JP6539746B2 - Decorative part and method of manufacturing the same - Google Patents

Description

  The present invention relates to a decorative part provided with a satin plating film.

  Satin plating means plating having a satin-like appearance of a semi-glossy satin which is intermediate between gloss plating and matte plating, and has a width from a shallow textured near gloss to a deep textured near matte.

  In satin plating, in order to obtain a satin-like appearance, a satin Ni plating layer is often formed. In addition, since the satin Ni plating layer has poor ductility to follow the substrate, the ductile Cu plating layer is often formed therebelow. Furthermore, since the satin Ni plating layer is gradually oxidized and discolored, a Cr plating layer is often formed thereon. Therefore, conventional satin plating requires a five-layer configuration such as Cu / semi-bright Ni (SBN) / satin Ni / Joule Ni (DN) / Cr.

  Patent Document 1 discloses a process of depositing a first Cu layer from a first electrolytic solution containing a polyether compound to produce matte Cu plating, and a second Cu layer with an alkylsulfonic acid derivative and an aromatic sulfone. The invention of a method is disclosed, which comprises, in order, depositing from a second electrolyte solution containing an acid derivative. According to the detailed description, Cu deposited from the first electrolyte has a strong matte (Comparative Example 1), Cu deposited from the second electrolyte has a gloss (Comparative Example 2), the second electrolyte When Cu is deposited from the first electrolyte solution on Cu deposited from above, the matting is excessive (comparative example 3) and the aromatic sulfonic acid derivative is not contained on Cu deposited from the first electrolyte solution When Cu is precipitated from the second electrolytic solution, it becomes non-uniform matting or matting with black spots (comparative examples 4 and 5), but in the example in which the invention is practiced, it becomes uniform matting (Examples 6, 7 and 8) ). It also states that a relatively matte appearance can be achieved with a relatively thin second Cu layer, and a relatively matte appearance can be achieved with a relatively thick second Cu layer.

  According to this method, since a matte coating is obtained using a ductile Cu plating layer without using a satin Ni plating layer, a satin appearance may be obtained with a small number of layers. However, in this method, although there is disclosure of each composition of the first electrolytic solution and the second electrolytic solution, there is no specific disclosure about the film thickness and surface roughness of the first Cu layer deposited from the first electrolytic solution, Moreover, there is no specific disclosure about the film thickness and surface roughness of the second Cu layer deposited from the second electrolytic solution. For this reason, it is difficult to obtain a satin-like appearance reliably and stably.

JP-A-2015-510038

  An object of the present invention is to obtain a satin-like appearance with a small number of layers and reliably and stably using a ductile Cu plating layer without using a satin Ni plating layer.

  The present invention is based on the finding that as a result of intensive studies by the present inventors, satin-like appearance can be obtained by appropriately filling the surface irregularities of the Cu plating layer with the Cu plating layer thereon in the decorative part. It is.

In order to achieve the above object, the decorative component of the present invention comprises a substrate, and a first Cu plating having a surface roughness (arithmetic average roughness) Ra of 0.1 to 0.8 μm formed on the substrate. And a second Cu plated layer formed on the first Cu plated layer, having a thickness of 1 to 6.1 μm, and a surface roughness Ra of 15 to 80% of the surface roughness Ra of the first Cu plated layer And has a semi-glossy satin-like appearance based on the surface roughness of the second Cu plating layer.
According to this configuration, the second Cu plated layer having a thickness of 1 to 6.1 μm formed on the first Cu plated layer having a surface roughness Ra of 0.1 to 0.8 μm is the surface of the first Cu plated layer Since the second Cu plating layer having a surface roughness Ra of 15 to 80% of the surface roughness Ra of the first Cu plating layer is well controlled and formed by appropriately reducing unevenness, the number of layers having a satin-like appearance is reduced Can be obtained stably.

  Furthermore, it is preferable to include a silver-white metal plating layer formed on the second Cu plating layer for adjusting the color tone of the satin appearance. According to this configuration, the color tone of the satin appearance can be easily and accurately adjusted.

  The silver white metal plated layer is preferably a Sn or Sn alloy plated layer. According to this configuration, surface hardness and the like can be improved.

  The silver white metal plating layer is preferably a Cr plating layer. According to this configuration, surface hardness and the like can be improved.

Moreover, the manufacturing method of the decorative component of this invention is the 1st step of forming 1st Cu plating layer whose surface roughness Ra is 0.1-0.8 micrometers by performing electrolytic matte Cu plating on a base material. And by performing electrolytic gloss Cu plating on the first Cu plating layer, the film thickness is 1 to 6.1 μm, and the surface roughness Ra is 15 to 80% of the surface roughness Ra of the first Cu plating layer And a second step of forming a 2Cu plating layer.
According to this configuration, the second Cu plated layer having a thickness of 1 to 6.1 μm formed on the first Cu plated layer having a surface roughness Ra of 0.1 to 0.8 μm is the surface of the first Cu plated layer Since the second Cu plating layer having a surface roughness Ra of 15 to 80% of the surface roughness Ra of the first Cu plating layer is well controlled and formed by appropriately reducing unevenness, a layer having a satin-like appearance and a small layer It can be obtained stably by the number.

  According to the present invention, a satin-like appearance can be stably obtained with a small number of layers by using a ductile Cu plating layer without using a satin Ni plating layer.

It is sectional drawing of the decorative component of an Example. It is a figure explaining the manufacturing method of the decoration part of an Example. It is a graph which shows the relationship of the plating time-film thickness of the 1st Cu plating layer in an Example. It is a graph which shows the relationship of film thickness-surface roughness of the 1st Cu plating layer in an example. It is a graph which shows the relationship of the film thickness-surface roughness reduction rate of the 2nd Cu plating layer in an Example. It is a graph which shows the relationship of the film thickness-surface roughness and glossiness of the 2nd Cu plating layer in an Example.

1. The base material is not particularly limited, and known materials can be appropriately selected depending on the purpose. As a base material, resin, metal, glass, ceramic etc. can be mentioned, for example. The base material made of resin can be appropriately selected in consideration of rigidity, ease of processing, heat resistance, functionality such as ease of plating, purpose of use, and the like. Examples of the resin include, for example, acrylonitrile-butadiene-styrene copolymer (ABS) resin, polycarbonate (PC) resin, PC / ABS alloy (PC / ABS blend resin), polypropylene (PP) resin, polyacrylic resin (polymethacrylic resin) And polymethyl methacrylate (PMMA) resin, modified polyphenylene ether (PPE) resin, polyamide resin, polyacetal resin and the like. In addition, the base material made of resin can be molded using a known molding method such as an injection molding method, an extrusion molding method, a blow molding method, a compression molding method and the like. As a metal used for a base material, iron, stainless steel, Al, Al alloy, Ti, Ti alloy etc. can be mentioned, for example. One of these substrates may be selected and used, or two or more of them may be used in combination. The shape of the base material can be appropriately designed according to the purpose of use of the decorative part and the like.

  When the material of the substrate is a nonconductive material, the surface is subjected to a conductivity imparting treatment. Examples of the conductivity imparting treatment include electroless plating and sputtering.

2. First Cu plating layer If the surface roughness Ra of the first Cu plating layer is 0.1 to 0.8 μm, it is easy to control the surface unevenness by the second Cu plating layer, so the satin appearance is stable. Obtained. If the surface roughness Ra of the first Cu plated layer is less than 0.1 μm, it is difficult to control the thickness of the second Cu plated layer so as to be thin. If the surface roughness Ra of the first Cu plated layer exceeds 0.8 μm, it becomes difficult to control the thickness of the second Cu plated layer to a satin tone.
The film thickness of the first Cu plated layer is not particularly limited, as long as the film has the above-mentioned surface roughness Ra.

  The first Cu plating layer is preferably formed by performing electrolytic matte Cu plating. This is because it is easy to obtain the target surface roughness Ra of 0.1 to 0.8 μm. The Cu source of the plating bath is not particularly limited, and examples thereof include Cu sulfate, Cu cyanide, Cu pyrophosphate, Cu borofluoride, and the like. The plating bath does not add an additive (leveling agent, growth inhibitor, growth accelerator, anti-burning agent, etc.) contributing to the smoothing of the plating surface, or the amount of addition (electroless gloss Cu of the second Cu plating layer It is preferred that the amount be relatively small).

3. Second Cu plating layer The satin tone by the second Cu plating layer that the film thickness of the second Cu plating layer is 1 to 6.1 μm and the surface roughness Ra is 15 to 80% of the surface roughness Ra of the first Cu plating layer The appearance is stably obtained. If the film thickness of the second Cu plating layer is less than 1 μm and the Ra ratio exceeds 80%, it becomes difficult to control the film thickness thinly in order to make the second Cu plating layer have a satin tone. If the thickness of the second Cu plating layer exceeds 6.1 μm and the Ra ratio is less than 15%, it becomes difficult to control the thickness of the second Cu plating layer so as to have a satin tone. The film thickness of the second Cu plating layer is more preferably 2 to 5 μm.

  The second Cu plating layer is preferably formed by performing electrolytic gloss Cu plating. It is because it is easy to reduce the surface asperity of a 1st Cu plating layer. The Cu source of the plating bath is not particularly limited, and examples thereof include Cu sulfate, Cu cyanide, Cu pyrophosphate, Cu borofluoride, and the like. The plating bath preferably contains additives (leveling agent, growth inhibitor, growth accelerator, anti-bumping agent, etc.) contributing to the smoothing of the plating surface by appropriately adjusting the blending amount, ratio, etc. The amount is preferably relatively large (relative to the electroless bright Cu plating of the second Cu plating layer).

4. Silver White Metal Plating Layer As described above, the silver white metal plating layer is preferably a Sn or Sn alloy plating layer or a Cr plating layer. As a Sn alloy applied to formation of a Sn alloy plating layer, for example, Sn-Co alloy, Sn-Ni alloy, Sn-Pb alloy, Sn-Ni-Cu alloy, Sn-Cu-Zn alloy, Sn-Fe alloy And Sn-Fe-Zn alloys. One of these Sn alloys may be selected and used, or two or more of them may be used in combination. The Sn or Sn alloy plating process can be performed by a known electroplating method. The Cr plating process can also be performed by a known electroplating method.

  The thickness of the silver-white metal plating layer is not particularly limited as long as it can adjust the color tone of the satin-like appearance.

5. Transparent or Semitransparent Protective Layer It is preferable to form a transparent or semitransparent protective layer on the second Cu plating layer (on the silver white metal plating layer when the silver white metal plating layer is formed). Examples of the transparent or semitransparent protective layer include an organic protective layer, an inorganic protective layer, and a silicon resin protective layer. One type of transparent or translucent protective layer may be selected and used, or two or more types may be used in combination.

  Examples of the resin formed by the organic protective layer include acrylic resin (methacrylic resin), polycarbonate resin, urethane resin, melamine resin and the like. Among them, UV curable polyfunctional acrylic resins are preferable from the viewpoint of excellent corrosion resistance, chemical resistance, scratch resistance, ductility, transparency, handleability and the like. Examples of the method of forming the organic protective layer and the silicon-based resin protective layer include known electrodeposition coating, spin coating, coater, spray, flow, dip (immersion), electrostatic coating, ultraviolet curing coating method, and the like.

  Examples of the inorganic material used to form the inorganic protective layer include transparent or semitransparent metal oxides such as zirconium oxide, zinc oxide, titanium oxide, silicon oxide, and aluminum oxide. Examples of the method of forming the inorganic protective layer include known sol-gel methods, hydrothermal synthesis methods, physical vapor deposition methods, CVD methods, chemical solution deposition methods, electrolytic deposition methods, and the like.

  The film thickness of the transparent or translucent protective layer can exert a protective function, and the protective layer is penetrated to visually recognize the second Cu plating layer (silver white metal plating layer in the case of forming a silver white metal plating layer) The thickness is not particularly limited as long as the thickness can be achieved.

6. Application of Decorative Parts The application of the decorative parts is not particularly limited, and examples may be interior parts or exterior parts for vehicles, electric / electronic parts, daily goods and the like.

  Next, the present invention will be more specifically described with reference to Examples 1 to 7 and Comparative Examples 1 to 7. The present invention is not limited to the embodiments.

As shown in FIG. 1 and Table 1, the decorative component of Examples 1 to 7 comprises a substrate 1 and a first Cu plated layer having a surface roughness Ra of 0.25 μm or 0.67 μm formed on the substrate. 2 and a first Cu plating layer 2 having a thickness of 1.0 to 6.1 μm and a surface roughness Ra of 16 to 84% of the surface roughness Ra of the first Cu plating layer 2 It consists of a 2Cu plating layer 3 and a Sn—Co alloy plating layer 4 as a silver white metal plating layer formed on the second Cu plating layer 3.
The decorative part has a satin-like appearance based on the surface roughness of the second Cu plated layer 3, and the Sn--Co alloy plated layer 4 is for adjusting the color tone of the satin-like appearance. Therefore, the satin plating film 5 of the present embodiment has a three-layer structure of first Cu plating layer 2 \ second Cu plating layer 3 \ Sn-Co alloy plating layer 4. A transparent or translucent protective layer 6 may be formed on the Sn—Co alloy plated layer 4 as necessary.

The comparative example 1 does not contain the 2nd Cu plating layer 3 with respect to Examples 1-6.
The film thickness of the 2nd Cu plating layer 3 is 0.35 micrometer with respect to the comparative example 2 with respect to Examples 1-6.
The comparative example 3 is 7.0 micrometers in film thickness of 2nd Cu plating layer 3 with respect to Examples 1-6.
The comparative example 4 does not contain the 1st Cu plating layer 2 with respect to Examples 1-6.
The comparative example 5 does not include the second Cu plating layer 3 as compared with the example 7.
In Comparative Example 6, the film thickness of the second Cu plated layer 3 is 0.35 μm, as compared with Example 7.
In Comparative Example 7, the film thickness of the second Cu plated layer 3 is 0.7 μm, as compared with Example 7.

The decorative parts of Examples 1 to 7 and Comparative Examples 2, 3, 6 and 7 were produced by the following method.
<1> Substrate and its Treatment A plate-like substrate made of ABS was treated in the following order. Each treatment can be carried out by any known method.
The substrate surface was degreased by immersion in a surfactant-containing bath.
The substrate surface was etched by immersion in a Cr acid / sulfuric acid solution.
-The substrate surface was activated by applying a catalyst represented by Pd / Sn mixed colloid catalyst and the like.
Electroconductive Ni plating or electroless Cu plating was performed to impart conductivity to the substrate surface.

<2> Formation of 1st Cu plating layer As shown on the left side of FIG. 2, plating which mixes suitably only "CuSOFT" by JCU as an additive in the known Cu plating bath as a base material 1 after the above-mentioned processing It was immersed in the bath 11, and electrolytic matte Cu plating was performed under plating conditions of cathode current density 4 A / dm ² . When the film thickness and surface roughness Ra of the formed first Cu plated layer were measured while changing the plating time stepwise within the range of 50 seconds to 60 minutes, the relationship between the plating time and the film thickness shown in FIG. The approximate curve is also shown), and the relationship between the film thickness and Ra shown in FIG. 4 was obtained.
Then, the first Cu plated layer having a film thickness of 8 μm and a surface roughness Ra of 0.25 μm obtained in a plating time of 20 minutes was used as the first Cu plated layer 2 in Examples 1 to 6 and Comparative Examples 2 and 3.
Further, a first Cu plated layer having a film thickness of 10 μm and a surface roughness Ra of 0.67 μm obtained in a plating time of 25 minutes was taken as the first Cu plated layer 2 in Example 7 and Comparative Examples 6 and 7.

<3> Formation of Second Cu Plating Layer As shown on the right side of FIG. 2, the base 1 on which the first Cu plating layer 2 having a thickness of 8 μm is formed is used as a known leveling agent as an additive to a known Cu plating bath. And immersing in a plating bath 12 formed by appropriately blending a growth inhibitor, a growth promoter and an anti-bumper agent and a reagent "EP30-A, B, C" manufactured by JCU, and the conditions of a cathode current density of 3 A / dm ² Performed electrolytic luster Cu plating. The film thickness of the second Cu plating layer formed by stepwise changing the plating time to 1 minute, 3 minutes, 7.5 minutes, 10 minutes, 12.5 minutes, 15 minutes, 17.5 minutes, and 20 minutes, When the surface roughness Ra and the glossiness were measured, the results shown in Table 1 were obtained.

  Table 1 also shows the reduction rate ΔRa of the surface roughness Ra of the second Cu plated layer 3 with respect to the surface roughness Ra of the first Cu plated layer 2. FIG. 5 shows the relationship between the film thickness of the second Cu plated layer 3 and ΔRa together with the approximate curve. FIG. 6 also shows the relationship between the film thickness of the second Cu plated layer 3 and the surface roughness Ra and the degree of gloss.

And as shown in Table 1, the surface roughness Ra of the second Cu plating layer 3 was 1.0 to 6.1 μm, and the surface roughness Ra of the first Cu plating layer 2 was a satin-like appearance in visual observation. Six examples which were 16 to 84% of are Examples 1-6. An example of the film thickness of 0.35 μm of the second Cu plating layer 3 having a matte appearance is Comparative Example 2. An example having a film thickness of 7.0 μm of the second Cu plating layer 3 having a substantially glossy appearance is Comparative Example 3.
Moreover, about the example in which the 1st Cu plating layer 2 with a film thickness of 10 micrometers was formed, it was 1.0 micrometer of film thickness of 2nd Cu plating layer 3 whose appearance was satin-like by visual observation, and surface roughness Ra is 1st Cu An example in which the surface roughness Ra of the plating layer 2 is 24% is a seventh embodiment. The example of the film thickness of 0.35-0.7 micrometer of the 2nd Cu plating layer 3 whose appearance was matte is Comparative Examples 6 and 7.

Formation of a <4> Sn-Co alloy plating layer The plating bath (not shown) which consists of a commercially available pyrophosphoric acid bath which uses Sn-Co medicine made from JCU the base material 1 in which the 2nd above-mentioned Cu plating layer 3 was formed. And electrolytic Sn—Co alloy plating was performed under the plating conditions of a cathode current density of 0.5 A / dm ² . The Sn—Co alloy plated layer 4 with a film thickness of 0.3 μm was formed in a plating time of 3 minutes.

  Due to the Sn--Co alloy plating layer 4, the color tone of the satin-like appearance of Examples 1 to 7 of the second Cu plating layer 3 is the Cr color tone with almost no change in the surface roughness Ra and the glossiness of the second Cu plating layer 3. became.

Formation of <5> Transparent or Semitransparent Protective Layer A transparent or semitransparent protective layer 6 having a film thickness of 10 μm can be formed on the Sn—Co alloy plated layer 4 by, for example, electrodeposition coating of an acrylic resin. . The transparent or translucent protective layer 6 does not affect the satin appearance of the first to seventh embodiments.

Next, in the decorative component of Comparative Example 1, the first Cu plated layer 2 similar to those of Examples 1 to 6 is formed on the base material 1, and the first Cu plated layer 2 is not formed. The same Sn—Co alloy plated layer 4 as in each of the examples was formed on the top. The appearance was matte.
In the decorative component of Comparative Example 4, the second Cu plating layer 3 having a film thickness of 10.0 μm is formed on the second Cu plating layer 3 without forming the first Cu plating layer 2 on the base material 1. It produced by forming the Sn-Co alloy plating layer 4 similar to each Example. The appearance was shiny.
In addition, the decorative component of Comparative Example 5 forms the first Cu plated layer 2 similar to that of Example 7 on the base material 1, and does not form the second Cu plated layer 3. It produced by forming the same Sn-Co alloy plating layer 4 as an example. The appearance was matte.

  As described above, the decorative parts of Examples 1 to 7 do not use the conventional satin Ni plating layer, but use ductile first Cu plating layer 2 and second Cu plating layer 3 to reduce the satin appearance with a small number of layers. It was possible to obtain stably.

The present invention is not limited to the embodiments described above, and can be appropriately modified and embodied without departing from the spirit of the invention.
(1) The base material 1 is not limited to the base material made of resin, For example, the base material made of metal (brass etc.) can also be used.
(2) As the first Cu plating layer, as described above, the surface roughness Ra of 0.25 μm or 0.67 μm was adopted in each example as described above, but the surface roughness Ra of 0.1 to 0.8 μm may be adopted. it can. Also in that case, the satin appearance is stabilized by forming a second Cu plated layer having a thickness of 1 to 6.1 μm and a surface roughness Ra of 15 to 80% of the surface roughness Ra of the first Cu plated layer. Can be obtained.

DESCRIPTION OF SYMBOLS 1 base material 2 1st Cu plating layer 3 2nd Cu plating layer 4 Sn-Co alloy plating layer 5 satin plating film 6 transparent or semitransparent protective layer 11 plating bath (for 1st Cu plating layer)
12 Plating bath (for 2nd Cu plating layer)

Claims (5)

A substrate,
A first Cu plated layer having a surface roughness Ra of 0.1 to 0.8 μm formed on a substrate;
And a second Cu plated layer having a thickness of 1 to 6.1 μm and a surface roughness Ra of 15 to 80% of the surface roughness Ra of the first Cu plated layer, formed on the first Cu plated layer,
A decorative part having a semi-glossy satin-like appearance based on the surface roughness of a second Cu plating layer.   The decorative part according to claim 1, further comprising a silver-white metal plating layer formed on the second Cu plating layer for adjusting the color tone of the satin-like appearance.   The decorative part according to claim 2, wherein the silver white metal plating layer is a Sn or Sn alloy plating layer.   The decorative part according to claim 2, wherein the silver white metal plating layer is a Cr plating layer. A first step of forming a first Cu plated layer having a surface roughness Ra of 0.1 to 0.8 μm by performing electrolytic matte Cu plating on a substrate;
By performing electrolytic luster Cu plating on the first Cu plating layer, the second Cu plating having a thickness of 1 to 6.1 μm and a surface roughness Ra of 15 to 80% of the surface roughness Ra of the first Cu plating layer And 2. a second step of forming a layer.

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