WO2018097186A1 - Colored copper plating method, colored copper plating solution, and colored copper plating film - Google Patents
Colored copper plating method, colored copper plating solution, and colored copper plating film Download PDFInfo
- Publication number
- WO2018097186A1 WO2018097186A1 PCT/JP2017/042031 JP2017042031W WO2018097186A1 WO 2018097186 A1 WO2018097186 A1 WO 2018097186A1 JP 2017042031 W JP2017042031 W JP 2017042031W WO 2018097186 A1 WO2018097186 A1 WO 2018097186A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper plating
- electroless
- colored
- copper
- film
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
Definitions
- the present invention relates to a colored copper plating method, a colored copper plating solution used in the method, and a colored copper plating film obtained by the method.
- the copper film usually has a so-called copper color, but it is desired to have various colors other than the copper color according to the consumer's taste.
- Patent Document 1 As a method for obtaining a copper plating film having a color tone other than copper, in Patent Document 1, an article provided with a copper plating film is immersed in a chemical conversion treatment solution containing chlorites and an alkali metal hydroxide. Thus, a technique for coloring the appearance of the surface of the copper plating film in blue is disclosed.
- Patent Document 1 requires a step of immersing the article in a chemical conversion solution after forming a copper plating film on the article, resulting in an increase in cost. Further, the technique disclosed in Patent Document 1 has a disadvantage that a copper plating film having a color tone other than blue cannot be obtained.
- An object of the present invention is to provide a copper plating method and a copper plating solution capable of obtaining a copper plating film having a color tone other than copper color, and a copper plating film having a color tone other than copper color.
- the colored copper plating method of the present invention is a copper plating method for obtaining a colored electroless copper plating film, and the surface of the plating object is immersed in an electroless copper plating solution and electroless plating treatment is performed. An electroless copper plating film is formed on the substrate, and the color tone of the electroless copper plating film is changed by continuing the immersion after the completion of the copper precipitation reaction.
- reduction type electroless plating or displacement type electroless plating can be employed as the electroless plating treatment.
- the colored copper plating solution of the present invention is a copper plating solution used for forming and coloring an electroless copper plating film, and the electroless copper plating film is formed on the surface of an object to be plated by electroless plating treatment.
- the color tone of the electroless copper plating film is changed by continuing immersion of the object to be plated even after the completion of the copper precipitation reaction.
- the colored copper plating solution of the present invention has a copper sulfate pentahydrate of 10 to 30 g / L, boric acid of 5 to 30 g / L, citric acid when the reduction type electroless plating process is adopted as the electroless plating process. It preferably contains trisodium acid 20-50 g / L, sodium hydroxide 5-30 g / L and sodium hypophosphite 10-40 g / L.
- the colored copper plating solution of the present invention has a copper sulfate pentahydrate of 10 to 30 g / L, boric acid of 5 to 30 g / L, citric acid when the substitutional electroless plating process is adopted as the electroless plating process. It preferably contains trisodium acid 20-50 g / L and sodium hydroxide 5-30 g / L.
- the colored copper plating film of the present invention is a copper plating film that is a colored electroless copper plating film, and the hue when expressed in silver or Munsell color system is YR (yellow red), Y (yellow), One of the hues classified by YG (yellowish green), G (green), BG (blue green), B (blue), and RP (red purple) is provided.
- the colored copper plating film of the present invention preferably includes a protective film having translucency on the surface of the colored copper plating film.
- the colored copper plating method and the colored copper plating solution of the present invention by changing the color tone of the electroless copper plating film by continuously immersing the object to be plated even after the completion of the copper precipitation reaction, various color tones are obtained.
- a colored copper plating film can be obtained.
- the colored copper plating film of the present embodiment is a colored electroless copper plating film, and the hue when expressed in silver or Munsell color system is YR (yellow red), Y (yellow), YG (yellow green) ), G (green), BG (blue-green), B (blue), or RP (red purple).
- the colored copper plating film of this embodiment has been confirmed to contain oxygen in addition to copper and phosphorus by energy dispersive X-ray analysis (EDS). Moreover, although the color tone of the colored copper plating film of this embodiment does not change in an air atmosphere and an alkaline atmosphere, it has been confirmed that the color tone changes in an oxidizing atmosphere. From these things, the colored copper plating film of this embodiment is considered that the surface of the electroless copper plating film is changed to a copper oxide film. It is known that the color tone of the titanium oxide film changes depending on the film thickness. However, in the colored copper plating film of this embodiment, the film thickness of the copper oxide film changes to the color tone as well as the titanium oxide film. It is thought to have influenced.
- EDS energy dispersive X-ray analysis
- the colored copper plating film of the present embodiment preferably includes a protective film having translucency on its surface.
- a protective film having translucency for example, silicon acrylic resin, acrylic urethane resin, urethane resin, or the like can be used. Since the surface of the colored copper plating film provided with the protective film is protected by the protective film, the color tone can be prevented from changing even in an oxidizing atmosphere, and the surface can be It is possible to prevent the non-oxidized electroless copper plating film located inside the possible surface layer portion from being exposed, that is, the copper-colored electroless copper plating film.
- the colored copper plating film having the above-described color tone can be obtained by, for example, a colored copper plating method.
- a colored copper plating method e.g., a copper plating method
- the first embodiment and the second embodiment of the colored copper plating method will be described in order.
- the colored copper plating solution used for each colored copper plating method will also be described.
- the colored copper plating method of the first embodiment performs reduction type electroless plating as an electroless plating treatment. Therefore, the colored copper plating solution used for the colored copper plating method of this embodiment contains a reducing agent.
- a substrate made of acrylonitrile-butadiene-styrene (ABS) resin, which is a commonly used plastic plating material (hereinafter referred to as an ABS substrate) is used as an object to be plated will be described as an example.
- a resin substrate made of COP, PPE, PET, PEN, PPS, PEEK, PA, SPS, AES, PBT, POM, PI, PC-ABS, glass, ceramics, metal, or the like may be used. Is possible.
- UV modification treatment ultraviolet modification treatment
- alkali degreasing treatment alkali degreasing treatment
- conditioning conditioning.
- the treatment, the catalytic treatment, and the reduction treatment are performed in this order. Between each process, a water washing process is performed as needed.
- UV modification treatment improves the adhesion between the ABS substrate and the plating film by modifying the surface of the ABS substrate by irradiating ultraviolet rays in an air atmosphere (Sugimoto). Shoji, Hideo Honma (2008), plating adhesion mechanism in resin surface modification using UV irradiation, surface technology, Vol. 59, No. 5, pp. 294-298).
- the UV modification treatment is performed, for example, by irradiating the object to be plated for 1 to 10 minutes with the main wavelength of ultraviolet light being 184 to 254 nm and the ultraviolet intensity being 10 to 30 mW / cm 2 .
- Alkaline degreasing treatment In the alkali degreasing treatment, the ABS substrate that has been subjected to the UV modification treatment is placed in an alkaline degreasing solution (NaOH: 10 to 150 g / L) heated to 20 to 70 ° C. for 1 to 5 minutes, for example. This is done by dipping.
- an alkaline degreasing solution NaOH: 10 to 150 g / L
- Conditioning treatment was performed by heating an ABS substrate subjected to alkaline degreasing treatment to a temperature of 20 to 60 ° C. (CC-231 (Rohm and Haas Electronic Materials Co., Ltd.): 5 to 20 volumes. %) For 1 to 5 minutes.
- Catalytic treatment In the catalytic treatment, the ABS substrate that has been subjected to the conditioning treatment is immersed in a catalyst application liquid (PdCl: 0.2 to 0.5 g / L) heated to 20 to 60 ° C. for 1 to 5 minutes. To do. A Pd catalyst is imparted to the surface of the ABS substrate by the catalytic treatment.
- a catalyst application liquid PdCl: 0.2 to 0.5 g / L
- Reduction treatment In the reduction treatment, the catalytically treated ABS substrate is placed in a reduction treatment solution (NaH 2 PO 2 .H 2 O: 1 to 100 g / L) heated to 20 to 60 ° C. for 30 seconds to This is done by dipping for 5 minutes.
- a reduction treatment solution NaH 2 PO 2 .H 2 O: 1 to 100 g / L
- Reduction-type electroless plating is performed by immersing a reduced ABS substrate in a colored copper plating solution (pH 8-10) heated at 40-90 ° C. for 1-45 minutes. Do.
- a colored copper plating solution for example, one having the following composition can be used.
- Cold copper plating solution composition Copper sulfate pentahydrate 10-30g / L Boric acid 5-30g / L Trisodium citrate 20-50g / L Sodium hydroxide 5-30g / L Sodium hypophosphite 10-40g / L
- the ABS substrate When the ABS substrate is immersed in the colored copper plating solution, since the colored copper plating solution contains a reducing agent, a reduction reaction occurs on the surface of the ABS substrate, copper is deposited, and an electroless copper plating film containing copper is formed.
- the surface of the ABS substrate is usually covered with copper in about 30 seconds to 2 minutes, and then the copper precipitation reaction is completed.
- the color tone of the electroless copper plating film immediately after the film formation, that is, immediately after the completion of the copper deposition reaction, is copper.
- the ABS substrate is pulled up from the plating solution when the copper precipitation reaction is completed.
- the immersion of the ABS substrate in the colored copper plating solution is continued for, for example, 1 to 45 minutes even after the copper precipitation reaction is completed.
- the electroless copper plating film has a copper color immediately after the completion of the copper precipitation reaction, but the surface color changes as the immersion time increases. Specifically, when the surface of the electroless copper plating film is expressed in silver or Munsell color system, the hue is YR (yellow red), Y (yellow), YG (yellow green), G (green), BG It changes to one of the hues classified by (blue green), B (blue), and RP (red purple).
- the change in the color tone of the electroless copper plating film is stopped by pulling up the ABS substrate provided with the electroless copper plating film from the colored copper plating solution. Can do. As described above, a colored copper plating film having various color tones other than the copper color can be obtained.
- the colored copper plating method of the second embodiment performs substitution type electroless plating as an electroless plating treatment. Therefore, the colored copper plating solution used for the colored copper plating method of this embodiment does not contain a reducing agent.
- a functional component made of zinc die-casting is used as an object to be plated, but a metal-plated resin substrate such as ABS, a copper material, or the like can also be used.
- substitutional electroless plating is performed after pretreatment.
- the pretreatment can be performed by a conventionally known method.
- an alkaline degreasing treatment, a copper cyanide plating treatment, and an electrogalvanizing treatment are sequentially performed. Between each process, a water washing process is performed as needed.
- Alkaline degreasing treatment In the alkaline degreasing treatment, a functional part made of zinc die cast as an object to be plated is added, for example, to an alkaline degreasing solution (NaOH: 10 to 150 g / L) heated to 20 to 70 ° C. This is done by dipping for 5 minutes.
- an alkaline degreasing solution NaOH: 10 to 150 g / L
- Copper cyanide plating treatment The copper cyanide plating treatment is performed to give gloss to the electroless copper plating film obtained in the subsequent step.
- the object to be plated that has been subjected to alkaline degreasing treatment is immersed in, for example, a commercially available copper cyanide plating solution heated to 20 to 60 ° C., and the cathode current density is set to 1 to 6 A / dm. 2 is performed by energizing for 1 to 30 minutes.
- Electrogalvanizing treatment In the electrogalvanizing treatment, an object to be plated that has been subjected to copper cyanide plating treatment is immersed in, for example, a galvanizing solution heated to 50 to 70 ° C., and the cathode current density is set to 0.1. It is carried out by energizing for 2 to 10 minutes at ⁇ 10 A / dm 2 .
- the zinc plating solution for example, one having the following composition can be used.
- the pH is preferably 8.5 to 9.5. (Composition of zinc plating solution)
- zinc which is a base metal rather than copper
- a substitution reaction is caused by an electroless plating treatment in a subsequent process.
- Substitutional electroless plating involves immersing an object to be plated that has been subjected to electrogalvanizing treatment in a colored copper plating solution (pH 8 to 10) heated to 40 to 90 ° C for 1 to 45 minutes. To do.
- a colored copper plating solution for example, one having the following composition can be used.
- Cold copper plating solution composition Copper sulfate pentahydrate 10-30g / L Boric acid 5-30g / L Trisodium citrate 20-50g / L Sodium hydroxide 5-30g / L
- the immersion of the object to be plated in the colored copper plating solution is continued for, for example, 1 to 45 minutes even after the completion of the copper precipitation reaction.
- the electroless copper plating film has a copper color immediately after the completion of the copper precipitation reaction, but the surface color changes as the immersion time increases.
- the hues are YR (yellow red), Y (yellow), YG (yellowish green), G (green), BG (blue green) ), B (blue), and RP (red purple).
- the change in the color tone of the electroless copper plating film is stopped by pulling up the object to be plated with the electroless copper plating film from the electroless copper plating solution. Can be made. As described above, a colored copper plating film having various color tones other than the copper color can be obtained.
- the colored copper plating method of the present embodiment including the first embodiment and the second embodiment, various types other than the copper color can be obtained simply by immersing the object to be plated in a colored copper plating solution and performing an electroless plating treatment.
- a colored copper plating film having a color tone can be easily obtained. Therefore, unlike the technique disclosed in Patent Document 1, it is not necessary to perform a process of immersing and coloring in other chemical conversion treatment liquids after performing electroless plating treatment, thereby preventing an increase in cost. Can do.
- the colored copper plating film can be changed to various colors only by controlling the immersion time of the object to be plated in the colored copper plating solution.
- the colored copper plating method of this embodiment since the electroplating process is performed by immersing the object to be plated in the colored copper plating solution under the above conditions, the copper precipitation reaction is completed in a short time. As a result, it is possible to reduce the overall processing time until the target color tone is changed, that is, the time required to obtain a colored copper plating film having a desired color tone can be reduced. Furthermore, according to the colored copper plating method of this embodiment, since the colored copper plating solution does not contain noble metals such as gold and silver, an electroless copper plating film can be obtained at low cost, and the colored copper plating solution Since nickel, chromium, etc. are not included, the load on the human body and the environment can be reduced.
- the colored copper plating film provided with the color tone other than copper color obtained by the colored copper plating method of the present embodiment is used for clothing such as fasteners and buttons, the case of mobile phones, digital audio players, etc. It can be applied to various fields such as industrial products.
- an ABS substrate Hishiplate (registered trademark), Y-268, Mitsubishi Chemical Corporation, thickness 2 mm
- a colored copper plating method for performing reduction-type electroless plating as an electroless plating treatment was performed on the object to be plated by the procedure shown in Table 3.
- a small ultraviolet surface treatment device KOL1-300, Koto Electric Co., Ltd.
- the distance from the lower end of the high-power / low-pressure mercury lamp in the device to the ABS substrate surface is adjusted to 30 mm.
- the main wavelength is 253.7nm and 184.9 nm
- the intensity of ultraviolet light having a wavelength of 253.7nm 62mW / cm 2 the intensity of ultraviolet light having a wavelength of 184.9 nm as 6 mW / cm 2
- an alkaline degreasing solution NaOH: 100 g / L
- a conditioning treatment solution (CC-231 (Rohm and Haas Electronic Materials Co., Ltd.): 10% by volume) was used.
- a catalyst application liquid (PdCl: 0.3 g / L) was used.
- a catalyst application liquid (PdCl: 0.3 g / L) was used.
- a reduction treatment solution (solution containing NaH 2 PO 2 .H 2 O) was used.
- Reduction type electroless plating was performed by immersing the ABS substrate in a colored copper plating solution (pH 9.0) having the following composition heated to 80 ° C. for 1 to 30 minutes. As soon as the immersion time reached the target time, the ABS substrate was pulled up from the colored copper plating solution. As described above, a colored copper plating film was formed on the surface of the ABS substrate.
- a colored copper plating solution composition Copper sulfate pentahydrate 15g / L Boric acid 15g / L Trisodium citrate 30g / L Sodium hydroxide 10g / L Sodium hypophosphite 38g / L
- the SCI mode is a specular reflection measurement mode in which the original color of the measurement object is measured.
- the SCE mode is a regular reflection light removal measurement mode in which a color close to the observation color is measured with the naked eye.
- Table 4 the color expressed in Munsell system was described as the visual color tone, but the color was described without using the Munsell system expression for the achromatic color or a color close to the achromatic color.
- a functional component made of zinc die cast was used as the object to be plated.
- a colored copper plating method for performing substitutional electroless plating as an electroless plating treatment was performed on the object to be plated by the procedure shown in Table 5.
- an alkaline degreasing solution NaOH: 20 g / L
- the copper cyanide plating treatment was performed by energizing for 10 minutes using a copper cyanide plating solution (pH 11.0) having the following composition at a cathode current density of 2 A / dm 2 .
- a copper cyanide plating solution pH 11.0
- a zinc plating solution (pH 9.0) having the following composition was used, and the cathode current density was set to 2 A / dm 2 and energized for 5 minutes.
- Composition of zinc plating solution Zinc sulfate 15g / L Potassium pyrophosphate 100g / L
- Substitutional electroless plating was performed by immersing a functional component that had been subjected to electrogalvanizing treatment in a colored copper plating solution (pH 9.0) having the following composition heated to 80 ° C. for 1 to 30 minutes. . As soon as the immersion time reached the target time, the functional component was pulled up from the colored copper plating solution. As described above, a colored copper plating film was formed on the surface of the functional component.
- a colored copper plating solution composition Copper sulfate pentahydrate 15g / L Boric acid 15g / L Trisodium citrate 30g / L Sodium hydroxide 10g / L
- the electroless plating process is performed on the object to be plated, and only the immersion time of the object to be plated in the colored copper plating solution is controlled.
- Colored copper plating films that have been changed to various color tones, specifically, the hue when expressed in silver or Munsell color system is YR (yellow red), Y (yellow), YG (yellowish green), G ( A colored copper plating film having any hue classified by green), BG (blue green), B (blue), and RP (red purple) can be easily obtained.
- the colored copper plating solution does not contain noble metals such as gold and silver, a colored copper plating film can be obtained at a low cost, and the colored copper plating solution is nickel. Since it does not contain chromium or the like, the load on the human body and the environment can be reduced.
- the colored copper plating film provided with the color tone other than copper color obtained by the colored copper plating method of the present embodiment is used for clothing such as fasteners and buttons, the case of mobile phones, digital audio players, etc. It can be applied to various fields such as industrial products.
Abstract
The purpose of the present invention is to provide: a copper plating method and copper plating solution with which a copper plating film with a color different from a copper color can be obtained; and a copper plating film having a color different from the copper color. To achieve this purpose, the colored copper plating method for obtaining a colored electroless copper plating film is characterized in that an electroless copper plating film is formed on the surface of an object to be plated by immersing the object in an electroless copper plating solution and performing electroless plating, and the color of the electroless copper plating film is changed by continuing immersion even after completion of deposition of copper. The colored copper plating film is a colored electroless copper plating film and is characterized by having a silver color or a color classified according to the Munsell color system into YR (yellow-red), Y (yellow), YG (yellow-green), G (green), BG (blue-green), B (blue) or RP (red-purple).
Description
本件発明は、着色銅めっき方法、その方法に用いる着色銅めっき液、及び、その方法によって得られる着色銅めっき皮膜に関する。
The present invention relates to a colored copper plating method, a colored copper plating solution used in the method, and a colored copper plating film obtained by the method.
ファスナー、ボタン等の衣類に用いられる服飾品や、携帯電話、デジタルオーディオプレーヤーの筐体等の工業製品等、種々の分野において、物品の表面に銅皮膜を設ける技術が知られている。銅皮膜は、通常、いわゆる銅色を呈しているが、消費者の趣向に合わせて銅色以外の様々な色調を備えることが望まれる。
In various fields, such as clothing used for clothing such as fasteners and buttons, and industrial products such as mobile phones and digital audio player housings, a technique for providing a copper film on the surface of an article is known. The copper film usually has a so-called copper color, but it is desired to have various colors other than the copper color according to the consumer's taste.
銅色以外の色調を備える銅めっき皮膜を得る方法として、特許文献１に、銅めっき皮膜が設けられた物品を亜塩素酸塩類及びアルカリ金属の水酸化物を含有する化成処理液に浸漬処理することにより、銅めっき皮膜の表面の外観を青色に着色する技術が開示されている。
As a method for obtaining a copper plating film having a color tone other than copper, in Patent Document 1, an article provided with a copper plating film is immersed in a chemical conversion treatment solution containing chlorites and an alkali metal hydroxide. Thus, a technique for coloring the appearance of the surface of the copper plating film in blue is disclosed.
しかしながら、特許文献１に開示の技術では、物品に銅めっき皮膜を形成した後に当該物品を化成処理液に浸漬するという工程が必要となり、コスト増となるという不都合がある。また、特許文献１に開示の技術では、青色以外の色調を備える銅めっき皮膜を得られないという不都合がある。
However, the technique disclosed in Patent Document 1 requires a step of immersing the article in a chemical conversion solution after forming a copper plating film on the article, resulting in an increase in cost. Further, the technique disclosed in Patent Document 1 has a disadvantage that a copper plating film having a color tone other than blue cannot be obtained.
本発明の課題は、銅色以外の色調を備える銅めっき皮膜を得ることができる銅めっき方法及び銅めっき液、さらに、銅色以外の色調を備える銅めっき皮膜を提供することを目的とする。
An object of the present invention is to provide a copper plating method and a copper plating solution capable of obtaining a copper plating film having a color tone other than copper color, and a copper plating film having a color tone other than copper color.
本件発明の着色銅めっき方法は、着色された無電解銅めっき皮膜を得る銅めっき方法であって、被めっき物を無電解銅めっき液に浸漬して無電解めっき処理によって当該被めっき物の表面に無電解銅めっき皮膜を成膜し、銅の析出反応の終了後も当該浸漬を継続することにより当該無電解銅めっき皮膜の色調を変化させることを特徴とする。
The colored copper plating method of the present invention is a copper plating method for obtaining a colored electroless copper plating film, and the surface of the plating object is immersed in an electroless copper plating solution and electroless plating treatment is performed. An electroless copper plating film is formed on the substrate, and the color tone of the electroless copper plating film is changed by continuing the immersion after the completion of the copper precipitation reaction.
本件発明の着色銅めっき方法では、前記無電解めっき処理として、還元型無電解めっき又は置換型無電解めっきを採用することができる。
In the colored copper plating method of the present invention, reduction type electroless plating or displacement type electroless plating can be employed as the electroless plating treatment.
本件発明の着色銅めっき液は、無電解銅めっき皮膜を成膜し着色するのに用いられる銅めっき液であって、無電解めっき処理によって被めっき物の表面に無電解銅めっき皮膜を成膜させ、銅の析出反応の終了後も当該被めっき物の浸漬が継続されることにより当該無電解銅めっき皮膜の色調を変化させることを特徴とする。
The colored copper plating solution of the present invention is a copper plating solution used for forming and coloring an electroless copper plating film, and the electroless copper plating film is formed on the surface of an object to be plated by electroless plating treatment. The color tone of the electroless copper plating film is changed by continuing immersion of the object to be plated even after the completion of the copper precipitation reaction.
本件発明の着色銅めっき液は、無電解めっき処理として還元型無電解めっき処理を採用する場合には、硫酸銅五水和物１０～３０ｇ／Ｌと、ホウ酸５～３０ｇ／Ｌと、クエン酸三ナトリウム２０～５０ｇ／Ｌと、水酸化ナトリウム５～３０ｇ／Ｌと、次亜リン酸ナトリウム１０～４０ｇ／Ｌとを含有することが好ましい。
The colored copper plating solution of the present invention has a copper sulfate pentahydrate of 10 to 30 g / L, boric acid of 5 to 30 g / L, citric acid when the reduction type electroless plating process is adopted as the electroless plating process. It preferably contains trisodium acid 20-50 g / L, sodium hydroxide 5-30 g / L and sodium hypophosphite 10-40 g / L.
本件発明の着色銅めっき液は、無電解めっき処理として置換型無電解めっき処理を採用する場合には、硫酸銅五水和物１０～３０ｇ／Ｌと、ホウ酸５～３０ｇ／Ｌと、クエン酸三ナトリウム２０～５０ｇ／Ｌと、水酸化ナトリウム５～３０ｇ／Ｌとを含有することが好ましい。
The colored copper plating solution of the present invention has a copper sulfate pentahydrate of 10 to 30 g / L, boric acid of 5 to 30 g / L, citric acid when the substitutional electroless plating process is adopted as the electroless plating process. It preferably contains trisodium acid 20-50 g / L and sodium hydroxide 5-30 g / L.
本件発明の着色銅めっき皮膜は、着色された無電解銅めっき皮膜である銅めっき皮膜であって、銀色又はマンセル表色系で表した場合の色相がＹＲ（黄赤）、Ｙ（黄）、ＹＧ（黄緑）、Ｇ（緑）、ＢＧ（青緑）、Ｂ（青）、ＲＰ（赤紫）で分類されるいずれかの色相を備えることを特徴とする。
The colored copper plating film of the present invention is a copper plating film that is a colored electroless copper plating film, and the hue when expressed in silver or Munsell color system is YR (yellow red), Y (yellow), One of the hues classified by YG (yellowish green), G (green), BG (blue green), B (blue), and RP (red purple) is provided.
本件発明の着色銅めっき皮膜は、当該着色銅めっき皮膜の表面に透光性を有する保護皮膜を備えることが好ましい。
The colored copper plating film of the present invention preferably includes a protective film having translucency on the surface of the colored copper plating film.
本件発明の着色銅めっき方法及び着色銅めっき液によれば、銅の析出反応の終了後も被めっき物の浸漬を継続して無電解銅めっき皮膜の色調を変化させることにより、種々の色調を備える着色銅めっき皮膜を得ることができる。
According to the colored copper plating method and the colored copper plating solution of the present invention, by changing the color tone of the electroless copper plating film by continuously immersing the object to be plated even after the completion of the copper precipitation reaction, various color tones are obtained. A colored copper plating film can be obtained.
以下、本件発明に係る着色銅めっき方法、着色銅めっき液及び着色銅めっき皮膜の実施の形態を説明する。
Hereinafter, embodiments of the colored copper plating method, the colored copper plating solution, and the colored copper plating film according to the present invention will be described.
＜着色銅めっき皮膜＞
本実施形態の着色銅めっき皮膜は、着色された無電解銅めっき皮膜であって、銀色又はマンセル表色系で表した場合の色相がＹＲ（黄赤）、Ｙ（黄）、ＹＧ（黄緑）、Ｇ（緑）、ＢＧ（青緑）、Ｂ（青）、ＲＰ（赤紫）で分類されるいずれかの色相を備えることを特徴とする。 <Colored copper plating film>
The colored copper plating film of the present embodiment is a colored electroless copper plating film, and the hue when expressed in silver or Munsell color system is YR (yellow red), Y (yellow), YG (yellow green) ), G (green), BG (blue-green), B (blue), or RP (red purple).
本実施形態の着色銅めっき皮膜は、着色された無電解銅めっき皮膜であって、銀色又はマンセル表色系で表した場合の色相がＹＲ（黄赤）、Ｙ（黄）、ＹＧ（黄緑）、Ｇ（緑）、ＢＧ（青緑）、Ｂ（青）、ＲＰ（赤紫）で分類されるいずれかの色相を備えることを特徴とする。 <Colored copper plating film>
The colored copper plating film of the present embodiment is a colored electroless copper plating film, and the hue when expressed in silver or Munsell color system is YR (yellow red), Y (yellow), YG (yellow green) ), G (green), BG (blue-green), B (blue), or RP (red purple).
本実施形態の着色銅めっき皮膜は、エネルギー分散型Ｘ線分析（ＥＤＳ）によって、銅及びリンに加えて酸素を含むことが確認されている。また、本実施形態の着色銅めっき皮膜は、大気雰囲気下及びアルカリ雰囲気下ではその色調が変化しないが、酸化雰囲気下ではその色調が変化することが確認されている。これらのことから、本実施形態の着色銅めっき皮膜は、無電解銅めっき皮膜の表面が銅酸化皮膜に変化したものであると考えられる。チタン酸化皮膜は膜厚によって表面の色調が変化することが知られているが、本実施形態の着色銅めっき皮膜においても、チタン酸化皮膜と同様に、銅酸化皮膜の膜厚が色調の変化に影響しているものと考えられる。
The colored copper plating film of this embodiment has been confirmed to contain oxygen in addition to copper and phosphorus by energy dispersive X-ray analysis (EDS). Moreover, although the color tone of the colored copper plating film of this embodiment does not change in an air atmosphere and an alkaline atmosphere, it has been confirmed that the color tone changes in an oxidizing atmosphere. From these things, the colored copper plating film of this embodiment is considered that the surface of the electroless copper plating film is changed to a copper oxide film. It is known that the color tone of the titanium oxide film changes depending on the film thickness. However, in the colored copper plating film of this embodiment, the film thickness of the copper oxide film changes to the color tone as well as the titanium oxide film. It is thought to have influenced.
本実施形態の着色銅めっき皮膜は、その表面に透光性を有する保護皮膜を備えることが好ましい。透光性を有する保護皮膜として、例えば、シリコンアクリル樹脂、アクリルウレタン樹脂、ウレタン樹脂等を用いることができる。保護皮膜を備える着色銅めっき皮膜は、保護皮膜によって表面が保護されるため、酸化雰囲気下であっても色調の変化を防止することができる上に、表面が傷付くことによって、銅酸化皮膜と考えられる表層部分の内部に位置する酸化されていない無電解銅めっき皮膜、すなわち、銅色の無電解銅めっき皮膜が露出するのを防ぐことができる。
The colored copper plating film of the present embodiment preferably includes a protective film having translucency on its surface. As the protective film having translucency, for example, silicon acrylic resin, acrylic urethane resin, urethane resin, or the like can be used. Since the surface of the colored copper plating film provided with the protective film is protected by the protective film, the color tone can be prevented from changing even in an oxidizing atmosphere, and the surface can be It is possible to prevent the non-oxidized electroless copper plating film located inside the possible surface layer portion from being exposed, that is, the copper-colored electroless copper plating film.
上述した色調を備える着色銅めっき皮膜は、例えば、着色銅めっき方法によって得ることができる。以下、着色銅めっき方法の第１実施形態及び第２実施形態について順に説明する。各実施形態の中で、各着色銅めっき方法に用いる着色銅めっき液についても併せて説明する。
The colored copper plating film having the above-described color tone can be obtained by, for example, a colored copper plating method. Hereinafter, the first embodiment and the second embodiment of the colored copper plating method will be described in order. In each embodiment, the colored copper plating solution used for each colored copper plating method will also be described.
＜第１実施形態の着色銅めっき方法＞
第１実施形態の着色銅めっき方法は、無電解めっき処理として還元型無電解めっきを行うものである。そのため、本実施形態の着色銅めっき方法に用いられる着色銅めっき液は、還元剤を含むものとなっている。以下、被めっき物として、一般的に用いられるプラスチックめっき材料であるアクリロニトリル－ブタジエン－スチレン（ＡＢＳ）樹脂からなる基板（以下、ＡＢＳ基板と記載する）を用いる場合を一例として説明する。その他、被めっき物として、ＣＯＰ、ＰＰＥ、ＰＥＴ、ＰＥＮ、ＰＰＳ、ＰＥＥＫ、ＰＡ、ＳＰＳ、ＡＥＳ、ＰＢＴ、ＰＯＭ、ＰＩ、ＰＣ－ＡＢＳ等からなる樹脂基板、ガラス、セラミックス、金属等を用いることも可能である。 <The colored copper plating method of 1st Embodiment>
The colored copper plating method of the first embodiment performs reduction type electroless plating as an electroless plating treatment. Therefore, the colored copper plating solution used for the colored copper plating method of this embodiment contains a reducing agent. Hereinafter, a case where a substrate made of acrylonitrile-butadiene-styrene (ABS) resin, which is a commonly used plastic plating material (hereinafter referred to as an ABS substrate) is used as an object to be plated will be described as an example. In addition, as the object to be plated, a resin substrate made of COP, PPE, PET, PEN, PPS, PEEK, PA, SPS, AES, PBT, POM, PI, PC-ABS, glass, ceramics, metal, or the like may be used. Is possible.
第１実施形態の着色銅めっき方法は、無電解めっき処理として還元型無電解めっきを行うものである。そのため、本実施形態の着色銅めっき方法に用いられる着色銅めっき液は、還元剤を含むものとなっている。以下、被めっき物として、一般的に用いられるプラスチックめっき材料であるアクリロニトリル－ブタジエン－スチレン（ＡＢＳ）樹脂からなる基板（以下、ＡＢＳ基板と記載する）を用いる場合を一例として説明する。その他、被めっき物として、ＣＯＰ、ＰＰＥ、ＰＥＴ、ＰＥＮ、ＰＰＳ、ＰＥＥＫ、ＰＡ、ＳＰＳ、ＡＥＳ、ＰＢＴ、ＰＯＭ、ＰＩ、ＰＣ－ＡＢＳ等からなる樹脂基板、ガラス、セラミックス、金属等を用いることも可能である。 <The colored copper plating method of 1st Embodiment>
The colored copper plating method of the first embodiment performs reduction type electroless plating as an electroless plating treatment. Therefore, the colored copper plating solution used for the colored copper plating method of this embodiment contains a reducing agent. Hereinafter, a case where a substrate made of acrylonitrile-butadiene-styrene (ABS) resin, which is a commonly used plastic plating material (hereinafter referred to as an ABS substrate) is used as an object to be plated will be described as an example. In addition, as the object to be plated, a resin substrate made of COP, PPE, PET, PEN, PPS, PEEK, PA, SPS, AES, PBT, POM, PI, PC-ABS, glass, ceramics, metal, or the like may be used. Is possible.
第１実施形態の着色銅めっき方法では、前処理を行った後に還元型無電解めっきを行う。前処理は、従来公知の方法で行うことが可能であるが、本実施形態では、表１に示すように、紫外線改質処理（以下、ＵＶ改質処理と記載する）、アルカリ脱脂処理、コンディショニング処理、触媒化処理、還元処理を順に行う。各処理の間では、必要に応じて水洗処理を行う。
In the colored copper plating method of the first embodiment, reduction type electroless plating is performed after pretreatment. The pretreatment can be performed by a conventionally known method. In this embodiment, as shown in Table 1, ultraviolet modification treatment (hereinafter referred to as UV modification treatment), alkali degreasing treatment, conditioning. The treatment, the catalytic treatment, and the reduction treatment are performed in this order. Between each process, a water washing process is performed as needed.
ＵＶ改質処理： ＵＶ改質処理は、大気雰囲気下で紫外線を照射することにより、ＡＢＳ基板の表面を改質することにより、ＡＢＳ基板とめっき皮膜間の密着性を向上させるものである（杉本将治、本間英夫（２００８）、ＵＶ照射を用いた樹脂表面改質におけるめっき密着メカニズム、表面技術、５９巻、５号、２９４～２９８頁）。ＵＶ改質処理は、例えば、紫外線の主波長を１８４～２５４ｎｍとし、紫外線強度を１０～３０ｍＷ／ｃｍ２として、被めっき物に１～１０分間照射することにより行う。
UV modification treatment: The UV modification treatment improves the adhesion between the ABS substrate and the plating film by modifying the surface of the ABS substrate by irradiating ultraviolet rays in an air atmosphere (Sugimoto). Shoji, Hideo Honma (2008), plating adhesion mechanism in resin surface modification using UV irradiation, surface technology, Vol. 59, No. 5, pp. 294-298). The UV modification treatment is performed, for example, by irradiating the object to be plated for 1 to 10 minutes with the main wavelength of ultraviolet light being 184 to 254 nm and the ultraviolet intensity being 10 to 30 mW / cm 2 .
アルカリ脱脂処理： アルカリ脱脂処理は、ＵＶ改質処理が施されたＡＢＳ基板を、例えば、２０～７０℃に加温されたアルカリ脱脂処理液（ＮａＯＨ：１０～１５０ｇ／Ｌ）に１～５分間浸漬することにより行う。
Alkaline degreasing treatment: In the alkali degreasing treatment, the ABS substrate that has been subjected to the UV modification treatment is placed in an alkaline degreasing solution (NaOH: 10 to 150 g / L) heated to 20 to 70 ° C. for 1 to 5 minutes, for example. This is done by dipping.
コンディショニング処理： コンディショニング処理は、アルカリ脱脂処理が施されたＡＢＳ基板を、２０～６０℃に加温されたコンディショニング処理液（ＣＣ－２３１（ローム・アンド・ハース電子材料株式会社）：５～２０体積％）に１～５分間浸漬することにより行う。
Conditioning treatment: Conditioning treatment was performed by heating an ABS substrate subjected to alkaline degreasing treatment to a temperature of 20 to 60 ° C. (CC-231 (Rohm and Haas Electronic Materials Co., Ltd.): 5 to 20 volumes. %) For 1 to 5 minutes.
触媒化処理： 触媒化処理は、コンディショニング処理が施されたＡＢＳ基板を、２０～６０℃に加温された触媒付与液（ＰｄＣｌ：０．２～０．５ｇ／Ｌ）に１～５分間浸漬することにより行う。触媒化処理によって、ＡＢＳ基板の表面にＰｄ触媒が付与される。
Catalytic treatment: In the catalytic treatment, the ABS substrate that has been subjected to the conditioning treatment is immersed in a catalyst application liquid (PdCl: 0.2 to 0.5 g / L) heated to 20 to 60 ° C. for 1 to 5 minutes. To do. A Pd catalyst is imparted to the surface of the ABS substrate by the catalytic treatment.
還元処理： 還元処理は、触媒化処理が施されたＡＢＳ基板を、２０～６０℃に加温された還元処理液（ＮａＨ２ＰＯ２・Ｈ２Ｏ：１～１００ｇ／Ｌ）に３０秒～５分間浸漬することにより行う。
Reduction treatment: In the reduction treatment, the catalytically treated ABS substrate is placed in a reduction treatment solution (NaH 2 PO 2 .H 2 O: 1 to 100 g / L) heated to 20 to 60 ° C. for 30 seconds to This is done by dipping for 5 minutes.
還元型無電解めっき： 還元型無電解めっきは、還元処理が施されたＡＢＳ基板を、４０～９０℃に加温された着色銅めっき液（ｐＨ８～１０）に１～４５分間浸漬することにより行う。着色銅めっき液として、例えば以下の組成のものを用いることができる。
（着色銅めっき液組成）
硫酸銅五水和物 １０～３０ｇ／Ｌ
ホウ酸 ５～３０ｇ／Ｌ
クエン酸三ナトリウム ２０～５０ｇ／Ｌ
水酸化ナトリウム ５～３０ｇ／Ｌ
次亜リン酸ナトリウム １０～４０ｇ／Ｌ Reduction-type electroless plating: Reduction-type electroless plating is performed by immersing a reduced ABS substrate in a colored copper plating solution (pH 8-10) heated at 40-90 ° C. for 1-45 minutes. Do. As the colored copper plating solution, for example, one having the following composition can be used.
(Colored copper plating solution composition)
Copper sulfate pentahydrate 10-30g / L
Boric acid 5-30g / L
Trisodium citrate 20-50g / L
Sodium hydroxide 5-30g / L
Sodium hypophosphite 10-40g / L
（着色銅めっき液組成）
硫酸銅五水和物 １０～３０ｇ／Ｌ
ホウ酸 ５～３０ｇ／Ｌ
クエン酸三ナトリウム ２０～５０ｇ／Ｌ
水酸化ナトリウム ５～３０ｇ／Ｌ
次亜リン酸ナトリウム １０～４０ｇ／Ｌ Reduction-type electroless plating: Reduction-type electroless plating is performed by immersing a reduced ABS substrate in a colored copper plating solution (pH 8-10) heated at 40-90 ° C. for 1-45 minutes. Do. As the colored copper plating solution, for example, one having the following composition can be used.
(Colored copper plating solution composition)
Copper sulfate pentahydrate 10-30g / L
Boric acid 5-30g / L
Trisodium citrate 20-50g / L
Sodium hydroxide 5-30g / L
Sodium hypophosphite 10-40g / L
ＡＢＳ基板を着色銅めっき液に浸漬すると、着色銅めっき液が還元剤を含むことから、ＡＢＳ基板の表面で還元反応が生じて銅が析出し、銅を含む無電解銅めっき皮膜が成膜される。ＡＢＳ基板を上記条件の着色銅めっき液に浸漬すると、通常、３０秒～２分間程度でＡＢＳ基板の表面が銅で覆われた後、銅の析出反応が終了する。成膜直後、すなわち、銅の析出反応が終了した直後における無電解銅めっき皮膜の色調は、銅色である。従来の無電解めっき処理では、銅の析出反応が終了した段階で、ＡＢＳ基板をめっき液から引き上げている。
When the ABS substrate is immersed in the colored copper plating solution, since the colored copper plating solution contains a reducing agent, a reduction reaction occurs on the surface of the ABS substrate, copper is deposited, and an electroless copper plating film containing copper is formed. The When the ABS substrate is immersed in the colored copper plating solution under the above conditions, the surface of the ABS substrate is usually covered with copper in about 30 seconds to 2 minutes, and then the copper precipitation reaction is completed. The color tone of the electroless copper plating film immediately after the film formation, that is, immediately after the completion of the copper deposition reaction, is copper. In the conventional electroless plating treatment, the ABS substrate is pulled up from the plating solution when the copper precipitation reaction is completed.
これに対し、本実施形態の着色銅めっき方法では、銅の析出反応が終了した後も、ＡＢＳ基板の着色銅めっき液への浸漬を例えば１～４５分間継続する。無電解銅めっき皮膜は、銅の析出反応が終了した直後は銅色を呈しているが、浸漬時間が長くなるにつれて表面の色調が変化する。具体的には、無電解銅めっき皮膜の表面が、銀色又はマンセル表色系で表した場合の色相がＹＲ（黄赤）、Ｙ（黄）、ＹＧ（黄緑）、Ｇ（緑）、ＢＧ（青緑）、Ｂ（青）、ＲＰ（赤紫）で分類されるいずれかの色相に変化する。そして、無電解銅めっき皮膜が所望の色調に変化した時点で、当該無電解銅めっき皮膜を備えるＡＢＳ基板を着色銅めっき液から引き上げることにより、無電解銅めっき皮膜の色調の変化を停止させることができる。以上により、銅色以外の種々の色調を備える着色銅めっき皮膜を得ることができる。
On the other hand, in the colored copper plating method of the present embodiment, the immersion of the ABS substrate in the colored copper plating solution is continued for, for example, 1 to 45 minutes even after the copper precipitation reaction is completed. The electroless copper plating film has a copper color immediately after the completion of the copper precipitation reaction, but the surface color changes as the immersion time increases. Specifically, when the surface of the electroless copper plating film is expressed in silver or Munsell color system, the hue is YR (yellow red), Y (yellow), YG (yellow green), G (green), BG It changes to one of the hues classified by (blue green), B (blue), and RP (red purple). When the electroless copper plating film changes to a desired color tone, the change in the color tone of the electroless copper plating film is stopped by pulling up the ABS substrate provided with the electroless copper plating film from the colored copper plating solution. Can do. As described above, a colored copper plating film having various color tones other than the copper color can be obtained.
＜第２実施形態の着色銅めっき方法＞
第２実施形態の着色銅めっき方法は、無電解めっき処理として置換型無電解めっきを行うものである。そのため、本実施形態の着色銅めっき方法に用いられる着色銅めっき液は、還元剤を含まないものとなっている。以下、被めっき物として、亜鉛ダイキャストからなる機能部品を用いるが、金属めっきされたＡＢＳ等の樹脂基板、銅材等を用いることも可能である。 <The colored copper plating method of 2nd Embodiment>
The colored copper plating method of the second embodiment performs substitution type electroless plating as an electroless plating treatment. Therefore, the colored copper plating solution used for the colored copper plating method of this embodiment does not contain a reducing agent. Hereinafter, a functional component made of zinc die-casting is used as an object to be plated, but a metal-plated resin substrate such as ABS, a copper material, or the like can also be used.
第２実施形態の着色銅めっき方法は、無電解めっき処理として置換型無電解めっきを行うものである。そのため、本実施形態の着色銅めっき方法に用いられる着色銅めっき液は、還元剤を含まないものとなっている。以下、被めっき物として、亜鉛ダイキャストからなる機能部品を用いるが、金属めっきされたＡＢＳ等の樹脂基板、銅材等を用いることも可能である。 <The colored copper plating method of 2nd Embodiment>
The colored copper plating method of the second embodiment performs substitution type electroless plating as an electroless plating treatment. Therefore, the colored copper plating solution used for the colored copper plating method of this embodiment does not contain a reducing agent. Hereinafter, a functional component made of zinc die-casting is used as an object to be plated, but a metal-plated resin substrate such as ABS, a copper material, or the like can also be used.
第２実施形態の着色銅めっき方法では、前処理を行った後に置換型無電解めっきを行う。前処理は、従来公知の方法で行うことが可能であるが、本実施形態では、表２に示すように、アルカリ脱脂処理、シアン化銅めっき処理、電気亜鉛めっき処理を順に行う。各処理の間では、必要に応じて水洗処理を行う。
In the colored copper plating method of the second embodiment, substitutional electroless plating is performed after pretreatment. The pretreatment can be performed by a conventionally known method. In this embodiment, as shown in Table 2, an alkaline degreasing treatment, a copper cyanide plating treatment, and an electrogalvanizing treatment are sequentially performed. Between each process, a water washing process is performed as needed.
アルカリ脱脂処理： アルカリ脱脂処理は、被めっき物としての亜鉛ダイキャストからなる機能部品を、例えば、２０～７０℃に加温されたアルカリ脱脂処理液（ＮａＯＨ：１０～１５０ｇ／Ｌ）に１～５分間浸漬することにより行う。
Alkaline degreasing treatment: In the alkaline degreasing treatment, a functional part made of zinc die cast as an object to be plated is added, for example, to an alkaline degreasing solution (NaOH: 10 to 150 g / L) heated to 20 to 70 ° C. This is done by dipping for 5 minutes.
シアン化銅めっき処理： シアン化銅めっき処理は、後工程で得られる無電解銅めっき皮膜に光沢を持たせるために行うものである。シアン化銅めっき処理は、アルカリ脱脂処理が施された被めっき物を、例えば、２０～６０℃に加温された市販のシアン化銅めっき液に浸漬し、カソード電流密度を１～６Ａ／ｄｍ２として１～３０分間通電することにより行う。
Copper cyanide plating treatment: The copper cyanide plating treatment is performed to give gloss to the electroless copper plating film obtained in the subsequent step. In the copper cyanide plating treatment, the object to be plated that has been subjected to alkaline degreasing treatment is immersed in, for example, a commercially available copper cyanide plating solution heated to 20 to 60 ° C., and the cathode current density is set to 1 to 6 A / dm. 2 is performed by energizing for 1 to 30 minutes.
電気亜鉛めっき処理： 電気亜鉛めっき処理は、シアン化銅めっき処理が施された被めっき物を、例えば、５０～７０℃に加温された亜鉛めっき液に浸漬し、カソード電流密度を０．１～１０Ａ／ｄｍ２として、２～１０分間通電することにより行う。亜鉛めっき液として、例えば以下の組成のものを用いることができる。この場合、ｐＨは８．５～９．５とすることが好ましい。
（亜鉛めっき液の組成）
硫酸亜鉛 １０～３０ｇ／Ｌ
ピロリン酸カリウム ５０～２００ｇ／Ｌ Electrogalvanizing treatment: In the electrogalvanizing treatment, an object to be plated that has been subjected to copper cyanide plating treatment is immersed in, for example, a galvanizing solution heated to 50 to 70 ° C., and the cathode current density is set to 0.1. It is carried out by energizing for 2 to 10 minutes at ˜10 A / dm 2 . As the zinc plating solution, for example, one having the following composition can be used. In this case, the pH is preferably 8.5 to 9.5.
(Composition of zinc plating solution)
Zinc sulfate 10-30g / L
Potassium pyrophosphate 50-200g / L
（亜鉛めっき液の組成）
硫酸亜鉛 １０～３０ｇ／Ｌ
ピロリン酸カリウム ５０～２００ｇ／Ｌ Electrogalvanizing treatment: In the electrogalvanizing treatment, an object to be plated that has been subjected to copper cyanide plating treatment is immersed in, for example, a galvanizing solution heated to 50 to 70 ° C., and the cathode current density is set to 0.1. It is carried out by energizing for 2 to 10 minutes at ˜10 A / dm 2 . As the zinc plating solution, for example, one having the following composition can be used. In this case, the pH is preferably 8.5 to 9.5.
(Composition of zinc plating solution)
Zinc sulfate 10-30g / L
Potassium pyrophosphate 50-200g / L
電気亜鉛めっき処理は、被めっき物の表面に銅よりも卑な金属である亜鉛を成膜し、後工程の無電解めっき処理で置換反応を生じさせるものである。置換型無電解めっきを行う時点で、被めっき物の表面に銅よりも卑な金属が成膜されていればよいため、電気亜鉛めっき処理に代えて、銅よりも卑な金属である鉄、ニッケル、錫等を成膜する処理を行ってもよい。
In the electrogalvanizing treatment, zinc, which is a base metal rather than copper, is formed on the surface of an object to be plated, and a substitution reaction is caused by an electroless plating treatment in a subsequent process. At the time of performing substitutional electroless plating, it is sufficient that a base metal than copper is formed on the surface of the object to be plated, so instead of electrogalvanizing treatment, iron that is a base metal than copper, A process of forming a film of nickel, tin, or the like may be performed.
置換型無電解めっき： 置換型無電解めっきは、電気亜鉛めっき処理が施された被めっき物を、４０～９０℃に加温された着色銅めっき液（ｐＨ８～１０）に１～４５分間浸漬することにより行う。着色銅めっき液として、例えば以下の組成のものを用いることができる。
（着色銅めっき液組成）
硫酸銅五水和物 １０～３０ｇ／Ｌ
ホウ酸 ５～３０ｇ／Ｌ
クエン酸三ナトリウム ２０～５０ｇ／Ｌ
水酸化ナトリウム ５～３０ｇ／Ｌ Substitutional electroless plating: Substitutional electroless plating involves immersing an object to be plated that has been subjected to electrogalvanizing treatment in a colored copper plating solution (pH 8 to 10) heated to 40 to 90 ° C for 1 to 45 minutes. To do. As the colored copper plating solution, for example, one having the following composition can be used.
(Colored copper plating solution composition)
Copper sulfate pentahydrate 10-30g / L
Boric acid 5-30g / L
Trisodium citrate 20-50g / L
Sodium hydroxide 5-30g / L
（着色銅めっき液組成）
硫酸銅五水和物 １０～３０ｇ／Ｌ
ホウ酸 ５～３０ｇ／Ｌ
クエン酸三ナトリウム ２０～５０ｇ／Ｌ
水酸化ナトリウム ５～３０ｇ／Ｌ Substitutional electroless plating: Substitutional electroless plating involves immersing an object to be plated that has been subjected to electrogalvanizing treatment in a colored copper plating solution (pH 8 to 10) heated to 40 to 90 ° C for 1 to 45 minutes. To do. As the colored copper plating solution, for example, one having the following composition can be used.
(Colored copper plating solution composition)
Copper sulfate pentahydrate 10-30g / L
Boric acid 5-30g / L
Trisodium citrate 20-50g / L
Sodium hydroxide 5-30g / L
被めっき物としての亜鉛皮膜が成膜された機能部品を着色銅めっき液に浸漬すると、亜鉛皮膜の表面で置換反応が生じて銅が析出し、銅を含む無電解銅めっき皮膜が成膜される。当該被めっき物を上記条件の着色銅めっき液に浸漬すると、通常、３０秒～１分間程度で銅の析出反応が終了する。成膜直後、すなわち、銅の析出反応が終了した直後における無電解銅めっき皮膜の色調は、銅色である。従来の無電解めっき処理では、銅の析出反応が終了した段階で、被めっき物をめっき液から引き上げている。
When a functional part on which a zinc film is to be plated is immersed in a colored copper plating solution, a substitution reaction occurs on the surface of the zinc film and copper is deposited, and an electroless copper plating film containing copper is formed. The When the object to be plated is immersed in the colored copper plating solution under the above conditions, the copper precipitation reaction is usually completed in about 30 seconds to 1 minute. The color tone of the electroless copper plating film immediately after the film formation, that is, immediately after the completion of the copper deposition reaction, is copper. In the conventional electroless plating treatment, the object to be plated is pulled up from the plating solution when the copper precipitation reaction is completed.
これに対し、本実施形態の無電解銅めっき方法では、銅の析出反応が終了した後も、被めっき物の着色銅めっき液への浸漬を例えば１～４５分間継続する。無電解銅めっき皮膜は、銅の析出反応が終了した直後は銅色を呈しているが、浸漬時間が長くなるにつれて表面の色調が変化する。例えば、無電解銅めっき皮膜の表面が、銀色又はマンセル表色系で表した場合の色相がＹＲ（黄赤）、Ｙ（黄）、ＹＧ（黄緑）、Ｇ（緑）、ＢＧ（青緑）、Ｂ（青）、ＲＰ（赤紫）で分類されるいずれかの色相に変化する。そして、無電解銅めっき皮膜が所望の色調に変化した時点で、当該無電解銅めっき皮膜を備える被めっき物を無電解銅めっき液から引き上げることにより、無電解銅めっき皮膜の色調の変化を停止させることができる。以上により、銅色以外の種々の色調を備える着色銅めっき皮膜を得ることができる。
On the other hand, in the electroless copper plating method of the present embodiment, the immersion of the object to be plated in the colored copper plating solution is continued for, for example, 1 to 45 minutes even after the completion of the copper precipitation reaction. The electroless copper plating film has a copper color immediately after the completion of the copper precipitation reaction, but the surface color changes as the immersion time increases. For example, when the surface of the electroless copper plating film is expressed in silver or Munsell color system, the hues are YR (yellow red), Y (yellow), YG (yellowish green), G (green), BG (blue green) ), B (blue), and RP (red purple). When the electroless copper plating film changes to the desired color tone, the change in the color tone of the electroless copper plating film is stopped by pulling up the object to be plated with the electroless copper plating film from the electroless copper plating solution. Can be made. As described above, a colored copper plating film having various color tones other than the copper color can be obtained.
第１実施形態及び第２実施形態を含む本実施形態の着色銅めっき方法によれば、被めっき物を着色銅めっき液に浸漬して無電解めっき処理を施すだけで、銅色以外の種々の色調を備える着色銅めっき皮膜を容易に得ることができる。そのため、特許文献１に開示の技術のように、無電解めっき処理を行った後に、他の化成処理液に浸漬して着色させるような工程を行う必要がなく、コスト増となることを防ぐことができる。また、本実施形態の着色銅めっき方法によれば、被めっき物の着色銅めっき液への浸漬時間を制御するだけで、着色銅めっき皮膜を種々の色調に変化させることができる。
According to the colored copper plating method of the present embodiment including the first embodiment and the second embodiment, various types other than the copper color can be obtained simply by immersing the object to be plated in a colored copper plating solution and performing an electroless plating treatment. A colored copper plating film having a color tone can be easily obtained. Therefore, unlike the technique disclosed in Patent Document 1, it is not necessary to perform a process of immersing and coloring in other chemical conversion treatment liquids after performing electroless plating treatment, thereby preventing an increase in cost. Can do. Moreover, according to the colored copper plating method of the present embodiment, the colored copper plating film can be changed to various colors only by controlling the immersion time of the object to be plated in the colored copper plating solution.
また、本実施形態の着色銅めっき方法によれば、被めっき物を上記条件の着色銅めっき液に浸漬して無電解めっき処理を行っているため、銅の析出反応を短時間で終了させることができ、その結果、目的の色調に変化させるまでの全体の処理時間を短縮することができ、すなわち、所望の色調を備える着色銅めっき皮膜を得るのに要する時間を短縮することができる。さらに、本実施形態の着色銅めっき方法によれば、着色銅めっき液が金、銀等の貴金属を含まないため、安価に無電解銅めっき皮膜を得ることができる上に、着色銅めっき液がニッケル、クロム等を含まないため、人体や環境への負荷を低下することができる。
Moreover, according to the colored copper plating method of this embodiment, since the electroplating process is performed by immersing the object to be plated in the colored copper plating solution under the above conditions, the copper precipitation reaction is completed in a short time. As a result, it is possible to reduce the overall processing time until the target color tone is changed, that is, the time required to obtain a colored copper plating film having a desired color tone can be reduced. Furthermore, according to the colored copper plating method of this embodiment, since the colored copper plating solution does not contain noble metals such as gold and silver, an electroless copper plating film can be obtained at low cost, and the colored copper plating solution Since nickel, chromium, etc. are not included, the load on the human body and the environment can be reduced.
そして、本実施形態の着色銅めっき方法によって得られた銅色以外の色調を備える着色銅めっき皮膜は、ファスナー、ボタン等の衣類に用いられる服飾品や、携帯電話、デジタルオーディオプレーヤーの筐体等の工業製品等、種々の分野に適用することができる。
And the colored copper plating film provided with the color tone other than copper color obtained by the colored copper plating method of the present embodiment is used for clothing such as fasteners and buttons, the case of mobile phones, digital audio players, etc. It can be applied to various fields such as industrial products.
以下、実施例を挙げて、本件発明をより具体的に説明するが、下記実施例に本件発明が限定されるものではないのは勿論である。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
本実施例では、ＡＢＳ基板（ヒシプレート（登録商標）、Ｙ－２６８、三菱ケミカル株式会社、厚さ２ｍｍ）を、５０ｍｍ×１５ｍｍの寸法に裁断し、被めっき物とした。被めっき物に対して、表３に示す手順で、無電解めっき処理として還元型無電解めっきを行う着色銅めっき方法を行った。
In this example, an ABS substrate (Hishiplate (registered trademark), Y-268, Mitsubishi Chemical Corporation, thickness 2 mm) was cut into a size of 50 mm × 15 mm to obtain an object to be plated. A colored copper plating method for performing reduction-type electroless plating as an electroless plating treatment was performed on the object to be plated by the procedure shown in Table 3.
ＵＶ改質処理は、小型紫外線表面処理装置（ＫＯＬ１－３００、江東電気株式会社）を用い、当該装置内の高出力低圧水銀ランプの下端からＡＢＳ基板表面までの距離が３０ｍｍとなるように調整し、主波長を２５３．７ｎｍ及び１８４．９ｎｍとし、波長２５３．７ｎｍの紫外線強度を６２ｍＷ／ｃｍ２、波長１８４．９ｎｍの紫外線強度を６ｍＷ／ｃｍ２として、ＡＢＳ基板に３分間照射することにより行った。アルカリ脱脂処理では、アルカリ脱脂処理液（ＮａＯＨ：１００ｇ／Ｌ）を用いた。コンディショニング処理では、コンディショニング処理液（ＣＣ－２３１（ローム・アンド・ハース電子材料株式会社）：１０体積％）を用いた。触媒化処理では、触媒付与液（ＰｄＣｌ：０．３ｇ／Ｌ）を用いた。触媒化処理では、触媒付与液（ＰｄＣｌ：０．３ｇ／Ｌ）を用いた。還元処理では、還元処理液（ＮａＨ２ＰＯ２・Ｈ２Ｏを含有する溶液）を用いた。
For the UV modification treatment, a small ultraviolet surface treatment device (KOL1-300, Koto Electric Co., Ltd.) is used, and the distance from the lower end of the high-power / low-pressure mercury lamp in the device to the ABS substrate surface is adjusted to 30 mm. the main wavelength is 253.7nm and 184.9 nm, the intensity of ultraviolet light having a wavelength of 253.7nm 62mW / cm 2, the intensity of ultraviolet light having a wavelength of 184.9 nm as 6 mW / cm 2, performed by irradiating the ABS substrate 3 minutes It was. In the alkaline degreasing treatment, an alkaline degreasing solution (NaOH: 100 g / L) was used. In the conditioning treatment, a conditioning treatment solution (CC-231 (Rohm and Haas Electronic Materials Co., Ltd.): 10% by volume) was used. In the catalyst treatment, a catalyst application liquid (PdCl: 0.3 g / L) was used. In the catalyst treatment, a catalyst application liquid (PdCl: 0.3 g / L) was used. In the reduction treatment, a reduction treatment solution (solution containing NaH 2 PO 2 .H 2 O) was used.
還元型無電解めっきは、ＡＢＳ基板を、８０℃に加温された以下の組成の着色銅めっき液（ｐＨ９．０）に１～３０分間浸漬することにより行った。浸漬時間が目標時間に達したら、直ちにＡＢＳ基板を着色銅めっき液から引き上げた。以上により、ＡＢＳ基板の表面に着色銅めっき皮膜を形成した。
（着色銅めっき液組成）
硫酸銅５水和物 １５ｇ／Ｌ
ホウ酸 １５ｇ／Ｌ
クエン酸３ナトリウム ３０ｇ／Ｌ
水酸化ナトリウム １０ｇ／Ｌ
次亜リン酸ナトリウム ３８ｇ／Ｌ Reduction type electroless plating was performed by immersing the ABS substrate in a colored copper plating solution (pH 9.0) having the following composition heated to 80 ° C. for 1 to 30 minutes. As soon as the immersion time reached the target time, the ABS substrate was pulled up from the colored copper plating solution. As described above, a colored copper plating film was formed on the surface of the ABS substrate.
(Colored copper plating solution composition)
Copper sulfate pentahydrate 15g / L
Boric acid 15g / L
Trisodium citrate 30g / L
Sodium hydroxide 10g / L
Sodium hypophosphite 38g / L
（着色銅めっき液組成）
硫酸銅５水和物 １５ｇ／Ｌ
ホウ酸 １５ｇ／Ｌ
クエン酸３ナトリウム ３０ｇ／Ｌ
水酸化ナトリウム １０ｇ／Ｌ
次亜リン酸ナトリウム ３８ｇ／Ｌ Reduction type electroless plating was performed by immersing the ABS substrate in a colored copper plating solution (pH 9.0) having the following composition heated to 80 ° C. for 1 to 30 minutes. As soon as the immersion time reached the target time, the ABS substrate was pulled up from the colored copper plating solution. As described above, a colored copper plating film was formed on the surface of the ABS substrate.
(Colored copper plating solution composition)
Copper sulfate pentahydrate 15g / L
Boric acid 15g / L
Trisodium citrate 30g / L
Sodium hydroxide 10g / L
Sodium hypophosphite 38g / L
得られた着色銅めっき皮膜について、目視によってその色調を観察した。さらに、得られた着色銅めっき皮膜について、分光測色計（ＣＭ－７００ｄ、コニカミノルタ株式会社）を用い、光源Ｄ６５、測定視野１０°として、測定モードＳＣＩ及びＳＣＥにおけるＬ＊、ａ＊、ｂ＊と、８°グロス値とを測定した。ＳＣＩモードは、正反射光込み測定モードであり、測定物本来の色が測定される。ＳＣＥモードは、正反射光除去測定モードであり、肉眼で観察色に近い色が測定される。結果を表４に示す。表４で、目視による色調として、マンセル系で表現した色を記載したが、無彩色又は無彩色に近い色についてはマンセル系での表現を用いずにその色を記載した。
About the obtained colored copper plating film, the color tone was observed visually. Furthermore, the colored copper plated film obtained, spectrophotometer (CM-700 d, Konica Minolta, Inc.) using a light source D65, a measurement field 10 °, L in the measurement mode SCI and SCE *, a *, b * And an 8 ° gloss value were measured. The SCI mode is a specular reflection measurement mode in which the original color of the measurement object is measured. The SCE mode is a regular reflection light removal measurement mode in which a color close to the observation color is measured with the naked eye. The results are shown in Table 4. In Table 4, the color expressed in Munsell system was described as the visual color tone, but the color was described without using the Munsell system expression for the achromatic color or a color close to the achromatic color.
表４から理解できるように、本実施例の無電解めっき処理として還元型無電解めっきを行う着色銅めっき方法によれば、ＡＢＳ基板の着色銅めっき液への浸漬時間を調整することにより、銀色系、又は、マンセル表色系で表した場合の色相がＹＧ（黄緑）系、Ｙ（黄）系、ＹＲ（黄赤）系、ＲＰ（赤紫）系、ＢＧ（青緑）系で分類されるいずれかの色相の色調を備える着色銅めっき皮膜を得ることができた。
As can be understood from Table 4, according to the colored copper plating method in which reduction type electroless plating is performed as the electroless plating treatment of this example, by adjusting the immersion time of the ABS substrate in the colored copper plating solution, The hue when expressed in the Munsell color system is classified into YG (yellow-green), Y (yellow), YR (yellow-red), RP (red-purple), and BG (blue-green). It was possible to obtain a colored copper plating film having any hue.
本実施例では、亜鉛ダイキャストからなる機能部品を被めっき物とした。被めっき物に対して、表５に示す手順で、無電解めっき処理として置換型無電解めっきを行う着色銅めっき方法を行った。
In this example, a functional component made of zinc die cast was used as the object to be plated. A colored copper plating method for performing substitutional electroless plating as an electroless plating treatment was performed on the object to be plated by the procedure shown in Table 5.
アルカリ脱脂処理では、アルカリ脱脂処理液（ＮａＯＨ：２０ｇ／Ｌ）を用いた。シアン化銅めっき処理は、以下の組成のシアン化銅めっき液（ｐＨ１１．０）を用い、カソード電流密度を２Ａ／ｄｍ２として１０分間通電することにより行った。
（シアン化銅めっき液の組成）
シアン化第一銅 ５０ｇ／Ｌ
シアン化ナトリウム ５０ｇ／Ｌ
酒石酸カリウムナトリウム ２０ｇ／Ｌ
炭酸ナトリウム １２ｇ／Ｌ In the alkaline degreasing treatment, an alkaline degreasing solution (NaOH: 20 g / L) was used. The copper cyanide plating treatment was performed by energizing for 10 minutes using a copper cyanide plating solution (pH 11.0) having the following composition at a cathode current density of 2 A / dm 2 .
(Composition of copper cyanide plating solution)
Cuprous cyanide 50g / L
Sodium cyanide 50g / L
Potassium sodium tartrate 20g / L
Sodium carbonate 12g / L
（シアン化銅めっき液の組成）
シアン化第一銅 ５０ｇ／Ｌ
シアン化ナトリウム ５０ｇ／Ｌ
酒石酸カリウムナトリウム ２０ｇ／Ｌ
炭酸ナトリウム １２ｇ／Ｌ In the alkaline degreasing treatment, an alkaline degreasing solution (NaOH: 20 g / L) was used. The copper cyanide plating treatment was performed by energizing for 10 minutes using a copper cyanide plating solution (pH 11.0) having the following composition at a cathode current density of 2 A / dm 2 .
(Composition of copper cyanide plating solution)
Cuprous cyanide 50g / L
Sodium cyanide 50g / L
Potassium sodium tartrate 20g / L
Sodium carbonate 12g / L
電気亜鉛めっき処理では、以下の組成の亜鉛めっき液（ｐＨ９．０）を用い、カソード電流密度を２Ａ／ｄｍ２として５分間通電することにより行った。
（亜鉛めっき液の組成）
硫酸亜鉛 １５ｇ／Ｌ
ピロリン酸カリウム １００ｇ／Ｌ In the electrogalvanizing treatment, a zinc plating solution (pH 9.0) having the following composition was used, and the cathode current density was set to 2 A / dm 2 and energized for 5 minutes.
(Composition of zinc plating solution)
Zinc sulfate 15g / L
Potassium pyrophosphate 100g / L
（亜鉛めっき液の組成）
硫酸亜鉛 １５ｇ／Ｌ
ピロリン酸カリウム １００ｇ／Ｌ In the electrogalvanizing treatment, a zinc plating solution (pH 9.0) having the following composition was used, and the cathode current density was set to 2 A / dm 2 and energized for 5 minutes.
(Composition of zinc plating solution)
Zinc sulfate 15g / L
Potassium pyrophosphate 100g / L
置換型無電解めっきは、電気亜鉛めっき処理が施された機能部品を、８０℃に加温された以下の組成の着色銅めっき液（ｐＨ９．０）に１～３０分間浸漬することにより行った。浸漬時間が目標時間に達したら、直ちに機能部品を着色銅めっき液から引き上げた。以上により、機能部品の表面に着色銅めっき皮膜を形成した。
（着色銅めっき液組成）
硫酸銅５水和物 １５ｇ／Ｌ
ホウ酸 １５ｇ／Ｌ
クエン酸３ナトリウム ３０ｇ／Ｌ
水酸化ナトリウム １０ｇ／Ｌ Substitutional electroless plating was performed by immersing a functional component that had been subjected to electrogalvanizing treatment in a colored copper plating solution (pH 9.0) having the following composition heated to 80 ° C. for 1 to 30 minutes. . As soon as the immersion time reached the target time, the functional component was pulled up from the colored copper plating solution. As described above, a colored copper plating film was formed on the surface of the functional component.
(Colored copper plating solution composition)
Copper sulfate pentahydrate 15g / L
Boric acid 15g / L
Trisodium citrate 30g / L
Sodium hydroxide 10g / L
（着色銅めっき液組成）
硫酸銅５水和物 １５ｇ／Ｌ
ホウ酸 １５ｇ／Ｌ
クエン酸３ナトリウム ３０ｇ／Ｌ
水酸化ナトリウム １０ｇ／Ｌ Substitutional electroless plating was performed by immersing a functional component that had been subjected to electrogalvanizing treatment in a colored copper plating solution (pH 9.0) having the following composition heated to 80 ° C. for 1 to 30 minutes. . As soon as the immersion time reached the target time, the functional component was pulled up from the colored copper plating solution. As described above, a colored copper plating film was formed on the surface of the functional component.
(Colored copper plating solution composition)
Copper sulfate pentahydrate 15g / L
Boric acid 15g / L
Trisodium citrate 30g / L
Sodium hydroxide 10g / L
得られた着色銅めっき皮膜について、実施例１と同様にして、目視によってその色調を観察し、分光測色計にて測定モードＳＣＩ及びＳＣＥにおけるＬ＊、ａ＊、ｂ＊と８°グロス値とを測定した。結果を表６に示す。
About the obtained colored copper plating film, the color tone was visually observed in the same manner as in Example 1, and L * , a * , b * and 8 ° gloss value in the measurement modes SCI and SCE with a spectrocolorimeter. And measured. The results are shown in Table 6.
表６から理解できるように、本実施例の無電解めっき処理として置換型無電解めっきを行う着色銅めっき方法によれば、機能部品の着色銅めっき液への浸漬時間を調整することにより、マンセル表色系で表した場合の色相がＹＲ（黄赤）系、ＲＰ（赤紫）系、Ｂ（青）系、Ｙ（黄）系、Ｇ（緑）系で分類されるいずれかの色相の色調を備える着色銅めっき皮膜を得ることができた。
As can be understood from Table 6, according to the colored copper plating method in which substitutional electroless plating is performed as the electroless plating treatment of the present embodiment, by adjusting the immersion time of the functional component in the colored copper plating solution, Munsell The hue when expressed in the color system is one of the hues classified as YR (yellow red), RP (red purple), B (blue), Y (yellow), G (green) A colored copper plating film having a color tone could be obtained.
本件発明の着色銅めっき方法及び着色銅めっき液によれば、被めっき物に対して無電解めっき処理を施し、被めっき物の着色銅めっき液への浸漬時間を制御するだけで、銅色以外の種々の色調に変化された着色銅めっき皮膜、具体的には、銀色又はマンセル表色系で表した場合の色相がＹＲ（黄赤）、Ｙ（黄）、ＹＧ（黄緑）、Ｇ（緑）、ＢＧ（青緑）、Ｂ（青）、ＲＰ（赤紫）で分類されるいずれかの色相を備える着色銅めっき皮膜を容易に得ることができる。
According to the colored copper plating method and the colored copper plating solution of the present invention, the electroless plating process is performed on the object to be plated, and only the immersion time of the object to be plated in the colored copper plating solution is controlled. Colored copper plating films that have been changed to various color tones, specifically, the hue when expressed in silver or Munsell color system is YR (yellow red), Y (yellow), YG (yellowish green), G ( A colored copper plating film having any hue classified by green), BG (blue green), B (blue), and RP (red purple) can be easily obtained.
また、本実施形態の着色銅めっき方法によれば、着色銅めっき液が金、銀等の貴金属を含まないため、安価に着色銅めっき皮膜を得ることができる上に、着色銅めっき液がニッケル、クロム等を含まないため、人体や環境への負荷を低下することができる。
Moreover, according to the colored copper plating method of this embodiment, since the colored copper plating solution does not contain noble metals such as gold and silver, a colored copper plating film can be obtained at a low cost, and the colored copper plating solution is nickel. Since it does not contain chromium or the like, the load on the human body and the environment can be reduced.
そして、本実施形態の着色銅めっき方法によって得られた銅色以外の色調を備える着色銅めっき皮膜は、ファスナー、ボタン等の衣類に用いられる服飾品や、携帯電話、デジタルオーディオプレーヤーの筐体等の工業製品等、種々の分野に適用することができる。
And the colored copper plating film provided with the color tone other than copper color obtained by the colored copper plating method of the present embodiment is used for clothing such as fasteners and buttons, the case of mobile phones, digital audio players, etc. It can be applied to various fields such as industrial products.
Claims (8)
- 着色された無電解銅めっき皮膜を得る銅めっき方法であって、
被めっき物を無電解銅めっき液に浸漬して無電解めっき処理によって当該被めっき物の表面に無電解銅めっき皮膜を成膜し、銅の析出反応の終了後も当該浸漬を継続することにより当該無電解銅めっき皮膜の色調を変化させることを特徴とする着色銅めっき方法。 A copper plating method for obtaining a colored electroless copper plating film,
By immersing the object to be plated in an electroless copper plating solution, forming an electroless copper plating film on the surface of the object by electroless plating, and continuing the immersion after the completion of the copper precipitation reaction A colored copper plating method, wherein the color tone of the electroless copper plating film is changed. - 前記無電解めっき処理は、還元型無電解めっきであることを特徴とする請求項１に記載の着色銅めっき方法。 The colored copper plating method according to claim 1, wherein the electroless plating treatment is reduction type electroless plating.
- 前記無電解めっき処理は、置換型無電解めっきであることを特徴とする請求項１に記載の着色銅めっき方法。 The colored copper plating method according to claim 1, wherein the electroless plating treatment is substitutional electroless plating.
- 無電解銅めっき皮膜を成膜し着色するのに用いられる銅めっき液であって、
無電解めっき処理によって被めっき物の表面に無電解銅めっき皮膜を成膜させ、銅の析出反応の終了後も当該被めっき物の浸漬が継続されることにより当該無電解銅めっき皮膜の色調を変化させることを特徴とする着色銅めっき液。 A copper plating solution used for forming and coloring an electroless copper plating film,
An electroless copper plating film is formed on the surface of the object to be plated by electroless plating treatment, and the color of the electroless copper plating film is changed by continuing immersion of the object to be plated even after the completion of the copper precipitation reaction. A colored copper plating solution characterized by being changed. - 前記無電解めっき処理は、還元型無電解めっきであり、
硫酸銅五水和物１０～３０ｇ／Ｌと、ホウ酸５～３０ｇ／Ｌと、クエン酸三ナトリウム２０～５０ｇ／Ｌと、水酸化ナトリウム５～３０ｇ／Ｌと、次亜リン酸ナトリウム１０～４０ｇ／Ｌとを含有する請求項４に記載の着色銅めっき液。 The electroless plating treatment is reduction type electroless plating,
Copper sulfate pentahydrate 10-30 g / L, boric acid 5-30 g / L, trisodium citrate 20-50 g / L, sodium hydroxide 5-30 g / L, sodium hypophosphite 10- The colored copper plating solution according to claim 4 containing 40 g / L. - 前記無電解めっき処理は、置換型無電解めっきであり、
硫酸銅五水和物１０～３０ｇ／Ｌと、ホウ酸５～３０ｇ／Ｌと、クエン酸三ナトリウム２０～５０ｇ／Ｌと、水酸化ナトリウム５～３０ｇ／Ｌとを含有する請求項４に記載の着色銅めっき液。 The electroless plating treatment is substitutional electroless plating,
5. The copper sulfate pentahydrate 10-30 g / L, boric acid 5-30 g / L, trisodium citrate 20-50 g / L, and sodium hydroxide 5-30 g / L. Colored copper plating solution. - 着色された無電解銅めっき皮膜である銅めっき皮膜であって、
銀色又はマンセル表色系で表した場合の色相がＹＲ（黄赤）、Ｙ（黄）、ＹＧ（黄緑）、Ｇ（緑）、ＢＧ（青緑）、Ｂ（青）、ＲＰ（赤紫）で分類されるいずれかの色相を備えることを特徴とする着色銅めっき皮膜。 A copper plating film that is a colored electroless copper plating film,
The hue when expressed in silver or Munsell color system is YR (yellow red), Y (yellow), YG (yellowish green), G (green), BG (blue green), B (blue), RP (red purple A colored copper plating film comprising any one of the hues classified as - 前記着色銅めっき皮膜の表面に透光性を有する保護皮膜を備える請求項７に記載の着色銅めっき皮膜。 The colored copper plating film according to claim 7, further comprising a protective film having translucency on the surface of the colored copper plating film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016228545A JP6940130B2 (en) | 2016-11-25 | 2016-11-25 | Colored copper plating method, colored copper plating solution and colored copper plating film |
| JP2016-228545 | 2016-11-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2018097186A1 true WO2018097186A1 (en) | 2018-05-31 |
Family
ID=62195586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2017/042031 WO2018097186A1 (en) | 2016-11-25 | 2017-11-22 | Colored copper plating method, colored copper plating solution, and colored copper plating film |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6940130B2 (en) |
| TW (1) | TW201825710A (en) |
| WO (1) | WO2018097186A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7261908B1 (en) * | 2021-08-27 | 2023-04-20 | 日立ジョンソンコントロールズ空調株式会社 | air conditioner |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60159173A (en) * | 1984-01-25 | 1985-08-20 | コルモーゲン コーポレイション | Improved edtp-containing electroless copper bath |
| JPS6343962A (en) * | 1986-08-12 | 1988-02-25 | Shiseido Co Ltd | Mica/titanium composite material |
| JP3150310U (en) * | 2009-02-24 | 2009-05-07 | 株式会社トーヨー | Book stand |
| JP2012207258A (en) * | 2011-03-29 | 2012-10-25 | Fujifilm Corp | Composition for forming layered to be plated, and method for producing laminate having metal film |
| JP2014118623A (en) * | 2012-12-19 | 2014-06-30 | Kanto Gakuin | Method for producing plating film |
| JP2015196922A (en) * | 2014-04-02 | 2015-11-09 | ▲黄▼ 文昌 | Method for producing high strength hue fiber material and product thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6235843A (en) * | 1985-08-09 | 1987-02-16 | 日立化成工業株式会社 | Manufacture of laminate of metal and resin layer |
| JP2004149910A (en) * | 2002-11-01 | 2004-05-27 | Ykk Corp | Color-developed film, and production method therefor |
| JP2005272876A (en) * | 2004-03-23 | 2005-10-06 | Ykk Corp | Ornament having patterned and colored plating film, and method for manufacturing the same |
-
2016
- 2016-11-25 JP JP2016228545A patent/JP6940130B2/en active Active
-
2017
- 2017-11-22 WO PCT/JP2017/042031 patent/WO2018097186A1/en active Application Filing
- 2017-11-23 TW TW106140731A patent/TW201825710A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60159173A (en) * | 1984-01-25 | 1985-08-20 | コルモーゲン コーポレイション | Improved edtp-containing electroless copper bath |
| JPS6343962A (en) * | 1986-08-12 | 1988-02-25 | Shiseido Co Ltd | Mica/titanium composite material |
| JP3150310U (en) * | 2009-02-24 | 2009-05-07 | 株式会社トーヨー | Book stand |
| JP2012207258A (en) * | 2011-03-29 | 2012-10-25 | Fujifilm Corp | Composition for forming layered to be plated, and method for producing laminate having metal film |
| JP2014118623A (en) * | 2012-12-19 | 2014-06-30 | Kanto Gakuin | Method for producing plating film |
| JP2015196922A (en) * | 2014-04-02 | 2015-11-09 | ▲黄▼ 文昌 | Method for producing high strength hue fiber material and product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018083975A (en) | 2018-05-31 |
| TW201825710A (en) | 2018-07-16 |
| JP6940130B2 (en) | 2021-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI655042B (en) | Method for manufacturing surface-treated metal powder, laser sintered body, and method for manufacturing surface-treated metal powder for laser sintering | |
| JP4681936B2 (en) | Copper foil for plasma display electromagnetic wave shielding filter | |
| JP2009215590A (en) | Copper-zinc alloy electroplating method, steel wire using the same, steel wire-rubber bonded composite and tire | |
| JP2014095097A (en) | Method for producing trivalent chromium plated-molded article and trivalent chromium-plated molded article | |
| WO2018097186A1 (en) | Colored copper plating method, colored copper plating solution, and colored copper plating film | |
| JP5336762B2 (en) | Copper-zinc alloy electroplating bath and plating method using the same | |
| JP2017501305A (en) | Color-treated substrate and method for coloring the substrate for the same | |
| CN106048681A (en) | Electronic part, manufacturing method of electronic part and mobile terminal | |
| KR20000011009A (en) | Goods having painted metal film and production method thereof | |
| JP2010084224A (en) | Method of manufacturing plated molded article using no nickel, and plated molded article | |
| WO2004050959A3 (en) | Reduction of surface oxidation during electroplating | |
| WO2009075405A1 (en) | Manufacturing method of metal accessory | |
| JP2010270374A (en) | Copper-tin-zinc alloy electroplating bath, and method for producing alloy plating film using the same | |
| JP5888977B2 (en) | Black coated product and method for producing the same | |
| JP2010059508A (en) | Copper-zinc alloy electroplating bath | |
| US242338A (en) | Constant laval | |
| US3862850A (en) | Electroless gold plating on refractory metals | |
| JPH01113001A (en) | Button | |
| JP2018119169A (en) | Electroplating solution, electroplating method and electroplating film | |
| WO2024016182A1 (en) | Surface modification method, color change method, and article | |
| JP5079746B2 (en) | Electroless nickel plating method | |
| KR20080103717A (en) | Manufacturing method for color stainless steel with high scar resistance | |
| JP2018127697A (en) | Electroplating solution, electroplating method and electroplating film | |
| JP3962841B2 (en) | Plating member manufacturing method, plating member for jewelry manufactured by the method | |
| JP2022167393A (en) | Antimicrobial plating film, and method of producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17874014 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 17874014 Country of ref document: EP Kind code of ref document: A1 |