WO2012114737A1 - Method for producing trivalent chromium-plated molded article and trivalent chromium-plated molded article - Google Patents
Method for producing trivalent chromium-plated molded article and trivalent chromium-plated molded article Download PDFInfo
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- WO2012114737A1 WO2012114737A1 PCT/JP2012/001193 JP2012001193W WO2012114737A1 WO 2012114737 A1 WO2012114737 A1 WO 2012114737A1 JP 2012001193 W JP2012001193 W JP 2012001193W WO 2012114737 A1 WO2012114737 A1 WO 2012114737A1
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- trivalent chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
Definitions
- the present invention forms a trivalent chromium plating film having good appearance, corrosion resistance and wear resistance without using nickel on various metals and resin materials such as ABS, PC / ABS, and nylon.
- the present invention relates to a method for producing a trivalent chromium plated molded article and a trivalent chromium plated molded article obtained by the method.
- Nickel plating has characteristics such as excellent color tone and corrosion resistance, and is used as a base plating for decorative plating such as chromium plating.
- nickel-plated ornaments etc. when wearing nickel-plated ornaments etc., the nickel plating is eluted by sweat, etc., causing skin irritation, eczema, inflammation, etc. (nickel allergy). .
- resins typified by ABS, PC / ABS, nylon and the like are widely used as molded articles for low cost or light weight.
- chrome plating having excellent characteristics in terms of appearance, wear resistance, and corrosion resistance is often used for the outermost layer.
- this copper-tin alloy plating bath containing cyanide When this copper-tin alloy plating bath containing cyanide is used for resin plating, if it is immersed in a copper-tin alloy plating bath (containing cyan) after bright copper sulfate plating, the interface between the surface of the molded product and the copper sulfate plating film Soaking of the plating solution containing cyan occurs. This may cause peeling between the surface of the molded product / bright copper sulfate plating film.
- Patent Document 1 discloses a plate base material, a copper plating film provided on the surface of the plate base material and having a number of gravure cells formed on the surface, and a copper plating film And a chromium plating film obtained from a trivalent chromium plating solution that coats the surface of the film, and a gravure platemaking roll in which the chromium plating film is heated with superheated steam.
- hexavalent chromium having excellent appearance, corrosion resistance, and wear resistance can be formed directly on the surface of the bright copper sulfate plating.
- the problem is that the oxidizing power of the hexavalent chromium plating solution is very high.
- the hexavalent chromium plating solution contains a high concentration of chromic acid (typical composition: chromic acid 250 g / L + 98% sulfuric acid 2.5 g / L), and exhibits high oxidizability. For this reason, when the hexavalent chromium plating is directly formed on the copper sulfate plating film, the surface of the copper plating film is oxidized by chromic acid, resulting in poor appearance.
- the applicant of the present invention disclosed in Japanese Patent Application Laid-Open No. 2010-84224 as trivalent chromium plating on the surface of a molded product as bright copper sulfate plating, and then hexavalent chromium on the surface.
- a method for producing a molded article having appearance, corrosion resistance and wear resistance by using plating without using nickel was proposed.
- this method has a drawback that the manufacturing process is somewhat complicated, and uses hexavalent chromium, so it has a great influence on the human body and the environment.
- Another object of the present invention is to obtain a film having the same appearance, corrosion resistance and wear resistance as a hexavalent chromium plating film even when a trivalent chromium plating solution having a low oxidizing power is used without using hexavalent chromium.
- Another object of the present invention is to provide a method for producing a molded product by trivalent chromium plating and a trivalent chromium plated molded product.
- Still another object of the present invention is to provide a trivalent chromium plating molded article that can form a trivalent chromate film having high corrosion resistance on a copper plating film using a trivalent chromate liquid that has little influence on the human body and the environment. And a trivalent chromium plating molded product thereof.
- the present inventor has intensively studied to achieve the above object.
- this invention is a manufacturing method of the trivalent chromium plating molded product which processes trivalent chromium plating on the surface of a molded product by the method including the following processes, and the said objective is achieved by it.
- (Item 1) A method for producing a trivalent chromium plated molded product, in which plating is performed on the surface of the molded product by a method including the following steps: (A) forming a copper plating film on the surface of the molded product by bright copper sulfate plating; (B) a step of preparing a trivalent chromium plating bath containing trivalent chromium ions and a complexing agent, wherein the content of the complexing agent is 0.1 to 2 mol / L; (C) forming a trivalent chromium plating film by performing trivalent chromium plating on the surface of the copper plating film using the trivalent chromium plating bath;
- (Item 2) The method for producing a trivalent chromium plating molded article according to item 1, wherein the carbon content in the trivalent chromium plating film is 5 to 15 at%.
- (Item 3) Manufacture of a trivalent chromium plating molded article according to item 1, wherein the trivalent chromium plating bath contains a complexing agent in the range of 0.1 to 2.0 mol per 1 mol of trivalent chromium ions.
- Method. (Item 4) The method for producing a trivalent chromium plating molded article according to item 1, wherein the complexing agent is an organic carboxylic acid.
- (Item 5) The method for producing a trivalent chromium plating molded article according to item 4, wherein the organic carboxylic acid is a dicarboxylic acid, an oxycarboxylic acid, a polyvalent carboxylic acid or a salt thereof.
- (Item 6) The method for producing a trivalent chromium plated molded article according to item 1, wherein the chromium concentration contained in the trivalent chromium plating bath when performing the trivalent chromium plating is 5 to 35 g / L.
- (Item 7) The method for producing a trivalent chromium plated molded article according to item 1, wherein the pH of the trivalent chromium plating bath when performing the trivalent chromium plating is 1.5 to 4.0.
- (Item 8) The method for producing a trivalent chromium plated molded article according to item 1, wherein the thickness of the trivalent chromium plating film is 0.5 to 5 ⁇ m.
- (Item 9) A trivalent chromium plating molded product obtained by the method of any one of items 1 to 8, comprising a molded product and a copper plating film having a film thickness of 10 to 50 ⁇ m formed on the surface of the molded product. And a trivalent chromium plating molded article having a film thickness of 0.5 to 5 ⁇ m ⁇ m formed on the surface of the copper plating film.
- direct chrome plating on the copper plating film without toxic cyanide-containing or difficult-to-control copper-tin alloy plating is a simple, low-cost problem. It is possible to take measures against nickel plating allergies.
- the presence of the copper-tin alloy plating film is advantageous as a film structure in an abrasion resistance test or the like.
- a copper-tin alloy plating bath that exhibits stable performance is a cyan bath containing harmful cyanide, and this cyan bath is not preferable from the viewpoint of waste water treatment and work environment.
- a complexing agent that does not contain cyan has been developed, but there is a problem in terms of stability of a plating bath that does not contain cyan under actual severe working conditions.
- Bright copper sulfate plating bath is widely used.
- a complexing agent By adding a complexing agent, a plating film having an appearance, corrosion resistance, and wear resistance comparable to that of a hexavalent chromium film can be obtained even when a trivalent chromium plating solution having low oxidizing power is used.
- a Cr—C alloy plating film in which carbon is co-deposited in the film is formed by copper sulfate.
- the film can be formed directly on the plating film. Therefore, a plating film having an appearance, corrosion resistance, and wear resistance comparable to a hexavalent chromium film can be obtained.
- the plating bath does not contain highly oxidizable hexavalent chromium (CrO 3 ), when a molded article having a copper sulfate plating film is immersed in the plating solution, the appearance of the film is visible. It is difficult to form an oxide film that causes defects. Therefore, unlike the conventional case, the appearance defect that occurs when the hexavalent chromium plating is directly formed does not occur.
- the plating bath does not contain hexavalent chromium, there is little influence on the human body and the environment. Furthermore, a chromium plating film can be made into one layer, and the number of processes reduces.
- the film formed using a trivalent chromium plating bath with low oxidizability has insufficient formation of a passivation film (chromium hydrated oxide layer) on the surface of the film. Is inferior to hexavalent chromium plating film. However, the hexavalent chromium plating film is cracked at a certain thickness. On the other hand, the trivalent chromium plating film has a low film stress, and therefore, cracks are unlikely to occur. In particular, when the film thickness of the trivalent chromium plating film is thick, the corrosion resistance is improved.
- the crystal structure of the trivalent chromium plating film that does not contain impurities such as carbon in the film is the same crystalline as that of the hexavalent chromium plating film.
- the passivated film formed on the grain boundary (discontinuous atomic arrangement) between the particles also has low continuity.
- carbon is co-deposited in the film as in the present invention, a decrease in crystallinity (amorphization) is confirmed even in the XRD measurement, and the corrosion resistance is improved. Furthermore, the film hardness and wear resistance are improved by the eutectoid of carbon.
- Examples of the molded product used in the present invention include those molded from resins such as ABS resin, PC / ABS resin, and nylon.
- resins such as ABS resin, PC / ABS resin, and nylon.
- injection-molded molded products specifically, cellular phones, digital camera operation buttons, and the like.
- a two-color molded product having a primary molded product formed of ABS resin and a secondary molded product molded by two-color molding inside the primary molded product can be used.
- the secondary molded product can also be formed of a transparent resin such as PC.
- a molded product made of various metals can be plated in addition to the resin material.
- FIG. 1 shows a schematic process of bright copper sulfate plating.
- the surface of the molded product is degreased and washed with water, and then chromic acid-sulfuric acid etching is performed according to a conventional method.
- a CRP cleaner alkaline detergent, manufactured by Okuno Pharmaceutical Co., Ltd.
- Preferred etching conditions are as follows.
- An etching solution containing chromic acid 350 to 450 g / L, 98% sulfuric acid 350 to 450 g / L, and CRP etching additive 0.5 to 1.0 ml / L can be used.
- the molded product is preferably immersed in this etching solution at an etching temperature of 65 ° C. to 70 ° C. and an etching time of 5 to 15 minutes.
- Particularly preferred etching conditions are as shown in FIG. 1, using an etching solution containing chromic acid 400 g / L, 98% sulfuric acid 400 g / L, and CRP etching additive 0.7 ml / L.
- the etching temperature is 67 ° C., and the etching time is 8 to 10 minutes.
- the molded product is washed with water, then neutralized and washed with water, pre-dipped, and then catalyzed.
- Catalysis can be carried out using CRP catalyst 85H (Okuno Pharmaceutical Co., Ltd.) and aqueous hydrochloric acid solution at 30 to 40 ° C. for about 2 to 10 minutes. (4) After the molded catalyst product is washed with water, the surface of the molded product is converted into a conductor according to a conventional method.
- the plating temperature is preferably 20 to 30 ° C. and 2 to 5 A / dm 2 .
- the CRP cleaner (Okuno Pharmaceutical Co., Ltd.) shown in FIG. 1 is a degreasing agent (alkaline detergent), and the CRP conditioner 222 (Okuno Pharmaceutical Co., Ltd.) is a surface charge regulator, CRP catalyst 85H (Okuno Pharmaceutical Co., Ltd.).
- CRP selector AK (Okuno Pharmaceutical Co., Ltd.) is a conductive treatment agent (containing copper salt, complexing agent, reducing agent)
- CRP selector B (Okuno Pharmaceutical Co., Ltd.) Is made of conductive treatment agent (containing alkali salt)
- Top Lucina 2000MU (Okuno Pharmaceutical Co., Ltd.) is brightener for copper sulfate plating
- Top Lucina 2000A (Okuno Pharmaceutical Co., Ltd.) is for copper sulfate plating. Brightener.
- B. Copper plating bath type Most copper plating used for decoration is copper sulfate, and other pyrophosphate baths and cyan baths are not used.
- the brightener used in the copper plating bath is not particularly limited, and any conventionally known brightener can be used as long as the necessary gloss can be obtained.
- a polymer compound such as polyoxyethylene alkyl ether, a sulfur compound, or the like can be used as a brightener.
- Examples of commercially available products include Top Lucina 870, Top Lucina 2000, and Top Lucina 3000 (all manufactured by Okuno Pharmaceutical Co., Ltd.).
- the metal salt is a trivalent chromium salt (such as chromium sulfate)
- the metal concentration is lower than that of the hexavalent chromium bath, and the ORP (redox potential) is also low.
- the trivalent chromium plating bath generally has a pH of about 3, and even when the copper plating film is immersed in the trivalent chromium plating bath, oxidation or dissolution of the copper plating film hardly occurs. Divalent chromium plating seems to form normally.
- the trivalent chromium plating bath may contain the following (a) to (d).
- (A) As a chromium component water-soluble trivalent chromium compounds, such as chromium sulfate, basic chromium sulfate, chromium chloride, and chromium acetate, can be included.
- the said trivalent chromium supply source can use 1 type (s) or 2 or more types.
- the concentration of trivalent chromium ions in the treatment solution is preferably in the range of 5 to 35 g / L, more preferably in the range of 10 to 30 g / L, and still more preferably in the range of 15 to 25 g / L.
- inorganic acids such as sodium sulfate, potassium sulfate, ammonium sulfate, aluminum sulfate, sodium chloride, potassium chloride, ammonium chloride, potassium fluoride, ammonium fluoride, and potassium fluoride can be contained.
- the content of these inorganic acids can be arbitrary, but is preferably in the range of 1 to 200 g / L, more preferably in the range of 10 to 100 g / L.
- an organic carboxylic acid is preferably used.
- organic carboxylic acids monocarboxylic acids such as formic acid and acetic acid or salts thereof, dicarboxylic acids such as oxalic acid, malonic acid and maleic acid, hydroxycarboxylic acids such as citric acid, malic acid and glycolic acid, or their Salts can be included.
- One or more complexing agents can be used.
- the concentration of the complexing agent in the treatment solution is preferably in the range of 0.1 to 2 mol, more preferably in the range of 0.2 to 1.0 mol, per 1 mol of trivalent chromium ions.
- Fe, Ni, etc. may be added for the purpose of improving the throwing power.
- the carbon content in the film is preferably 3 at% or more, more preferably 5 to 15 at%.
- the film hardness and the wear resistance can be improved by eutectizing carbon.
- the carbon content in the film is less than 3 at%, the hardness tends to decrease and the friction resistance tends to decrease.
- boric acid sodium borate, aluminum sulfate or the like may be included as a pH buffer.
- the redox potential of the trivalent chromium plating bath is preferably 100 to 250 mV. More preferably, it is 140 to 200 mV.
- the pH of the trivalent chromium plating bath is preferably 1.5 to 5.0. More preferably, it is 1.5 to 4.0, and most preferably 2.0 to 3.5.
- the plating method of the present invention as a method for forming a trivalent chromium plating film, it is common to immerse a copper-plated substrate in the trivalent chromium plating bath.
- the immersion is preferably performed at a liquid temperature of 30 to 50 ° C. for 2 to 10 minutes, more preferably 3 to 8 minutes.
- the thickness of the film formed by this trivalent chromium plating is preferably 0.5 to 5.0 ⁇ m. More preferably, it is 1.0 to 3.0 ⁇ m.
- chromium plating film is preferably 0.5 to 5.0 ⁇ m. More preferably, it is 1.0 to 3.0 ⁇ m.
- the film hardness of trivalent chrome plating is about 900 to 1000 Hv, which is almost the same as the film hardness of hexavalent chrome plating.
- the bright copper sulfate plating film preferably has a thickness of about 10 to 50 ⁇ m in order to obtain a glossy appearance. More preferably, it is 20 to 40 ⁇ m.
- the film thickness of the trivalent chromium plating film does not need to be increased and is preferably 0.5 to 5.0 ⁇ m, and particularly preferably 0.5 to 4 ⁇ m.
- a particularly preferred film thickness of trivalent chromium is 1 to 3 ⁇ m.
- the carbon content in the trivalent chromium plating film is preferably 3 to 15 at%, more preferably 5 to 15 at%, and most preferably 5 to 12 at%.
- Comparative Example 1 and Examples 1 to 4 a two-color molded product of PC / ABS resin was used as a material to be plated.
- This molded article was subjected to chromic acid-sulfuric acid etching treatment to form hydrophilicity and fine pores on the surface of the molded article. Thereafter, using a direct copper sulfate plating process (CRP process, manufactured by Okuno Pharmaceutical Co., Ltd.), catalyst application, conductive treatment, and direct copper sulfate plating were performed.
- CRP process manufactured by Okuno Pharmaceutical Co., Ltd.
- catalyst application catalyst application
- conductive treatment conductive treatment
- direct copper sulfate plating were performed.
- Example 2 Trivalent chromium plating was directly performed on the surface of the molded product to form a chromium plating film having a thickness of 2.1 ⁇ m.
- Example 2 Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 ⁇ m). Then, trivalent chromium plating was directly performed to form a 2.3 ⁇ m thick chromium plating film.
- Example 3 Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 ⁇ m). Then, trivalent chromium plating was performed directly to form a 2.0 ⁇ m thick chromium plating film.
- Example 4 Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 ⁇ m).
- the film thickness of the chromium plating film was measured with a fluorescent X-ray film thickness meter (SEA5120 manufactured by Seiko Instruments Inc.).
- Carbon content in the film The carbon content in the obtained chromium plating film was measured using XPS (photoelectron spectrometer, ESCA-5800 manufactured by ULVAC-PHI).
- Example 5 In Example 5, similarly to Example 1, a two-color molded product of PC / ABS resin was used as a material to be plated.
- this molded product was subjected to a chromic acid-sulfuric acid etching treatment to form hydrophilicity and fine pores on the surface of the molded product. Thereafter, using a direct copper sulfate plating process (CRP process, manufactured by Okuno Pharmaceutical Co., Ltd.), catalyst application, conductive treatment, and direct copper sulfate plating were performed.
- CRP process manufactured by Okuno Pharmaceutical Co., Ltd.
- a plating solution having the composition shown in Table 2 is used without performing copper-tin alloy plating.
- trivalent chromium plating was directly performed on the surface of the molded product to form a chromium plating film having a thickness of 2.0 ⁇ m.
- the appearance of the trivalent chrome plating molded article was good “ ⁇ ”
- the C content in the film was 9.1 at%
- the Vickers hardness of the film was 830 Hv
- the amount of wear of the film by the Suga abrasion tester was 3.
- the eraser abrasion test of the film was 5 ", and the film was good.
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Abstract
Provided is a trivalent chromium-plated film structure having excellent appearance, corrosion resistance, and abrasion resistance. Also provided is a treatment step that can be used industrially. A method for producing a trivalent chromium-plated molded article in which the surface of a molded article is plated comprises (a) a step for forming a copper plating film on the surface of a molded article by lustrous copper sulfate plating, (b) a step for preparing a trivalent chromium plating bath comprising trivalent chromium ions and a complexing agent, wherein the complexing agent content ratio is 0.1 to 2 mol/L, and (c) a step for forming a trivalent chromium plating film on the surface of the copper plating film by performing trivalent chromium plating using the trivalent chromium plating bath, with the carbon content in the trivalent chromium plating film being 3 at% or greater.
Description
本発明は、各種の金属、およびＡＢＳ、ＰＣ/ＡＢＳ、ナイロンなどの樹脂素材に対して、ニッケルを使用することなく良好な外観、耐食性および耐磨耗性を有する３価クロムめっき皮膜を形成する、３価クロムめっき成形品の製造方法およびその方法によって得られた３価クロムめっき成形品に関する。
The present invention forms a trivalent chromium plating film having good appearance, corrosion resistance and wear resistance without using nickel on various metals and resin materials such as ABS, PC / ABS, and nylon. The present invention relates to a method for producing a trivalent chromium plated molded article and a trivalent chromium plated molded article obtained by the method.
ニッケルめっきは、優れた色調、耐食性などの特性を有し、クロムめっきを始めとする装飾めっきの下地めっきとして使用される。
Nickel plating has characteristics such as excellent color tone and corrosion resistance, and is used as a base plating for decorative plating such as chromium plating.
しかし、ニッケルめっきが施された装飾品などを身に付けた場合、汗などによってニッケルめっきが溶出することで、肌にかぶれ、湿疹、炎症などを引き起こすこと（ニッケルアレルギー）が問題となっている。
However, when wearing nickel-plated ornaments etc., the nickel plating is eluted by sweat, etc., causing skin irritation, eczema, inflammation, etc. (nickel allergy). .
携帯電話、デジタルカメラなどの携帯機器を含む電化製品では、低コストあるいは軽量化のために、成形品としてＡＢＳ，ＰＣ/ＡＢＳ、ナイロンなどに代表される樹脂が広く使用されている。これらの樹脂よりなるめっき成形品では、最外層に外観、耐磨耗性、耐食性の点で優れた特性を有するクロムめっきが使用される場合が多い。
In electrical appliances including mobile devices such as mobile phones and digital cameras, resins typified by ABS, PC / ABS, nylon and the like are widely used as molded articles for low cost or light weight. In plating molded products made of these resins, chrome plating having excellent characteristics in terms of appearance, wear resistance, and corrosion resistance is often used for the outermost layer.
このような場合においても、下地層であるニッケルが外部に溶出しないこと、あるいはニッケルめっきを使用しないことが要求される。
Even in such a case, it is required that nickel as an underlayer does not elute to the outside or that nickel plating is not used.
現在、ニッケル代替めっきとして、銅４０～５５％、スズ（スペキュラム）の合金めっき皮膜が検討されている。ニッケルめっきを使用しないめっき樹脂成形品の一般的な皮膜構造は、樹脂素材/光沢硫酸銅めっき/銅－スズ合金めっき/クロムめっきである。
Currently, an alloy plating film of 40-55% copper and tin (speculum) is being studied as an alternative to nickel plating. The general film structure of a plated resin molded product that does not use nickel plating is resin material / bright copper sulfate plating / copper-tin alloy plating / chrome plating.
しかしながら、銅－スズ合金めっきは、銅（Ｅ０＝+0.337Ｖ）とスズ（Ｅ０＝-0.136Ｖ）の析出電位の差が大きく、合金めっきを得るためには析出電位を接近させる必要がある。このために、めっき浴中に錯化剤を添加することが必要となるが、銅－スズ合金めっき浴では、有害なシアンを錯化剤に使用したものが多い。
However, the copper-tin alloy plating has a large difference in precipitation potential between copper (E 0 = + 0.337 V) and tin (E 0 = −0.136 V), and it is necessary to bring the precipitation potential close to obtain alloy plating. is there. For this reason, it is necessary to add a complexing agent to the plating bath, but many copper-tin alloy plating baths use harmful cyanide as the complexing agent.
このシアンを含有する銅－スズ合金めっき浴を樹脂めっきに使用する場合、光沢硫酸銅めっき後に銅－スズ合金めっき浴（シアン含有）に浸漬すると、成形品の表面と硫酸銅めっき皮膜の界面部分からシアンを含むめっき液のしみ込みが起こる。このことが原因となり、成形品の表面/光沢硫酸銅めっき皮膜の間で剥離が発生する場合がある。
When this copper-tin alloy plating bath containing cyanide is used for resin plating, if it is immersed in a copper-tin alloy plating bath (containing cyan) after bright copper sulfate plating, the interface between the surface of the molded product and the copper sulfate plating film Soaking of the plating solution containing cyan occurs. This may cause peeling between the surface of the molded product / bright copper sulfate plating film.
近年では、有害なシアンを含有しない銅－スズ合金めっき浴（ピロリン酸浴など）が開発されており、この浴を使用した場合には、上記のめっき液の染み込みによる剥離に関する問題は解決される。
In recent years, copper-tin alloy plating baths (such as pyrophosphoric acid baths) that do not contain harmful cyanides have been developed, and when these baths are used, the above problems related to peeling due to the penetration of the plating solution are solved. .
しかし、シアンを含有しない銅－スズ合金めっき浴を使用する場合においても以下に示すような問題が存在する。
However, there are the following problems even when using a copper-tin alloy plating bath not containing cyanide.
（１）シアン含有のめっき浴を使用して形成した皮膜と比較すると、シアンを含有しない銅－スズ合金めっき浴を用いて形成しためっき皮膜の硬度が低い。そのため、必要な耐磨耗性を確保するためにめっき皮膜の膜厚を厚くすることが必要である。
(1) Compared with a film formed using a cyanide-containing plating bath, the hardness of the plating film formed using a copper-tin alloy plating bath not containing cyan is low. Therefore, it is necessary to increase the thickness of the plating film in order to ensure the necessary wear resistance.
（２）シアンを含有しない銅－スズ合金めっき浴を用いて形成した皮膜の応力が、シアン含有のめっき浴を用いためっき皮膜と比較すると高い。そのため、充分な耐磨耗性を確保するために皮膜の膜厚を増加すると、皮膜にクラックが発生する。
(2) The stress of the film formed using a copper-tin alloy plating bath not containing cyan is higher than that of the plating film using a cyan-containing plating bath. Therefore, if the film thickness is increased in order to ensure sufficient wear resistance, cracks occur in the film.
（３）強い錯化剤であるシアンを使用していないため、めっき液が不安定であり、浴寿命が短くなり、生産コストが上がる。
(3) Since cyan, which is a strong complexing agent, is not used, the plating solution is unstable, the bath life is shortened, and the production cost is increased.
例えば、特開２００８－１４３１６９号公報（特許文献１）には、版母材と、その版母材の表面に設けられかつ表面に多数のグラビアセルが形成された銅めっき皮膜と、銅めっき皮膜の表面を被覆する３価クロムめっき液から得られるクロムめっき皮膜とを含み、クロムめっき皮膜を過熱水蒸気によって加熱処理したグラビア製版ロールが開示されている。
For example, Japanese Patent Application Laid-Open No. 2008-143169 (Patent Document 1) discloses a plate base material, a copper plating film provided on the surface of the plate base material and having a number of gravure cells formed on the surface, and a copper plating film And a chromium plating film obtained from a trivalent chromium plating solution that coats the surface of the film, and a gravure platemaking roll in which the chromium plating film is heated with superheated steam.
しかし、この特許文献１では、３価クロムめっき皮膜を過熱水蒸気によって加熱処理することが必要であるので、生産性が低下する。また、得られた３価クロムめっき皮膜は、外観、耐食性および耐磨耗性が不十分である。
However, in this Patent Document 1, since it is necessary to heat-treat the trivalent chromium plating film with superheated steam, productivity is lowered. Further, the obtained trivalent chromium plating film has insufficient appearance, corrosion resistance and wear resistance.
また、理想的には、光沢硫酸銅めっきの表面に、直接、外観、耐食性、耐磨耗性に優れた６価クロムを成膜できることが望ましい。
Ideally, it is desirable that hexavalent chromium having excellent appearance, corrosion resistance, and wear resistance can be formed directly on the surface of the bright copper sulfate plating.
しかし、その場合には、６価クロムめっき液の酸化力が非常に高いことが問題となる。６価クロムめっき液中には高濃度のクロム酸（代表的な組成：クロム酸250ｇ/Ｌ＋９８％硫酸2.5ｇ/Ｌ）が含まれており、高い酸化性を示す。このため、硫酸銅めっき皮膜上に直接６価クロムめっきを成膜しようとすると、銅めっき皮膜の表面がクロム酸により酸化され、その結果、外観不良を引き起こす。
However, in that case, the problem is that the oxidizing power of the hexavalent chromium plating solution is very high. The hexavalent chromium plating solution contains a high concentration of chromic acid (typical composition: chromic acid 250 g / L + 98% sulfuric acid 2.5 g / L), and exhibits high oxidizability. For this reason, when the hexavalent chromium plating is directly formed on the copper sulfate plating film, the surface of the copper plating film is oxidized by chromic acid, resulting in poor appearance.
そこで、本出願人は、これらの問題を解消するため、特開２０１０－８４２２４号公報において、光沢硫酸銅めっきとして、成形品の表面に３価クロムめっきを行い、次いで、その表面に６価クロムめっきを行うことにより、ニッケルを使用することなく、外観と耐食性、耐摩耗性を有する成形品を製造する方法を提案した。
Therefore, in order to solve these problems, the applicant of the present invention disclosed in Japanese Patent Application Laid-Open No. 2010-84224 as trivalent chromium plating on the surface of a molded product as bright copper sulfate plating, and then hexavalent chromium on the surface. A method for producing a molded article having appearance, corrosion resistance and wear resistance by using plating without using nickel was proposed.
しかし、この方法では、製造工程がやや複雑となる欠点があり、また６価クロムを使用するため、人体や環境に与える影響が大きい。
However, this method has a drawback that the manufacturing process is somewhat complicated, and uses hexavalent chromium, so it has a great influence on the human body and the environment.
本発明は、上記した従来技術の問題点に鑑みてなされたものであり、その主な目的は、従来のニッケルを使用しないめっきの問題点、特に、銅－スズ合金めっきを用いることなく、優れた外観、耐食性、および耐磨耗性を有するめっき皮膜構造および工業的に使用可能な処理工程を提供することを目的とする。
The present invention has been made in view of the above-mentioned problems of the prior art, and its main object is to solve the problems of conventional plating not using nickel, particularly without using copper-tin alloy plating. Another object of the present invention is to provide a plating film structure having a good appearance, corrosion resistance, and wear resistance, and a process that can be used industrially.
本発明の他の目的は、６価クロムを用いることなく酸化力の低い３価クロムめっき液を用いた場合でも、６価クロムめっき皮膜と同等の外観、耐食性および耐摩耗性を有する皮膜が得られる、３価クロムめっきによる成形品の製造方法およびその３価クロムめっき成形品を提供することにある。
Another object of the present invention is to obtain a film having the same appearance, corrosion resistance and wear resistance as a hexavalent chromium plating film even when a trivalent chromium plating solution having a low oxidizing power is used without using hexavalent chromium. Another object of the present invention is to provide a method for producing a molded product by trivalent chromium plating and a trivalent chromium plated molded product.
本発明のさらに他の目的は、人体や環境に与える影響が少ない３価クロメート液を用いて高い耐食性を有する３価クロメート皮膜を、銅めっき皮膜上に形成することができる３価クロムめっき成形品の製造方法およびその３価クロムめっき成形品を提供することにある。
Still another object of the present invention is to provide a trivalent chromium plating molded article that can form a trivalent chromate film having high corrosion resistance on a copper plating film using a trivalent chromate liquid that has little influence on the human body and the environment. And a trivalent chromium plating molded product thereof.
本発明者は、上記の目的を達成するべく、鋭意研究を重ねてきた。
The present inventor has intensively studied to achieve the above object.
その結果、ニッケルめっきを使用することなく、従来の膜構造と同等の外観、耐食性、および耐磨耗性を有する皮膜構造が得られること、およびそのような皮膜構造を得る処理工程を見出し、ここに本発明を完成するに至ったものである。
As a result, a film structure having the same appearance, corrosion resistance, and wear resistance as that of a conventional film structure can be obtained without using nickel plating, and a process for obtaining such a film structure has been found. Thus, the present invention has been completed.
すなわち、本発明は、以下の工程を包含する方法により、成形品の表面に３価クロムめっきを処理する３価クロムめっき成形品の製造方法であり、そのことにより上記目的が達成される。
（項目１） 以下の工程を包含する方法により、成形品の表面にめっきを処理する３価クロムめっき成形品の製造方法：
（ａ）成形品の表面に、光沢硫酸銅めっきによって銅めっき皮膜を形成する工程、
（ｂ）３価クロムイオンと、錯化剤とを含有し、該錯化剤の含有割合が０．１～２モル/Ｌである３価クロムめっき浴を調製する工程、
（ｃ）該銅めっき皮膜の表面に、該３価クロムめっき浴を用いて３価クロムめっきを行い３価クロムめっき皮膜を形成する工程、
ここで、該３価クロムめっき皮膜中の炭素含有量が３at％以上である、３価クロムめっき成形品の製造方法。
（項目２） 前記３価クロムめっき皮膜中の炭素含有量が５～１５at％である項目１に記載の３価クロムめっき成形品の製造方法。
（項目３） 前記３価クロムめっき浴が、３価クロムイオン１モルに対し、錯化剤を０．1～２．０モルの範囲で含有する項目１記載の３価クロムめっき成形品の製造方法。
（項目４） 前記錯化剤が有機カルボン酸である、項目１記載の３価クロムめっき成形品の製造方法。
（項目５） 前記有機カルボン酸が、ジカルボン酸、オキシカルボン酸、多価カルボン酸又はそれらの塩である、項目４記載の３価クロムめっき成形品の製造方法。
（項目６） 前記３価クロムめっきを行う際の、３価クロムめっき浴に含まれるクロム濃度が5～35ｇ/Ｌである項目１に記載の３価クロムめっき成形品の製造方法。
（項目７） 前記３価クロムめっきを行う際の、３価クロムめっき浴のｐＨが1.5～4.0である項目１に記載の３価クロムめっき成形品の製造方法。
（項目８） 前記３価クロムめっき皮膜の厚みが０．５～５μｍである項目１に記載の３価クロムめっき成形品の製造方法。
（項目９） 項目１～８のいずれかの方法によって得られる３価クロムめっき成形品であって、成形品と、該成形品の表面に形成された膜厚が１０～５０μｍの銅めっき皮膜と、該銅めっき皮膜の表面に形成された膜厚が０．５～５μｍμｍの３価クロムめっき皮膜と、を有する３価クロムめっき成形品。
（項目１０） 前記成形品が携帯電話の操作用ボタンである項目９に記載の３価クロムめっき成形品。 That is, this invention is a manufacturing method of the trivalent chromium plating molded product which processes trivalent chromium plating on the surface of a molded product by the method including the following processes, and the said objective is achieved by it.
(Item 1) A method for producing a trivalent chromium plated molded product, in which plating is performed on the surface of the molded product by a method including the following steps:
(A) forming a copper plating film on the surface of the molded product by bright copper sulfate plating;
(B) a step of preparing a trivalent chromium plating bath containing trivalent chromium ions and a complexing agent, wherein the content of the complexing agent is 0.1 to 2 mol / L;
(C) forming a trivalent chromium plating film by performing trivalent chromium plating on the surface of the copper plating film using the trivalent chromium plating bath;
Here, a method for producing a trivalent chromium plating molded product, wherein the carbon content in the trivalent chromium plating film is 3 at% or more.
(Item 2) The method for producing a trivalent chromium plating molded article according to item 1, wherein the carbon content in the trivalent chromium plating film is 5 to 15 at%.
(Item 3) Manufacture of a trivalent chromium plating molded article according to item 1, wherein the trivalent chromium plating bath contains a complexing agent in the range of 0.1 to 2.0 mol per 1 mol of trivalent chromium ions. Method.
(Item 4) The method for producing a trivalent chromium plating molded article according to item 1, wherein the complexing agent is an organic carboxylic acid.
(Item 5) The method for producing a trivalent chromium plating molded article according to item 4, wherein the organic carboxylic acid is a dicarboxylic acid, an oxycarboxylic acid, a polyvalent carboxylic acid or a salt thereof.
(Item 6) The method for producing a trivalent chromium plated molded article according to item 1, wherein the chromium concentration contained in the trivalent chromium plating bath when performing the trivalent chromium plating is 5 to 35 g / L.
(Item 7) The method for producing a trivalent chromium plated molded article according to item 1, wherein the pH of the trivalent chromium plating bath when performing the trivalent chromium plating is 1.5 to 4.0.
(Item 8) The method for producing a trivalent chromium plated molded article according to item 1, wherein the thickness of the trivalent chromium plating film is 0.5 to 5 μm.
(Item 9) A trivalent chromium plating molded product obtained by the method of any one of items 1 to 8, comprising a molded product and a copper plating film having a film thickness of 10 to 50 μm formed on the surface of the molded product. And a trivalent chromium plating molded article having a film thickness of 0.5 to 5 μm μm formed on the surface of the copper plating film.
(Item 10) The trivalent chromium plating molded product according to Item 9, wherein the molded product is a button for operating a mobile phone.
（項目１） 以下の工程を包含する方法により、成形品の表面にめっきを処理する３価クロムめっき成形品の製造方法：
（ａ）成形品の表面に、光沢硫酸銅めっきによって銅めっき皮膜を形成する工程、
（ｂ）３価クロムイオンと、錯化剤とを含有し、該錯化剤の含有割合が０．１～２モル/Ｌである３価クロムめっき浴を調製する工程、
（ｃ）該銅めっき皮膜の表面に、該３価クロムめっき浴を用いて３価クロムめっきを行い３価クロムめっき皮膜を形成する工程、
ここで、該３価クロムめっき皮膜中の炭素含有量が３at％以上である、３価クロムめっき成形品の製造方法。
（項目２） 前記３価クロムめっき皮膜中の炭素含有量が５～１５at％である項目１に記載の３価クロムめっき成形品の製造方法。
（項目３） 前記３価クロムめっき浴が、３価クロムイオン１モルに対し、錯化剤を０．1～２．０モルの範囲で含有する項目１記載の３価クロムめっき成形品の製造方法。
（項目４） 前記錯化剤が有機カルボン酸である、項目１記載の３価クロムめっき成形品の製造方法。
（項目５） 前記有機カルボン酸が、ジカルボン酸、オキシカルボン酸、多価カルボン酸又はそれらの塩である、項目４記載の３価クロムめっき成形品の製造方法。
（項目６） 前記３価クロムめっきを行う際の、３価クロムめっき浴に含まれるクロム濃度が5～35ｇ/Ｌである項目１に記載の３価クロムめっき成形品の製造方法。
（項目７） 前記３価クロムめっきを行う際の、３価クロムめっき浴のｐＨが1.5～4.0である項目１に記載の３価クロムめっき成形品の製造方法。
（項目８） 前記３価クロムめっき皮膜の厚みが０．５～５μｍである項目１に記載の３価クロムめっき成形品の製造方法。
（項目９） 項目１～８のいずれかの方法によって得られる３価クロムめっき成形品であって、成形品と、該成形品の表面に形成された膜厚が１０～５０μｍの銅めっき皮膜と、該銅めっき皮膜の表面に形成された膜厚が０．５～５μｍμｍの３価クロムめっき皮膜と、を有する３価クロムめっき成形品。
（項目１０） 前記成形品が携帯電話の操作用ボタンである項目９に記載の３価クロムめっき成形品。 That is, this invention is a manufacturing method of the trivalent chromium plating molded product which processes trivalent chromium plating on the surface of a molded product by the method including the following processes, and the said objective is achieved by it.
(Item 1) A method for producing a trivalent chromium plated molded product, in which plating is performed on the surface of the molded product by a method including the following steps:
(A) forming a copper plating film on the surface of the molded product by bright copper sulfate plating;
(B) a step of preparing a trivalent chromium plating bath containing trivalent chromium ions and a complexing agent, wherein the content of the complexing agent is 0.1 to 2 mol / L;
(C) forming a trivalent chromium plating film by performing trivalent chromium plating on the surface of the copper plating film using the trivalent chromium plating bath;
Here, a method for producing a trivalent chromium plating molded product, wherein the carbon content in the trivalent chromium plating film is 3 at% or more.
(Item 2) The method for producing a trivalent chromium plating molded article according to item 1, wherein the carbon content in the trivalent chromium plating film is 5 to 15 at%.
(Item 3) Manufacture of a trivalent chromium plating molded article according to item 1, wherein the trivalent chromium plating bath contains a complexing agent in the range of 0.1 to 2.0 mol per 1 mol of trivalent chromium ions. Method.
(Item 4) The method for producing a trivalent chromium plating molded article according to item 1, wherein the complexing agent is an organic carboxylic acid.
(Item 5) The method for producing a trivalent chromium plating molded article according to item 4, wherein the organic carboxylic acid is a dicarboxylic acid, an oxycarboxylic acid, a polyvalent carboxylic acid or a salt thereof.
(Item 6) The method for producing a trivalent chromium plated molded article according to item 1, wherein the chromium concentration contained in the trivalent chromium plating bath when performing the trivalent chromium plating is 5 to 35 g / L.
(Item 7) The method for producing a trivalent chromium plated molded article according to item 1, wherein the pH of the trivalent chromium plating bath when performing the trivalent chromium plating is 1.5 to 4.0.
(Item 8) The method for producing a trivalent chromium plated molded article according to item 1, wherein the thickness of the trivalent chromium plating film is 0.5 to 5 μm.
(Item 9) A trivalent chromium plating molded product obtained by the method of any one of items 1 to 8, comprising a molded product and a copper plating film having a film thickness of 10 to 50 μm formed on the surface of the molded product. And a trivalent chromium plating molded article having a film thickness of 0.5 to 5 μm μm formed on the surface of the copper plating film.
(Item 10) The trivalent chromium plating molded product according to Item 9, wherein the molded product is a button for operating a mobile phone.
上記したように、有害なシアンを含有する、あるいは制御の困難である銅－スズ合金めっきを行うことなく、銅めっき皮膜上に直接クロムめっきを行うことにより、簡単に、低コストで問題となるニッケルめっきアレルギー対策を行うことが可能である。
As mentioned above, direct chrome plating on the copper plating film without toxic cyanide-containing or difficult-to-control copper-tin alloy plating is a simple, low-cost problem. It is possible to take measures against nickel plating allergies.
銅－スズ合金めっき皮膜は、光沢硫酸銅めっき皮膜と比較して硬度が高いため、耐磨耗性試験などでは銅－スズ合金めっき皮膜が存在することは皮膜構造としては有利である。
Since the copper-tin alloy plating film has a higher hardness than the bright copper sulfate plating film, the presence of the copper-tin alloy plating film is advantageous as a film structure in an abrasion resistance test or the like.
しかし、現状、銅－スズ合金めっき浴として安定な性能を示すものは有害なシアンを含有するシアン浴であり、このシアン浴は、排水処理、作業環境上からも好ましくない。近年では、錯化剤としてシアンを含有しないものも開発されてはいるが、実際の過酷な作業条件では、シアンを含有しないめっき浴の安定性の点から問題がある。
However, at present, a copper-tin alloy plating bath that exhibits stable performance is a cyan bath containing harmful cyanide, and this cyan bath is not preferable from the viewpoint of waste water treatment and work environment. In recent years, a complexing agent that does not contain cyan has been developed, but there is a problem in terms of stability of a plating bath that does not contain cyan under actual severe working conditions.
光沢硫酸銅めっき浴は広く用いられている。錯化剤を添加することで、酸化力の低い３価クロムめっき液を用いた場合でも、６価クロム皮膜に匹敵する外観、耐食性、および耐摩耗性を有するめっき皮膜が得られる。
Bright copper sulfate plating bath is widely used. By adding a complexing agent, a plating film having an appearance, corrosion resistance, and wear resistance comparable to that of a hexavalent chromium film can be obtained even when a trivalent chromium plating solution having low oxidizing power is used.
すなわち、クロム源として３価クロム塩を用い、錯化剤として、シアン以外の、ある種の錯化剤を用いることで、皮膜中に炭素を共析させたＣｒ－Ｃ合金めっき皮膜を硫酸銅めっき皮膜上に直接成膜することができる。そのため、６価クロム皮膜に匹敵する外観、耐食性、および耐摩耗性を有するめっき皮膜が得られる。
That is, by using a trivalent chromium salt as a chromium source and using a certain complexing agent other than cyan as a complexing agent, a Cr—C alloy plating film in which carbon is co-deposited in the film is formed by copper sulfate. The film can be formed directly on the plating film. Therefore, a plating film having an appearance, corrosion resistance, and wear resistance comparable to a hexavalent chromium film can be obtained.
本発明の方法では、めっき浴が酸化性の高い６価クロム（ＣｒＯ３）を含有しないので、該めっき液中に硫酸銅めっき皮膜を有する成形品を浸漬した場合に、その皮膜の表面に外観不良の原因となる酸化皮膜が形成され難い。そのため、従来のように、６価クロムめっきを直接成膜した場合に起こる外観不良が発生しない。また、めっき浴が６価クロムを含有しないため、人体や環境に与える影響も少ない。さらに、クロムめっき皮膜を１層とすることができ、工程数が低減する。
In the method of the present invention, since the plating bath does not contain highly oxidizable hexavalent chromium (CrO 3 ), when a molded article having a copper sulfate plating film is immersed in the plating solution, the appearance of the film is visible. It is difficult to form an oxide film that causes defects. Therefore, unlike the conventional case, the appearance defect that occurs when the hexavalent chromium plating is directly formed does not occur. In addition, since the plating bath does not contain hexavalent chromium, there is little influence on the human body and the environment. Furthermore, a chromium plating film can be made into one layer, and the number of processes reduces.
耐食性に関しては、酸化性の低い３価クロムめっき浴を用いて形成された皮膜は、その皮膜表面に不動態化膜（クロムの水和酸化物層）の形成が不十分であり、一般的には６価クロムめっき皮膜に劣る。しかし、６価クロムめっき皮膜はある程度の膜厚以上ではクラックが発生する。これに対して３価クロムめっき皮膜は皮膜の応力が低く、そのためクラックが発生しにくい。特に、３価クロムめっき皮膜の膜厚が厚い場合には、耐食性が向上する。
With respect to corrosion resistance, the film formed using a trivalent chromium plating bath with low oxidizability has insufficient formation of a passivation film (chromium hydrated oxide layer) on the surface of the film. Is inferior to hexavalent chromium plating film. However, the hexavalent chromium plating film is cracked at a certain thickness. On the other hand, the trivalent chromium plating film has a low film stress, and therefore, cracks are unlikely to occur. In particular, when the film thickness of the trivalent chromium plating film is thick, the corrosion resistance is improved.
また、皮膜中に炭素などの不純物を含有しない３価クロムめっき皮膜の結晶構造は、６価クロムめっき皮膜と同様の結晶質である。皮膜が結晶性を示す場合には、粒子間に存在する粒界（原子配列が不連続）部分では、その上に形成される不動態化膜も連続性が低いと考えられる。これに対して、本発明のように、皮膜中に炭素を共析させた場合、ＸＲＤ測定においても結晶性の低下（アモルファス化）が確認されており、耐食性が向上する。さらに、炭素の共析により、皮膜硬度および耐磨耗性が向上する。
The crystal structure of the trivalent chromium plating film that does not contain impurities such as carbon in the film is the same crystalline as that of the hexavalent chromium plating film. When the film exhibits crystallinity, it is considered that the passivated film formed on the grain boundary (discontinuous atomic arrangement) between the particles also has low continuity. On the other hand, when carbon is co-deposited in the film as in the present invention, a decrease in crystallinity (amorphization) is confirmed even in the XRD measurement, and the corrosion resistance is improved. Furthermore, the film hardness and wear resistance are improved by the eutectoid of carbon.
以下に、本発明を詳細に説明する。
Hereinafter, the present invention will be described in detail.
本発明で使用する成形品は、ＡＢＳ樹脂、ＰＣ/ＡＢＳ樹脂、ナイロンなどの樹脂によって成形されたものがあげられる。例えば、射出成形された成形品があり、具体的には携帯電話、デジタルカメラの操作ボタンなどがある。
Examples of the molded product used in the present invention include those molded from resins such as ABS resin, PC / ABS resin, and nylon. For example, there are injection-molded molded products, specifically, cellular phones, digital camera operation buttons, and the like.
特に、ＡＢＳ樹脂にて形成された一次成形品と、該一次成形品の内側に二色成形によって成形された二次成形品とを有する２色成形品を使用することができる。２次成形品はＰＣ等の透明な樹脂にて形成することもできる。また、樹脂素材以外に、各種の金属よりなる成形品を対象として本発明の方法に従って、該成形品にめっきすることもできる。
In particular, a two-color molded product having a primary molded product formed of ABS resin and a secondary molded product molded by two-color molding inside the primary molded product can be used. The secondary molded product can also be formed of a transparent resin such as PC. Moreover, according to the method of the present invention, a molded product made of various metals can be plated in addition to the resin material.
この成形品の表面に以下の工程によりめっき処理が行われる。
Ａ．光沢硫酸銅めっき
図１に光沢硫酸銅めっきの概略工程を示す。 Plating treatment is performed on the surface of this molded product by the following steps.
A. Bright Copper Sulfate Plating FIG. 1 shows a schematic process of bright copper sulfate plating.
Ａ．光沢硫酸銅めっき
図１に光沢硫酸銅めっきの概略工程を示す。 Plating treatment is performed on the surface of this molded product by the following steps.
A. Bright Copper Sulfate Plating FIG. 1 shows a schematic process of bright copper sulfate plating.
はじめに、成形品の表面を脱脂し、水洗した後、定法に基づいてクロム酸－硫酸エッチングを行う。
（１）成形品の表面を脱脂するには、ＣＲＰクリーナー（アルカリ洗浄剤、奥野製薬工業社製）を用いて、このクリーナーの５０ｇ/リットルの液中に、成形品を５０℃、５分間浸漬する。
（２）好ましいエッチング条件は、次のとおりである。 First, the surface of the molded product is degreased and washed with water, and then chromic acid-sulfuric acid etching is performed according to a conventional method.
(1) To degrease the surface of the molded product, use a CRP cleaner (alkaline detergent, manufactured by Okuno Pharmaceutical Co., Ltd.) and immerse the molded product in 50 g / liter of this cleaner at 50 ° C. for 5 minutes. To do.
(2) Preferred etching conditions are as follows.
（１）成形品の表面を脱脂するには、ＣＲＰクリーナー（アルカリ洗浄剤、奥野製薬工業社製）を用いて、このクリーナーの５０ｇ/リットルの液中に、成形品を５０℃、５分間浸漬する。
（２）好ましいエッチング条件は、次のとおりである。 First, the surface of the molded product is degreased and washed with water, and then chromic acid-sulfuric acid etching is performed according to a conventional method.
(1) To degrease the surface of the molded product, use a CRP cleaner (alkaline detergent, manufactured by Okuno Pharmaceutical Co., Ltd.) and immerse the molded product in 50 g / liter of this cleaner at 50 ° C. for 5 minutes. To do.
(2) Preferred etching conditions are as follows.
クロム酸３５０～４５０ｇ/Ｌと９８％硫酸３５０～４５０ｇ/Ｌと、ＣＲＰエッチング添加剤0.5～1.0ｍｌ/Ｌとを含有するエッチング液を使用することができる。このエッチング液に、成形品を、エッチング温度６５℃～７０℃、エッチング時間５～１５分で、浸漬するのが好ましい。
An etching solution containing chromic acid 350 to 450 g / L, 98% sulfuric acid 350 to 450 g / L, and CRP etching additive 0.5 to 1.0 ml / L can be used. The molded product is preferably immersed in this etching solution at an etching temperature of 65 ° C. to 70 ° C. and an etching time of 5 to 15 minutes.
特に好ましいエッチング条件は図１に示したとおり、クロム酸４００ｇ/Ｌと９８％硫酸４００ｇ/Ｌと、ＣＲＰエッチング添加剤0.7ｍｌ/Ｌとを含有するエッチング液を使用する。エッチングの温度は６７℃、エッチング時間は８～１０分である。
（３）次に、成形品を水洗した後、中和、水洗を行い、プレディップし、次いで触媒化する。 Particularly preferred etching conditions are as shown in FIG. 1, using an etching solution containing chromic acid 400 g / L, 98% sulfuric acid 400 g / L, and CRP etching additive 0.7 ml / L. The etching temperature is 67 ° C., and the etching time is 8 to 10 minutes.
(3) Next, the molded product is washed with water, then neutralized and washed with water, pre-dipped, and then catalyzed.
（３）次に、成形品を水洗した後、中和、水洗を行い、プレディップし、次いで触媒化する。 Particularly preferred etching conditions are as shown in FIG. 1, using an etching solution containing chromic acid 400 g / L, 98% sulfuric acid 400 g / L, and CRP etching additive 0.7 ml / L. The etching temperature is 67 ° C., and the etching time is 8 to 10 minutes.
(3) Next, the molded product is washed with water, then neutralized and washed with water, pre-dipped, and then catalyzed.
触媒化は、CRPキャタリスト８５H（奥野製薬工業社製）および塩酸水溶液を用いて、３０～４０℃で２～１０分間程度、その水溶液に浸漬すればよい。
（４）触媒化した成形品を水洗した後、定法に従って、成形品の表面を導体化する。 Catalysis can be carried out usingCRP catalyst 85H (Okuno Pharmaceutical Co., Ltd.) and aqueous hydrochloric acid solution at 30 to 40 ° C. for about 2 to 10 minutes.
(4) After the molded catalyst product is washed with water, the surface of the molded product is converted into a conductor according to a conventional method.
（４）触媒化した成形品を水洗した後、定法に従って、成形品の表面を導体化する。 Catalysis can be carried out using
(4) After the molded catalyst product is washed with water, the surface of the molded product is converted into a conductor according to a conventional method.
成形品表面の導体化は、ＣＲＰセレクターA-K（奥野製薬工業社製）を１５０ｍｌ/リットルおよびＣＲＰセレクターＢ（奥野製薬工業社製）２００ｍｌ/リットルを含む溶液を用いて、成形品を溶液中に、３０～５０℃、２～５分間浸漬する。
（５）次に、水洗した後、電気銅めっきを行う。 Conducting the molded product surface with a solution containing 150 ml / liter of CRP selector AK (Okuno Pharmaceutical Co., Ltd.) and 200 ml / liter of CRP selector B (Okuno Pharmaceutical Co., Ltd.) Soak at 30-50 ° C. for 2-5 minutes.
(5) Next, after washing with water, electrolytic copper plating is performed.
（５）次に、水洗した後、電気銅めっきを行う。 Conducting the molded product surface with a solution containing 150 ml / liter of CRP selector AK (Okuno Pharmaceutical Co., Ltd.) and 200 ml / liter of CRP selector B (Okuno Pharmaceutical Co., Ltd.) Soak at 30-50 ° C. for 2-5 minutes.
(5) Next, after washing with water, electrolytic copper plating is performed.
硫酸銅１８０～２２０ｇ/リットル、９８％硫酸４５～５５ｇ/リットル、トップルチナ2000MUを３－６ｍｌ/リットル、およびトップルチナ2000Aを0.3～0.8ｍｌ/リットル含有するめっき液中に成形品を浸漬することにより、実施することができる。めっき温度は２０～３０℃、２～５A/ｄｍ２で実施するのが好ましい。
By immersing the molded article in a plating solution containing copper sulfate 180-220 g / liter, 98% sulfuric acid 45-55 g / liter, Top Lucina 2000MU 3-6 ml / liter, and Top Lucina 2000A 0.3-0.8 ml / liter, Can be implemented. The plating temperature is preferably 20 to 30 ° C. and 2 to 5 A / dm 2 .
なお、上記光沢硫酸銅めっき方法は、一例であるので、その他の公知の方法に従って、実施してもよい。
In addition, since the said bright copper sulfate plating method is an example, you may implement according to another well-known method.
なお、図１に示すＣＲＰクリーナー（奥野製薬工業社製）とは脱脂剤（アルカリ洗浄剤）、ＣＲＰコンディショナー２２２（奥野製薬工業社製）とは表面電荷調整剤、ＣＲＰキャタリスト８５Ｈ（奥野製薬工業社製）とはスズ-パラジウム触媒、ＣＲＰセレクターＡ－Ｋ（奥野製薬工業社製）とは導電化処理剤（銅塩、錯化剤、還元剤を含有する）、ＣＲＰセレクターＢ（奥野製薬工業社製）とは導電化処理剤（アルカリ塩を含有する）、トップルチナ2000ＭＵ（奥野製薬工業社製）とは硫酸銅めっき用光沢剤、トップルチナ2000Ａ（奥野製薬工業社製）とは硫酸銅めっき用光沢剤である。
Ｂ．銅めっきの浴種
装飾用に使用される銅めっきとしては、ほとんどが、硫酸銅であり、他のピロリン酸浴、シアン浴が使用されることはない。 The CRP cleaner (Okuno Pharmaceutical Co., Ltd.) shown in FIG. 1 is a degreasing agent (alkaline detergent), and the CRP conditioner 222 (Okuno Pharmaceutical Co., Ltd.) is a surface charge regulator,CRP catalyst 85H (Okuno Pharmaceutical Co., Ltd.). Is a tin-palladium catalyst, CRP selector AK (Okuno Pharmaceutical Co., Ltd.) is a conductive treatment agent (containing copper salt, complexing agent, reducing agent), CRP selector B (Okuno Pharmaceutical Co., Ltd.) Is made of conductive treatment agent (containing alkali salt), Top Lucina 2000MU (Okuno Pharmaceutical Co., Ltd.) is brightener for copper sulfate plating, and Top Lucina 2000A (Okuno Pharmaceutical Co., Ltd.) is for copper sulfate plating. Brightener.
B. Copper plating bath type Most copper plating used for decoration is copper sulfate, and other pyrophosphate baths and cyan baths are not used.
Ｂ．銅めっきの浴種
装飾用に使用される銅めっきとしては、ほとんどが、硫酸銅であり、他のピロリン酸浴、シアン浴が使用されることはない。 The CRP cleaner (Okuno Pharmaceutical Co., Ltd.) shown in FIG. 1 is a degreasing agent (alkaline detergent), and the CRP conditioner 222 (Okuno Pharmaceutical Co., Ltd.) is a surface charge regulator,
B. Copper plating bath type Most copper plating used for decoration is copper sulfate, and other pyrophosphate baths and cyan baths are not used.
銅めっき浴に使用される光沢剤は、特に限定的でなく、必要な光沢を得ることができれば、従来より公知のものを使用可能である。例えば、光沢剤として、ポリオキシエチレンアルキルエーテルなどの高分子化合物、イオウ化合物等を使用することができる。市販品としては、例えば、トップルチナ870、トップルチナ2000、トップルチナ3000(いずれも奥野製薬工業製)があげられる。
The brightener used in the copper plating bath is not particularly limited, and any conventionally known brightener can be used as long as the necessary gloss can be obtained. For example, a polymer compound such as polyoxyethylene alkyl ether, a sulfur compound, or the like can be used as a brightener. Examples of commercially available products include Top Lucina 870, Top Lucina 2000, and Top Lucina 3000 (all manufactured by Okuno Pharmaceutical Co., Ltd.).
この段階で、光沢が不十分であれば、３価クロムめっき処理後の光沢が出にくい。
Ｃ．３価クロムめっきを行う必要性
硫酸銅めっきによって形成された皮膜上に、６価クロムめっきを直接製膜することは困難である。この理由は、６価クロムめっき浴のｐＨや酸化力が影響しているものと思われる。すなわち、一般的な、６価クロムめっき浴（サージェント浴）は、クロム酸２５０ｇ/Ｌ+９８％硫酸２．５ｇ/Ｌ程度の組成であり、ｐＨが低く、めっき浴の酸化力が高い（酸化還元電位（ORP）が高い）ことが特徴である。このため、銅めっき皮膜が６価クロムめっき浴中に浸漬された時点で銅表面の酸化、溶解が起こるために正常に（きれいに）クロムめっきができないものと推測される。 At this stage, if the gloss is insufficient, the gloss after the trivalent chromium plating treatment is difficult to be obtained.
C. Necessity of performing trivalent chromium plating It is difficult to directly form hexavalent chromium plating on a film formed by copper sulfate plating. This is probably because the pH and oxidizing power of the hexavalent chromium plating bath are affected. That is, a general hexavalent chromium plating bath (sergeant bath) has a composition of about 250 g / L of chromic acid + 2.5 g / L of 98% sulfuric acid, has a low pH, and has a high oxidizing power of the plating bath (oxidation). It is characterized by a high reduction potential (ORP). For this reason, when the copper plating film is immersed in a hexavalent chromium plating bath, it is presumed that the copper surface cannot be oxidized properly (cleanly) because the copper surface is oxidized and dissolved.
Ｃ．３価クロムめっきを行う必要性
硫酸銅めっきによって形成された皮膜上に、６価クロムめっきを直接製膜することは困難である。この理由は、６価クロムめっき浴のｐＨや酸化力が影響しているものと思われる。すなわち、一般的な、６価クロムめっき浴（サージェント浴）は、クロム酸２５０ｇ/Ｌ+９８％硫酸２．５ｇ/Ｌ程度の組成であり、ｐＨが低く、めっき浴の酸化力が高い（酸化還元電位（ORP）が高い）ことが特徴である。このため、銅めっき皮膜が６価クロムめっき浴中に浸漬された時点で銅表面の酸化、溶解が起こるために正常に（きれいに）クロムめっきができないものと推測される。 At this stage, if the gloss is insufficient, the gloss after the trivalent chromium plating treatment is difficult to be obtained.
C. Necessity of performing trivalent chromium plating It is difficult to directly form hexavalent chromium plating on a film formed by copper sulfate plating. This is probably because the pH and oxidizing power of the hexavalent chromium plating bath are affected. That is, a general hexavalent chromium plating bath (sergeant bath) has a composition of about 250 g / L of chromic acid + 2.5 g / L of 98% sulfuric acid, has a low pH, and has a high oxidizing power of the plating bath (oxidation). It is characterized by a high reduction potential (ORP). For this reason, when the copper plating film is immersed in a hexavalent chromium plating bath, it is presumed that the copper surface cannot be oxidized properly (cleanly) because the copper surface is oxidized and dissolved.
これに対して、３価クロムめっきでは、金属塩が３価クロム塩（硫酸クロムなど）であり、金属濃度も６価クロム浴と比較すると、低く、ＯＲＰ（酸化還元電位）も低い値を示す。３価クロムめっき浴は、一般にｐＨも３程度であり、３価クロムめっき浴中に銅めっき皮膜が浸漬された場合でも、銅めっき皮膜の酸化あるいは溶解が起こりにくいため、銅めっき皮膜上に３価クロムめっきは正常に製膜するものと思われる。
In contrast, in trivalent chromium plating, the metal salt is a trivalent chromium salt (such as chromium sulfate), the metal concentration is lower than that of the hexavalent chromium bath, and the ORP (redox potential) is also low. . The trivalent chromium plating bath generally has a pH of about 3, and even when the copper plating film is immersed in the trivalent chromium plating bath, oxidation or dissolution of the copper plating film hardly occurs. Divalent chromium plating seems to form normally.
本発明においては、このようにして基体（成形品）上に銅めっき皮膜を析出させた後、水洗し、３価クロムめっき液で処理を行う。
Ｄ．３価クロムめっき浴
３価クロムめっき浴は、以下（ａ）～（ｄ）を含有することができる。
（ａ）クロム成分としては、硫酸クロム、塩基性硫酸クロム、塩化クロム、酢酸クロムなどの水溶性３価クロム化合物を含むことができる。上記３価クロムの供給源は、１種あるいは２種以上を使用することができる。処理溶液中の３価クロムイオンの濃度は、５～３５ｇ/Ｌの範囲が好ましく、より好ましくは１０～３０ｇ/Ｌの範囲であり、さらに好ましくは１５～２５ｇ／Ｌの範囲である。
（ｂ）導電性塩として硫酸ナトリウム、硫酸カリウム、硫酸アンモニウム、硫酸アルミニウム、塩化ナトリウム、塩化カリウム、塩化アンモニウム、フッ化カリウム、フッ化アンモニウム、フッ化カリウムなど無機酸を含むことができる。これらの無機酸の含有量は任意とすることができるが、好ましくは１～２００ｇ/Ｌの範囲であり、より好ましくは１０～１００ｇ/Ｌの範囲である。
（ｃ）クロムの錯化剤として、好ましくは有機カルボン酸を使用する。また、有機カルボン酸の中でも、蟻酸、酢酸などのモノカルボン酸またはその塩、シュウ酸、マロン酸、マレイン酸などのジカルボン酸、クエン酸、リンゴ酸、グリコール酸などのヒドロキシカルボン酸、またはそれらの塩を含有することができる。錯化剤は、１種又は２種以上を使用することができる。処理溶液中の錯化剤の濃度は、３価クロムイオン１モルに対し、０．1～２モルの範囲が好ましく、さらに好ましくは０．２～１．０モルの範囲である。錯化剤を所定量含有することにより、３価クロム化成処理皮膜の加熱による皮膜硬度の低下を防止し、耐摩耗性などを向上することができる。 In the present invention, after the copper plating film is deposited on the substrate (molded product) in this way, it is washed with water and treated with a trivalent chromium plating solution.
D. Trivalent chromium plating bath The trivalent chromium plating bath may contain the following (a) to (d).
(A) As a chromium component, water-soluble trivalent chromium compounds, such as chromium sulfate, basic chromium sulfate, chromium chloride, and chromium acetate, can be included. The said trivalent chromium supply source can use 1 type (s) or 2 or more types. The concentration of trivalent chromium ions in the treatment solution is preferably in the range of 5 to 35 g / L, more preferably in the range of 10 to 30 g / L, and still more preferably in the range of 15 to 25 g / L.
(B) As a conductive salt, inorganic acids such as sodium sulfate, potassium sulfate, ammonium sulfate, aluminum sulfate, sodium chloride, potassium chloride, ammonium chloride, potassium fluoride, ammonium fluoride, and potassium fluoride can be contained. The content of these inorganic acids can be arbitrary, but is preferably in the range of 1 to 200 g / L, more preferably in the range of 10 to 100 g / L.
(C) As the chromium complexing agent, an organic carboxylic acid is preferably used. Among organic carboxylic acids, monocarboxylic acids such as formic acid and acetic acid or salts thereof, dicarboxylic acids such as oxalic acid, malonic acid and maleic acid, hydroxycarboxylic acids such as citric acid, malic acid and glycolic acid, or their Salts can be included. One or more complexing agents can be used. The concentration of the complexing agent in the treatment solution is preferably in the range of 0.1 to 2 mol, more preferably in the range of 0.2 to 1.0 mol, per 1 mol of trivalent chromium ions. By containing a predetermined amount of the complexing agent, it is possible to prevent a decrease in film hardness due to heating of the trivalent chromium chemical conversion film and to improve wear resistance and the like.
Ｄ．３価クロムめっき浴
３価クロムめっき浴は、以下（ａ）～（ｄ）を含有することができる。
（ａ）クロム成分としては、硫酸クロム、塩基性硫酸クロム、塩化クロム、酢酸クロムなどの水溶性３価クロム化合物を含むことができる。上記３価クロムの供給源は、１種あるいは２種以上を使用することができる。処理溶液中の３価クロムイオンの濃度は、５～３５ｇ/Ｌの範囲が好ましく、より好ましくは１０～３０ｇ/Ｌの範囲であり、さらに好ましくは１５～２５ｇ／Ｌの範囲である。
（ｂ）導電性塩として硫酸ナトリウム、硫酸カリウム、硫酸アンモニウム、硫酸アルミニウム、塩化ナトリウム、塩化カリウム、塩化アンモニウム、フッ化カリウム、フッ化アンモニウム、フッ化カリウムなど無機酸を含むことができる。これらの無機酸の含有量は任意とすることができるが、好ましくは１～２００ｇ/Ｌの範囲であり、より好ましくは１０～１００ｇ/Ｌの範囲である。
（ｃ）クロムの錯化剤として、好ましくは有機カルボン酸を使用する。また、有機カルボン酸の中でも、蟻酸、酢酸などのモノカルボン酸またはその塩、シュウ酸、マロン酸、マレイン酸などのジカルボン酸、クエン酸、リンゴ酸、グリコール酸などのヒドロキシカルボン酸、またはそれらの塩を含有することができる。錯化剤は、１種又は２種以上を使用することができる。処理溶液中の錯化剤の濃度は、３価クロムイオン１モルに対し、０．1～２モルの範囲が好ましく、さらに好ましくは０．２～１．０モルの範囲である。錯化剤を所定量含有することにより、３価クロム化成処理皮膜の加熱による皮膜硬度の低下を防止し、耐摩耗性などを向上することができる。 In the present invention, after the copper plating film is deposited on the substrate (molded product) in this way, it is washed with water and treated with a trivalent chromium plating solution.
D. Trivalent chromium plating bath The trivalent chromium plating bath may contain the following (a) to (d).
(A) As a chromium component, water-soluble trivalent chromium compounds, such as chromium sulfate, basic chromium sulfate, chromium chloride, and chromium acetate, can be included. The said trivalent chromium supply source can use 1 type (s) or 2 or more types. The concentration of trivalent chromium ions in the treatment solution is preferably in the range of 5 to 35 g / L, more preferably in the range of 10 to 30 g / L, and still more preferably in the range of 15 to 25 g / L.
(B) As a conductive salt, inorganic acids such as sodium sulfate, potassium sulfate, ammonium sulfate, aluminum sulfate, sodium chloride, potassium chloride, ammonium chloride, potassium fluoride, ammonium fluoride, and potassium fluoride can be contained. The content of these inorganic acids can be arbitrary, but is preferably in the range of 1 to 200 g / L, more preferably in the range of 10 to 100 g / L.
(C) As the chromium complexing agent, an organic carboxylic acid is preferably used. Among organic carboxylic acids, monocarboxylic acids such as formic acid and acetic acid or salts thereof, dicarboxylic acids such as oxalic acid, malonic acid and maleic acid, hydroxycarboxylic acids such as citric acid, malic acid and glycolic acid, or their Salts can be included. One or more complexing agents can be used. The concentration of the complexing agent in the treatment solution is preferably in the range of 0.1 to 2 mol, more preferably in the range of 0.2 to 1.0 mol, per 1 mol of trivalent chromium ions. By containing a predetermined amount of the complexing agent, it is possible to prevent a decrease in film hardness due to heating of the trivalent chromium chemical conversion film and to improve wear resistance and the like.
また、付き回り性を向上させる目的でＦｅ、Ｎｉなどを添加してもよい。
Further, Fe, Ni, etc. may be added for the purpose of improving the throwing power.
また、皮膜中の炭素含有量は３at％以上が好ましく、さらに好ましくは５～１５at％である。このように、炭素を共析させることにより、皮膜硬度および耐磨耗性を向上させることができる。皮膜中の炭素含有量が３at％未満の場合には、硬度が低下し、また耐摩擦性が低下する傾向にある。
Also, the carbon content in the film is preferably 3 at% or more, more preferably 5 to 15 at%. Thus, the film hardness and the wear resistance can be improved by eutectizing carbon. When the carbon content in the film is less than 3 at%, the hardness tends to decrease and the friction resistance tends to decrease.
さらに、（ｄ）ｐＨ緩衝剤として、ホウ酸、ホウ酸ナトリウム、硫酸アルミニウムなどを含んでもよい。
Furthermore, (d) boric acid, sodium borate, aluminum sulfate or the like may be included as a pH buffer.
また、３価クロムめっき浴の酸化還元電位は、１００～２５０ｍＶが好ましい。さらに好ましくは、１４０～２００ｍＶである。
The redox potential of the trivalent chromium plating bath is preferably 100 to 250 mV. More preferably, it is 140 to 200 mV.
３価クロムめっき浴のｐＨは、１．５～５．０が好ましい。さらに好ましくは、１．５～４．０、最も好ましくは２．０～３．5である。
The pH of the trivalent chromium plating bath is preferably 1.5 to 5.0. More preferably, it is 1.5 to 4.0, and most preferably 2.0 to 3.5.
市販品としては、奥野製薬工業製の「トップファインクロムＳＰ」および「トップファインクロムＷＲ」を使用することができる。
Commercially available “Top Fine Chrome SP” and “Top Fine Chrome WR” manufactured by Okuno Pharmaceutical Co., Ltd. can be used.
本発明のめっき方法において、３価クロムめっき皮膜を形成する方法としては、上記３価クロムめっき浴に銅めっきした基体を浸漬するのが一般的である。例えば３０～５０℃の液温で２～１０分浸漬するのが好ましく、より好ましくは３～８分浸漬する。
In the plating method of the present invention, as a method for forming a trivalent chromium plating film, it is common to immerse a copper-plated substrate in the trivalent chromium plating bath. For example, the immersion is preferably performed at a liquid temperature of 30 to 50 ° C. for 2 to 10 minutes, more preferably 3 to 8 minutes.
この３価クロムめっきによって形成される皮膜（クロムめっき皮膜）の厚みは０．５～５．0μｍが好ましい。さらに好ましくは、１．０～３．０μｍである。
Ｅ．３価クロムめっきの構造が必要である理由
ニッケルめっきが要求される部品は、人が触れる部分（携帯電話、デジタルカメラの操作ボタンなど）に用いられるため、ある程度の耐磨耗性が要求される。 The thickness of the film formed by this trivalent chromium plating (chromium plating film) is preferably 0.5 to 5.0 μm. More preferably, it is 1.0 to 3.0 μm.
E. Reasons why a trivalent chromium plating structure is required Parts that require nickel plating are used for parts that are touched by humans (cell phones, digital camera operation buttons, etc.), and therefore require a certain level of wear resistance. .
Ｅ．３価クロムめっきの構造が必要である理由
ニッケルめっきが要求される部品は、人が触れる部分（携帯電話、デジタルカメラの操作ボタンなど）に用いられるため、ある程度の耐磨耗性が要求される。 The thickness of the film formed by this trivalent chromium plating (chromium plating film) is preferably 0.5 to 5.0 μm. More preferably, it is 1.0 to 3.0 μm.
E. Reasons why a trivalent chromium plating structure is required Parts that require nickel plating are used for parts that are touched by humans (cell phones, digital camera operation buttons, etc.), and therefore require a certain level of wear resistance. .
一般的に３価クロムめっきの皮膜硬度は６価クロムめっきの皮膜硬度とほぼ同程度の９００～１０００Ｈｖ程度を示す。
Generally, the film hardness of trivalent chrome plating is about 900 to 1000 Hv, which is almost the same as the film hardness of hexavalent chrome plating.
本発明の方法における、ニッケルめっきを使用しない工程では、銅－スズ合金めっきを行わないため、耐磨耗性を維持するために、クロムめっき皮膜の膜厚を１μｍ以上製膜することが望ましい。
Ｆ．基本的なめっき皮膜構造（膜厚など）
ＡＢＳ樹脂などで成形品を製造する場合には、光沢外観を得るために光沢硫酸銅めっき皮膜は、１０～５０μｍ程度の膜厚が好ましい。さらに好ましくは２０～４０μｍである。 In the method of the present invention, in the step not using nickel plating, copper-tin alloy plating is not performed. Therefore, in order to maintain wear resistance, it is desirable to form a chromium plating film with a thickness of 1 μm or more.
F. Basic plating film structure (film thickness, etc.)
When a molded product is manufactured with ABS resin or the like, the bright copper sulfate plating film preferably has a thickness of about 10 to 50 μm in order to obtain a glossy appearance. More preferably, it is 20 to 40 μm.
Ｆ．基本的なめっき皮膜構造（膜厚など）
ＡＢＳ樹脂などで成形品を製造する場合には、光沢外観を得るために光沢硫酸銅めっき皮膜は、１０～５０μｍ程度の膜厚が好ましい。さらに好ましくは２０～４０μｍである。 In the method of the present invention, in the step not using nickel plating, copper-tin alloy plating is not performed. Therefore, in order to maintain wear resistance, it is desirable to form a chromium plating film with a thickness of 1 μm or more.
F. Basic plating film structure (film thickness, etc.)
When a molded product is manufactured with ABS resin or the like, the bright copper sulfate plating film preferably has a thickness of about 10 to 50 μm in order to obtain a glossy appearance. More preferably, it is 20 to 40 μm.
３価クロムめっき皮膜の膜厚は厚くする必要はなく、0.5～5.0μｍか好ましく、特に０．５～４μｍであれば十分である。特に好ましい３価クロムの膜厚は、１～３μｍである。
The film thickness of the trivalent chromium plating film does not need to be increased and is preferably 0.5 to 5.0 μm, and particularly preferably 0.5 to 4 μm. A particularly preferred film thickness of trivalent chromium is 1 to 3 μm.
３価クロムめっき皮膜中の炭素含有量は、３～１５at％が好ましく、さらに好ましくは５～１５at％、最も好ましくは５～１２at％である。
The carbon content in the trivalent chromium plating film is preferably 3 to 15 at%, more preferably 5 to 15 at%, and most preferably 5 to 12 at%.
以下に実施例および比較例を挙げて本発明を説明する。
Hereinafter, the present invention will be described with reference to examples and comparative examples.
比較例１および実施例１～４では、めっきする素材として、ＰＣ/ＡＢＳ樹脂の２色成形品を使用した。
In Comparative Example 1 and Examples 1 to 4, a two-color molded product of PC / ABS resin was used as a material to be plated.
この成形品にクロム酸－硫酸エッチング処理を行い、成形品の表面に親水性および微細孔を形成した。その後、直接硫酸銅めっきプロセス（ＣＲＰプロセス、奥野製薬工業製）を用いて、触媒付与、導電化処理、直接硫酸銅めっきを行った。
（実施例１）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅－スズ合金めっきを行わずに、表１に示す組成のめっき液を用い、表１に示す条件で、直接成形品の表面に３価クロムめっきを行い、厚み２．１μｍのクロムめっき皮膜を形成した。
（実施例２）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅－スズ合金めっきを行わずに、表１に示す組成のめっき液を用い、表１に示す条件で、直接３価クロムめっきを行い、厚み２．３μｍのクロムめっき皮膜を形成した。
（実施例３）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅－スズ合金めっきを行わずに、表１に示す組成のめっき液を用い、表１に示す条件で、直接３価クロムめっきを行い、厚み２．０μｍのクロムめっき皮膜を形成した。
（実施例４）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅－スズ合金めっきを行わずに、表１に示す組成のめっき液を用い、表１に示す条件で、直接３価クロムめっきを行い、厚み２．３μｍのクロムめっき皮膜を形成した。
（比較例１）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅－スズ合金めっきを行わずに、表１に示す組成のめっき液を用い、表１に示す条件で、直接３価クロムめっきを行い、厚み２．１μｍのクロムめっき皮膜を形成した。
（評価方法）
（皮膜外観）
処理外観については、目視により曇りなどの外観不良について評価を行った。
（膜厚測定）
クロムめっき皮膜の膜厚は、蛍光Ｘ線膜厚計（セイコーインスツルメンツ製ＳＥＡ5120）により測定した。
（皮膜中の炭素含有量）
得られたクロムめっき皮膜中の炭素含有量は、ＸＰＳ（光電子分光分析装置、アルバック・ファイ社製ＥＳＣＡ－5800）を用いて測定した。 This molded article was subjected to chromic acid-sulfuric acid etching treatment to form hydrophilicity and fine pores on the surface of the molded article. Thereafter, using a direct copper sulfate plating process (CRP process, manufactured by Okuno Pharmaceutical Co., Ltd.), catalyst application, conductive treatment, and direct copper sulfate plating were performed.
Example 1
Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm). Then, trivalent chromium plating was directly performed on the surface of the molded product to form a chromium plating film having a thickness of 2.1 μm.
(Example 2)
Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm). Then, trivalent chromium plating was directly performed to form a 2.3 μm thick chromium plating film.
(Example 3)
Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm). Then, trivalent chromium plating was performed directly to form a 2.0 μm thick chromium plating film.
Example 4
Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm). Then, trivalent chromium plating was directly performed to form a 2.3 μm thick chromium plating film.
(Comparative Example 1)
Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm). Then, trivalent chromium plating was directly performed to form a 2.1 μm thick chromium plating film.
(Evaluation methods)
(Film appearance)
About the processing external appearance, the external appearance defects, such as cloudiness, were evaluated visually.
(Film thickness measurement)
The film thickness of the chromium plating film was measured with a fluorescent X-ray film thickness meter (SEA5120 manufactured by Seiko Instruments Inc.).
(Carbon content in the film)
The carbon content in the obtained chromium plating film was measured using XPS (photoelectron spectrometer, ESCA-5800 manufactured by ULVAC-PHI).
（実施例１）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅－スズ合金めっきを行わずに、表１に示す組成のめっき液を用い、表１に示す条件で、直接成形品の表面に３価クロムめっきを行い、厚み２．１μｍのクロムめっき皮膜を形成した。
（実施例２）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅－スズ合金めっきを行わずに、表１に示す組成のめっき液を用い、表１に示す条件で、直接３価クロムめっきを行い、厚み２．３μｍのクロムめっき皮膜を形成した。
（実施例３）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅－スズ合金めっきを行わずに、表１に示す組成のめっき液を用い、表１に示す条件で、直接３価クロムめっきを行い、厚み２．０μｍのクロムめっき皮膜を形成した。
（実施例４）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅－スズ合金めっきを行わずに、表１に示す組成のめっき液を用い、表１に示す条件で、直接３価クロムめっきを行い、厚み２．３μｍのクロムめっき皮膜を形成した。
（比較例１）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅－スズ合金めっきを行わずに、表１に示す組成のめっき液を用い、表１に示す条件で、直接３価クロムめっきを行い、厚み２．１μｍのクロムめっき皮膜を形成した。
（評価方法）
（皮膜外観）
処理外観については、目視により曇りなどの外観不良について評価を行った。
（膜厚測定）
クロムめっき皮膜の膜厚は、蛍光Ｘ線膜厚計（セイコーインスツルメンツ製ＳＥＡ5120）により測定した。
（皮膜中の炭素含有量）
得られたクロムめっき皮膜中の炭素含有量は、ＸＰＳ（光電子分光分析装置、アルバック・ファイ社製ＥＳＣＡ－5800）を用いて測定した。 This molded article was subjected to chromic acid-sulfuric acid etching treatment to form hydrophilicity and fine pores on the surface of the molded article. Thereafter, using a direct copper sulfate plating process (CRP process, manufactured by Okuno Pharmaceutical Co., Ltd.), catalyst application, conductive treatment, and direct copper sulfate plating were performed.
Example 1
Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm). Then, trivalent chromium plating was directly performed on the surface of the molded product to form a chromium plating film having a thickness of 2.1 μm.
(Example 2)
Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm). Then, trivalent chromium plating was directly performed to form a 2.3 μm thick chromium plating film.
(Example 3)
Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm). Then, trivalent chromium plating was performed directly to form a 2.0 μm thick chromium plating film.
Example 4
Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm). Then, trivalent chromium plating was directly performed to form a 2.3 μm thick chromium plating film.
(Comparative Example 1)
Conditions shown in Table 1 using a plating solution having the composition shown in Table 1 without using a copper-tin alloy plating, using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm). Then, trivalent chromium plating was directly performed to form a 2.1 μm thick chromium plating film.
(Evaluation methods)
(Film appearance)
About the processing external appearance, the external appearance defects, such as cloudiness, were evaluated visually.
(Film thickness measurement)
The film thickness of the chromium plating film was measured with a fluorescent X-ray film thickness meter (SEA5120 manufactured by Seiko Instruments Inc.).
(Carbon content in the film)
The carbon content in the obtained chromium plating film was measured using XPS (photoelectron spectrometer, ESCA-5800 manufactured by ULVAC-PHI).
スパッタ速度３nm/min（ＳｉＯ２換算）のＡｒイオン銃を用い、最表面から１分間スパッタを行い、Ｃｒ２ｐ、Ｏ１ｓ、Ｃ１ｓ、Ｃ２ｐ光電子スペクトルについて測定を行い、付属の定量ソフトを用いて皮膜中に存在する各元素の存在比率を計算した。
（ビッカース硬度測定）
得られた皮膜について、荷重１００ｇでビッカース硬度を測定した。
（耐摩耗性の評価）
スガ磨耗試験器（ＮＶＳ－ＩＳＯ－３）を用い、荷重550ｇ、研磨紙＃320、摩耗回数300回の条件で皮膜の磨耗減量を測定した。 Using an Ar ion gun with a sputtering rate of 3 nm / min (SiO 2 conversion), sputtering is performed for 1 minute from the outermost surface, Cr2p, O1s, C1s, C2p photoelectron spectra are measured, and the attached quantitative software is used to coat the film. The abundance ratio of each element present was calculated.
(Vickers hardness measurement)
About the obtained film | membrane, Vickers hardness was measured by the load of 100g.
(Evaluation of wear resistance)
Using a Suga abrasion tester (NVS-ISO-3), the weight loss of the film was measured under the conditions of a load of 550 g, abrasive paper # 320, and the number of abrasions of 300 times.
（ビッカース硬度測定）
得られた皮膜について、荷重１００ｇでビッカース硬度を測定した。
（耐摩耗性の評価）
スガ磨耗試験器（ＮＶＳ－ＩＳＯ－３）を用い、荷重550ｇ、研磨紙＃320、摩耗回数300回の条件で皮膜の磨耗減量を測定した。 Using an Ar ion gun with a sputtering rate of 3 nm / min (SiO 2 conversion), sputtering is performed for 1 minute from the outermost surface, Cr2p, O1s, C1s, C2p photoelectron spectra are measured, and the attached quantitative software is used to coat the film. The abundance ratio of each element present was calculated.
(Vickers hardness measurement)
About the obtained film | membrane, Vickers hardness was measured by the load of 100g.
(Evaluation of wear resistance)
Using a Suga abrasion tester (NVS-ISO-3), the weight loss of the film was measured under the conditions of a load of 550 g, abrasive paper # 320, and the number of abrasions of 300 times.
消しゴム磨耗試験は、市販の砂消しゴムを用い、荷重500ｇで１分間に３０往復させる条件で300回往復させた場合に、下地である銅めっき皮膜の露出で判定した。
In the eraser abrasion test, a commercially available sand eraser was used, and when it was reciprocated 300 times under the condition of reciprocating 30 times per minute with a load of 500 g, the judgment was made based on the exposure of the copper plating film as a base.
上記実施例および比較例で得られた各めっき成形品について、上記試験項目を評価し、その結果を表１に示した。
The above test items were evaluated for each of the plated products obtained in the above examples and comparative examples, and the results are shown in Table 1.
実施例５でも、実施例１と同様に、めっきする素材として、ＰＣ/ＡＢＳ樹脂の２色成形品を使用した。
In Example 5, similarly to Example 1, a two-color molded product of PC / ABS resin was used as a material to be plated.
この成形品に、図１に示したように、クロム酸－硫酸エッチング処理を行い、成形品の表面に親水性および微細孔を形成した。その後、直接硫酸銅めっきプロセス（ＣＲＰプロセス、奥野製薬工業製）を用いて、触媒付与、導電化処理、直接硫酸銅めっきを行った。
As shown in FIG. 1, this molded product was subjected to a chromic acid-sulfuric acid etching treatment to form hydrophilicity and fine pores on the surface of the molded product. Thereafter, using a direct copper sulfate plating process (CRP process, manufactured by Okuno Pharmaceutical Co., Ltd.), catalyst application, conductive treatment, and direct copper sulfate plating were performed.
このようにして光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅－スズ合金めっきを行わずに、表２に示す組成のめっき液を用い、表２に示す条件で、直接成形品の表面に３価クロムめっきを行い、厚み２．０μｍのクロムめっき皮膜を形成した。
Using a molded product made of PC / ABS resin that has been subjected to bright copper sulfate plating (film thickness 30 μm) in this way, a plating solution having the composition shown in Table 2 is used without performing copper-tin alloy plating. Under the conditions shown in 2, trivalent chromium plating was directly performed on the surface of the molded product to form a chromium plating film having a thickness of 2.0 μm.
その結果、３価クロムめっき成形品の外観は良好「○」であり、皮膜中のＣ含有率は９．１at％、皮膜のビッカース硬度は８３０Ｈｖ、皮膜のスガ磨耗試験機による磨耗量は３．５ｍｇ、皮膜の消しゴム磨耗試験は良好「○」であった。
As a result, the appearance of the trivalent chrome plating molded article was good “◯”, the C content in the film was 9.1 at%, the Vickers hardness of the film was 830 Hv, and the amount of wear of the film by the Suga abrasion tester was 3. The eraser abrasion test of the film was 5 ", and the film was good.
以上の結果から次のことがわかる。
From the above results, the following can be understood.
実施例１～５で示した光沢硫酸銅めっき上に直接３価クロムめっきを行った場合では、耐食性、耐磨耗性を満足させるための膜厚を厚くすることが必要であるが、外観、耐食性、耐磨耗性を満足することが可能である。加えて、比較的浴寿命が短く、管理が難しい銅－スズ合金めっきを使用することなく、ニッケルめっきを使用しない簡単な皮膜構造により生産コストも低減できる。
When trivalent chromium plating is directly performed on the bright copper sulfate plating shown in Examples 1 to 5, it is necessary to increase the film thickness to satisfy the corrosion resistance and wear resistance. It is possible to satisfy corrosion resistance and wear resistance. In addition, the production cost can be reduced by using a simple film structure that does not use nickel plating without using copper-tin alloy plating, which has a relatively short bath life and is difficult to manage.
また、皮膜中に炭素を共析させることができるので、皮膜硬度および耐磨耗性が向上した。
Moreover, since carbon can be co-deposited in the film, the film hardness and wear resistance are improved.
Claims (10)
- 以下の工程を包含する方法により、成形品の表面にめっきを処理する３価クロムめっき成形品の製造方法：
（ａ）成形品の表面に、光沢硫酸銅めっきによって銅めっき皮膜を形成する工程、
（ｂ）３価クロムイオンと、錯化剤とを含有し、該錯化剤の含有割合が０．１～２モル/Ｌである３価クロムめっき浴を調製する工程、
（ｃ）該銅めっき皮膜の表面に、該３価クロムめっき浴を用いて３価クロムめっきを行い３価クロムめっき皮膜を形成する工程、
ここで、該３価クロムめっき皮膜中の炭素含有量が３at％以上である、３価クロムめっき成形品の製造方法。 A method for producing a trivalent chromium plated molded article, in which plating is performed on the surface of the molded article by a method including the following steps:
(A) forming a copper plating film on the surface of the molded product by bright copper sulfate plating;
(B) a step of preparing a trivalent chromium plating bath containing trivalent chromium ions and a complexing agent, wherein the content of the complexing agent is 0.1 to 2 mol / L;
(C) forming a trivalent chromium plating film by performing trivalent chromium plating on the surface of the copper plating film using the trivalent chromium plating bath;
Here, a method for producing a trivalent chromium plating molded product, wherein the carbon content in the trivalent chromium plating film is 3 at% or more. - 前記３価クロムめっき皮膜中の炭素含有量が５～１５at％である請求項１に記載の３価クロムめっき成形品の製造方法。 The method for producing a trivalent chromium plated molded article according to claim 1, wherein the carbon content in the trivalent chromium plated film is 5 to 15 at%.
- 前記３価クロムめっき浴が、３価クロムイオン１モルに対し、錯化剤を０．1～２．０モルの範囲で含有する請求項１記載の３価クロムめっき成形品の製造方法。 The method for producing a trivalent chromium plating molded article according to claim 1, wherein the trivalent chromium plating bath contains a complexing agent in the range of 0.1 to 2.0 mol per 1 mol of trivalent chromium ions.
- 前記錯化剤が有機カルボン酸である、請求項１記載の３価クロムめっき成形品の製造方法。 The manufacturing method of the trivalent chromium plating molded article of Claim 1 whose said complexing agent is organic carboxylic acid.
- 前記有機カルボン酸が、ジカルボン酸、オキシカルボン酸、多価カルボン酸又はそれらの塩である、請求項４記載の３価クロムめっき成形品の製造方法。 The manufacturing method of the trivalent chromium plating molded article of Claim 4 whose said organic carboxylic acid is dicarboxylic acid, oxycarboxylic acid, polyhydric carboxylic acid, or those salts.
- 前記３価クロムめっきを行う際の、３価クロムめっき浴に含まれるクロム濃度が5～35ｇ/Ｌである請求項１に記載の３価クロムめっき成形品の製造方法。 The method for producing a trivalent chromium plated molded article according to claim 1, wherein the concentration of chromium contained in the trivalent chromium plating bath when performing the trivalent chromium plating is 5 to 35 g / L.
- 前記３価クロムめっきを行う際の、３価クロムめっき浴のｐＨが1.5～4.0である請求項１に記載の３価クロムめっき成形品の製造方法。 The method for producing a trivalent chromium plating molded article according to claim 1, wherein the pH of the trivalent chromium plating bath when performing the trivalent chromium plating is 1.5 to 4.0.
- 前記３価クロムめっき皮膜の厚みが０．５～５μｍである請求項１に記載の３価クロムめっき成形品の製造方法。 The method for producing a trivalent chromium plating molded article according to claim 1, wherein the thickness of the trivalent chromium plating film is 0.5 to 5 µm.
- 請求項１の方法によって得られる３価クロムめっき成形品であって、成形品と、該成形品の表面に形成された膜厚が１０～５０μｍの銅めっき皮膜と、該銅めっき皮膜の表面に形成された膜厚が０．５～５μｍμｍの３価クロムめっき皮膜と、を有する３価クロムめっき成形品。 A trivalent chromium plating molded article obtained by the method of claim 1, wherein the molded article, a copper plating film having a thickness of 10 to 50 μm formed on the surface of the molded article, and a surface of the copper plating film are formed. A trivalent chromium plating molded article having a formed trivalent chromium plating film having a film thickness of 0.5 to 5 μm μm.
- 前記成形品が携帯電話の操作用ボタンである請求項９に記載の３価クロムめっき成形品。 The trivalent chromium plating molded product according to claim 9, wherein the molded product is a button for operating a mobile phone.
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| WO2014115203A1 (en) * | 2013-01-25 | 2014-07-31 | 上村工業株式会社 | Chrome plating solution and method for forming chrome plating film using same |
| WO2015037391A1 (en) * | 2013-09-12 | 2015-03-19 | 奥野製薬工業株式会社 | Trivalent chromium plating bath |
| JP2016113662A (en) * | 2014-12-15 | 2016-06-23 | 株式会社Ｊｃｕ | Trivalent chromium plating liquid and trivalent chromium plating method |
| JP7070822B1 (en) * | 2020-12-21 | 2022-05-18 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet and its manufacturing method |
| JP7070823B1 (en) * | 2020-12-21 | 2022-05-18 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet and its manufacturing method |
| WO2022138005A1 (en) * | 2020-12-21 | 2022-06-30 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet and production method therefor |
| WO2022138006A1 (en) * | 2020-12-21 | 2022-06-30 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet and production method therefor |
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| FI129420B (en) * | 2020-04-23 | 2022-02-15 | Savroc Ltd | An aqueous electroplating bath |
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| JP2010189673A (en) * | 2009-02-16 | 2010-09-02 | Okuno Chem Ind Co Ltd | Trivalent chromium plating bath |
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| JP2010084224A (en) * | 2008-10-02 | 2010-04-15 | Taiyo Manufacturing Co Ltd | Method of manufacturing plated molded article using no nickel, and plated molded article |
| JP2010189673A (en) * | 2009-02-16 | 2010-09-02 | Okuno Chem Ind Co Ltd | Trivalent chromium plating bath |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014115203A1 (en) * | 2013-01-25 | 2014-07-31 | 上村工業株式会社 | Chrome plating solution and method for forming chrome plating film using same |
| WO2015037391A1 (en) * | 2013-09-12 | 2015-03-19 | 奥野製薬工業株式会社 | Trivalent chromium plating bath |
| JPWO2015037391A1 (en) * | 2013-09-12 | 2017-03-02 | 奥野製薬工業株式会社 | Trivalent chromium plating bath |
| JP2016113662A (en) * | 2014-12-15 | 2016-06-23 | 株式会社Ｊｃｕ | Trivalent chromium plating liquid and trivalent chromium plating method |
| JP7070822B1 (en) * | 2020-12-21 | 2022-05-18 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet and its manufacturing method |
| JP7070823B1 (en) * | 2020-12-21 | 2022-05-18 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet and its manufacturing method |
| WO2022138005A1 (en) * | 2020-12-21 | 2022-06-30 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet and production method therefor |
| WO2022138006A1 (en) * | 2020-12-21 | 2022-06-30 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet and production method therefor |
| TWI792744B (en) * | 2020-12-21 | 2023-02-11 | 日商Ｊｆｅ鋼鐵股份有限公司 | Surface-treated steel sheet and manufacturing method thereof |
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