyfunctional silicone (meth)acrylate, fluororesin, and photopolymerization initiator, and the solids of the inorganic oxidized fine particles, if present, equals 100 parts by mass.

[0116] In one embodiment, the clear coating layer forming composition contains 5 to 70 parts by mass, for example, 10 to 70 parts by mass, of polyfunctional (meth)acrylate and / or polyfunctional urethane (meth)acrylate per 100 parts by mass of solids contained in the composition, and in another embodiment, 13 to 68 parts by mass.

[0117] In one embodiment, the clear coating layer forming composition contains 5 to 50 parts by mass, for example, 10 to 48 parts by mass, of polyfunctional silicone (meth)acrylate per 100 parts by mass of solids contained in the composition, and in another embodiment, 15 to 48 parts by mass.

[0118] In one embodiment, the clear coating layer forming composition contains 0.1 parts by mass to 10 parts by mass of fluororesin, for example, 1 part by mass to 8 parts by mass, per 100 parts by mass of solids contained in the composition, and in another embodiment, 1.5 parts by mass to 7 parts by mass.

[0119] In one embodiment, the clear coating layer forming composition contains 1 to 55 parts by mass, for example, 10 to 50 parts by mass, of inorganic oxidized fine particles per 100 parts by mass of solid content in the composition, and in another embodiment, 12 to 40 parts by mass. By including inorganic oxide fine particles within this range in a clear coating layer formation composition, rigidity can be imparted to the uncured coating film, for example, resulting in a better coating appearance. The appearance of the resulting molded product can be maintained well. Furthermore, the abrasion resistance of the cured coating film can be improved.

[0120] In one embodiment, the clear coating layer-forming composition in the unirradiated state of active energy rays is a composition in which the molecular weight distribution shape does not change before and after heating for 30 to 60 seconds in an atmosphere of 150 to 190°C. For example, the coating composition contained in the clear coating layer of the heated sample (1) for stretching test, which is a sample before irradiation with active energy rays, is a composition in which the molecular weight distribution shape does not change before and after heating for 30 to 60 seconds in an atmosphere of 150 to 190°C. Here, "no change in the shape of the molecular weight distribution" means that, for the weight-average molecular weight peak, or each molecular weight peak if there are multiple quantitative peaks, the height shift and lateral shift of each molecular weight peak before and after heating for 30 to 60 seconds in an atmosphere of 150 to 190°C are both within the range of ±5%.

[0121] The clear coating layer forming composition according to the present invention can increase the crosslinking density after curing, enhance the effect of improving surface hardness, and enhance the effect of improving transparency, Polyfunctional (meth)acrylate compounds such as polyfunctional (meth)acrylate monomers, polyfunctional (meth)acrylate oligomers, or polyfunctional (meth)acrylate polymers (in this specification, polyfunctional (meth)acrylate compounds may be abbreviated as "polyfunctional (meth)acrylate"); Polyfunctional urethane (meth)acrylate compounds such as polyfunctional urethane (meth)acrylate monomers, polyfunctional urethane (meth)acrylate oligomers, and polyfunctional urethane (meth)acrylate polymers (in this specification, polyfunctional urethane (meth)acrylate compounds may be abbreviated as "polyfunctional urethane (meth)acrylate"); Polyfunctional silicone (meth)acrylate compounds such as polyfunctional silicone (meth)acrylate monomers, polyfunctional silicone (meth)acrylate oligomers, and polyfunctional silicone (meth)acrylate polymers (in this specification, polyfunctional silicone (meth)acrylate compounds may also be abbreviated as "polyfunctional silicone (meth)acrylate"); Preferably, it contains at least one selected from polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, and polyfunctional silicone (meth)acrylate compounds.

[0122] Commercially available (meth)acrylate monomers or oligomers having one unsaturated double bond group may be used. Examples of commercially available products include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, acrylic acid, methacrylic acid, isostearyl (meth)acrylate, ethoxylated o-phenylphenol acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol acrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, N-methylol(meth)acrylamide, and N-hydroxy(meth)acrylamide.

[0123] The polyfunctional (meth)acrylate monomer or oligomer may be modified as necessary. However, in this specification, neither "polyfunctional urethane (meth)acrylate" nor "polyfunctional silicone (meth)acrylate" is included in "polyfunctional (meth)acrylate".

[0124] Commercially available products may be used as polyfunctional (meth)acrylate monomers or oligomers. Examples of commercially available products include DPHA (manufactured by Daicel Ornex), PETRA (manufactured by Daicel Ornex: pentaerythritol triacrylate), PETIA (manufactured by Daicel Ornex), Aronics M-403 (manufactured by Toagosei Co., Ltd.: dipentaerythritol penta and hexaacrylate), Aronics M-402 (manufactured by Toagosei Co., Ltd.: dipentaerythritol penta and hexaacrylate), Aronics M-400 (manufactured by Toagosei Co., Ltd.: dipentaerythritol penta and hexaacrylate), SR-399 (manufactured by Arkema: dipentaerythritol hydroxypentaacrylate), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), KAYARAD DPHA-2C (manufactured by Nippon Kayaku Co., Ltd.), Aronics M-404, M-405, M-406, M-450, M-305, M-309, M-310, M-315, M-320, TO-1200, TO-1231, TO-595, TO-756 (all manufactured by Toagosei Co., Ltd.), KAYARD Products such as D-310, D-330, DPHA, DPHA-2C (all manufactured by Nippon Kayaku Co., Ltd.), Nikalac MX-302 (manufactured by Sanwa Chemical Co., Ltd.), A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, and A-DPH (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.) can be used.

[0125] Examples of monofunctional or polyfunctional (meth)acrylate polymers include high molecular weight compounds of the above-mentioned monofunctional or polyfunctional (meth)acrylate monomers or oligomers.

[0126] In this specification, the various polymers described above may be simply referred to as unsaturated double bond-containing acrylic polymers or unsaturated double bond-containing acrylic resins.

[0127] Commercially available products may be used as polyfunctional urethane (meth)acrylate monomers or oligomers. Commercially available products include, for example, bifunctional urethane (meth)acrylate (UX-2201, UX-8101, UX-6101 from Nippon Kayaku Co., Ltd., UF-8001, UF-8003 from Kyoeisha Chemical Co., Ltd., Ebecryl244, Ebecryl284, Ebecryl2002, Ebecryl4835, Ebecryl4883, Ebecryl8807, Ebecryl6700 from Daicel Ornex Co., Ltd.), trifunctional urethane (meth)acrylate (Ebecryl254, Ebecryl264, Ebecryl265 from Daicel Ornex Co., Ltd.), tetrafunctional urethane (meth)acrylate (Ebecryl8210 from Daicel Ornex Co., Ltd.), and hexafunctional urethane (meth)acrylate (Daicel Ornex's "Ebecryl1290k", "Ebecryl5129", "Ebecryl220", "KRM8200", "Ebecryl1290N"), 9-functional urethane (meth)acrylate (Daicel Ornex's "KRM7804"), 10-functional urethane (meth)acrylate (Daicel Ornex's "KRM8452", "KRM8509"), 15-functional urethane (meth)acrylate (Daicel You can use "KRM8655" from Ornex Co., Ltd., and Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-904, Art Resin UN-901T, Art Resin UN-905, Art Resin UN-952 (all from Negami Kogyo Co., Ltd.), U-6HA, U-15HA, UA-100H, U-4HA, U-6LPA, UA-32P, U-324A, U-4H (all from Shin Nakamura Chemical Co., Ltd.).

[0128] Monofunctional or polyfunctional urethane (meth)acrylate monomers or oligomers can also be prepared, for example, by reacting a polycarbonate diol with a (meth)acrylate compound containing a hydroxyl group and an unsaturated double bond group in the molecule and a polyisocyanate.

[0129] Examples of monofunctional or polyfunctional urethane (meth)acrylate polymers include high molecular weight compounds of the above monofunctional or polyfunctional urethane (meth)acrylate monomers or oligomers.

[0130] The polyfunctional silicone (meth)acrylate monomer or oligomer is a compound having a silicone skeleton. For example, the compound having a silicone skeleton may have a fluorine atom-containing group, and the fluororesin may have a silicone skeleton. Commercially available products may be used as the polyfunctional silicone (meth)acrylate monomer or oligomer. Examples of commercially available products include the following. Compounds having methacryloyl and acryloyl groups Manufactured by BYK: BYK-UV3500, BYK-UV3570 Manufactured by Shin-Etsu Chemical Co., Ltd.: Shin-Etsu Silicone X-22-164, Shin-Etsu Silicone X-22-164AS, Shin-Etsu Silicone X-22-164A, Shin-Etsu Silicone X-22-164B, Shin-Etsu Silicone X-22-164C, Shin-Etsu Silicone X-22-164E, Shin-Etsu Silicone X-22-174DX, Shin-Etsu Silicone X-22-2426, Shin-Etsu Silicone X-22-2475, KER-4000-UV, KER-4700-UV, KER-4710-UV, KER-4800-UV, Manufactured by JNC: FM-0711, FM-0721, FM-0725, TM-0701, FM-7711, FM-7721, FM-7725 Evonik Japan: TEGO ( Registered Trademark) Rad 2010, TEGO (Registered Trademark) Rad 2011. Materials containing fluorine atoms and (meth)acryloyl groups, and materials having a fluororesin compound with a silicone backbone. Manufactured by Nippon Synthetic Chemical Industry Co., Ltd.:紫光 UV-AF305 T&K TOKA: ZX-212, ZX-214-A Manufactured by Shin-Etsu Chemical Co., Ltd.: KY-1203 etc. may be mentioned.

[0131] The active energy ray curable clear coating layer forming composition may also contain, for example, a fluororesin in addition to the resin described above. The inclusion of a fluororesin in the composition can further improve the wear resistance of the molded product. In the present invention, the term "fluororesin" refers to a fluorine-containing resin that does not contain a silicone skeleton compound. Examples include perfluorooctyl acrylate and acrylic-modified perfluoropolyether. The fluorine-containing resin may have modified methacryloyl and acryloyl functional groups. The fluororesin may be, for example, one of the following commercially available products. DIC Corporation products: MegaFuck RS-72-K, MegaFuck RS-75, MegaFuck RS-76-E, MegaFuck RS-76-NS, MegaFuck RS-77 Daikin Industries, Ltd.: Optool DAC-HP Solvay Solexis: FLUOROLINK MD700, FLUOROLINK AD1700 Neos Corporation products: such as Futergent 601ADH2.

[0132] Furthermore, the clear coating layer-forming composition is less prone to tack formation in its uncured state, and the clear coating layer can suppress the adhesion of dust. In addition, it can suppress or significantly reduce the occurrence of appearance defects in the clear coating layer when the protective film layer is peeled off.

[0133] In one embodiment, the clear coating layer forming composition includes inorganic oxidized fine particles. The inorganic oxidized fine particles may be inorganic oxidized fine particles whose surface is modified with unsaturated double bonds. Examples of inorganic oxide fine particles include silica (SiO2) particles, alumina particles, titania particles, tin oxide particles, antimond-doped tin oxide (ATO) particles, and zinc oxide particles. Among these, silica particles and alumina particles are preferable from the viewpoint of cost and paint stability, and those with modified functional groups are even more desirable. The functional group is preferably a (meth)acryloyl group. For example, the primary particle size of inorganic oxide fine particles is 5 nm to 100 nm from the viewpoint of transparency and paint stability. The average particle size of granular material in this specification is a value measured from cross-sectional electron microscope images using image processing software. For example, by incorporating inorganic oxide fine particles, volume shrinkage of the uncured coating film can be mitigated. Furthermore, by incorporating inorganic oxide fine particles, in addition to the above effect, rigidity can be imparted to the coating film. Furthermore, by incorporating inorganic oxide fine particles, it is possible to suppress the occurrence of curling due to curing shrinkage in the cured coating film. For example, by incorporating inorganic oxide fine particles, in addition to the above effects, wear resistance can be provided.

[0134] For example, commercially available inorganic oxide fine particles may be used, such as silica particles (colloidal silica) manufactured by Nissan Chemical Industries: IPA-ST, MEK-S™, IBK-S T, PGM-ST, XBA-S T, MEK-AC-2101, MEK-AC-2202, MEK-AC-4101M, IBK-SD Manufactured by Fuso Chemical Industry Co., Ltd.: PL-1-IPA, PL-1-TOL, PL-2-IPA, PL-2-MEK, PL-3-TOL JGC Catalysts & Chemicals Co., Ltd.: OSCAL series, ELECOM series Examples include the NANOBYK-3605 manufactured by Big Chemie Japan. For example, as alumina particles, Sumitomo Osaka Cement Co., Ltd.: AS-150I, AS-150T Examples of products manufactured by Big Chemie Japan include NANOBYK-3601, NANOBYK-3602, and NANOBYK-3610.

[0135] (Photopolymerization initiator) The clear coating layer-forming composition of the present invention preferably contains a photopolymerization initiator. The presence of a photopolymerization initiator allows the resin component to polymerize well when exposed to active energy rays, such as ultraviolet light. Examples of photopolymerization initiators include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, titanocene-based photopolymerization initiators, oxime ester-based polymerization initiators, and intramolecular hydrogen abstraction type photopolymerization initiators. Examples of alkylphenone-based photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone. Examples of acylphosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Examples of titanocene-based photopolymerization initiators include bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium. Examples of oxime ester polymerization initiators include 1,2-octanedione,1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, and 2-(2-hydroxyethoxy)ethyl ester.Examples of intramolecular hydrogen abstraction type photopolymerization initiators include benzophenone, methyl benzoyl formate, and ketocoumarin. These photopolymerization initiators may be used individually or in combination of two or more.

[0136] Among the above photopolymerization initiators, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2,2-dimethoxy-1,2-diphenylethane-1-one are more preferably used.

[0137] The preferred amount of photopolymerization initiator is 0.01 to 10 parts by mass per 100 parts by mass of the solid content of the clear coating layer forming composition, for example, 1 to 10 parts by mass. The photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination.

[0138] (solvent) The clear coating layer-forming composition may contain a solvent. The solvent is not particularly limited and can be selected as appropriate, taking into consideration the components contained in the composition, the type of substrate to be coated, and the method of application of the composition. Specific examples of solvents that can be used include, for example, aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenethole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and isobutyl alcohol; and halogen solvents such as dichloromethane and chloroform. These solvents may be used individually or in combination of two or more. Of these solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, and ketone-based solvents are preferably used.

[0139] The clear coating layer forming composition may contain various additives as needed. Examples of such additives include commonly used additives such as antistatic agents, plasticizers, surfactants, antioxidants, UV absorbers, light stabilizers, surface modifiers, and leveling agents. The inclusion of these additives in the clear coating layer forming composition offers the advantage of further improving the durability of decorative molded members and decorative molded articles. These additives can be those commonly used in the field of clear coating layer formation.

[0140] A composition for forming a clear coating layer can be prepared by methods commonly used by those skilled in the art. For example, it can be prepared by mixing the above-mentioned components using commonly used mixing equipment such as a paint shaker or mixer.

[0141] (Protective film layer (F)) The decorative laminated member of the present invention may further have a protective film layer (F). The protective film layer (F) may or may not be peeled off.

[0142] The resin film that can be applied to the substrate of the protective film layer is not particularly limited. For example, it may be a polyolefin film such as polyethylene film and polypropylene film, a modified polyolefin film obtained by modifying these polyolefins and adding further functions, a polyester film such as polyethylene terephthalate, polycarbonate and polylactic acid, a polystyrene film, a polystyrene-based resin film such as AS resin film and ABS resin film, a nylon film, a polyamide film, a polyvinyl chloride film and a polyvinylidene chloride film, a polymethylpentene film, or any other film. Furthermore, if necessary, additives such as antistatic agents and UV inhibitors can be applied, and the surface of the substrate can be treated with corona treatment or low-temperature plasma treatment.

[0143] In one embodiment, the resin film applicable to the substrate of the protective film layer is at least one film selected from polyethylene film, polystyrene film, modified polyolefin film, polymethylpentene film, unoriented polypropylene film (CPP film), and biaxially oriented polypropylene film (OPP film). In another embodiment, the resin film that can be applied to the substrate of the protective film layer is a polypropylene film, for example, an oriented polypropylene film (OPP film) or an unoriented polypropylene film (CPP film). The thickness of the protective film layer is not particularly limited, but it is preferably 10 μm at the lower limit and 100 μm at the upper limit, and more preferably 20 μm at the lower limit and 80 μm at the upper limit.

[0144] Furthermore, an adhesive layer may be provided between the protective film layer and the clear coating layer as needed. Having an adhesive layer on the protective film layer helps maintain the conformability and adhesion of the protective film layer to the clear coating layer, better protecting the uncured clear coating layer from external factors (e.g., scratches caused by the equipment) and suppressing air bubbles. Furthermore, even when winding up the uncured clear coating layer and the protective film layer, such problems can be prevented or significantly reduced.

[0145] (Method of manufacturing decorative laminated material) Each layer other than the opaque heat-resistant film layer (B) and the resin substrate layer (D) constituting the decorative laminated member of the present invention can be formed by preparing a paint composition in which the components constituting each layer are dissolved in a solvent, and then applying and drying this on another layer. Each layer other than the opaque heat-resistant film layer (B) and the resin substrate layer (D) may also be formed by preparing a paint composition in which the components constituting each layer are dissolved in a solvent, applying and drying this on a transfer film, and then laminating it with another layer. For example, it can be manufactured through the following process. First, a design layer may be formed on one side of the resin substrate layer, and a protective film layer may be formed if necessary. Next, a clear coating layer may be formed on the other side, and a protective film layer may be formed if necessary. Note that the formation of the design layer and the clear coating layer may be in reverse order. Subsequently, a laminated member can be obtained by performing steps such as forming an adhesive layer on the design layer and bonding it to the heat-resistant film layer, forming an adhesive layer on the heat-resistant film layer and bonding it to the design layer, or preparing an adhesive layer sheet and laminating the design layer and the heat-resistant film layer with this sheet sandwiched in between.

[0146] The coating method for forming each of the above layers is not particularly limited, but for example, it may be applied by spraying, or by using an applicator, die coater, bar coater, roll coater, comma coater, roller brush, brush, spatula, etc. After applying the paint solution using the above coating method, the layers can be formed by heating and drying to remove the solvent in the paint solution.

[0147] The heating and / or irradiation with active energy rays to cure each of the above layers may be performed sequentially for each layer after the layer has been formed, or the heating and / or irradiation with energy rays may be performed after the entire laminated structure has been formed. For the clear coating layer, it is particularly preferable to cure it by heating and / or irradiation with energy rays after the pre-molding process (after-cure) in order to achieve both high stretchability and high chemical resistance.

[0148] (How to use) When decorating a molded product using the decorative laminated member of the present invention, the method may be the same as conventionally known methods and is not particularly limited. That is, if necessary, the protective film layer (F) may be peeled off from the decorative laminated member, and the decorative laminated member may be pressed tightly against the molded surface so that the heat-resistant film layer (B) faces the surface of the molded product to decorate it. After that, electromagnetic wave irradiation or heating may be performed to cure each layer and obtain a coating film. Alternatively, the protective film layer (F) may be peeled off after pressing and curing. Alternatively, pre-molding may be performed before pressing, and the pressing process may be performed after the pre-molding and curing. When the decorative laminated member is pressed tightly against the surface of the molded product, in-mold molding, insert molding, etc. can be used, but it can be preferably used in insert molding.

[0149] The present invention also relates to a decorative molded product obtained by pressing the above-mentioned decorative laminated member onto the surface of a molded body. The method for manufacturing the decorative molded product of the present invention is not particularly limited, but it is preferably obtained by the following insert molding process. Specifically, the method involves placing the decorative laminated member in an injection molding die so that the main surface on the design layer (A) side is in contact with the die, closing the injection molding die, injecting molten resin into the injection molding die toward the main surface on the heat-resistant film layer (B) side, and integrating the cooled and solidified resin with the decorative laminated member in an injection molding process. Finally, after the molten resin has cooled and solidified, the injection molding die is opened, and the insert molded product, whose surface is covered with the decorative laminated member, is removed from the injection molding die. The manufacturing method for the above-described decorative molded product may include a pre-molding step before the injection molding step in which the decorative laminated member is molded to conform to the three-dimensional shape of the mold. Furthermore, a curing step may be included before the pre-molding step for the purpose of improving the film strength of the coating, improving interlayer adhesion, reducing residual solvent, and reducing absorbed moisture. In addition, if a clear coating layer is present, a step of curing the clear coating layer may be included before the injection molding step.

[0150] The above-mentioned molten resin is not particularly limited and includes, for example, acrylonitrile styrene resin, acrylonitrile butadiene styrene resin, polycarbonate resin, polystyrene resin, acrylic resin, polyester resin, polypropylene resin, olefin-based elastomer resin, etc. In one aspect of the present invention, since the total light transmittance after stretching the decorative laminated member by 200% is 20% or less, changes in design can be suppressed regardless of the color of the above-mentioned molten resin. As a result of this effect, a variety of designs can be expressed by changing only the design layer and the opaque heat-resistant film layer without changing the molten resin.

[0151] The molded articles that can be suitably decorated with the decorative laminated member of the present invention are not particularly limited, but examples include automotive exterior parts such as bumpers, front under spoilers, rear under spoilers, side under skirts, side garnishes, and door mirrors; automotive interior parts such as instrument panels, center consoles, and door switch panels; housings for home appliances such as mobile phones, audio products, refrigerators, fan heaters, and lighting fixtures; and washbasins. [Examples]

[0152] The present invention will be described below with reference to examples. In the examples, percentages in the formulation ratios refer to weight percentages unless otherwise specified. The present invention is not limited to the examples described below.

[0153] (glue) The following adhesive was used. Adhesive 1: SK Dyne 1701DT (manufactured by Soken Chemical Co., Ltd., acrylic adhesive)

[0154] (Preparation of composition for forming a clear coating layer) A clear coating layer composition 1 with a solid content of 35% was prepared by mixing 15 parts by mass of KRM-8452 (manufactured by Daicel Ornex Co., Ltd., polyfunctional urethane acrylate 1) as an active energy ray curable component, 40 parts by mass of Unidick V-6850 (manufactured by DIC Corporation, unsaturated double bond-containing acrylic resin), 40 parts by mass of Shiko UV-AF305 (manufactured by Mitsubishi Chemical Corporation, polyfunctional urethane acrylate), and 5 parts by mass of a photopolymerization initiator (product name: Omnirad184, manufactured by IGM RESINS) in a container containing 130 parts of methyl isobutyl ketone. Furthermore, a clear coating layer composition 2 with a solid content of 50% was prepared by mixing 80 parts by mass of acrylic polyol with a weight-average molecular weight of 16,000 and a hydroxyl value of 40 mgKOH / g, 20 parts by mass of polycarbonate diol with a weight-average molecular weight of 1,000 and a hydroxyl value of 100 mgKOH / g, and 5 parts by mass of hexamethylene diisocyanate in a container containing 105 parts of methyl isobutyl ketone.

[0155] (Preparation of coating compositions for decorative layers) A coating composition for decorative layers (silver) with a solid content of 30% was prepared by mixing 50 parts by mass of Cortax A228 (manufactured by Toray Fine Chemicals Co., Ltd.) as an acrylic resin, 40 parts by mass of a solution of CAB381-20 (manufactured by EASTMAN Co., Ltd.) diluted to 10% with butyl acetate, 5 parts by mass of aluminum paste 07-0674 (Toyo Aluminum Co., Ltd.) as a glossing agent, and 1 part by mass of Disparon 6901-20X (manufactured by Kusumoto Chemicals Co., Ltd., an anti-settlement agent for aluminum pigments) as an additive in a container containing methyl isobutyl ketone.

[0156] The coating compositions for the decorative layer (black), the decorative layer (white), and the decorative layer (blue) were manufactured in the same manner as the above-mentioned coating composition for the decorative layer (silver), except that the aluminum paste was replaced with the following components. Black: RAVEN 5000ULTRA3 (manufactured by Degussa Hürss Co., Ltd.), 1 unit of mass White: Typeque CR-95 (manufactured by Ishihara Sangyo Co., Ltd.), 14 parts by mass Blue: Shanin Blue G314 (manufactured by Sanyo Pigment Co., Ltd.), 3.5 parts by mass XIRALLC T60-22WNT AMETHYSDREAM (Merck Performance Materials) 2 parts by mass XIRALLC T60-22WNT GALAXY (Merck Performance Materials) 3.5 parts by mass

[0157] (Heat-resistant film layer) The following heat-resistant film layers were used. Heat-resistant film layer (white): PP sheet, white (manufactured by Shinwa Co., Ltd., polypropylene resin film, thickness 250 μm, total light transmittance 8.4%) Heat-resistant film layer (black): TP24005-2 (manufactured by Okamoto Co., Ltd., polypropylene resin film, 400 μm thickness, 0% total light transmittance) Heat-resistant film layer (gray): TP23030A (manufactured by Okamoto Co., Ltd., polypropylene resin film, 400 μm thickness, total light transmittance 0.4%) Heat-resistant film layer (transparent): Parapure HI-001 (manufactured by Kuraray Co., Ltd., acrylic resin film, 125 μm thickness, total light transmittance 92.3%)

[0158] The resin substrates used are as follows: Resin base material 1: Parapure HI-001 (manufactured by Kuraray Co., Ltd., acrylic resin film, thickness 125 μm)

[0159] Example 1 and Comparative Examples 1-2 On each heat-resistant film layer (B), the above-mentioned coating composition for the design layer (black) or coating composition for the design layer (white) was applied using an applicator so as to obtain a design layer (A) with a dry film thickness (hereinafter referred to as dry film thickness) of 25 μm. Then, it was dried at 80°C for 5 minutes to obtain a decorative laminated member.

[0160] Example 2 and Comparative Examples 3-4 Adhesive 1 was applied to each heat-resistant film layer (B) using an applicator to obtain an adhesive layer (C) with a dry film thickness of 25 μm, and dried at 80°C for 5 minutes. Next, the above-mentioned coating composition for the design layer (black) was applied to the transfer film 1 (Trefan, manufactured by Toray Industries, Inc.) using an applicator to obtain a design layer (A) with a dry film thickness of 20 μm, and then dried at 80°C for 5 minutes. Next, the obtained adhesive layer and the design layer were laminated so that they were in contact, and after lamination, the transfer film 1 was peeled off to obtain a decorative laminated member.

[0161] Examples 3-7, 9 and Comparative Examples 5-11 On a resin substrate layer (D), the clear coating composition 1 was applied using a bar coater to obtain a clear coating layer (E) with a dry film thickness of 20 μm. After drying at 80°C for 2 minutes, a protective film was laminated without UV curing to form the clear coating layer (E). Next, on the side of the resin substrate layer (D) opposite to the clear coating layer (E), each design layer coating composition was applied using an applicator to obtain a design layer (A) with a dry film thickness of 20 μm. After drying at 80°C for 5 minutes, the design layer (A) was formed. Next, adhesive 1 was applied to each heat-resistant film (B) using an applicator to obtain an adhesive layer (C) with a dry film thickness of 25 μm, and dried at 80°C for 5 minutes. The side of the film having the protective film, clear coating layer, resin substrate layer, and design layer obtained in the above step was laminated at room temperature with the design layer (A) side to obtain a decorative laminated member.

[0162] Example 8 The clear coating composition 2 was applied to the resin substrate layer (D) using an applicator to obtain a clear coating layer (E) with a dry film thickness of 20 μm, dried at 80°C for 5 minutes, and then a protective film was laminated to form the clear coating layer (E). Next, each design layer coating composition was applied to the side of the resin substrate layer (D) opposite to the clear coating layer (E) using an applicator to obtain a design layer (A) with a dry film thickness of 20 μm, and then dried at 80°C for 5 minutes to form the design layer (A). Next, adhesive 1 was applied to the heat-resistant film (B) using an applicator to obtain an adhesive layer (C) with a dry film thickness of 25 μm, and dried at 80°C for 5 minutes. The side of the film having the protective film, clear coating layer, resin substrate layer, and design layer obtained in the above step was laminated at room temperature with the design layer (A) side to obtain a decorative laminated member.

[0163] (L * a * , and b * (Measurement) Test specimens of decorative laminated members obtained in Examples 1-2 and Comparative Examples 1-4, and test specimens of decorative laminated members prepared in Examples 3-9 and Comparative Examples 5-11 with the protective film removed, were subjected to L from the heat-resistant film layer side and from the design layer or clear coating layer side. * a * b * The hue in the color system was measured using a colorimeter (Konica Minolta, CR-400). The measurement was performed by placing the test specimen on a gray table (L * =42,a * =0,b * The procedure was performed with the pressure set to -0.6. The results are shown in Tables 1 and 2.

[0164] After curing each of the above test specimens at 50°C for 3 days, they were compressed using a small TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.) under conditions of a film temperature of 160°C and compressed air pressure of 150kPa, and stretched to 200%. After stretching, each test specimen was again subjected to L from the design layer or clear coating layer side. * a * , and b * Measurements were taken. The results are shown in Tables 1 and 2.

[0165] (Calculation of ΔE) Initial L in each of the above test specimens * a * , and b * The value of and L after 100% stretching * a * , and b * From the value, ΔE(100) around 100% stretching is obtained, and the initial L in each of the above test specimens is also obtained. * a * , and b * The value of and L after 200% stretching * a * , and b * From the values ​​of , ΔE(200) was calculated before and after 200% stretching. The results are shown in Tables 1 and 2.

[0166] (Measurement of Sz0) For the decorative laminated members obtained in Examples 1-2 and Comparative Examples 1-4, and for the decorative laminated members prepared in Examples 3-9 and Comparative Examples 5-11 with the protective film removed, the surface on the design layer (A) or clear coating layer (E) side was magnified 60 times, and the maximum surface roughness Sz was measured at five points in a 3mm x 3mm area, with the average value defined as Sz0. The results are shown in Tables 1 and 2.

[0167] (Measurement of Sz1) After curing each of the above test specimens at 50°C for 3 days, they were compressed using a small TOM molding machine NGF-0709 (manufactured by Fuse Vacuum Co., Ltd.) under conditions of a film temperature of 160°C and compressed air pressure of 150kPa, and then stretched by 40%. From each stretched test specimen, the maximum surface roughness value Sz1 was obtained using the same method as for Sz0. The results are shown in Tables 1 and 2.

[0168] (Calculation of ΔSz) ΔSz was calculated from Sz0 and Sz1 as follows. ΔSz = Sz1 - Sz0 The results are shown in Tables 1 and 2.

[0169] (Measurement of Sv) For each heat-resistant film, the surface on the design layer (A) side was magnified 480 times, and the maximum valley depth Sv was measured at five points in a 300 μm × 300 μm area. The average value was defined as Sv. The results are shown in Tables 1 and 2.

[0170] Test specimens from the decorative laminated members prepared in Example 4 and Comparative Examples 2 and 8, with the protective film removed, were cured at 50°C for 3 days. Then, using a small TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.), they were compressed and molded under conditions of a film temperature of 160°C and compressed air pressure of 150kPa, and stretched to 200%. After stretching, the test specimens were placed on a black sheet (L) from the clear coating layer side. * =6, a * = -0.8, b * = -0.8) placed on top of, and the test piece placed on a white sheet (L * =91.5, a * = -1, b * In each of the states where it is placed on =5), L * a * , and b * The following measurements were taken: The color difference ΔE between the color measured on the black sheet and the color measured on the white sheet. bw The result was calculated and is shown in Table 3.

[0171] (Measurement of chemical resistance) The 60° gloss was measured from either the design layer side or the clear coating layer side for test specimens of the decorative laminated members obtained in Examples 1-2 and Comparative Examples 1-4, as well as for test specimens obtained in Examples 3-9 and Comparative Examples 5-11 from which the protective film had been removed. In addition, the integrated light intensity of 2000 mJ / cm² was measured for these test specimens. 2 After irradiating with UV light, the surface of the decorative laminated material's design layer or clear coating layer is cleaned with gauze soaked in acetone for 4 cm. 2After 10 cycles of wear under a vertical load of 4.9 N, the 60° gross was measured again at the worn area, and the absolute difference between these values ​​was calculated as the change in 60° gross. The results are shown in Tables 1 and 2.

[0172] [Table 1]

[0173] [Table 2]

[0174] [Table 3]

[0175] Decorative molded products were manufactured using the obtained decorative laminated material. The resulting decorative laminate was cured at 50°C for 3 days, then heated to 160°C in a vacuum forming machine to shape it into a plate measuring 100 mm (length) x 150 mm (width) x 2 mm (height). For Examples 3-7, the cumulative light intensity was 2000 mJ / cm². 2 After UV curing, the excess portion of the film other than the 100mm x 150mm x 2mm size was trimmed to create a preformed film. For Examples 1, 2, and 8, the excess portion of the film other than the 100mm x 150mm x 2mm size was trimmed after shaping to create a preformed film. The preform film created as described above was injected with PP resin using an injection molding machine, and a film insert molded product was successfully obtained. [Industrial applicability]

[0176] The decorative laminated member of the present invention can be used particularly suitably when performing decoration by insert molding. [Explanation of symbols]

[0177] (E) Clear coating layer (D) Resin base layer (A) Design layer (C) Adhesive layer (B) Heat-resistant film layer

Claims

1. A decorative laminate having a design layer (A) and an opaque heat-resistant film layer (B), A decorative laminated member characterized in that the difference ΔL* between the L* value measured from one side of the decorative laminated member and the L* value measured from the other side of the decorative laminated member is -30 or more and 30 or less.

2. Furthermore, the decorative laminated member according to claim 1 further comprises at least one of the adhesive layer (C), the resin substrate layer (D), and the clear coating layer (E).

3. Maximum surface roughness Sz measured from the design layer (A) side of the decorative laminated member. ０ The maximum value Sz of surface roughness measured from the design layer (A) side of the decorative laminated member stretched by 40% １ The decorative laminated member according to claim 1 or 2, wherein the difference ΔSz is 40 μm or less.

4. The heat-resistant film layer (B) is a decorative laminated member according to claim 1 or 2, wherein the maximum valley depth Sv on the side facing the design layer (A) is Sv ≤ 5 μm.

5. The decorative laminated member according to claim 1 or 2, wherein the color difference ΔE(100) between the color measured from the design layer (A) side of the decorative laminated member and the color measured from the design layer (A) side of the decorative laminated member that has been 100% stretched is 1.5 or less.

6. The decorative laminated member according to claim 1 or 2, wherein the color difference ΔE(200) between the color measured from the design layer (A) side of the decorative laminated member and the color measured from the design layer (A) side of the decorative laminated member stretched by 200% is 3 or less.

7. The decorative laminated member according to claim 1 or 2, wherein the decorative laminated member stretched by 200% has a total light transmittance of 20% or less as measured from the design layer (A) side.

8. The decorative laminated member according to claim 1 or 2, wherein the 60° gloss measured from the design layer (A) side of the decorative laminated member is 60 or more.

9. The decorative laminated material has an integrated light intensity of 2000 mJ / cm ２ After irradiating with the active energy rays, the outermost surface of the decorative laminated member on the design layer (A) side was covered with gauze soaked in acetone for 4 cm. ２ The decorative laminated member according to claim 1 or 2, wherein when subjected to 10 cycles of wear while a vertical load of 4.9 N is applied, the change in the 60° gloss of the outermost layer surface is 10 or less.

10. The decorative laminate member according to claim 1 or 2, wherein the heat-resistant film layer (B) has a thickness of 50 to 500 μm.

11. The decorative laminate member according to claim 1 or 2, wherein the heat-resistant film layer (B) comprises at least one of polypropylene resin, ABS resin, PC resin, PMMA resin, and PC-ABS resin.

12. The design layer (A) has an acrylic resin as a binder component and at least one of a glossing agent and a coloring pigment. The decorative laminated member according to claim 1 or 2, wherein the total solid content of the binder component, the luminous material, and the coloring pigment is 100 parts by mass, and the luminous material and coloring pigment are contained in parts 0.5 to 60 parts by mass in terms of solid content.

13. The decorative laminate member according to claim 2, wherein the resin substrate layer (D) consists of at least one of polymethyl methacrylate (PMMA), polycarbonate (PC), and PMMA / PC, and has a thickness of 50 to 300 μm.

14. The decorative laminated member according to claim 2, wherein the clear coating layer (E) is formed by an after-cure type radiation-curable clear coating layer forming composition or a thermosetting type urethane resin composition.

15. A decorative molded product characterized by being obtained by pressing a decorative laminated member according to claim 1 or 2 onto the surface of a molded body.

16. A method for manufacturing a decorative molded product according to claim 15, A method for manufacturing a decorated molded product, characterized by comprising an injection molding process in which the main surface on the design layer (A) side is brought into contact with a mold, and molten resin is injected toward the main surface on the heat-resistant film layer (B) side.

17. A method for manufacturing a decorative molded product according to claim 16, comprising a preforming step of shaping a decorative laminated member into a shape that conforms to the three-dimensional shape of the mold before the injection molding step.

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