WO2023003001A1

WO2023003001A1 - Plated decorative article

Info

Publication number: WO2023003001A1
Application number: PCT/JP2022/028135
Authority: WO
Inventors: 雄二郎原田; 敦遊佐; 浩明上野; 建輝鈴木
Original assignee: マクセル株式会社
Priority date: 2021-07-21
Filing date: 2022-07-20
Publication date: 2023-01-26
Also published as: CN117693428A; JP2023016073A

Abstract

Provided is a plated decorative article having a plating film pattern with high design quality and high definition. The plated decorative article comprises a substrate that includes a molded resin body made of a resin material and a plating film that forms, on a surface of the substrate, a given pattern including a linear part. On the surface of the substrate, the surface roughness Ra of a plated region in which the plating film is formed is greater than the surface roughness Ra of a non-plated region in which the plating film is not formed. The minimum value of the width of the linear part of the plating film is 0.1-5.0 mm.

Description

decorative plating

The present invention relates to decorative plated products (design plated products).

In recent years, design parts using plating (decorative plating products) are often used for interior and exterior parts of automobiles. A two-color molding method is generally used as a technique for selectively applying decorative plating to a part of a resin base material. In the two-color molding method, the plated portion on which the plated film is formed and the non-plated portion on which the plated film is not formed are formed by two-color molding using different resin materials to prepare the resin base material, and only the plated portion is formed. A plating film is formed on the For example, the non-plated portion is made of a high-design resin called piano black, which is made of polycarbonate or the like, and the plated portion is made of an ABS resin that can be etched as a pretreatment for plating. As a result, a decorative plated product is obtained in which a plated film pattern is formed on the piano black substrate.

In addition, 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 in a pattern to a substrate, and a plated film is selectively formed according to the applied pattern. Since the pretreatment ink composition functions as a binder, the adhesion strength of the plated film increases.

JP 2019-206640 A

However, since the two-color molding method requires two types of molds, the manufacturing cost is high, and a high-definition plating film pattern cannot be formed. Moreover, the technique disclosed in Patent Document 1 requires a masking step or the like for applying the pretreatment ink composition in a pattern, which also increases the manufacturing cost. Moreover, it is expected that, for example, it will be difficult to form a high-definition plating film pattern with a line width of 1 mm or less.

The present invention solves these problems, and provides a decorative plated product that can be manufactured through a simpler manufacturing process and has a high-definition plated film pattern with a high degree of design.

According to an aspect of the present invention, a decorative plated article, comprising: a substrate including a resin molded body made of a resin material; and plating forming a predetermined pattern including linear portions on the surface of the substrate. on the surface of the base material, the surface roughness Ra of the plated region where the plated film is formed is greater than the surface roughness Ra of the non-plated region where the plated film is not formed, A decorative plated product is provided in which the minimum line width of the linear portion of the plated film is 0.1 mm to 5 mm.

The resin molding may be composed of a single resin material. The plated region may have a surface roughness Ra of 0.5 μm to 8.0 μm, and the non-plated region may have a surface roughness Ra of less than 0.5 μm. The resin material may contain polyamide or polycarbonate. A color tone of the non-plating region may be piano black.

The resin material contains polyamide, and a mixed layer of the resin material and the metal or metal compound contained in the plating film is provided in the vicinity of the surface of the resin molding, including the interface between the plating film and the resin molding. is formed, 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 base material. Further, the base material further has a coating film having a piano black color tone provided on the resin molded body, and the non-plating region on the surface of the base material is formed of the coating film. good too.

The plating film may be composed of a plurality of 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 plated film containing hexavalent chromium or trivalent chromium. The outermost layer may be an electrolytic plated film containing copper or gold. The outermost layer may be an electrolytic plated film containing trivalent chromium.

The decorative plated product of the present invention has a high-definition plated film pattern with a high degree of design.

FIG. 1 is a schematic cross-sectional view of the peripheral portion of the plating film (linear portion) in the decorative plated product of the first embodiment. 2(a) to 2(c) are diagrams for explaining the manufacturing method of the decorative plated product of the first embodiment, and are schematic cross-sectional views of the peripheral portion of the plated film (linear portion). 3(a) and 3(b) are diagrams for explaining the method of manufacturing the decorative plated product of the second embodiment, and are schematic cross-sectional views of the peripheral portion of the plated film (linear portion). FIGS. 4A to 4D are diagrams for explaining the method of manufacturing the decorative plated product according to the third embodiment, and are schematic cross-sectional views of the peripheral portion of the plating film (linear portion). 5 is a photograph of the decorative plated product manufactured in Example 1. FIG. 6 is a photograph of the decorative plated product manufactured in Example 2. FIG. 7 is a cross-sectional SEM photograph of the decorative plated product manufactured in Example 1. FIG.

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

The resin material constituting the resin molded body 10 contains resin. The resin contained in the resin material is not particularly limited, and for example, thermoplastic resin, thermosetting resin, and ultraviolet curable resin can be used. Examples of thermoplastic resins include nylon 6 (PA6), nylon 66 (PA66), nylon 11 (PA11), nylon 12 (PA12), 6T nylon (6TPA), 9T nylon (9TPA), 10T nylon (10TPA), Polyamides such as 12T nylon (12TPA), MXD6 nylon (MXDPA) and their alloy materials, polycarbonate (PC), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polyetheretherketone (PEEK), polyetherimide (PEI ), polyphenylsulfone (PPSU) and the like can be used. As the thermosetting resin, for example, epoxy resin, silicone resin, polyimide resin, or the like can be used. As the photocurable resin, for example, polyimide resin, epoxy resin, or the like can be used. These resins may be used alone or in combination of two or more.

Among the resins mentioned above, nylon and polycarbonate are preferable. By using nylon or polycarbonate, it becomes easy to obtain the base material 70 having a piano black color tone which is excellent in decoration. Resin materials for piano black moldings containing nylon or polycarbonate, colorants, etc. are also commercially available.

The resin material that constitutes the resin molded body 10 may be composed only of the resins described above, or may contain fillers, colorants, and other general-purpose additives, which will be described later. The amount of resin in the resin molded body 10 (resin material) may be, for example, 20 to 100% by weight, or 50 to 100% by weight.

In order to improve the strength, linear expansion coefficient, etc. of the resin molded body 10, the resin material may contain a filler such as glass fiber, calcium titanate, potassium titanate, or the like. Among them, potassium titanate is preferable. Potassium titanate lowers the coefficient of linear expansion of the resin molding 10 and interacts with the plated film 20 to increase the adhesion strength of the plated film 20 . By reducing the coefficient of linear expansion of the resin molding 10, the reliability of the decorative plated product 100 can be enhanced. Further, by including potassium titanate, it is not necessary to greatly roughen the surface region (plating region 70B described later) of the base material 70 on which the plating film 20 is formed in order to increase the adhesion strength of the plating film 20. Thereby, the glossiness of the plated film 20 can be further enhanced.

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

The resin molding 10 of the base material 70 is preferably made of a single resin material. The resin molded body 10 may be a one-color molded body (single-color 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 composed of two kinds of resin materials. In the resin molding 10 of the present embodiment, the plated portion and the non-plated portion are made of the same resin material (resin material having the same composition). The resin molded article 10 (single-color molded article) of the present embodiment, which can be molded by one-color molding, can reduce manufacturing costs compared to two-color molded articles. 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 composed only of resin, or may contain fillers, colorants, additives, etc. in addition to resin, if necessary.

As shown in FIG. 1, the surface 70a of the substrate 70 has a non-plating area 70A where the plating film 20 is not formed and a plating area 70B where the plating film 20 is formed. The color tone of the non-plating region 70A is preferably a glossy black (jet black) called piano black. As a result, the decorative plated product 100 having a fine wire plating film pattern formed on the piano black substrate and having a high design property can be obtained. Piano black may be defined by glossiness and color tone evaluation based on the L ^* a ^* b ^* color system. For example, piano black preferably has a 60-degree specular gloss of 90 or more, and in the L ^* a ^* b ^* color system, L ^* is 8 or less, a ^* is −0.5 to 0, and b ^* is −1.5 to 0, more preferably 60-degree specular glossiness of 90 or more, and in the L ^* a ^* b ^* color system, L ^* is 1 or less, a ^* is −0.2 to 0, b ^* is from -1 to 0.

The surface roughness Ra of the plated region 70B is preferably larger than the surface roughness Ra of the non-plated region 70A. By increasing the surface roughness Ra of the plated region 70B, the adhesion strength of the plated film 20 formed thereon is increased. Further, by reducing the surface roughness Ra of the non-plating region 70A, for example, when the color tone of the non-plating region 70A is piano black, the gloss can be further enhanced. As shown in FIG. 1, a groove (recess) 70b may be formed in the plating region 70B. The groove (recess) 70b extends along the plating pattern on the substrate surface 70a.

The surface roughness Ra of the plated region 70B is preferably 0.5 μm to 8.0 μm, or 0.5 μm to 3.0 μm, for example. If the surface roughness Ra of the plating region 70B is equal to or greater than the lower limit value of the above range, sufficient adhesion strength of the plating film 20 can be obtained. decrease in gloss can be suppressed. The surface roughness Ra of the non-plating region 70A is preferably less than 0.5 μm, for example. If the surface roughness Ra of the non-plating area 70A is within the above range, the gloss of the non-plating area 70A is enhanced.

The plated film 20 may be composed of multiple layers. The plated film 20 may include an electroless plated film (base plated film) 21 formed on the base material 70 and a plurality of electrolytic plated films 22 to 24 formed on the electroless plated film 21 . Although the electroless plated film 21 is not particularly limited, it may be, for example, an electroless nickel phosphorus plated film or an electroless copper plated film. Among them, the electroless nickel phosphorus plated film is preferable. The electrolytic plated

films

22 and 23, which are intermediate layers of the plated film 20, are not particularly limited, but may be, for example, an electrolytic copper plated film or an electrolytic nickel plated film.
The electrolytic plated film 24, which is the outermost layer (outermost layer) of the plated film 20, preferably contains, for example, hexavalent chromium, trivalent chromium, copper, or gold. By using an electrolytic plated film containing hexavalent chromium, trivalent chromium, copper, or gold as the outermost layer, the gloss of the plated film 20 is increased, and the design of the decorative plated product 100 is further enhanced. Further, when the resin molding 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. An electrolytic plated film containing trivalent chromium is more preferable. The hexavalent chromium electroplating solution may erode the surface of the resin molded body 10 to make it cloudy, making it impossible to maintain the piano black color tone of the non-plating region 70A. On the other hand, the trivalent chromium electrolytic plating solution does not affect the piano black color tone of the resin molding 10, although it is the same chromium-based plating solution. Therefore, by forming the electrolytic plated film containing trivalent chromium as the outermost layer, the luster of the plated film 20 can be enhanced while maintaining the glossy piano black color tone of the non-plated region 70A.

The thickness of the plated film 20 is not particularly limited, and may be appropriately designed based on the application of the decorative plated product 100, the type of resin material of the resin molding 10, the type and/or configuration of the plated film 20, and the like. For example, the thickness of the plating film 20 (when 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. Further, in the present embodiment, the thickness of each plated film forming the plated film 20 may be, for example, within the following range. Electroless plating film 21 (base plating film): 0.2 μm to 3 μm, electrolytic plating film 22 (eg, electrolytic copper plating film): 3 μm to 30 μm, electrolytic plating film 23 (eg, electrolytic nickel plating film): 2 μm to 20 μm , electrolytic plating film 24 (outermost layer): 0.02 μm to 1 μm. In this embodiment, both of 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.

The plated film 20 has thin (narrow width) linear portions (linear portions). The thin line-shaped plating film 20 can form a high-definition plating film pattern with a high degree of design. The minimum line width (minimum line width) 20d of the linear portion 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 the present embodiment, the plating film 20 is formed on the resin molding 10 using laser drawing, as will be described later. As described above, in the present embodiment, a high-definition plating film pattern with a high degree of design, which could not be realized by a conventional two-color molding method or a method using the application of a treatment ink composition, can be achieved by a simple method rather than laser drawing. It can be realized using a process.

The predetermined pattern formed by the plated film of the present embodiment is not particularly limited as long as it has a thin (narrow width) linear portion (linear plated film). It may be a pattern formed only of linear portions, or a pattern in which linear portions and shape portions (polygons, circles, sectors, characters (alphabet), etc.) are combined. Also, the linear portion may be a straight line or a curved line.

Even if the mixed layer 11 of the resin material constituting the resin molded body 10 and the metal or metal compound 20P contained in the plated film 20 is formed in the vicinity of the surface of the resin molded body 10 on which the plated film 20 is formed. good. 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 20</b>P may be a metal or metal compound having the same composition as the electroless plated film 21 . Although the details will be described later, the metal or metal compound 20P is generated simultaneously with the electroless plating film 21 by an electroless plating reaction. A part of the metal or metal compound 20P may be connected to the electroless plated film 21 . That is, the metal or metal compound 20P is part of the electroless plated film 21, and it can be interpreted that the electroless plated film 21 grows from the inside (near the surface) of the resin molding 10. FIG. By having the mixed layer 11, the adhesion strength of the plated film 20 to the base material 70 is further increased. Further, when the resin molding 10 contains, for example, polyamide, the base material 70 is easily permeated with the electroless plating solution, so that the mixed layer 11 is easily formed. The thickness 11d of the mixed layer 11 is preferably, for example, 0.5 μm or more, or 0.5 μm to 10 μm. If the thickness 11d is less than the lower limit of the above range, there is a risk that a high adhesion strength with the plated film 20 cannot be obtained. Also in this case, high adhesion strength with the plating film 20 cannot be obtained.

In addition, the decorative plated product 100 may further have a catalytic activity hindrance layer 80 formed on the non-plating region 70A of the resin molded body 10 (base material 70). By having the catalytic activity hindering layer 80, it is possible to more reliably suppress the formation of a plating film on the non-plating region 70A. As a result, the contrast between the presence or absence of the plating film 20 on the surface 70a can be made clearer, and the design of the decorative plated product 100 is further enhanced. Materials and the like that constitute the catalytic activity hindrance 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 product 100 .

<Manufacturing method of decorative plated product>
A method for manufacturing the decorative plated product 100 of this embodiment will be described below.
(1) Preparation of base material 70 First, the resin molding 10 is prepared as the base material 70 . The resin molding 10 may be a commercially available product, or may be obtained by molding a resin material. In the base material 70, the plated portion and the non-plated portion are made of the same resin material (made of a single resin material). Therefore, the base material 70 can be manufactured by one-color molding (single-color molding), and the manufacturing cost can be suppressed as compared with the case of using two-color molding.

The color tone of the surface 70a of the base material 70 (resin molding 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. Moreover, the surface roughness Ra of the surface 70a is preferably less than 0.5 μm so as to obtain high gloss.

(2) Formation of Plated Film 20 Next, the plated film 20 composed of a plurality of layers is formed on the resin molding 10 . First, an electroless plated film 21 is formed as a base plated film on the resin molding 10 . A method for forming the electroless plated 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 plated film 21 is formed by the method disclosed in International Publication No. 2018/131492 and described below, for example.

First, a catalytic activity hindering layer 80 is formed on the surface 70a of the base material 70 (resin molding 10) (see FIG. 2(a)). The catalytic activity hindering layer 80 contains a catalytic activity hindering agent (catalyst deactivator) that hinders (obstructs) the catalytic activity of the electroless plating catalyst. The catalyst activity inhibitor (catalyst deactivator) is not particularly limited, but is preferably, for example, a dendrimer, hyperbranched polymer, or other dendritic polymer disclosed in WO2018/131492. Since these materials are excellent in catalyst deactivation ability and are polymers, the catalyst activity hindering layer 80 can be formed without using a binder resin.

Next, a region of the surface 70a on which the catalytic activity hindering layer 80 is formed, where the plating film 20 is to be formed (plating region 70B), is irradiated with a laser beam to remove the catalytic activity hindering layer 80 (FIG. 2 ( b) see). The type of laser beam used for laser beam irradiation and the laser processing apparatus are not particularly limited, and can be appropriately selected in consideration of the type of the resin molded body 10 and the like. The plated region 70B is irradiated with a laser beam to remove the catalytic activity hindering layer 80 and roughen the plated region 70B. The surface roughness Ra of the plated region 70B after laser beam irradiation is larger than the surface roughness Ra of the non-plated region 70A (that is, the surface roughness Ra of the surface 70a of the substrate 70). The surface roughness Ra of the plating region 70B after laser light irradiation is preferably 0.5 μm to 8.0 μm, or 0.5 μm to 3.0 μm, for example. As a result, sufficient adhesion strength of the plated film 20 formed thereon can be obtained, and reduction in gloss of the plated film 20 can be suppressed. In the plated region 70B irradiated with the laser beam, a groove (recess) 70b may be formed by removing part of the surface 70a of the resin molding 10 together with the catalytic activity hindering layer 80. FIG.

Next, an electroless plating catalyst is applied to the plated region 70B irradiated with the laser beam, and then brought into contact with an electroless plating solution. The catalytic activity impeding layer 80 impedes (prevents) the catalytic activity of the electroless plating catalyst applied thereon. Therefore, formation of an electroless plating film is suppressed on the catalytic activity hindering layer 80 in the non-plating region 70A. On the other hand, since the catalytic activity hindering layer 80 is removed from the plated region 70B, the electroless plated film 21 is formed (see FIG. 2(c)).

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 may be used. Moreover, the electroless plating solution is not particularly limited, and a general-purpose one can be appropriately selected and used. For example, it may be an electroless nickel phosphorous plating solution or an electroless copper plating solution, and among them, an electroless nickel phosphorous plating solution is preferable.

Simultaneously with the formation of the electroless plating film 21, the resin material constituting the resin molding 10 and the metal or metal compound 20P contained in the plating film 20 are placed in the vicinity of the surface of the resin molding 10 on which the plating film 20 is formed. A mixed layer 11 of may be formed. The mixed layer 11 is formed by permeation of the electroless plating solution into the resin molding 10 and growth of the electroless plating film 21 from the inside of the resin molding 10 . By forming the mixed layer 11, the adhesion strength of the plated film 20 to the substrate 70 is increased.

In order to facilitate formation of the mixed layer 11, the resin molding 10 may contain polyamide. Containing polyamide facilitates penetration of the electroless plating solution into the base during electroless plating. As a pretreatment for electroless plating, a swelling treatment may be performed in which the surface of the resin molding 10 is brought into contact with water (hot water), an organic solvent, or the like. Swelling of the resin molding 10 makes it easier for the electroless plating solution to permeate and the mixed layer 11 to be formed more easily.

Electroplated films 22 to 24 are formed on the electroless plated film 21 by a general-purpose electrolytic plating method to obtain the decorative plated product 100 shown in FIG.

In the decorative plated product 100 described above, a high-definition plated film pattern with a high degree of design, which could not be realized by a conventional two-color molding method or a method using application (printing) of a treatment ink composition, is called laser drawing. It can be formed using a simpler process. For example, a decorative plated product 100 having a fine-line plating film pattern formed on a shiny piano black substrate can be obtained. Further, by adjusting the surface roughness Ra of the non-plating region 70A and the surface roughness Ra of the plating region 70B within an appropriate range, the adhesion strength of the plating film 20 can be maintained while maintaining the luster and brightness of the non-plating region 70A. And the gloss of the plating film 20 can be enhanced.

[Second embodiment]
A decorative plated product (design plated product) 200 of this embodiment shown in FIG. 3(b) will be described. In the decorative plated product 200, a plurality of holes (recesses, non-through holes) 71 are formed in the plated region 70B of the substrate surface 70a. Since other configurations are substantially the same as those of the decorative plated product 100 described in the first embodiment, description thereof will be omitted.

In this embodiment, the plurality of holes (concave portions, non-through holes) 71 increase the adhesion strength of the plated film 20 formed thereon. A plurality of holes 71 may be regularly arranged on the plating region 70B. The hole 71 preferably has a circular or elliptical opening shape in the plating region 70B. The size of the hole 71 can be appropriately adjusted according to the width of the plating film 20 . For example, the diameter of the hole 71 (the diameter of the opening in the plating region 70B, 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.

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

The decorative plated product 200 described above has the same effect as the decorative plated product of the first embodiment. Further, the bonding strength of the plating film 20 is further enhanced by the plurality of concave portions (non-through holes) 71 .

[Third embodiment]
A decorative plated product (design plated product) 300 of this embodiment shown in FIG. 4(d) will be described. In the decorative plated product 300 , the base material 70 is composed of the resin molded body 10 and the coating film 30 provided on the surface of the resin molded body 10 . That is, the non-plating region 70A of the substrate surface 70a is formed of the coating film 30. As shown in FIG. Since other configurations are substantially the same as those of the decorative plated product 100 described in the first embodiment, description thereof will be omitted.

The coating film 30 preferably has a piano black color tone. As a result, a decorative plated product 300 having a fine wire plating film pattern formed on a piano black substrate and having a high design property can be obtained. By providing the coating film 30 having a piano black color tone, the resin molding 10 that is covered with the coating film 30 and becomes invisible does not necessarily need to have a high design. Thereby, the range of selection of materials used for the resin molded body 10 is widened. The coating film 30 may be, for example, a coating film (piano black acrylic urethane coating film) formed using a commercially available two-pack acrylic urethane resin piano black coating.

The coating film 30 forms the non-plating region 70A of the substrate surface 70a. Therefore, the surface roughness Ra of the coating film 30 is preferably less than 0.5 μm, for example. Thereby, the glossiness of the coating film 30 can be improved. The thickness of the coating film 30 may be, for example, 5 μm to 50 μm, or 8 μm to 40 μm.

The decorative plated product 300 of this embodiment can be manufactured by the same method as the decorative plated product 100 of the first embodiment, except that the coating film 30 is formed on the surface of the resin molding 10 .

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

A laser beam is applied to a region (plating region 70B) of the surface 70a on which the catalytic activity hindering layer 80 is formed, where the plating film 20 is to be formed, to remove the catalytic activity hindering layer 80 (see FIG. 4B). ). At this time, the coating film 30 is also removed together with the catalytic activity hindering layer 80 . Furthermore, a part of the surface of the resin molding 10 may be removed to form the groove (recess) 70b. Next, an electroless plated film 21 is formed by the same method as in the first embodiment (FIG. 4(c)), followed by electrolytic plated films 22 to 24 (FIG. 4(d)). The decorative plated product 300 is obtained by the method described above.

The decorative plated product 300 has the same effects as the decorative plated product 100 of the first embodiment. Moreover, by providing the coating film 30, the design of the resin molding 10, which is covered with the coating film 30 and cannot be seen, does not necessarily need to be high, and the selection of materials used for the resin molding 10 is widened.
For example, it is possible to select a resin having a low coefficient of linear expansion as the material of the resin molded body 10 while maintaining a high design property by the coating film 30 . By selecting a resin with a low coefficient of linear expansion, the reliability of the decorative plated product 300 can be enhanced.

The multiple embodiments described above may be combined with each other as long as they do not exclude each other.

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited by the following examples and comparative examples.

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

(1) Molding of resin molding 10 (base material 70) Polyamide 6 (PA6) (manufactured by Unitika, M1030DHSZ) of piano black tone containing a filler with a nano-sized particle size is injection molded using a general-purpose molding machine. , a resin molding 10 having a piano black color tone was obtained. The molding conditions were mold temperature: 120°C and resin temperature: 250°C. The surface roughness Ra of the surface 70a of the resin molding 10 was measured with a Keyence laser microscope. The measurement results are shown in Table 1 as the surface roughness Ra of the non-plating region 70A. In addition, the linear expansion coefficient of the polyamide 6 (unreinforced resin) containing no filler used in Example 2 described later is 80 ppm, whereas the linear expansion coefficient of the resin used in this example contains a filler. By doing so, the value was suppressed to a low value of 50 ppm.

(2) Formation of Plated Film 20 In this example, the plated film 20 was formed on the resin molding 10 by the method described below.

(a) Formation of Catalytic Activity Hindering Layer 80 A catalytic activity hindering 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 . A hyperbranched polymer represented by formula (1) was synthesized by the method disclosed in WO2018/131492. In formula (1), R ⁰ is a vinyl group or an ethyl group.

A polymer solution having a polymer concentration of 0.5% by weight was prepared by dissolving the synthesized polymer represented by formula (1) in methyl ethyl ketone. The substrate was immersed in the room temperature polymer solution for 5 seconds and then dried in an 80° C. dryer for 10 minutes. Thus, a catalytic activity hindering layer 80 was formed on the surface 70a of the resin molded body 10. Next, as shown in FIG. The thickness of the catalytically active impeding layer 80 was 0.08 μm.

(b) Laser drawing A region (plating region 70B) where the plating film 20 is to be formed on the surface 70a of the resin molded body 10 was irradiated with a laser beam (laser drawing). Using a UV laser (manufactured by KEYENCE CORPORATION), the plating regions 70B were drawn in a lattice pattern at a pitch of 20 μm under laser drawing conditions of power 20%, speed 2000 mm/s, and frequency 80 kHz. The plated region 70B irradiated with the laser light was roughened while the catalytic activity hindering layer 80 was removed. The surface roughness Ra of the plated region 70B was measured with a Keyence laser microscope. Table 1 shows the measurement results.

(c) Electroless plating (formation of underlying plating film)
After the resin molding 10 was immersed in 0.3N hydrochloric acid adjusted to 30° C., it was immersed in a commercially available palladium chloride (PdCl ₂ ) aqueous solution (manufactured by Okuno Chemical Industry Co., Ltd., Activator) adjusted to 30° C. for 5 minutes. After washing the resin molded body 10, the resin molded body 10 was immersed in an aqueous solution containing 20% 1,3-butanediol adjusted to 70° C. for 5 minutes to swell near the surface of the resin molded body 10 (swelling treatment).

After the swelling treatment, the resin molding 10 was immersed for 5 minutes in an electroless nickel phosphorous plating solution (manufactured by Okuno Chemical Industry Co., Ltd., Top Nicolon RCH) adjusted to 70°C. An electroless nickel-phosphorus plating film 21 grew on the laser-drawn portion (plating region 70B) on the resin molded body 10 .

(d) Electroplating (formation of finish plating film)
Electrolytic copper plating film 22, electrolytic nickel plating film 23, and electrolytic trivalent chromium plating film 24 are further laminated in this order on the electroless nickel phosphorus plating film 21 by a general-purpose electrolytic plating method. A plated film 20 having a structure was formed. Table 1 shows the thickness of each plating film. The decorative plated product 100 of this example was obtained by the method described above.

A cross section of the decorative plated product 100 was observed with an SEM. As shown in FIG. 7, from the interface 11a between the plated film 20 and the resin molded body 10, toward the inside of the resin molded body 10, the resin material (filler mixed PA6) and the metal compound (nickel It was confirmed that a mixed layer 11 with phosphorus) 20P was formed. The thickness 11d of the mixed layer 11 was 5 μm.
It is presumed that the plating film 20 of this embodiment exhibits high adhesion strength due to the formation of the mixed layer 11 .

[Example 2]
In this example, the decorative plated product shown in FIG. 6 was produced as the decorative plated product 100 shown in FIG. As shown in FIG. 6, in the decorative plated product 100 of this embodiment, a plated film pattern including a linear portion (linear plated film) is formed on the plane of a plate-shaped base material. The minimum width 20d and the maximum width of the linear portion (linear plated film) were set to 0.3 mm and 0.5 mm, respectively, as in the first embodiment.

In this example, the resin molded body 10 was molded using polyamide 6 (PA6) (manufactured by BASF, D3K) with a piano black tone that does not contain a filler, and the thicknesses of the

electrolytic plating films

22 and 23 are shown in Table 1. A decorative plated product 100 (see FIG. 1) was produced in the same manner as in Example 1, except for the following changes.

By the same method as in Example 1, the surface roughness Ra of the non-plated region 70A and the surface roughness Ra of the plated region 70B were measured. Table 1 shows the results. In addition, in this example, the resin molding contained polyamide 6 in the same manner as in Example 1, and was subjected to a swelling treatment as a pretreatment for plating. Therefore, also in this embodiment, as in the first embodiment, the mixed layer 11 of the resin material (PA6) and the metal compound (nickel phosphorus) 20P contained in the plating film 20 is formed. is presumed to exhibit high adhesion strength.

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

(1) Molding of resin molded body 10 First, a resin material (piano black tone bio-polycarbonate (bio-PC) (Durabio D7340R, manufactured by Mitsubishi Chemical Co., Ltd.) containing no filler) was molded using a general-purpose molding machine in the same manner as in Example 1. A resin molded product 10 having a piano black color tone was obtained by injection molding using the resin. The molding conditions were mold temperature: 120°C and resin temperature: 280°C.

(2) Formation of plated film 20 (a) Formation of catalytic activity hindering layer 80, laser drawing (formation of holes 71)
After forming the catalytic activity obstructing layer 80 by the same method as in Example 1, the plating region 70B is subjected to laser drawing to remove the catalytic activity obstructing layer 80, and a plurality of holes (recesses) arranged in a straight line at predetermined intervals. ) 71 were formed (see FIG. 3A). The shape of the opening of the hole 71 in the plated region 70B was circular, and the diameter was 20 μm. The depth of the hole 71 was set to 5 μm. The formation of the plurality of holes 71 was performed under laser light irradiation conditions of power 20%, speed 1000 mm/s, and frequency 60 kHz.
(b) Electroless Plating, Electroplating After immersing the substrate 70 in a 2N sodium hydroxide solution (50° C.) for 1 minute, the same electroless plating catalyst solution and electroless plating solution as used in Example 1 were applied. was used to form the electroless plated film 21 . The immersion time in the electroless plating solution was 8 minutes. Further, electroplated films 22 to 24 were formed on the electroless plated film 21 by the same method as in Example 1 to obtain a decorative plated product 200 of this example. Table 1 shows the thickness of each plating film.

By the same method as in Example 1, the surface roughness Ra of the non-plated region 70A and the surface roughness Ra of the plated region 70B were measured. Table 1 shows the results. In this embodiment, since a plurality of holes 71 are formed, the surface roughness Ra of the plated region 70B is larger than that of the first embodiment. 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 plating region 70B was not conspicuous (see Table 1).

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

(1) Production of base material 70 Polyamide 9T (PA9T) (manufactured by Otsuka Chemical Co., Ltd., NMA964B) containing potassium titanate as a filler is injection-molded using a general-purpose molding machine similar to that of Example 1, and a resin molded body 10 is obtained. got A commercially available acrylic urethane piano black paint was applied to the surface of the obtained resin molding 10 to form a coating film 30 having a thickness of 10 μm, thereby obtaining a substrate 70 . The filler (potassium titanate) contained in the base material 70 had a diameter (fiber diameter) of 0.3 μm to 0.6 μm and a length (fiber length) of 10 μm to 20 μm.

(2) Formation of Plated Film 20 (a) Formation of Catalytic Activity Hindering Layer 80 and Laser Drawing A catalytic activity hindering layer 80 was formed in the same manner as in Example 1 (see FIG. 4A). Next, laser drawing was performed on the plated region 70B by the same method as in Example 1 to remove the catalytic activity hindering layer 80 and the coating film 30 (see FIG. 4A).

(b) Electroless Plating and Electrolytic Plating Electroless plated film 21 and electrolytic plated films 22 to 24 were formed in the same manner as in Example 3 to obtain a decorative plated product 300 of this example. Table 1 shows the thickness of each plating film. Further, the surface roughness Ra of the non-plating region 70A (coating film 30) and the surface roughness Ra of the plating region 70B were measured in the same manner as in Example 1. Table 1 shows the results.

The resin molded body 10 of this embodiment contains potassium titanate as a filler, and thus has a low coefficient of linear expansion. In addition, since the diameter of the filler is small (the filler is thin), the filler does not increase the surface roughness of the resin molded body 10 . Further, since potassium titanate interacts with the plated film 20, the adhesion strength of the plated film 20 can be increased without increasing the surface roughness of the plated region 70B. On the other hand, the resin molding 10 of this example does not have a glossy color tone like piano black. In the decorative plated product 300 of this embodiment, by covering the non-plating region 70A of the resin molded product 10 with the piano black-tone paint film 30, the decorative plated product 300 has the advantages of the resin molded product 10 described above. Enhanced design.

[Evaluation of decorative plated products]
(1) Observation of Appearance 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 plated film patterns as designed. In addition, the glossy piano black color tone was maintained in the non-plating region 70A, and the plating film 20 also had sufficient gloss. That is, the decorative plated products produced in Examples 1 to 4 had high designability.

For comparison with Example 1, the same as the decorative plated product 100 of Example 1 except that the outermost layer 24 of the plating film 20 was replaced with an electrolytic hexavalent chromium plating film instead of an electrolytic trivalent chromium plating film. A decorative plated product having the configuration of was produced. In the obtained decorative plated product, a highly precise plated film pattern was formed as designed, and the plated film 20 also had gloss. The piano black color tone of the plating region 70A could not be maintained. From this result, from the viewpoint of maintaining the piano black color tone of the resin molded body 10, it is preferable to use, for example, an electrolytic trivalent chromium plating film instead of an electrolytic hexavalent chromium plating film for the outermost layer 24 of the plating film 20. I was able to confirm that.

(2) Reliability Evaluation A heat shock test was performed on the decorative plated products of Examples 1-4. As samples for evaluation, three decorative plated products of Examples 1 to 4 were prepared. The evaluation sample was alternately left in an environment of −35° C. for 30 minutes and left in an environment of 90° C. for 30 minutes, and the evaluation sample was taken out every 10 cycles. I checked it visually. In each of Examples 1 to 4, the heat shock test was performed until swelling or peeling of the plating film occurred in one or more samples for evaluation. The maximum number of cycles at which no blistering or peeling of the plating film was observed for all three samples for evaluation was defined as the number of acceptable cycles. Table 1 shows the number of acceptable cycles for each of Examples 1-4.

As shown in Table 1, the minimum acceptable number of cycles in the reliability evaluation result was 100 cycles in Example 2, but the reliability was at a level where there was no problem in practical use. That is, the decorative plated products produced in Examples 1 to 4 had sufficient reliability. Further, it was confirmed that in the decorative plated products of Examples 1 to 4, the smaller the coefficient of linear expansion of the resin molded body 10, the better the reliability evaluation result (the number of acceptable cycles is large).

The decorative plated product of the present invention has high designability and reliability. The decorative plated product of the present invention can be applied, for example, to interior and exterior parts of automobiles.

REFERENCE SIGNS LIST 10 resin molding 11 mixed layer 20 plating film 30 coating film 70 base material 71 hole (concave portion, non-through hole)
80 Catalytic

activity hindrance layer

100, 200, 300 Decorative plated product

Claims

It is a decorative plated product,
a base material including a resin molded body made of a resin material;
a plated film that forms a predetermined pattern including linear portions on the surface of the base material;
On the surface of the base material, the surface roughness Ra of the plated region where the plated film is formed is greater than the surface roughness Ra of the non-plated region where the plated film is not formed,
A decorative plated product, wherein the minimum line width of the linear portion of the plated film is 0.1 mm to 5 mm.
The decorative plated product according to claim 1, wherein the resin molded body is composed of a single resin material.
The decorative plated article according to claim 1 or 2, wherein the plated region has a surface roughness Ra of 0.5 µm to 8.0 µm, and the non-plated region has a surface roughness Ra of less than 0.5 µm.
The decorative plated product according to any one of claims 1 to 3, wherein the resin material contains polyamide or polycarbonate.
The decorative plated product according to any one of claims 1 to 4, wherein the color tone of the non-plated area is piano black.
The resin material contains 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 the surface of the resin molding, including the interface between the plating film and the resin molding,
The decorative plated article according to any one of claims 1 to 5, wherein the mixed layer has a thickness of 0.5 µm or more.
The decorative plated product according to any one of claims 1 to 5, wherein a plurality of holes are formed in the plated region on the surface of the base material.
The base material further has a coating film having a piano black color tone provided on the resin molded body,
The decorative plated product according to any one of claims 1 to 5, wherein the non-plated region on the surface of the base material is formed of the coating film.
The plating film is composed of a plurality of layers, and the outermost layer is an electrolytic plating film containing one selected from the group consisting of hexavalent chromium, trivalent chromium, copper, and gold. 9. The decorative plated product according to any one of 8.
The decorative plated article according to claim 9, wherein the outermost layer is an electrolytic plating film containing hexavalent chromium or trivalent chromium.
The decorative plated article according to claim 9, wherein the outermost layer is an electrolytic plated film containing copper or gold.
10. The decorative plated article according to claim 9, wherein said outermost layer is an electrolytic plated film containing trivalent chromium.