Decorative plated products

Abstract

To provide a decorative plated article having high-definition plating film pattern with high designability.SOLUTION: A decorative plated article has: a substrate 70 which includes a resin molding 10 constituted of a resin material; and a plating film 20 which forms a predetermined pattern including a linear portion on a surface of the substrate. On the surface of the substrate, a surface roughness Ra of a plated region 70B where the plating film is formed is larger than a surface roughness Ra of a non-plating region 70A where the plating film is not formed, and a minimum value 20d of a line width of the linear portion of the plating film is 0.1 mm to 5 mm.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to decorative plated products (design plated products). [Background technology]

[0002] In recent years, decorative plated parts (decorative plated products) have become increasingly popular for automotive interior and exterior components. Two-color molding is a common method for selectively applying decorative plating to parts of a resin substrate. In this method, the resin substrate is created by two-color molding using different resin materials to create the plated areas (where a plating film is to be formed) and the non-plated areas (where no plating film is to be formed), and the plating film is then formed only on the plated areas. For example, the non-plated areas are made of a highly decorative resin with a color tone known as piano black, such as polycarbonate, while the plated areas are made of ABS resin, which can be etched as a pre-plating treatment. This results in a decorative plated product with a plating film pattern formed on a piano black base.

[0003] Furthermore, Patent Document 1 discloses a technique for selectively forming a plating film on a piano black polycarbonate substrate without using two-color molding. In Patent Document 1, a pretreatment ink composition is applied to the substrate in a pattern, and a plating film is selectively formed according to the applied pattern. The pretreatment ink composition functions as a binder, thereby increasing the adhesion strength of the plating film. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-206640 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the two-color molding method requires two types of molds, which increases production costs, and it is not possible to form high-resolution plating film patterns. Furthermore, the technology disclosed in Patent Document 1 requires a masking process or the like to apply the pretreatment ink composition in a pattern, which also increases production costs. Furthermore, it is expected to be difficult to form high-resolution plating film patterns with line widths of 1 mm or less.

[0006] The present invention solves these problems and provides a decorative plated product that can be manufactured through a simpler manufacturing process and has a highly decorative, high-definition plating film pattern. [Means for solving the problem]

[0007] According to one aspect of the present invention, there is provided a decorative plated product comprising a substrate including a resin molded body made of a resin material, and a plating film on the surface of the substrate that forms a predetermined pattern including linear portions, wherein the surface roughness Ra of the plating region on the surface of the substrate where the plating film is formed is greater than the surface roughness Ra of the non-plated region where the plating film is not formed, and the minimum line width of the linear portions of the plating film is 0.1 mm to 5 mm.

[0008] The resin molded body may be made of a single resin material. The surface roughness Ra of the plated region may be 0.5 μm to 8.0 μm, and the surface roughness Ra of the non-plated region may be less than 0.5 μm. The resin material may include polyamide or polycarbonate. The color tone of the non-plated region may be piano black.

[0009] The resin material may include polyamide, and a mixed layer of the resin material and the metal or metal compound contained in the plating film may be formed near the surface of the resin molded body, including the interface between the plating film and the resin molded body, and the mixed layer may have a thickness of 0.5 μm or more. Also, a plurality of holes may be formed in the plated region on the surface of the substrate. Also, the substrate may further have a paint film having a piano black color tone provided on the resin molded body, and the non-plated region on the surface of the substrate may be formed by the paint film.

[0010] The plating film may be composed of multiple layers, and the outermost layer may be an electrolytic plating film containing one selected from the group consisting of hexavalent chromium, trivalent chromium, copper, and gold. The outermost layer may be an electrolytic plating film containing trivalent chromium. [Effects of the Invention]

[0011] The decorative plated product of the present invention has a highly detailed plated film pattern with excellent design quality. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic diagram of a cross section of the periphery of a plating film (linear portion) in a decorative plated product according to the first embodiment. [Figure 2] 2(a) to 2(c) are diagrams illustrating the method for producing a decorative plated product according to the first embodiment, and are schematic cross-sectional views of the periphery of a plating film (linear portion). [Figure 3] 3(a) and 3(b) are diagrams illustrating the method for producing a decorative plated product according to the second embodiment, and are schematic cross-sectional views of the periphery of a plating film (linear portion). [Figure 4] 4(a) to 4(d) are diagrams illustrating the method for producing a decorative plated product according to the third embodiment, and are schematic cross-sectional views of the periphery of a plating film (linear portion). [Figure 5] FIG. 5 is a photograph of the decorative plated product produced in Example 1. [Figure 6] FIG. 6 is a photograph of the decorative plated product produced in Example 2. [Figure 7] FIG. 7 is a cross-sectional SEM photograph of the decorative plated product produced in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0013] [First embodiment] <Decorative plated products> The decorative plated product (designed plated product) 100 shown in Figure 1 will now be described. The decorative plated product 100 has a substrate 70 including a resin molded body 10 made of a resin material, and a plating film 20 formed on a surface 70a of the substrate 70. The plating film 20 forms a predetermined pattern including linear portions. In the decorative plated product 100, the plating film 20 may be formed three-dimensionally across multiple surfaces of the substrate 70, or along the surface of a three-dimensional shape including a spherical surface.

[0014] The resin material constituting the resin molded body 10 includes a resin. The resin contained in the resin material is not particularly limited, and for example, a thermoplastic resin, a thermosetting resin, or an ultraviolet-curable resin can be used. Examples of the thermoplastic resin include polyamides such as nylon 6 (PA6), nylon 66 (PA66), nylon 11 (PA11), nylon 12 (PA12), 6T nylon (6TPA), 9T nylon (9TPA), 10T nylon (10TPA), 12T nylon (12TPA), and MXD6 nylon (MXDPA), as well as alloys thereof, polycarbonate (PC), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polyether ether ketone (PEEK), polyetherimide (PEI), and polyphenylsulfone (PPSU). Examples of the thermosetting resin include epoxy resin, silicone resin, and polyimide resin. Examples of the photocurable resin include polyimide resin and epoxy resin. These resins may be used alone or in combination of two or more.

[0015] Among the resins mentioned above, nylon and polycarbonate are preferred. By using nylon or polycarbonate, it becomes easy to obtain the substrate 70 having a decorative piano black color tone. Resin materials for piano black molded bodies containing nylon or polycarbonate and a colorant, etc., are also commercially available.

[0016] The resin material constituting the resin molded body 10 may be composed solely of the above-mentioned resin, or may contain fillers, colorants, and other general-purpose additives, which will be described later. The blending amount of the resin in the resin molded body 10 (resin material) may be, for example, 20 to 100 wt %, or 50 to 100 wt %.

[0017] To improve the strength, linear expansion coefficient, etc. of the resin molded body 10, the resin material may contain fillers such as glass fiber, calcium titanate, potassium titanate, etc. Among these, potassium titanate is preferred. Potassium titanate reduces the linear expansion coefficient of the resin molded body 10 and interacts with the plating film 20 to increase the adhesion strength of the plating film 20. By reducing the linear expansion coefficient of the resin molded body 10, the reliability of the decorative plated product 100 can be improved. Furthermore, by including potassium titanate, it is not necessary to significantly roughen the surface region of the substrate 70 on which the plating film 20 is formed (plating region 70B, described below) in order to increase the adhesion strength of the plating film 20. This further enhances the gloss of the plating film 20.

[0018] The filler contained in the resin molded body 10 is preferably a rod-, needle-, or fiber-shaped filler with a small diameter so as not to adversely affect the appearance of the decorative plated product 100. The diameter (fiber diameter) of the filler may be, for example, 0.3 μm to 0.6 μm, and the length (fiber length) of the filler may be, for example, 10 μm to 20 μm.

[0019] The resin molded body 10 of the substrate 70 is preferably made of a single resin material. The resin molded body 10 may be a single-color molded body (monochrome molded body) made of a single resin material. Therefore, the resin molded body 10 of this embodiment is different from a two-color molded body made of two types of resin materials. In the resin molded body 10 of this embodiment, the plated portion and the non-plated portion are made of the same resin material (a resin material of the same composition). The resin molded body 10 (single-color molded body) of this embodiment, which can be molded by single-color molding, can reduce manufacturing costs compared to a two-color molded body. Note that, here, "made of a single resin material" does not mean that the resin molded body 10 is made of only one type of resin. As described above, the resin material may be made of only resin, or may contain fillers, colorants, additives, etc. in addition to resin as necessary.

[0020] As shown in FIG. 1, the surface 70a of the substrate 70 has a non-plated area 70A where the plating film 20 is not formed, and a plated area 70B where the plating film 20 is formed. The color tone of the non-plated area 70A is preferably a glossy black (jet black) called piano black. This results in a decorative plated product 100 with a highly decorative design, in which a thin-line plating film pattern is formed on a piano black base. Piano black has a high gloss and a low L * a * b * For example, piano black is preferably a black having a 60-degree specular gloss of 90 or more and a L * a * b * In the color system, L * is 8 or less, a * is -0.5 to 0, b * is -1.5 to 0, and more preferably, the 60-degree specular gloss is 90 or more, and L * a * b * In the color system, L * is less than or equal to 1, a * is -0.2 to 0, b * is between -1 and 0.

[0021] The surface roughness Ra of the plated region 70B is preferably greater than the surface roughness Ra of the non-plated region 70A. Increasing the surface roughness Ra of the plated region 70B increases the adhesion strength of the plating film 20 formed thereon. Furthermore, decreasing the surface roughness Ra of the non-plated region 70A can further enhance the gloss of the non-plated region 70A, for example, when the color tone of the non-plated region 70A is piano black. As shown in FIG. 1, grooves (recesses) 70b may be formed in the plated region 70B. The grooves (recesses) 70b extend along the plating pattern on the substrate surface 70a.

[0022] The surface roughness Ra of the plated region 70B is preferably, for example, 0.5 μm to 8.0 μm, or 0.5 μm to 3.0 μm. If the surface roughness Ra of the plated region 70B is equal to or greater than the lower limit of the above range, sufficient adhesion strength of the plating film 20 can be obtained, and if it is equal to or less than the upper limit of the above range, reduction in gloss of the plating film 20 formed thereon can be suppressed. The surface roughness Ra of the non-plated region 70A is preferably, for example, less than 0.5 μm. If the surface roughness Ra of the non-plated region 70A is within the above range, the gloss of the non-plated region 70A is enhanced.

[0023] The plating film 20 may be composed of multiple layers. The plating film 20 may include an electroless plating film (primer plating film) 21 formed on the substrate 70 and multiple electrolytic plating films 22 to 24 formed on the electroless plating film 21. The electroless plating film 21 is not particularly limited, but may be, for example, an electroless nickel-phosphorus plating film or an electroless copper plating film, with an electroless nickel-phosphorus plating film being preferred. The electrolytic plating films 22 and 23, which are intermediate layers of the plating film 20, are not particularly limited, but may be, for example, an electrolytic copper plating film or an electrolytic nickel plating film. Furthermore, the electrolytic plating film 24, which is the outermost layer (topmost layer) of the plating film 20, preferably contains, for example, hexavalent chromium, trivalent chromium, copper, or gold. Using an electrolytic plating film containing hexavalent chromium, trivalent chromium, copper, or gold as the outermost layer increases the gloss of the plating film 20, further enhancing the design of the decorative plated product 100. Furthermore, when the resin molded body 10 has a piano black color tone, the outermost layer 24 of the plating film 20 is preferably an electrolytic plating film containing trivalent chromium, copper, or gold, excluding hexavalent chromium, and more preferably an electrolytic plating film containing trivalent chromium. A hexavalent chromium electrolytic plating solution corrodes the surface of the resin molded body 10, causing it to become cloudy and potentially preventing the piano black color tone of the non-plated region 70A from being maintained. In contrast, a trivalent chromium electrolytic plating solution, while also being a chromium-based plating solution, does not affect the piano black color tone of the molded body 10. Therefore, by using an electrolytic plating film containing trivalent chromium as the outermost layer, the gloss of the plating film 20 can be enhanced while maintaining the glossy piano black color tone of the non-plated region 70A.

[0024] The thickness of the plating film 20 is not particularly limited and may be designed appropriately based on the application of the decorative plated article 100, the type of resin material of the resin molded article 10, the type and / or configuration of the plating film 20, etc. For example, the thickness of the plating film 20 (if the plating film 20 is composed of multiple layers, the total thickness of the multiple layers) may be 3 μm to 60 μm or 5 μm to 40 μm. In addition, in this embodiment, the thickness of each plating film constituting the plating film 20 may be, for example, in the following ranges: electroless plating film 21 (base plating film): 0.2 μm to 3 μm, electrolytic plating film 22 (e.g., electrolytic copper plating film): 3 μm to 30 μm, electrolytic plating film 23 (e.g., electrolytic nickel plating film): 2 μm to 20 μm, and electrolytic plating film 24 (outermost layer): 0.02 μm to 1 μm. In this embodiment, both the electrolytic plated film 22 (for example, electrolytic copper plated film) and the electrolytic plated film 23 (for example, electrolytic nickel plated film) are not essential, and only one of them may be used.

[0025] The plating film 20 has thin (narrow width) linear portions (linear portions). The thin linear plating film 20 allows for the formation of a highly decorative, high-definition plating film pattern. The minimum line width 20d of the linear portions of the plating film 20 is preferably 0.1 mm to 20 mm, 0.1 mm to 5 mm, 0.2 mm to 5 mm, or 0.2 mm to 1 mm. In this embodiment, the plating film 20 is formed on the resin molded body 10 using laser drawing, as described below. In this manner, in this embodiment, a highly decorative, high-definition plating film pattern that could not be achieved using conventional two-color molding methods or methods using the application of a treatment ink composition can be achieved using a simpler process than laser drawing.

[0026] The predetermined pattern formed by the plating film of this embodiment is not particularly limited as long as it has thin (narrow) linear portions (linear plating film). It may be a pattern formed only with linear portions, or a pattern combining linear portions and shaped portions (polygons, circles, sectors, letters (alphabet), etc.). Furthermore, the linear portions may be straight or curved.

[0027] A mixed layer 11 of the resin material constituting the resin molded body 10 and the metal or metal compound 20P contained in the plating film 20 may be formed near the surface of the resin molded body 10 on which the plating film 20 is formed. The mixed layer 11 is formed from the interface 11a between the plating film 20 and the resin molded body 10 toward the interior of the resin molded body 10. The metal or metal compound 20P may be a metal or metal compound having the same composition as the electroless plating film 21. As will be described in detail later, the metal or metal compound 20P is generated by the electroless plating reaction simultaneously with the electroless plating film 21. The metal or metal compound 20P may be partially connected to the electroless plating film 21. In other words, the metal or metal compound 20P is part of the electroless plating film 21, and the electroless plating film 21 can be interpreted as growing from the interior (near the surface) of the resin molded body 10. The presence of the mixed layer 11 further enhances the adhesion strength of the plating film 20 to the substrate 70. Furthermore, when the resin molded body 10 contains, for example, polyamide, the base material 70 is more easily permeated with the electroless plating solution, facilitating the formation of the mixed layer 11. The thickness 11d of the mixed layer 11 is, for example, preferably 0.5 μm or more, or 0.5 μm to 10 μm. If the thickness 11d is thinner than the lower limit of the above range, there is a risk that high adhesive strength with the plating film 20 cannot be obtained, and if the thickness 11d is thicker than the upper limit of the above range, there is a risk that the resin molded body 10 will suffer brittle fracture, and in this case too, high adhesive strength with the plating film 20 cannot be obtained.

[0028] The decorative plated article 100 may further have a catalytic activity impeding layer 80 formed on the non-plated region 70A of the resin molded body 10 (substrate 70). By having the catalytic activity impeding layer 80, the formation of a plating film on the non-plated region 70A can be more reliably suppressed. As a result, the contrast between the presence or absence of the plating film 20 on the surface 70a can be made clearer, further enhancing the design of the decorative plated article 100. The materials constituting the catalytic activity impeding layer 80 will be described later. The thickness of the catalytic activity impeding layer 80 is preferably, for example, 0.2 μm or less, or 0.1 μm or less, so as not to affect the appearance of the decorative plated article 100.

[0029] <Manufacturing methods for decorative plated products> A method for manufacturing the decorative plated article 100 of this embodiment will be described below. (1) Preparation of the base material 70 First, a resin molded body 10 is prepared as the substrate 70. The resin molded body 10 may be a commercially available product, or may be obtained by molding a resin material. The substrate 70 is made of the same resin material for both the plated and non-plated portions (made of a single resin material). Therefore, the substrate 70 can be manufactured by one-color molding (single-color molding), which reduces manufacturing costs compared to two-color molding.

[0030] The color tone of the surface 70a of the substrate 70 (resin molded body 10) is preferably piano black. For example, the resin molded body 10 may be molded using a commercially available resin material for piano black molded bodies. In addition, the surface roughness Ra of the surface 70a is preferably less than 0.5 μm to obtain high gloss.

[0031] (2) Formation of plating film 20 Next, a plating film 20 composed of multiple layers is formed on the resin molded body 10. First, an electroless plating film 21 is formed on the resin molded body 10 as an underlying plating film. The method for forming the electroless plating film 21 is not particularly limited, and a general-purpose method can be used. In this embodiment, as shown in FIGS. 2(a) to 2(c), the electroless plating film 21 is formed by, for example, the method disclosed in WO 2018 / 131492, which will be described below.

[0032] First, a catalytic activity interference layer 80 is formed on the surface 70a of the substrate 70 (resin molded body 10) (see FIG. 2(a)). The catalytic activity interference layer 80 contains a catalytic activity inhibitor (catalyst deactivator) that inhibits (hinders) the catalytic activity of the electroless plating catalyst. The catalytic activity inhibitor (catalyst deactivator) is not particularly limited, but preferred examples include dendritic polymers such as dendrimers and hyperbranched polymers disclosed in WO 2018 / 131492. These have excellent catalyst deactivation capabilities, and because they are polymers, the catalytic activity interference layer 80 can be formed without using a binder resin.

[0033] Next, the region (plating region 70B) of the surface 70a on which the catalytic activity hindering layer 80 has been formed, where the plating film 20 is to be formed, is irradiated with laser light to remove the catalytic activity hindering layer 80 (see FIG. 2(b)). The type of laser light and the laser processing device used for the laser light irradiation are not particularly limited and can be selected appropriately taking into consideration the type of resin molded body 10, etc. The plating region 70B is irradiated with laser light to remove the catalytic activity hindering layer 80 and roughen it. The surface roughness Ra of the plating region 70B after laser light irradiation is greater than the surface roughness Ra of the non-plating region 70A (i.e., the surface roughness Ra of the surface 70a of the base material 70). The surface roughness Ra of the plating region 70B after laser light irradiation is preferably, for example, 0.5 μm to 8.0 μm or 0.5 μm to 3.0 μm. This ensures sufficient adhesion strength of the plating film 20 formed thereon and prevents a decrease in the gloss of the plating film 20. In the plated region 70B irradiated with the laser light, a part of the surface 70a of the resin molded body 10 may be removed together with the catalytic activity obstructing layer 80, and a groove (groove) 70b may be formed.

[0034] Next, an electroless plating catalyst is applied to the laser-irradiated plating area 70B, and then the area is brought into contact with an electroless plating solution. The catalytic activity-hindering layer 80 inhibits (hinders) the catalytic activity of the electroless plating catalyst applied thereon. Therefore, the formation of an electroless plating film is suppressed on the catalytic activity-hindering layer 80 in the non-plating area 70A. On the other hand, in the plating area 70B, the catalytic activity-hindering layer 80 has been removed, so an electroless plating film 21 is formed (see FIG. 2(c)).

[0035] The electroless plating catalyst is not particularly limited, and a general-purpose one can be appropriately selected and used. For example, a plating catalyst solution containing a metal salt such as palladium chloride can be used. The electroless plating solution is also not particularly limited, and a general-purpose one can be appropriately selected and used. For example, an electroless nickel-phosphorus plating solution or an electroless copper plating solution can be used, and among these, an electroless nickel-phosphorus plating solution is preferred.

[0036] Simultaneously with the formation of electroless plating film 11, a mixed layer 11 of the resin material constituting resin molded body 10 and the metal or metal compound 20P contained in plating film 20 may be formed near the surface of resin molded body 10 on which plating film 20 is formed. Mixed layer 11 is generated when the electroless plating solution penetrates resin molded body 10 and electroless plating film 21 grows from the inside of resin molded body 10. The formation of mixed layer 11 increases the adhesive strength of plating film 20 to substrate 70.

[0037] To facilitate the formation of the mixed layer 11, the resin molded body 10 may contain polyamide. By containing polyamide, the electroless plating solution can easily penetrate into the interior of the base material during electroless plating. Furthermore, as a pretreatment for electroless plating, a swelling treatment can be performed by bringing water (hot water), an organic solvent, or the like into contact with the surface of the resin molded body 10. By swelling the resin molded body 10, the electroless plating solution can more easily penetrate, making it easier to form the mixed layer 11.

[0038] Electrolytic plating films 21 and 22 are formed on the electroless plating film 21 by a general-purpose electrolytic plating method, to obtain the decorative plated product 100 shown in FIG.

[0039] The decorative plated article 100 described above allows for the formation of highly decorative, high-definition plating film patterns using a simpler process than laser drawing, which is not possible with conventional two-color molding methods or methods using the application (printing) of a treatment ink composition. For example, a highly decorative plated article 100 can be obtained in which a thin-line plating film pattern is formed on a glossy piano black base. Furthermore, by adjusting the surface roughness Ra of the non-plated region 70A and the surface roughness Ra of the plated region 70B within appropriate ranges, the gloss of the non-plated region 70A and the gloss of the plating film 20 can be increased while maintaining the adhesion strength of the plating film 20.

[0040] [Second embodiment] A decorative plated article (designed plated article) 200 of this embodiment shown in Figure 3(b) will be described. In the decorative plated article 200, a plurality of holes (recesses, blind holes) 71 are formed in the plating region 70B of the substrate surface 70a. Other configurations are almost the same as those of the decorative plated article 100 described in the first embodiment, so description thereof will be omitted.

[0041] In this embodiment, the plurality of holes (recesses, blind holes) 71 increase the adhesion strength of the plating film 20 formed thereon. The plurality of holes 71 may be regularly arranged on the plating region 70B. The opening shape of the holes 71 in the plating region 70B is preferably circular or elliptical. The size of the holes 71 can be adjusted appropriately according to the width of the plating film 20. For example, the diameter of the holes 71 (the diameter of the opening in the plating region 70B, or the major axis in the case of an ellipse) may be 10 μm to 80 μm, and the depth may be 1 μm to 50 μm.

[0042] The decorative plated article 200 can be manufactured by the same method as the decorative plated article 100 of the first embodiment, except that multiple holes 71 are formed in the plating region 70B of the substrate surface 70a. The multiple holes 71 may be formed by laser light irradiation. For example, the multiple holes 71 may be formed in the step of removing the catalytic activity-hindering layer 80 in the plating region 70B by laser drawing (see FIG. 3(a)).

[0043] The decorative plated article 200 described above has the same effects as the decorative plated article of embodiment 1. In addition, the plurality of recesses (blind holes) 71 further increase the adhesion strength of the plating film 20.

[0044] [Third embodiment] A decorative plated product (designed plated product) 300 of this embodiment shown in Figure 4(d) will now be described. In the decorative plated product 300, a substrate 70 is composed of a resin molded body 10 and a coating film 30 provided on the surface of the resin molded body 10. That is, the non-plated area 70A of the substrate surface 70a is formed by the coating film 30. The rest of the configuration is almost the same as that of the decorative plated product 100 described in the first embodiment, so a description thereof will be omitted.

[0045] The coating film 30 preferably has a piano black color tone. This results in a decorative plated product 300 with a highly aesthetically pleasing design, in which a thin-line plating film pattern is formed on a piano black base. By providing a coating film 30 with a piano black color tone, the resin molded body 10, which is covered and hidden by the coating film 30, does not necessarily need to have a high aesthetic design. This broadens the range of materials that can be used for the resin molded body 10. The coating film 30 may be, for example, a coating film formed using a commercially available two-component acrylic urethane resin piano black paint (piano black acrylic urethane coating film).

[0046] The coating film 30 forms a non-plated region 70A on the substrate surface 70a. For this reason, the surface roughness Ra of the coating film 30 is preferably less than 0.5 μm, for example. This increases the gloss of the coating film 30. The thickness of the coating film 30 may be, for example, 5 μm to 50 μm, or 8 μm to 40 μm.

[0047] The decorative plated article 300 of this embodiment can be produced in the same manner as the decorative plated article 100 of the first embodiment, except that the coating film 30 is formed on the surface of the resin molded article 10.

[0048] First, a resin molded body 10 is prepared, and then a coating film 30 and a catalytic activity-blocking layer 80 are formed thereon in this order (FIG. 4(a)). The coating film 30 is formed by applying a paint having a piano black color tone to the surface of the resin molded body 10 by a general-purpose method. As the paint having a piano black color tone, for example, a commercially available two-component acrylic urethane resin piano black paint may be used.

[0049] The catalytic activity impeding layer 80 is removed by irradiating the area (plating area 70B) of the surface 70a on which the catalytic activity impeding layer 80 is formed with laser light, where the plating film 20 is to be formed (see FIG. 4(b)). At this time, the coating film 30 is also removed along with the catalytic activity impeding layer 80. Furthermore, a portion of the surface of the resin molded body 10 may be removed to form a groove (groove) 70b. Next, an electroless plating film 21 is formed (FIG. 4(c)) using the same method as in the first embodiment, and then electrolytic plating films 22 to 24 are formed (FIG. 4(d)). A decorative plated product 300 is obtained by the method described above.

[0050] The decorative plated article 300 achieves the same effects as the decorative plated article 100 of the first embodiment. Furthermore, by providing the coating film 30, the resin molded article 10, which is covered and hidden by the coating film 30, does not necessarily need to have a high level of design, broadening the range of materials that can be used for the resin molded article 10. For example, it becomes possible to select a resin with a low linear expansion coefficient as the material for the resin molded article 10 while maintaining high design quality thanks to the coating film 30. Selecting a resin with a low linear expansion coefficient increases the reliability of the decorative plated article 300.

[0051] The above-described embodiments may be combined with one another as long as they do not exclude one another. [Example]

[0052] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples and comparative examples.

[0053] [Example 1] In this example, the decorative plated article shown in Fig. 5 was produced as the decorative plated article 100 shown in Fig. 1. As shown in Fig. 5, in the decorative plated article 100 of this example, a plating film pattern including linear portions (linear plating film) is formed on a three-dimensional surface (curved surface). The minimum line width 20d and maximum line width of the linear portions of the plating film 20 were set to 0.3 mm and 0.5 mm, respectively.

[0054] (1) Molding of the resin molded body 10 (substrate 70) A piano black polyamide 6 (PA6) (M1030DHSZ, manufactured by Unitika) containing nano-sized fillers was injection molded using a general-purpose molding machine to obtain a piano black resin molded body 10. The molding conditions were a mold temperature of 120°C and a resin temperature of 250°C. The surface roughness Ra of the surface 70a of the resin molded body 10 was measured using a Keyence laser microscope. The measurement results are shown in Table 1 as the surface roughness Ra of the non-plated region 70A. Note that while the linear expansion coefficient of the filler-free polyamide 6 (unreinforced resin) used in Example 2 described below was 80 ppm, the linear expansion coefficient of the resin used in this example was reduced to a low value of 50 ppm due to the inclusion of a filler.

[0055] (2) Formation of plating film 20 In this example, the plating film 20 was formed on the resin molded body 10 by the method described below.

[0056] (a) Formation of catalytic activity obstruction layer 80 A catalytic activity-impeding layer 80 containing a hyperbranched polymer represented by the following formula (1), which is a catalyst deactivator, was formed on the surface 70a of the resin molded body 10. The hyperbranched polymer represented by formula (1) was synthesized by the method disclosed in WO 2018 / 131492. In formula (1), R 0 is a vinyl group or an ethyl group.

[0057] [ka]

[0058] The synthesized polymer represented by formula (1) was dissolved in methyl ethyl ketone to prepare a polymer solution with a polymer concentration of 0.5 wt %. The substrate was immersed in the polymer solution at room temperature for 5 seconds, and then dried in a dryer at 80°C for 10 minutes. This formed a catalytic activity interference layer 80 on the surface 70a of the resin molded body 10. The thickness of the catalytic activity interference layer 80 was 0.08 μm.

[0059] (b) Laser drawing The area (plating area 70B) on the surface 70a of the resin molded body 10 where the plating film 20 was to be formed was irradiated with laser light (laser drawing). Using a UV laser (manufactured by Keyence), the plating area 70B was drawn in a grid pattern with a 20 μm pitch under laser drawing conditions of 20% power, 2000 mm / s speed, and 80 kHz frequency. The plating area 70B irradiated with the laser light had the catalytic activity-blocking layer 80 removed and was roughened. The surface roughness Ra of the plating area 70B was measured using a laser microscope manufactured by Keyence. The measurement results are shown in Table 1.

[0060] (c) Electroless plating (forming a base plating film) The resin molded body 10 was immersed in 0.3 N hydrochloric acid adjusted to 30° C., and then immersed for 5 minutes in a commercially available aqueous solution of palladium chloride (PdCl2) (Activator, manufactured by Okuno Pharmaceutical Industries) adjusted to 30° C. After washing the resin molded body 10, it was immersed for 5 minutes in an aqueous solution containing 20% ​​1,3-butanediol adjusted to 70° C., causing the surface vicinity of the resin molded body 10 to swell (swelling treatment).

[0061] After the swelling treatment, the resin molded body 10 was immersed for 5 minutes in an electroless nickel phosphorus plating solution (Top Nicoron RCH, manufactured by Okuno Pharmaceutical Industries) adjusted to 70° C. An electroless nickel phosphorus plating film 21 was grown on the laser-drawn portion (plating area 70B) on the resin molded body 10.

[0062] (d) Electroplating (forming a final plating film) An electrolytic copper plating film 22, an electrolytic nickel plating film 23, and an electrolytic trivalent chromium plating film 24 were further laminated in this order on the electroless nickel phosphorus plating film 21 by a general-purpose electrolytic plating method to form a plating film 20 consisting of a multilayer plating film. The thickness of each plating film is shown in Table 1. By the method described above, the decorative plated product 100 of this example was obtained.

[0063] A cross section of the decorative plated article 100 was observed using an SEM. As shown in Figure 7, it was confirmed that a mixed layer 11 of the resin material (filler-mixed PA6) and the metal compound (nickel-phosphorus) 20P contained in the plating film 20 was formed from the interface 11a between the plating film 20 and the resin molded body 10 toward the inside of the resin molded body 10. The thickness 11d of the mixed layer 11 was 5 µm. It is presumed that the formation of the mixed layer 11 contributes to the high adhesion strength of the plating film 20 of this example.

[0064] [Example 2] In this example, the decorative plated article shown in Fig. 6 was produced as the decorative plated article 100 shown in Fig. 1. As shown in Fig. 6, the decorative plated article 100 of this example has a plating film pattern including linear portions (linear plating film) formed on the flat surface of a plate-shaped substrate. The minimum width 20d and maximum width of the linear portions (linear plating film) were set to 0.3 mm and 0.5 mm, respectively, as in Example 1.

[0065] In this example, a decorative plated product 100 (see Figure 1) was produced in the same manner as in Example 1, except that the resin molding 10 was formed using piano black polyamide 6 (PA6) (manufactured by BASF, D3K) containing no filler, and the thicknesses of the electrolytic plating films 22 and 23 were changed as shown in Table 1.

[0066] The surface roughness Ra of the non-plated region 70A and the surface roughness Ra of the plated region 70B were measured using the same method as in Example 1. The results are shown in Table 1. In this example, the resin molded body contained polyamide 6, as in Example 1, and a swelling treatment was performed as a pre-plating treatment. Therefore, in this example, as in Example 1, a mixed layer 11 of the resin material (PA6) and the metal compound (nickel phosphorus) 20P contained in the plating film 20 was formed, and it is presumed that this causes the plating film 20 to exhibit high adhesion strength.

[0067] [Example 3] In this example, a decorative plated product 200 was produced in which multiple holes (recesses, non-penetrating holes) 71 were formed in the plated area 70B of the substrate surface 70a in order to increase the adhesion strength of the plated film 20 (see Figure 3(b)).

[0068] (1) Molding of the resin molded body 10 First, a resin material (filler-free piano black colored biopolycarbonate (Bio PC) (Mitsubishi Chemical, Durabio D7340R)) was injection molded using a general-purpose molding machine in the same manner as in Example 1 to obtain a piano black colored resin molded body 10. The molding conditions were a mold temperature of 120°C and a resin temperature of 280°C.

[0069] (2) Formation of plating film 20 (a) Formation of catalytic activity-blocking layer 80, laser drawing (formation of holes 71) After forming the catalytic activity obstruction layer 80 in the same manner as in Example 1, laser writing was performed on the plating region 70B to remove the catalytic activity obstruction layer 80 and form multiple rows of recesses each consisting of multiple holes (recesses) 71 aligned in a straight line at a predetermined interval (see FIG. 3(a)). The opening shape of the holes 71 in the plating region 70B was circular, with a diameter of 20 μm. The depth of the holes 71 was 5 μm. The multiple holes 71 were formed under laser irradiation conditions of 20% power, 1000 mm / s speed, and 60 kHz frequency. (b) Electroless plating, electrolytic plating After immersing the substrate 70 in a 2N sodium hydroxide solution (50°C) for 1 minute, an electroless plating film 21 was formed using the same electroless plating catalyst solution and electroless plating solution as used in Example 1. The immersion time in the electroless plating solution was 8 minutes. Furthermore, electrolytic plating films 22 to 24 were formed on the electroless plating film 21 using the same method as in Example 1, thereby obtaining the decorative plated product 200 of this example. The thickness of each plating film is shown in Table 1.

[0070] The surface roughness Ra of the non-plated region 70A and the surface roughness Ra of the plated region 70B were measured using the same method as in Example 1. The results are shown in Table 1. In this example, since multiple holes 70 were formed, the surface roughness Ra of the plated region 70B was larger than in Example 1. For this reason, the line width of the plating film was made narrower than in Example 1 so that the surface roughness Ra of the plated region 70B would not be noticeable (see Table 1).

[0071] [Example 4] In this example, a decorative plated product 300 having a piano black coating film 30 was produced (see FIG. 4(d)).

[0072] (1) Preparation of the substrate 70 Polyamide 9T (PA9T) (Otsuka Chemical, NMA964B) containing potassium titanate as a filler was injection molded using the same general-purpose molding machine as in Example 1 to obtain a resin molded body 10. A commercially available acrylic urethane piano black paint was applied to the surface of the obtained resin molded body 10 to form a coating film 30 with a thickness of 10 μm, thereby obtaining a substrate 70. The diameter (fiber diameter) of the filler (potassium titanate) contained in the substrate 70 was 0.3 μm to 0.6 μm, and the length (fiber length) was 10 μm to 20 μm.

[0073] (2) Formation of plating film 20 (a) Formation of catalytic activity blocking layer 80, laser drawing A catalytic activity impeding layer 80 was formed by the same method as in Example 1 (see FIG. 4(a)). Next, by the same method as in Example 1, laser writing was performed on the plating area 70B to remove the catalytic activity impeding layer 80 and the coating film 30 (see FIG. 4(a)).

[0074] (b) Electroless plating, electrolytic plating Using the same method as in Example 3, electroless plating film 21 and electrolytic plating films 22-24 were formed to obtain decorative plated product 300 of this example. The thickness of each plating film is shown in Table 1. Furthermore, using the same method as in Example 1, the surface roughness Ra of non-plated region 70A (coating film 30) and the surface roughness Ra of plated region 70B were measured. The results are shown in Table 1.

[0075] The resin molded body 10 of this embodiment contains potassium titanate as a filler, resulting in a low coefficient of linear expansion. Furthermore, because the filler diameter is small (thin), the filler does not increase the surface roughness of the resin molded body 10. Furthermore, because potassium titanate interacts with the plating film 20, the adhesion strength of the plating film 20 can be increased without increasing the surface roughness of the plated region 70B. On the other hand, the resin molded body 10 of this embodiment does not have a glossy color tone like piano black. In the decorative plated product 300 of this embodiment, the non-plated region 70A of the resin molded body 10 is covered with a piano black-toned coating film 30, thereby maintaining the advantages of the resin molded body 10 described above and enhancing the design of the decorative plated product 300.

[0076] [Evaluation of decorative plated products] (1) External observation The appearance of the decorative plated products produced in Examples 1 to 4 was visually observed. The decorative plated products produced in Examples 1 to 4 had high-definition plating film patterns formed as designed. In addition, the glossy piano black color tone was maintained in the non-plated area 70B, and the wiring 20 also had a sufficient gloss. In other words, the decorative plated products produced in Examples 1 to 4 had high designability.

[0077] For comparison with Example 1, a decorative plated product was produced having the same configuration as the decorative plated product 100 of Example 1, except that the outermost layer 24 of the plating film 20 was an electrolytic hexavalent chromium plating film instead of the electrolytic trivalent chromium plating film. The resulting decorative plated product had a high-resolution plating film pattern as designed, and the plating film 20 was glossy. However, the hexavalent chromium electrolytic plating solution caused the molded product surface to become cloudy, and the piano black color tone of the non-plated region 70A could not be maintained. These results confirm that, from the perspective of maintaining the piano black color tone of the resin molded product 10, it is preferable to use, for example, an electrolytic trivalent chromium plating film for the outermost layer 24 of the plating film 20, rather than an electrolytic hexavalent chromium plating film.

[0078] (2) Reliability evaluation A heat shock test was conducted on the decorative plated products of Examples 1 to 4. Three decorative plated products of each of Examples 1 to 4 were prepared as evaluation samples. The evaluation samples were alternately left in an environment at -35°C for 30 minutes and then left in an environment at 90°C for 30 minutes, and the evaluation samples were removed every 10 cycles and visually inspected for blistering or peeling of the plating film 20. The heat shock test was conducted for each of Examples 1 to 4 until blistering or peeling of the plating film occurred in at least one evaluation sample. The maximum number of cycles at which no blistering or peeling of the plating film was observed in any of the three evaluation samples was defined as the pass cycle number. The pass cycle numbers for Examples 1 to 4 are shown in Table 1.

[0079] [Table 1]

[0080] As shown in Table 1, the smallest number of cycles required to pass the reliability evaluation was 100 for Example 2, but this was at a level that did not pose a problem in terms of practical reliability. That is, the decorative plated products produced in Examples 1 to 4 had sufficient reliability. Furthermore, it was confirmed that the smaller the linear expansion coefficient of the resin molded body 10 in the decorative plated products of Examples 1 to 4, the better the reliability evaluation results (the greater the number of cycles required to pass). [Industrial Applicability]

[0081] The decorative plated article of the present invention has high designability and reliability, and can be applied to, for example, interior and exterior parts of automobiles. [Explanation of symbols]

[0082] 10. Resin molding 11 Mixed layer 20 Plating film 30 Paint film 70 Base material 71 holes (recesses, non-through holes) 80 Catalytic activity blocking layer 100, 200, 300 decorative plated items

Claims

1. A decorative plated product, a substrate including a resin molded body made of a resin material; a plating film that forms a predetermined pattern including a linear portion on the surface of the base material, On the surface of the base material, a surface roughness Ra of a plating region where the plating film is formed is greater than a surface roughness Ra of a non-plating region where the plating film is not formed; the minimum line width of the linear portion of the plating film is 0.1 mm to 5 mm; The surface roughness Ra of the plated area is 0.5 μm to 8.0 μm, and the surface roughness Ra of the non-plated area is less than 0.5 μm; The decorative plated product, wherein the plating film is composed of a plurality of layers.

2. 2. The decorative plated product according to claim 1, wherein the resin molding is made of a single resin material.

3. The decorative plated product according to claim 1 or 2, wherein the resin material comprises polyamide or polycarbonate.

4. 4. The decorative plated product according to claim 1, wherein the color tone of the non-plated area is piano black.

5. the resin material includes polyamide, a mixed layer of the resin material and the metal or metal compound contained in the plating film is formed in the vicinity of a surface of the resin molded body, including an interface between the plating film and the resin molded body; The decorative plated product according to any one of claims 1 to 4, wherein the mixed layer has a thickness of 0.5 µm or more.

6. The decorative plated article according to any one of claims 1 to 4, wherein a plurality of holes are formed in the plated area on the surface of the base material.

7. the substrate further has a coating film having a piano black color tone provided on the resin molded body, 5. The decorative plated product according to claim 1, wherein the non-plated area on the surface of the base material is formed by the coating film.

8. A decorative plated product described in any one of claims 1 to 7, wherein the outermost layer of the plating film is an electrolytic plating film containing one selected from the group consisting of hexavalent chromium, trivalent chromium, copper, and gold.

9. 9. The decorative plated product according to claim 8, wherein the outermost layer is an electrolytic plating film containing trivalent chromium.

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