JP2010196100A - Black plated film and method for forming the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a black plated film which has equal or superior blackness to a conventional film formed by using a hexavalent chromium solution, though being formed by using a plating solution that does not contain a hexavalent chromium compound, is uniform, can be repeatedly produced with adequate reproducibility and is superior in film characteristics such as rust-preventive properties, and to provide a method for forming the same. <P>SOLUTION: This film-forming method comprises the steps of: degreasing and cleaning a member to be plated 10 (S10); washing the member with water to remove an alkaline degreasing and cleaning agent once (S11); electrolytically degreasing the member by using a direct-current power supply (S12); washing the member with water again (S13); immersing the member into hydrochloric acid and acid-cleaning the member to remove rust, an oxide film and the like of the member to be plated 10 (S14); washing the member with water (S15) to remove the acid cleaning agent depositing on the member to be plated 10; and immersing the member into a plating solution 11 (containing chromium chloride, cobalt carbonate, potassium hydroxide, sodium hydroxide and barium carbonate) in a plating tank and passing a direct current to the member for a fixed period of time to electrolytically plate the member (S16). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hexavalent chromium-free black plating film using a plating solution containing no hexavalent chromium and a method for forming the film, and in particular, a black plating film excellent in film characteristics such as rust prevention and the film. The present invention relates to a method of forming stably.

  The conventional black plating film with a hexavalent chromium compound-containing plating solution needs to remove the hexavalent chromium content of the plating solution component remaining on the plating film. However, extra cost is required, and complex parts to be plated are troublesome and inefficient. In addition, it is virtually impossible to confirm the complete removal, and the risk of residual hexavalent chromium cannot be wiped out. In addition, mist containing hexavalent chromium and washing wastewater are generated in production facilities, so measures to prevent environmental pollution that are detoxified and released are necessary, and these releases are also complete in the event of an emergency such as a disaster. However, there was a problem that the risk could not be avoided. Therefore, research and development on a black chromium plating film using a plating solution mainly composed of trivalent chromium not containing hexavalent chromium has been actively conducted.

Specifically, for example, in Patent Document 1, 200 to 600 g / l of chromium chloride (CrCl ₃ ) as a source of trivalent chromium, 10 g / l of barium carbonate as a catalyst, and 10 of ammonium formate as a complexing agent. Prepare a plating solution using ~ 30 g / l, use platinum-plated titanium as the anode, use a thin steel plate as the cathode, that is, the member to be plated, set the liquid temperature to 0 ° C to -4 ° C, voltage 15V, current value When electroplating was performed at 1.54 A to 2.09 A and an electrolysis time of 1.5 minutes to 5 minutes, a matte black film was obtained.

In Patent Document 2, a plating solution using 150 to 300 g / l of chromium chloride, 0 to 50 g / l of sodium sulfite, 0 to 100 g / l of potassium sulfite, and 10 to 20 g / l of potassium iodide is prepared. Then, using an insoluble anode as an anode, using a steel plate as a cathode, that is, a member to be plated, the liquid temperature was set to 30 ° C. to 50 ° C., the current density was ² to 50 A / dm ² , and electroplating was performed at an electrolysis time of 5 minutes. It is said that a uniform and dense matte black film was obtained.

Further, in Patent Document 3, chromium chloride is 200 g / dm ³ (0.75 mol / dm ³ ), ammonium chloride is 30 g / dm ³ (0.56 mol / dm ³ ), and oxalic acid is 3 g / dm ³ (0. 024 mol / dm ³ ), barium carbonate 5 g / dm ³ (0.025 mol / dm ³ ), boric acid 30 g / dm ³ (0.49 mol / dm ³ ), and barium fluoride 10 g / dm ³ (0.057 mol). / Dm ³ ) The used plating solution is prepared, a graphite electrode is used as the anode, a steel plate is used as the cathode, that is, a member to be plated, the temperature of the solution is −10 ° C. to 10 ° C., and electrolysis is performed at a current density of 33 A / dm ² . When plated, a black plating film having high blackness, uniformity, and good adhesion was obtained.

JP 2005-126769 A JP 2007-11826 Gazette Japanese Patent No. 3646805

  However, when the present inventors conducted a confirmation test, in the technique described in Patent Document 1 described above, the quality is unstable, and the black portion and the silver-white portion are unevenly plated, resulting in a uniform plating film. Some black films could not be produced, which was somewhat unstable. In the technique described in Patent Document 2, a black film is formed, but there is generation of sulfurous acid gas due to the composition of the plating solution, and the consumption of the components is severe, or the black film is also generated for the second and third times. It seems that there is a problem with the stability of the plating solution. Furthermore, in the technique described in Patent Document 3, although a uniform plating film was obtained, the blackness with a slightly grayish color tone could not be reproduced to the level of the film with the conventional hexavalent chromium solution. . As described above, the above-described conventional technique has a problem that a uniform black film cannot be obtained reliably and repeatedly.

  Therefore, the present invention has been made to solve such problems, and can be repeatedly processed with high blackness, uniformity and good reproducibility under a hexavalent chromium-free condition, and a film having antirust properties, etc. An object of the present invention is to provide a black plating film having excellent characteristics and a method for forming the film.

  The black plating film according to the invention of claim 1 comprises chromium metal and / or trivalent chromium oxide and / or trivalent chromium hydrate, cobalt metal and / or cobalt oxide and / or cobalt hydrate. Contains, and does not contain a hexavalent chromium compound.

  Here, “containing chromium metal and / or trivalent chromium oxide and / or trivalent chromium hydrate” means any one of chromium metal, trivalent chromium oxide and trivalent chromium hydrate. In the case of containing any two, it means that all three are contained, and similarly contains "cobalt metal and / or cobalt oxide and / or cobalt hydrate". The term "means" includes any one of cobalt metal, cobalt oxide, and cobalt hydrate, all two, and all three.

  According to a second aspect of the present invention, there is provided the black plating film according to the first aspect, wherein the chromium metal and / or the trivalent chromium oxide and / or the trivalent chromium hydrate is a total of 15% by weight to 85% by weight. The cobalt metal and / or cobalt oxide and / or cobalt hydrate is contained within a total range of 15% by weight to 85% by weight.

According to a third aspect of the present invention, there is provided a method for forming a black plating film, comprising subjecting a member to be plated to degreasing or degreasing and pretreatment for acid cleaning, etc. A method of forming a plating film, wherein the plating solution comprises chromium chloride in a saturated solution amount range of 150 g / l or more, more preferably in a range of 180 g / l or more saturated solution amount, potassium hydroxide and / or Sodium hydroxide in the range of 5 g / l to 100 g / l, more preferably in the range of 10 g / l to 50 g / l, and basic cobalt carbonate in the range of 3 g / l to 100 g / l, more preferably in the range of 8 g / to 100 g / l, respectively containing, temperature 0 ° C. to 60 ° C. of the plating solution, the conditions within a current density of 3A / dm ² ~40A / dm ² Is intended to electrolytic plating have.

  The method for forming a black plating film according to the invention of claim 4 is the structure of claim 3, wherein the plating solution further contains barium carbonate or barium hydroxide in the range of 1 g / l to 30 g / l, more preferably 3 g. / L to 10 g / l.

  The method for forming a black plating film according to the invention of claim 5 is the structure of claim 3 or claim 4, wherein the plating solution further contains manganese dioxide in a range of 30 g / l to 120 g / l, more preferably 50 g. / L to 80 g / l.

  The black plating film according to the invention of claim 1 comprises chromium metal and / or trivalent chromium oxide and / or trivalent chromium hydrate, cobalt metal and / or cobalt oxide and / or cobalt hydrate. Since it contains and does not contain a hexavalent chromium compound, a uniform black plating film excellent in blackness can be obtained repeatedly under conditions of hexavalent chromium free.

  That is, as a result of repeated experimental research on the method for forming a black plating film, the present inventors have carried out electroplating by adding a trivalent chromium compound and a cobalt compound to a plating solution, thereby providing chromium and cobalt. The present invention has been completed based on this finding, and it was found that this plating film exhibits a matte black color.

  In this way, under black hexavalent chromium-free conditions, the blackness is high and can be repeatedly produced with high uniformity and reproducibility, resulting in a black plating film excellent in film properties such as rust prevention.

  The black plating film according to the invention of claim 2 contains chromium metal and / or trivalent chromium oxide and / or trivalent chromium hydrate in a total amount of 15 wt% to 85 wt%, cobalt metal And / or cobalt oxide and / or cobalt hydrate in a total amount within the range of 15 wt% to 85 wt%, a more uniform black plating film with excellent blackness due to chromium and cobalt is obtained. You can definitely get it.

As for the method for forming a black plating film according to the invention of claim 3, the present inventors have conducted experimental research, and as a result, have made chromium chloride and / or water within a range of 150 g / l or more of saturated solution. The temperature of the plating solution is 0 ° C. using a plating solution containing sodium oxide within a total range of 5 g / l to 100 g / l and basic cobalt carbonate within a range of 3 g / l to 100 g / l. A uniform plating film containing chromium and cobalt can be stably obtained by electrolytic plating under the conditions of ˜60 ° C. and current density within the range of 3 A / dm ^{2 to} 40 A / dm ^2. The present invention has been completed on the basis of the finding of matte black.

  Note that chromium chloride is within a range of 180 g / l or more of saturated solution, potassium hydroxide and / or sodium hydroxide is within a total range of 10 g / l to 50 g / l, and basic cobalt carbonate is 8 g / l to By using a plating solution contained within the range of 100 g / l, a more preferable result can be obtained because a black plating film having excellent and uniform blackness can be obtained more reliably and stably.

  In this way, under the condition of hexavalent chromium free, a method for forming a black plating film that can be stably and repeatedly produced with high blackness, uniformity, and reproducibility, and excellent in film properties such as rust prevention, Become.

  In the method for forming a black plating film according to the invention of claim 4, since the plating solution further contains barium carbonate or barium hydroxide in the range of 1 g / l to 30 g / l, the conductivity of the plating solution is improved. And in addition to the effect of the invention which concerns on Claim 3, a black plating film can be formed more reliably and more reliably. In addition, since the plating solution containing barium carbonate or barium hydroxide in the range of 3 g / l to 10 g / l can be used, a black plating film having more uniform and excellent blackness can be obtained more reliably. preferable.

  In the method for forming a black plating film according to the invention of claim 5, since the plating solution further contains manganese dioxide within the range of 30 g / l to 120 g / l, the invention according to claim 3 or claim 4 is used. In addition to the effect, it is possible to repeatedly produce a black plating film with more excellent blackness. In addition, it is more preferable to use a plating solution containing manganese dioxide in the range of 50 g / l to 80 g / l because a black plating film having more uniform and excellent blackness can be obtained more reliably.

FIG. 1 is a flowchart showing an outline of a black plating film forming method according to an embodiment of the present invention. FIG. 2 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution according to Example 1. 3 is a photograph showing the surface of a plating film obtained by electrolytic plating using the plating solution according to Example 2. FIG. FIG. 4 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution according to Example 3. FIG. 5 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution according to Example 4. FIG. 6 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution according to Example 5. FIG. 7 is a photograph showing the surface of a plating film obtained by electrolytic plating using the plating solution of Comparative Example 1. FIG. 8 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution of Comparative Example 2. FIG. 9 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution of Comparative Example 3.

  Hereinafter, embodiments of the present invention will be described. First, a method for forming a black plating film according to an embodiment of the present invention will be described with reference to FIG. FIG. 1 is a flowchart showing an outline of a black plating film forming method according to an embodiment of the present invention.

  As shown in FIG. 1, first, a member to be plated 10 to be coated with a black plating film is immersed in an alkaline degreasing cleaner and degreased to remove oil and dirt attached to the member to be plated 10 ( Step S10). Subsequently, the alkaline degreasing cleaner adhering to the member to be plated 10 is removed by washing with water (step S11), dipped in the alkaline degreasing cleaner again, electrolytically degreased using a DC power supply device, Oil and dirt adhering to the plating member 10 are further removed (step S12).

  Next, after washing again with water (step S13) and removing the alkaline degreasing cleaner adhering to the member to be plated 10, it is immersed in hydrochloric acid and washed with acid to remove the rust, oxide film, etc. of the member to be plated 10. After performing (Step S14), washing with water (Step S15) and removing the acid cleaning agent adhering to the member to be plated 10, the plating solution 11 (chromium chloride, cobalt carbonate, potassium hydroxide, sodium hydroxide in the plating tank) Then, it is immersed in (containing barium carbonate) and a direct current is allowed to flow for a certain period of time to perform electroplating (step S16).

  When the electroplating is completed, the plated member 12 is removed from the plating tank, washed with water (step S17), and further rinsed with hot water (step S18) to remove the attached plating solution 11. And the plated member 12 is dried using a warm air generator (step S19), and the moisture adhering to the plated member 11 is removed. Thereby, the black plating product 13 is completed.

  Next, a specific composition of the plating solution according to the present embodiment will be described in detail. As a formulation of Example 1, chromium chloride hexahydrate 220 g / l, potassium hydroxide 10 g / l, sodium hydroxide 10 g / l, manganese dioxide 80 g / l, barium carbonate 3 g / l, basic cobalt carbonate 8 g / l A plating solution was prepared by dissolving in pure water at a concentration of 5%. In addition, the composition of Example 2 was pure at concentrations of chromium chloride hexahydrate 220 g / l, potassium hydroxide 10 g / l, sodium hydroxide 10 g / l, barium carbonate 3 g / l, basic cobalt carbonate 8 g / l. A plating solution was prepared by dissolving in water.

  Further, the composition of Example 3 was as follows: chromium chloride hexahydrate 220 g / l, potassium hydroxide 10 g / l, sodium hydroxide 10 g / l, manganese dioxide 60 g / l, barium carbonate 3 g / l, basic cobalt carbonate 6 g / L and oxalic acid at a concentration of 50 g / l were dissolved in pure water to prepare a plating solution.

  Further, the composition of Example 4 was as follows: chromium chloride hexahydrate 160 g / l, potassium hydroxide 10 g / l, sodium hydroxide 10 g / l, manganese dioxide 80 g / l, barium carbonate 3 g / l, basic cobalt carbonate 8 g A plating solution was prepared by dissolving in pure water at a concentration of / l. Further, the composition of Example 5 was as follows: chromium chloride hexahydrate 150 g / l, potassium hydroxide 10 g / l, sodium hydroxide 10 g / l, manganese dioxide 80 g / l, barium carbonate 3 g / l, basic cobalt carbonate 8 g A plating solution was prepared by dissolving in pure water at a concentration of / l.

  For comparison, a plating solution having the composition of Comparative Examples 1 to 3 was also prepared and electroplated. Comparative Example 1 is a blending example of the chromium chloride concentration limit confirmation experiment, chromium chloride hexahydrate 140 g / l, potassium hydroxide 10 g / l, sodium hydroxide 10 g / l, manganese dioxide 80 g / l, barium carbonate 3 g / l. A plating solution was prepared by dissolving in pure water at a concentration of 8 g / l of basic cobalt carbonate.

  Further, Comparative Example 2 was prepared by dissolving in pure water at a concentration of 220 g / l of chromium chloride hexahydrate, 10 g / l of potassium hydroxide, and 10 g / l of sodium hydroxide as a composition for the basic composition verification experiment for forming a black film. A liquid was prepared. Further, as a composition of Comparative Example 3, which is a black film formation basic composition verification experiment, a plating solution was prepared by dissolving in pure water at a concentration of 220 g / l of chromium chloride hexahydrate and 8 g / l of basic cobalt carbonate. . About the mixing | blending of Example 1- Example 5 and Comparative Example 1- Comparative Example 3, it shows in the upper stage of Table 1. FIG.

  As shown in the upper part of Table 1, the formulation of Example 2 is obtained by removing manganese dioxide from the formulation of Example 1, and the formulation of Example 3 is a basic carbonate with respect to the formulation of Example 1. While reducing the amount of cobalt and manganese dioxide, oxalic acid is added as a reducing agent. Further, the formulation of Example 4 is obtained by reducing the amount of chromium chloride hexahydrate to 160 g / l with respect to the formulation of Example 1, and the formulation of Example 5 is the amount of chromium chloride hexahydrate. Is further reduced to 150 g / l.

  Further, the blend of Comparative Example 1 is obtained by further reducing the amount of chromium chloride hexahydrate to 140 g / l with respect to the blend of Example 1. Further, the formulation of Comparative Example 2 was obtained by removing the basic cobalt carbonate, manganese dioxide, and barium carbonate from the formulation of Example 1, and the formulation of Comparative Example 3 was the same as that of Example 1 with potassium hydroxide and water. It excludes sodium oxide, manganese dioxide and barium carbonate, and consists only of chromium chloride hexahydrate and basic cobalt carbonate.

Using these plating solutions as a plating bath, using a mild steel plate (50 mm × 67 mm × 0.3 mm) as the member to be plated 10, a direct current is passed through the plating solution at a current density of 20 A / dm ² and electrolytic plating is performed for 10 minutes. went. Graphite carbon was used as the anode material. Moreover, although the temperature of the plating solution was measured, the temperature of the plating solution was kept within a range of 10 ° C. to 30 ° C. during the electroplating for 10 minutes. The obtained plating film is shown in FIGS.

  FIG. 2 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution according to Example 1. 3 is a photograph showing the surface of a plating film obtained by electrolytic plating using the plating solution according to Example 2. FIG. FIG. 4 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution according to Example 3. FIG. 5 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution according to Example 4. FIG. 6 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution according to Example 5. FIG. 7 is a photograph showing the surface of a plating film obtained by electrolytic plating using the plating solution of Comparative Example 1. FIG. 8 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution of Comparative Example 2. FIG. 9 is a photograph showing the surface of the plating film obtained by electrolytic plating using the plating solution of Comparative Example 3.

  The evaluation of these plating films is summarized in the lower part of Table 1. As shown in FIGS. 2, 3, and 4, the plating films obtained by electrolytic plating using the plating solutions according to Examples 1 to 3 are both excellent in blackness and uniformity. It is evaluated as ◎. In addition, when these plating solutions were repeatedly used and electrolytic plating was performed according to the flowchart of FIG. 1, even when the plating solution was used 10 times, the blackness and uniformity of the resulting plating film did not change.

  In addition, as shown in FIGS. 5 and 6, the plating films obtained by electrolytic plating using the plating solutions according to Example 4 and Example 5 are all reasonable in blackness and uniformity. It is an evaluation of ○. When the plating films according to Example 4 and Example 5 are compared with the plating film according to Example 1, it is found that the concentration of chromium chloride hexahydrate is more preferably 180 g / l or more. When the plating solution according to Example 4 and Example 5 was repeatedly used and electrolytic plating was performed according to the flowchart of FIG. 1, the blackness / uniformity of the obtained plating film was obtained even when the plating solution was used 10 times. It did not change.

  On the other hand, as shown in FIG. 7, the plating film obtained by electroplating using the plating solution of Comparative Example 1 does not adhere to the whole and has a blackness but is not uniform. It can be seen that the amount of chromium chloride hexahydrate is insufficient. As shown in FIG. 8, the plating film obtained by electrolytic plating using the plating solution of Comparative Example 2 is brown and has unevenness. Furthermore, as shown in FIG. 9, the plating film obtained by electroplating using the plating solution of Comparative Example 3 is still brown and uneven, and the blackness and uniformity are inferior. Yes.

  Moreover, in order to evaluate rust prevention property, the salt spray test was implemented about the plating film obtained by electroplating using the plating solution which concerns on Example 1. FIG. The test method was carried out in accordance with 7.2.1 “Neutral salt spray test” of JIS-Z-2371 salt spray test method. As a result, it was clarified that no rust was generated at all after 12 hours and the plating film was excellent in adhesion and rust prevention.

  In this way, in the black plating film and the method for forming the same according to the present embodiment, it can be repeatedly produced with high blackness, uniformity and good reproducibility under hexavalent chromium-free conditions, rust prevention, etc. A black plating film having excellent film properties can be obtained.

  In the present embodiment, only the formulations according to Examples 1 to 5 containing barium carbonate in the plating solution have been described. However, even in a formulation that does not use barium carbonate at all, the blackness is similarly high and uniform black. A plating film can be obtained.

  In the present embodiment, the case where 10 g of potassium hydroxide and sodium hydroxide are used per liter has been described. However, it is not necessary to use the same amount of potassium hydroxide and sodium hydroxide. Only one of potassium oxide and sodium hydroxide may be used.

  In practicing the present invention, the composition, composition, composition, component, shape, quantity, material, size, manufacturing method, etc. of other parts of the black plating film, and other steps of the black plating film manufacturing method are also included. The present invention is not limited to this embodiment and each example.

  In addition, since the numerical value quoted in the embodiment of the present invention does not indicate a critical value but indicates a preferable value suitable for implementation, even if the numerical value is slightly changed, the implementation is denied. is not.

Claims (5)

Chromium metal and / or trivalent chromium oxide and / or trivalent chromium hydrate,
Containing cobalt metal and / or cobalt oxide and / or cobalt hydrate,
A black plating film characterized by not containing a hexavalent chromium compound.   Containing the chromium metal and / or trivalent chromium oxide and / or trivalent chromium hydrate in a total amount of 15 to 85% by weight, and the cobalt metal and / or cobalt oxide and / or cobalt 2. The black plating film according to claim 1, comprising a hydrate in a range of 15 wt% to 85 wt% in total. A method of forming a black plating film on the member to be plated by immersing the member to be plated in a plating solution and performing electrolytic plating,
The plating solution includes chromium chloride within a range of 150 g / l or more of saturated solution, potassium hydroxide and / or sodium hydroxide within a total range of 5 g / l to 100 g / l, and 3 g of basic cobalt carbonate. Within the range of / l to 100 g / l,
A method for forming a black plating film, characterized in that electroplating is carried out under conditions where the temperature of the plating solution is in the range of 0 to 60 ° C. and the current density is in the range of 3 A / dm ^{2 to} 40 A / dm ² .   The method for forming a black plating film according to claim 3, wherein the plating solution further contains barium carbonate or barium hydroxide in a range of 1 g / l to 30 g / l.   The method for forming a black plating film according to claim 3 or 4, wherein the plating solution further contains manganese dioxide in a range of 30 g / l to 120 g / l.