CN117693428A

CN117693428A - Decorative plating product

Info

Publication number: CN117693428A
Application number: CN202280051471.8A
Authority: CN
Inventors: 原田雄二郎; 游佐敦; 上野浩明; 铃木建辉
Original assignee: Maxell Ltd
Current assignee: Maxell Ltd
Priority date: 2021-07-21
Filing date: 2022-07-20
Publication date: 2024-03-12
Also published as: JP2023016073A; WO2023003001A1

Abstract

The present invention provides a decorative plating product having a highly fine plating pattern with high design. A decorative plating having: a substrate comprising a resin molded body made of a resin material, and a plating film having a predetermined pattern including linear portions formed on the surface of the substrate. The surface roughness Ra of the plated area on which the plated film is formed is greater than the surface roughness Ra of the non-plated area on which the plated film is not formed, and the minimum value of the line width of the linear portion of the plated film is 0.1mm to 5mm.

Description

Decorative plating product

Technical Field

The present invention relates to decorative plating (design plating).

Background

In recent years, design members (decorative plated products) using plating have been widely used for interior and exterior decorative members of automobiles. As a method of selectively applying decorative plating to a part of a resin base material, a two-color molding method is generally used. In the two-shot molding method, a resin base material is produced by two-shot molding a plating portion to be plated with a film and a non-plating portion to be non-plated with a film, respectively, using different resin materials, and a film is formed only in the plating portion. For example, a highly designed resin having a color tone called piano black, which is made of polycarbonate or the like, is used in the non-plating portion, and an ABS resin capable of being etched as a pre-plating treatment is used in the plating portion. Thus, a decorative plating product having a plating pattern formed on a piano black substrate was obtained.

Further, patent document 1 discloses a technique of 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 on a substrate, and a plating film is selectively formed in accordance with the applied pattern. Since the pretreatment ink composition functions as a binder, the adhesion strength of the coating film is improved.

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2019-206640

Disclosure of Invention

Problems to be solved by the invention

However, the two-shot molding method requires two kinds of molds, and therefore, the manufacturing cost increases, and a high-definition plating pattern cannot be formed. In addition, the technique disclosed in patent document 1 requires a masking step or the like for applying the pretreatment ink composition in a pattern, and the manufacturing cost is still high. In addition, for example, it is expected that it is difficult to form a high-definition plating pattern having a line width of 1mm or less.

The present invention is to solve these problems and provide a decorative plated article which can be manufactured by a simpler manufacturing process and has a highly-precise plating pattern with high design.

Means for solving the problems

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

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 contain polyamide or polycarbonate. The tone of the non-plated region may be piano black.

The resin material may include polyamide, and a mixed layer of the resin material and a metal or a metal compound contained in the plating film may be formed near a surface of the resin molded body including an interface between the plating film and the resin molded body, and the mixed layer may have a thickness of 0.5 μm or more. In addition, a plurality of holes may be formed in the plating region on the surface of the base material. The base material may further have a coating film having a black tone of piano, which is provided on the resin molded body, and the non-plating region on the surface of the base material may be formed of the coating film.

The plating film may be formed of a plurality of layers, and the outermost layer may include a plating film of one selected from the group consisting of 6-valent chromium, 3-valent chromium, copper, and gold. The outermost layer may be a plating film containing 6-valent chromium or 3-valent chromium. The outermost layer may be a plating film containing copper or gold. The outermost layer may be a plating film containing 3-valent chromium.

Effects of the invention

The decorative plating product of the invention has a high-definition coating pattern with high designability.

Drawings

Fig. 1 is a schematic cross-sectional view of a peripheral portion of a plating film (linear portion) in a decorative plating article of a first embodiment.

Fig. 2 a to fig. 2 c are views for explaining a method of manufacturing a decorative plated product according to the first embodiment, and are schematic cross-sectional views of peripheral portions of plated films (linear portions).

Fig. 3 a and b are views for explaining a method for producing a decorative plated article according to the second embodiment, and are schematic cross-sectional views of peripheral portions of plated films (linear portions).

Fig. 4 a to fig. 4 d are views for explaining a method of manufacturing a decorative plated product according to a third embodiment, and are schematic cross-sectional views of peripheral portions of plated films (linear portions).

FIG. 5 is a photograph of the decorative plating product produced in example 1.

FIG. 6 is a photograph of the decorative plating product produced in example 2.

Fig. 7 is a cross-sectional SEM photograph of the decorative plating article produced in example 1.

Detailed Description

First embodiment

< decorative plating >

A decorative plated article (design plated article) 100 shown in fig. 1 will be described. The decorative plating article 100 has a base material 70 including a resin molded body 10 made of a resin material, and a plating film 20 formed on a surface 70a of the base material 70. The plating film 20 is formed with a predetermined pattern including linear portions. In the decorative plating article 100, the plating film 20 may be formed three-dimensionally over a plurality of surfaces of the base material 70 or along a three-dimensionally shaped surface including a spherical surface or the like.

The resin material constituting the resin molded body 10 contains a resin. The resin contained in the resin material is not particularly limited, and for example, a thermoplastic resin, a thermosetting resin, and an ultraviolet curable resin can be used. Examples of the thermoplastic resin include polyamides such as nylon 6 (PA 6), nylon 66 (PA 66), nylon 11 (PA 11), nylon 12 (PA 12), 6T nylon (6 TPA), 9T nylon (9 TPA), 10T nylon (10 TPA), 12T nylon (12 TPA), MXD6 nylon (MXDPA), and alloy materials thereof, polycarbonate (PC), polyphenylene sulfide (PPS), liquid Crystal Polymer (LCP), polyether ether ketone (PEEK), polyether imide (PEI), and polyphenylene sulfone (PPSU). 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 2 or more kinds.

Among the resins, nylon and polycarbonate are preferable. By using nylon or polycarbonate, the substrate 70 having a piano black tone excellent in decoration can be easily obtained. Resin materials for piano black molded bodies comprising nylon or polycarbonate and a colorant or the like are also commercially available.

The resin material constituting the resin molded body 10 may be composed of only the above resin, or may contain a filler, a colorant, and other general-purpose additives, which will be described later. The amount of the resin blended 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, and the like of the resin molded body 10, the resin material may contain a filler such as glass fiber, calcium titanate, and potassium titanate. Among them, potassium titanate is preferable. The potassium titanate reduces the linear expansion coefficient of the resin molded body 10 and interacts with the plating film 20 to improve 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 article 100 can be improved. Further, by including potassium titanate, it is not necessary to greatly roughen the surface region (plating region 70B described later) of the substrate 70 on which the plating film 20 is to be formed in order to improve the adhesion strength of the plating film 20. This can further improve the gloss of the plating film 20.

The filler contained in the resin molded body 10 is preferably a rod-like, needle-like or fibrous filler having a small diameter so as not to adversely affect the appearance of the decorative plated article 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.

The resin molded body 10 of the base material 70 is preferably composed of a single resin material. The resin molded body 10 may be a one-color molded body (a single-color molded body) of a single resin material. Therefore, the resin molded body 10 of the present embodiment is different from a two-color molded body composed of two resin materials. In the resin molded body 10 of the present embodiment, the plated portion and the non-plated portion are formed of the same resin material (resin material of the same composition). The resin molded body 10 (one-color molded body) of the present embodiment, which can be molded by one-color molding, can be manufactured at a lower cost than a two-color molded body. Here, "composed of a single resin material" does not mean that the resin molded body 10 is composed of only one resin. As described above, the resin material may be composed of only a resin, or may contain a filler, a colorant, an additive, and the like, as necessary, in addition to the resin.

As shown in fig. 1, the surface 70A of the base material 70 has an electroless plated region 70A where the plating film 20 is not formed and a plated region 70B where the plating film 20 is formed. The hue of the non-plated region 70A is preferably a glossy black (black paint) called piano black. Thus, the decorative plating 100 having high designability in which the thin film pattern is formed on the piano black substrate can be obtained. Piano black can pass through glossiness and L-based ^* a ^* b ^* The color tone evaluation of the color system is defined. For example, piano black preferably has a 60-degree specular glossiness of 90 or more, and is represented by L ^* a ^* b ^* In the color system, L ^* Is less than 8, a ^* Is (-0.5) - (0.b) ^* A specular glossiness of-1.5 to 0, more preferably 60 degrees, of 90 or more, and L ^* a ^* b ^* In the color system, L ^* Is less than 1, a ^* Is-0.2 to 0, b ^* Is (-1) - (0).

The surface roughness Ra of the plated region 70B is preferably greater than the surface roughness Ra of the non-plated region 70A. By increasing the surface roughness Ra of the plating region 70B, the adhesion strength of the plating film 20 formed thereon is improved. Further, by reducing the surface roughness Ra of the non-plated region 70A, for example, in the case where the hue of the non-plated region 70A is piano black, the glossiness thereof can be further improved. As shown in fig. 1, a groove (recess) 70B may be formed in the plating region 70B. Grooves (recesses) 70b extend along the plating pattern on the substrate surface 70a.

The surface roughness Ra of the plating region 70B is preferably, for example, 0.5 μm to 8.0 μm or 0.5 μm to 3.0 μm. When the surface roughness Ra of the plating 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 when it is equal to or less than the upper limit of the above range, the 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 less than 0.5 μm, for example. 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 improved.

The plating film 20 may be composed of a plurality of layers. The plating film 20 may include an electroless plating film (base plating film) 21 formed on the substrate 70 and a plurality of electric plating films 22 to 24 formed on the electroless plating film 21. The electroless plating film 21 is not particularly limited, and may be, for example, an electroless nickel-phosphorus plating film or an electroless copper plating film, and among them, an electroless nickel-phosphorus plating film is preferable. The plating films 22 and 23 as the intermediate layer of the plating film 20 are not particularly limited, and may be, for example, copper plating films or nickel plating films.

The plating film 24 as the outermost layer (outermost layer) of the plating film 20 preferably contains, for example, 6-valent chromium, 3-valent chromium, copper, or gold. By using an electroplating film containing 6-valent chromium, 3-valent chromium, copper, or gold as the outermost layer, the gloss of the plating film 20 is increased, and the design of the decorative plating product 100 is further improved. In the case where the resin molded body 10 has a piano black tone, the outermost layer 24 of the plating film 20 is preferably a plating film containing 3-valent chromium, copper, or gold in addition to 6-valent chromium, and more preferably a plating film containing 3-valent chromium. The 6-valent chromium plating solution may erode the surface of the resin molded body 10 to cause cloudiness, and may fail to maintain the black tone of the piano in the non-plated region 70A. In contrast, the 3-valent chromium plating solution is the same chromium plating solution, but does not affect the black tone of the piano of the resin molded article 10. Therefore, by using the plating film containing 3-valent chromium as the outermost layer, the glossy piano black tone of the non-plated region 70A can be maintained, and the gloss of the plating film 20 can be improved.

The thickness of the plating film 20 is not particularly limited, and may be appropriately designed based on the purpose of the decorative plating product 100, the type of the resin material of the resin molded body 10, the type and/or the composition of the plating film 20, and the like. For example, the thickness of the plating film 20 (in the case where the plating film 20 is composed of a plurality of layers, the total thickness of the plurality of layers) may be 3 μm to 60 μm or 5 μm to 40 μm. In the present embodiment, the thickness of each plating film constituting the plating film 20 can be set to, for example, the following range. Electroless plating film 21 (base plating film): 0.2 μm to 3 μm, plating film 22 (e.g., electroplated copper film): 3 μm to 30 μm, plating film 23 (e.g., electroplated nickel film): 2 μm to 20 μm, plating film 24 (outermost layer): 0.02 μm to 1 μm. In the present embodiment, both of the plating film 22 (e.g., copper plating film) and the plating film 23 (e.g., nickel plating film) are not necessarily required, and may be either one.

The plating film 20 has thin (narrow-width) linear portions (linear portions). By the thin linear plating film 20, a highly fine plating film pattern with high design can be formed. The minimum value (minimum line width) 20d of the line width of the linear portion of the plating film 20 is preferably 0.1mm to 20mm, 0.1mm to 5mm, 0.2mm to 5mm, or 0.2mm to 1mm. In the present embodiment, a plating film 20 is formed on the resin molded body 10 by laser drawing as will be described later. As described above, in the present embodiment, a high-definition plating pattern with high design, which cannot be achieved by the conventional two-color molding method or the method using the coating of the treatment ink composition, can be achieved by using a simpler process such as laser drawing.

The predetermined pattern formed by the plating film of the present embodiment is not particularly limited as long as it has a thin (narrow width) linear portion (linear plating film). The pattern may be formed only by the linear portion, or may be a pattern formed by combining a linear portion and a shape portion (polygon, circle, sector, letter, or the like). The linear portion may be a straight line or a curved line.

The 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 inside 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 formed by an electroless plating reaction simultaneously with the electroless plating film 21. The metal or metal compound 20P may be partially bonded to the electroless plated film 21. That is, the metal or metal compound 20P is a part of the electroless plating film 21, and it can be interpreted that the electroless plating film 21 starts to grow from the inside (near the surface) of the resin molded body 10. By providing the mixed layer 11, the adhesion strength of the plating film 20 to the substrate 70 is further improved. In addition, when the resin molded body 10 includes polyamide, for example, the base material 70 is likely to penetrate the electroless plating solution, and thus the mixed layer 11 is likely to be 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 smaller than the lower limit of the above range, high adhesion strength to the plating film 20 may not be obtained, and if it is larger than the upper limit of the above range, brittle fracture may occur in the resin molded body 10, and in this case, high adhesion strength to the plating film 20 may not be obtained.

The decorative plating product 100 may further have a catalytic activity barrier layer 80 formed on the non-plated region 70A of the resin molded body 10 (the base material 70). By providing the catalytically active barrier layer 80, the plating film formation on the non-plated region 70A can be more reliably suppressed. As a result, the contrast of the presence or absence of the plating film 20 can be made more clear on the surface 70a, and the design of the decorative plating 100 can be further improved. The material constituting the catalytically active barrier layer 80 and the like will be described later. The thickness of the catalytically active barrier layer 80 is preferably, for example, 0.2 μm or less or 0.1 μm or less, to avoid affecting the appearance of the decorative plating 100.

< method for producing decorative plated article >

The following describes a method for producing the decorative plated product 100 according to the present embodiment.

(1) Preparation of the substrate 70

First, the resin molded body 10 is prepared as the base material 70. The resin molded body 10 may be a commercially available product, or may be obtained by molding a resin material. The plating portion and the non-plating portion of the base material 70 are composed of the same resin material (composed of a single resin material). Therefore, the base material 70 can be manufactured by one-shot molding (single-shot molding), and the manufacturing cost can be reduced as compared with the case of using two-shot molding.

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

(2) Formation of coating film 20

Next, a plating film 20 composed of a plurality of layers is formed on the resin molded body 10. First, an electroless plating film 21 is formed as a base plating film on the resin molded body 10. The method of forming the electroless plating film 21 is not particularly limited, and a general method can be used. In the present embodiment, as shown in fig. 2 (a) to (c), the electroless plating film 21 is formed by the following method disclosed in, for example, international publication No. 2018/131492.

First, a catalytically active barrier layer 80 is formed on the surface 70a of the base material 70 (resin molded body 10) (see fig. 2 (a)). The catalytic activity blocking layer 80 contains a catalytic activity blocking agent (catalyst deactivator) that blocks (blocks) the catalytic activity of the electroless plating catalyst. The catalyst activity inhibitor (catalyst deactivator) is not particularly limited, and for example, dendritic polymers such as dendritic polymers and hyperbranched polymers disclosed in International publication No. 2018/131492 are preferable. These are excellent in catalyst deactivation ability, and since they are polymers, the catalyst-activity-inhibiting layer 80 can be formed without using a binder resin.

Next, a predetermined region (plating region 70B) of the surface 70a on which the catalytic-activity-preventing layer 80 is formed, where the plating film 20 is formed, is irradiated with laser light, and the catalytic-activity-preventing layer 80 is removed (see fig. 2B). The type of laser light used for the laser irradiation and the laser processing apparatus are not particularly limited, and may be appropriately selected in consideration of the type of the resin molded body 10 and the like. The plating region 70B is roughened while being irradiated with laser light to remove the catalytically active barrier layer 80. The surface roughness Ra of the plated region 70B after laser irradiation is greater than the surface roughness Ra of the non-plated region 70A (i.e., the surface roughness Ra of the surface 70A of the substrate 70). The surface roughness Ra of the plated region 70B after laser irradiation is preferably, for example, 0.5 μm to 8.0 μm or 0.5 μm to 3.0 μm. Thus, sufficient adhesion strength of the plating film 20 formed thereon can be obtained, and the reduction in gloss of the plating film 20 can be suppressed. In the plating region 70B irradiated with the laser beam, a part of the surface 70a of the resin molded body 10 may be removed together with the catalytic activity barrier layer 80 to form a groove (recess) 70B.

Next, an electroless plating catalyst is applied to the plating region 70B irradiated with the laser light, and then the plating region is brought into contact with an electroless plating solution. The catalytic activity blocking layer 80 blocks (blocks) the catalytic activity of the electroless plating catalyst imparted thereto. Therefore, the formation of electroless plating films on the catalytically active barrier layer 80 in the non-plated region 70A is suppressed. On the other hand, the plating region 70B is removed from the catalytic-activity-inhibiting layer 80, and thus the electroless plating film 21 is formed (see fig. 2 (c)).

The electroless plating catalyst is not particularly limited, and a general catalyst can be appropriately selected and used. For example, a plating catalyst solution containing a metal salt such as palladium chloride may be used. The electroless plating solution is not particularly limited, and a general electroless plating solution can be appropriately selected and used. For example, electroless nickel and phosphorus plating solutions and electroless copper plating solutions are preferable.

The electroless plating film 21 may be formed and the 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 by penetrating the electroless plating solution into the resin molded body 10, and growing the electroless plating film 21 from the inside of the resin molded body 10. By forming the mixed layer 11, the adhesion strength of the plating film 20 to the substrate 70 is improved.

In order to easily form the mixed layer 11, the resin molded body 10 may contain polyamide. By including polyamide, the electroless plating solution easily permeates into the substrate during electroless plating. Further, as the pretreatment of electroless plating, a swelling treatment may be performed in which water (hot water), an organic solvent, or the like is brought into contact with the surface of the resin molded body 10. By swelling the resin molded body 10, the electroless plating solution is more likely to permeate, and the mixed layer 11 is more likely to be formed.

The electroless plating films 22 to 24 were formed on the electroless plating film 21 by a general electroplating method, and the decorative plating product 100 shown in fig. 1 was obtained.

The decorative plated article 100 described above can form a highly-precise coating pattern with high design, which cannot be achieved by conventional two-color molding methods or by methods using coating (printing) of a treatment ink composition, by using a simpler process such as laser drawing. For example, a highly engineered decorative plating 100 in which a thin film pattern is formed on a glossy piano black substrate can be obtained. Further, by adjusting the surface roughness Ra of the non-plated region 70A and the surface roughness Ra of the plated region 70B to appropriate ranges, the gloss of the non-plated region 70A and the gloss of the plated film 20 can be improved while maintaining the adhesion strength of the plated film 20.

Second embodiment

A decorative plated article (design plated article) 200 of the present embodiment shown in fig. 3 b will be described. In the decorative plated article 200, a plurality of holes (recesses, non-through holes) 71 are formed in the plated region 70B of the substrate surface 70a. Other components are substantially the same as those of the decorative plated product 100 described in the first embodiment, and therefore, description thereof is omitted.

In the present embodiment, the adhesion strength of the plating film 20 formed thereon is improved by the plurality of holes (concave portions, non-through holes) 71. The plurality of holes 71 may be regularly arranged in the plating region 70B. The opening shape of the hole 71 in the plating region 70B is preferably circular or elliptical. 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 (opening diameter in the plating region 70B, long diameter in the case of ellipse) may be 10 μm to 80 μm, and the depth may be 1 μm to 50 μm.

The decorative plating article 200 can be produced by the same method as the decorative plating article 100 of the first embodiment, except that a plurality of holes 71 are formed in the plating region 70B of the substrate surface 70a. The plurality of holes 71 may be formed by laser irradiation. For example, in the step of removing the catalytically active barrier layer 80 of the plating region 70B by laser drawing, a plurality of holes 71 may be formed (see fig. 3 (a)).

The decorative plated article 200 described above has the same effects as the decorative plated article of the first embodiment. In addition, the adhesion strength of the plating film 20 is further improved by the plurality of concave portions (non-through holes) 71.

Third embodiment

A decorative plated article (design plated article) 300 of the present embodiment shown in fig. 4 d will be described. In the decorative plating 300, the base material 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-plating region 70A of the substrate surface 70A is formed by the coating film 30. Other components are substantially the same as those of the decorative plated product 100 described in the first embodiment, and therefore, description thereof is omitted.

The coating film 30 preferably has a piano black tone. Thus, the decorative plating 300 having high designability in which the thin film pattern is formed on the piano black substrate can be obtained. By providing the coating film 30 having a black tone of piano, the designability of the resin molded body 10, which is not visible by being covered with the coating film 30, is not necessarily high. Thus, the range of material selection for the resin molded body 10 is widened. The coating film 30 may be, for example, a coating film formed using a piano black coating material of a commercially available two-part acrylic urethane resin (piano black acrylic urethane coating film).

The coating film 30 forms an electroless 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. This improves the glossiness of the coating film 30. The thickness of the coating film 30 may be set to, for example, 5 μm to 50 μm or 8 μm to 40 μm.

The decorative plated article 300 of the present embodiment can be produced by the same method 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 body 10.

First, a resin molded body 10 is prepared, and a coating film 30 and a catalytic activity barrier 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 tone to the surface of the resin molded body 10 by a general method. As the paint having the tone of piano black, for example, a piano black paint of a commercially available two-part acrylic urethane resin can be used.

The predetermined area (plating area 70B) of the surface 70a on which the catalytic-activity-preventing layer 80 is formed, where the plating film 20 is formed, is irradiated with laser light, and the catalytic-activity-preventing layer 80 is removed (see fig. 4B). At this time, the coating film 30 is also removed together with the catalytic activity barrier layer 80. Further, a groove (recess) 70b may be formed by removing a part of the surface of the resin molded body 10. Next, electroless plated films 21 are formed by the same method as in the first embodiment (fig. 4 (c)), and then, electroless plated films 22 to 24 are formed (fig. 4 (d)). The decorative plating 300 is obtained by the method described above.

The decorative plating article 300 has the same effects as the decorative plating article 100 of the first embodiment. In addition, by providing the coating film 30, the designability of the resin molded body 10, which is not visible while being covered with the coating film 30, is not necessarily high, and the range of material selection for the resin molded body 10 is widened.

For example, a resin having a low linear expansion coefficient may be selected as the material of the resin molded body 10, while maintaining high design properties by the coating film 30. By selecting a resin having a low coefficient of linear expansion, the reliability of the decorative plating 300 can be improved.

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

Examples

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the examples and comparative examples.

Example 1

In this example, as the decorative plated article 100 shown in fig. 1, a decorative plated article shown in fig. 5 was produced. As shown in fig. 5, in the decorative plating article 100 of the present embodiment, a pattern including a plating film of a linear portion (a linear plating 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 plating film 20 were 0.3mm and 0.5mm, respectively.

(1) Molding of resin molded body 10 (base 70)

A piano black-colored polyamide 6 (PA 6) (manufactured by unitka, M1030 DHSZ) containing a filler having a particle size of nanometer size was injection-molded using a general-purpose molding machine to obtain a resin molded body 10 having a piano black color. The molding conditions were set to the mold temperature: 120 ℃, resin temperature: 250 ℃. The surface roughness Ra of the surface 70a of the resin molded body 10 was measured by a laser microscope manufactured by Keyence. The measurement results are shown in table 1 as the surface roughness Ra of the non-plated region 70A. In contrast to the linear expansion coefficient of polyamide 6 (non-reinforced resin) used in example 2 described below, which does not contain filler, which is 80ppm, the linear expansion coefficient of the resin used in this example is suppressed to a low value by containing filler, which is 50ppm.

(2) Formation of coating film 20

In this example, a plating film 20 was formed on a resin molded body 10 by a method described below.

(a) Formation of catalytically active barrier layer 80

A catalytic activity barrier layer 80 including a hyperbranched polymer represented by the following formula (1) as a catalyst deactivator is formed on the surface 70a of the resin molded body 10. The hyperbranched polymer represented by the formula (1) is synthesized by the method disclosed in International publication No. 2018/131492. In the formula (1), R ⁰ Vinyl or ethyl.

[ chemical 1]

The polymer represented by the formula (1) was dissolved in methyl ethyl ketone to prepare a polymer solution having a polymer concentration of 0.5% by weight. The substrate was immersed in a polymer solution at room temperature for 5 seconds and then dried in a dryer at 80 ℃ for 10 minutes. Thereby, the catalytically active barrier layer 80 is formed on the surface 70a of the resin molded body 10. The thickness of the catalytically active barrier layer 80 was 0.08 μm.

(b) Laser delineation

A predetermined region (plating region 70B) of the surface 70a of the resin molded body 10 where the plating film 20 is formed is irradiated with laser light (laser drawing). The plated regions 70B were drawn in a lattice shape at a pitch of 20 μm under a laser drawing condition of 20% power, 2000mm/s speed, and a frequency of 80kHz using a UV laser (manufactured by Keyence). The plating region 70B irradiated with the laser light is roughened at the same time as the catalytically active barrier layer 80 is removed. The surface roughness Ra of the plated region 70B was measured by a laser microscope made by Keyence. The measurement results are shown in Table 1.

(c) Electroless plating (formation of a coating film on a substrate)

After the resin molded body 10 was immersed in 0.3N hydrochloric acid adjusted to 30 ℃, commercially available palladium chloride (PdCl) adjusted to 30℃was used ₂ ) Immersing in aqueous solution (activator, manufactured by Aohfield pharmaceutical industry) for 5 minutes. After the resin molded body 10 was washed, it was immersed in a 20% aqueous solution containing 1, 3-butanediol at 70℃for 5 minutes to swell the vicinity of the surface of the resin molded body 10 (swelling treatment).

After the swelling treatment, the resin molded body 10 was immersed in an electroless nickel phosphorus plating solution (TOP NICORON RCH, manufactured by Okinawa pharmaceutical industry) adjusted to 70℃for 5 minutes. An electroless nickel-phosphorus plating film 21 is grown on the laser drawing portion (plating region 70B) of the resin molded body 10.

(d) Electroplating (formation of final coating)

Further, a copper plating film 22, a nickel plating film 23, and a chromium plating film 24 are laminated in this order on the electroless nickel/phosphorus plating film 21 by a general plating method, to form a plating film 20 composed of a plurality of plating films. The thickness of each plating film is shown in table 1. The decorative plating product 100 of this example was obtained by the method described above.

SEM observation was performed on a cross section of the decorative plating product 100. As shown in fig. 7, it was confirmed that the mixed layer 11 of the resin material (filler mixed PA 6) 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. Mu.m.

Speculation: the coating film 20 of this example exhibits high adhesion strength due to the formation of the mixed layer 11.

Example 2

In this example, as the decorative plated article 100 shown in fig. 1, a decorative plated article shown in fig. 6 was produced. As shown in fig. 6, in the decorative plating article 100 of the present embodiment, a pattern including a plating film of a linear portion (linear plating film) is formed on the plane of a plate-like base material. The minimum width 20d and the maximum width of the linear portion (linear plating film) were 0.3mm and 0.5mm, respectively, as in example 1.

In this example, a decorative plated article 100 (see fig. 1) was produced in the same manner as in example 1, except that the resin molded article 10 was molded using polyamide 6 (PA 6) (manufactured by BASF, D3K) having a piano black tone without filler, and the thicknesses of the plating films 22, 23 were changed as shown in table 1.

The surface roughness Ra of the non-plated region 70A and the surface roughness Ra of the plated region 70B were measured in the same manner as in example 1. The results are shown in Table 1. In this example, the resin molded article contained polyamide 6 and was subjected to swelling treatment as a pretreatment for plating in the same manner as in example 1. Therefore, in this example as well, as in example 1, the mixed layer 11 of the resin material (PA 6) and the metal compound (nickel phosphorus) 20P contained in the plating film 20 was formed, and it was assumed that the plating film 20 exhibited high adhesion strength.

Example 3

In this example, a decorative plated article 200 (see fig. 3B) 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 improve the adhesion strength of the plated film 20.

(1) Molding of resin molded body 10

First, a resin material (Bio polycarbonate (Bio PC) of piano black tone without filler (manufactured by mitsubishi chemical Co., ltd., DURABIO D7340R)) was injection molded using a general-purpose molding machine in the same manner as in example 1 to obtain a resin molded body 10 of piano black tone. The molding conditions were set to the mold temperature: 120 ℃, resin temperature: 280 ℃.

(2) Formation of coating film 20

(a) Formation of catalytically active barrier layer 80, laser mapping (formation of holes 71)

After the formation of the catalytically active barrier layer 80 in the same manner as in example 1, the plated region 70B was subjected to laser drawing to remove the catalytically active barrier layer 80, and a plurality of recess rows each formed of a plurality of holes (recesses) 71 aligned in a straight line at predetermined intervals were formed (see fig. 3 a). The opening shape of the hole 71 in the plating region 70B is a circle with a diameter of 20 μm. The depth of the hole 71 was 5. Mu.m. The formation of the plurality of holes 71 was performed under laser irradiation conditions of 20% power, 1000mm/s speed and 60kHz frequency.

(b) Electroless plating, electroplating

After immersing the substrate 70 in a 2N sodium hydroxide solution (50 ℃) for 1 minute, electroless plating film 21 was formed using the same electroless plating catalyst solution and electroless plating solution as those used in example 1. The immersion time in the electroless plating solution was 8 minutes. Further, by the same method as in example 1, plating films 22 to 24 were formed on the electroless plating film 21, and the decorative plating article 200 of this example was obtained. The thickness of each plating film is shown in table 1.

The surface roughness Ra of the non-plated region 70A and the surface roughness Ra of the plated region 70B were measured in the same manner as in example 1. The results are shown in Table 1. Further, in this embodiment, since the plurality of holes 71 are formed, the surface roughness Ra of the plated region 70B is larger than that of embodiment 1. Therefore, in order to make the surface roughness Ra of the plating region 70B insignificant, the line width of the plating film was made finer than that of example 1 (see table 1).

Example 4

In this example, a decorative plating 300 having a coating film 30 of piano black tone was produced (see fig. 4 (d)).

(1) Fabrication of the substrate 70

A resin molded body 10 was obtained by injection molding polyamide 9T (PA 9T) (NMA 964B, manufactured by kouka chemical) containing potassium titanate as a filler using the same general-purpose molding machine as in example 1. A commercially available coating material of urethane acrylate piano black tone was applied to the surface of the obtained resin molded body 10 to form a coating film 30 having a thickness of 10 μm, thereby obtaining a base material 70. The filler (potassium titanate) contained in the base material 70 has a diameter (fiber diameter) of 0.3 to 0.6 μm and a length (fiber length) of 10 to 20 μm.

(2) Formation of coating film 20

(a) Formation and laser mapping of catalytically active barrier layer 80

The catalytically active barrier layer 80 was formed in the same manner as in example 1 (see fig. 4 (a)). Next, the plating region 70B was subjected to laser drawing in the same manner as in example 1, and the catalytic activity barrier layer 80 and the coating film 30 were removed (see fig. 4 (a)).

(b) Electroless plating, electroplating

Electroless plated film 21 and plated films 22 to 24 were formed in the same manner as in example 3, to obtain decorative plated product 300 of this example. The thickness of each plating film is shown in table 1. Further, the surface roughness Ra of the non-plated region 70A (the coated film 30) and the surface roughness Ra of the plated region 70B were measured by the same method as in example 1. The results are shown in Table 1.

Since the resin molded body 10 of this example contains potassium titanate as a filler, the linear expansion coefficient is low. In addition, since the filler diameter is small (filler is fine), the surface roughness of the resin molded body 10 is not increased by the filler. In addition, since potassium titanate interacts with the plating film 20, the adhesion strength of the plating film 20 can be improved without increasing the surface roughness of the plating region 70B. On the other hand, the resin molded body 10 of the present embodiment does not have a glossy tone like piano black. In the decorative plated article 300 of the present embodiment, the non-plated region 70A of the resin molded body 10 is covered with the coating film 30 of piano black tone, thereby providing the above-described advantage of the resin molded body 10 and improving the design of the decorative plated article 300.

[ evaluation of decorative plating ]

(1) Appearance observation

The appearance of the decorative plated articles produced in examples 1 to 4 was visually observed. The decorative plating products produced in examples 1 to 4 were formed with a high-definition plating pattern according to the design. In addition, the non-plated region 70A maintains the glossy black tone of piano, and the plated film 20 also has a sufficient gloss. That is, the decorative plating products produced in examples 1 to 4 have high design properties.

In addition, for comparison with example 1, a decorative plated article having the same configuration as that of the decorative plated article 100 of example 1 was produced except that the outermost layer 24 of the plating film 20 was formed by plating a 6-valent chromium film instead of a 3-valent chromium film. In the obtained decorative plating product, a highly fine plating pattern is formed in accordance with the design, and the plating film 20 also has gloss, but the surface of the molded body is clouded due to the plating solution of 6-valent chromium, and the piano black tone of the non-plated region 70A cannot be maintained. From this result, it was confirmed that, from the viewpoint of maintaining the piano black tone of the resin molded body 10, it is preferable to use, for example, a plating of a chromium film of 3 valence instead of a plating of a chromium film of 6 valence for the outermost layer 24 of the plating film 20.

(2) Reliability evaluation

Thermal shock tests were conducted on the decorative plating products of examples 1 to 4. As evaluation samples, 3 decorative plated products of examples 1 to 4 were prepared. The operation of leaving the sample for evaluation at-35℃for 30 minutes and at 90℃for 30 minutes was alternately repeated, and the sample for evaluation was taken out every 10 cycles, and it was visually confirmed whether or not the plating film 20 had not swelled or peeled. In examples 1 to 4, the thermal shock test was performed until 1 or more samples for evaluation had swelled and peeled off. Then, the maximum number of cycles in which no swelling and peeling were confirmed in the plating film was set as the number of acceptable cycles for all 3 samples for evaluation. Table 1 shows the number of acceptable cycles in each of examples 1 to 4.

TABLE 1

As shown in table 1, the minimum number of acceptable cycles of the reliability evaluation results was 100 cycles of example 2, but the reliability was a practically unproblematic level. That is, the decorative plating products produced in examples 1 to 4 had sufficient reliability. In the decorative plated articles of examples 1 to 4, it was confirmed that the smaller the linear expansion coefficient of the resin molded article 10 was, the better the reliability evaluation result (the larger the number of pass cycles) was.

Industrial applicability

The decorative plating of the present invention has high design and reliability. The decorative plating of the present invention is applicable to, for example, automobile interior and exterior parts.

Description of the reference numerals

10: resin molded body, 11: hybrid layer, 20: coating film, 30: coating film, 70: a base material, 71: holes (recesses, non-through holes), 80: catalytically active barrier layers, 100, 200, 300: and decorating the plating product.

Claims

1. A decorative plating article having:

a base material comprising a resin molded body made of a resin material, and

a plating film which forms a predetermined pattern including a linear portion on the surface of the base material;

the surface roughness Ra of the plating area on which the plating film is formed is greater than the surface roughness Ra of the non-plating area on which the plating film is not formed,

the minimum value of the line width of the linear part of the coating film is 0.1 mm-5 mm.

2. The decorative plating article according to claim 1, wherein the resin molded body is composed of a single one of the resin materials.

3. The decorative plated article according to claim 1 or 2, wherein the surface roughness Ra of the plated region is 0.5 μm to 8.0 μm and the surface roughness Ra of the non-plated region is less than 0.5 μm.

4. The decorative plating article according to any one of claims 1 to 3, wherein the resin material comprises polyamide or polycarbonate.

5. The decorative plating article according to any one of claims 1 to 4, wherein the non-plated region is piano black in tone.

6. The decorative plating article according to any one of claims 1 to 5, wherein,

the resin material comprises a polyamide and,

a mixed layer of the resin material and a metal or a metal compound contained in the plating film is formed near the surface of the resin molded body including the interface between the plating film and the resin molded body,

the thickness of the mixed layer is more than 0.5 mu m.

7. The decorative plated article according to any one of claims 1 to 5, wherein a plurality of holes are formed in the plated region of the surface of the substrate.

8. The decorative plating article according to any one of claims 1 to 5, wherein,

the base material further has a coating film having a piano black tone provided on the resin molded body,

the non-plated region of the surface of the substrate is formed of the coating film.

9. The decorative plated article according to any one of claims 1 to 8, wherein the plating film is composed of a plurality of layers, and the outermost layer is an electroplated film containing one selected from the group consisting of 6-valent chromium, 3-valent chromium, copper, and gold.

10. The decorative plating of claim 9 wherein the outermost layer is an electroplated film comprising 6-valent chromium or 3-valent chromium.

11. The decorative plating article according to claim 9, wherein the outermost layer is a plating film containing copper or gold.

12. The decorative plating of claim 9 wherein the outermost layer is an electroplated film comprising 3-valent chromium.