JP3074762B2 - Tin-nickel alloy electroplating solution composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tin-nickel alloy electroplating solution composition for obtaining a film which develops a color from gray to black and has no cracks or the like.

[0002]

2. Description of the Related Art Conventionally, as a method of producing a black-based film from gray by electroplating, nickel-zinc alloy plating, nickel-tin-copper alloy plating, rhodium plating,
Ruthenium plating and the like are known.

[0003]

The plating film obtained by the conventional method can provide a desired coloration, but cannot be used in a thick film due to high stress. Therefore, it is used in the form of a thin film, but if the film is made thin, there is a problem that the wear resistance and corrosion resistance are reduced. Therefore, a coating film or the like is formed on the surface of the obtained plating film. It is the current situation.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above-mentioned problems, and has as its object to achieve good color development from gray to black, and to prevent the occurrence of cracks or the like in a film. Providing a tin-nickel alloy electroplating solution composition, comprising: a tin salt; a nickel salt;
The gist of the present invention is a tin-nickel alloy electroplating solution composition comprising at least a fluoride compound or a sulfamate salt and an aromatic aldehyde.

[0005] The composition of the tin-nickel alloy plating solution is composed of a tin salt as a plating film forming raw material, a nickel salt, and a complex forming agent, and an acidic bath and an alkaline bath are used. Specific examples of the acidic bath include tin salts such as stannous chloride and stannous sulfate, and nickel salts include nickel chloride and nickel sulfate.
Examples of the complexing agent include a fluoride compound such as ammonium bifluoride and a sulfamate such as sodium sulfamate and potassium sulfamate. The amount of tin salt and nickel salt used is 1-2
00 g / l is preferable, and the amount of the complexing agent is 0.1 to the total amount of the liquid.
5-300 g / l is preferred.

[0006] Aromatic aldehydes are used not only as a coloring agent but also to prevent the occurrence of cracks and the like in the film. Specific examples include salicylaldehyde, P-anisaldehyde, hydroxybenzaldehyde, phenyl Acetaldehyde, isophthalaldehyde, 2-pyridinecarbaldehyde and the like can be mentioned. Their use amount is preferably 0.1 to 20 g / l based on the total amount of the liquid.

The plating solution of the present invention contains at least the above components. For example, aqueous ammonia or an ammonium salt may be added to reduce internal stress, or other substances may be added as necessary.

In the case of plating using the above-mentioned plating solution, the plating solution is heated, and preferably the temperature of the solution is always 40 to
70 ° C (The reason for keeping the liquid temperature at 40 to 70 ° C is
If the temperature is lower than 70 ° C., the tin salt and the nickel salt may be crystallized. If the temperature exceeds 70 ° C., divalent tin is oxidized and becomes tetravalent, and plating may not be possible.) By performing the treatment at a cathode current density of about 0.1 to 5 A / dm ^2, a tin-nickel alloy plating film colored from gray to black can be obtained.

[0009]

The aromatic aldehyde, which is a color forming agent in the present invention, has a reducing property. These actions promote the dissolution of the anode and suppress the generation of reducing hydrogen by homogenizing the anode. Is reduced, and carbon deposition and complex formation in the film due to decomposition of the carbonyl group
With a fluoride compound or a sulfamate used as an agent
It is presumed that the color development becomes better due to the synergistic effect of .

[0010]

EXAMPLES Table 1 shows the plating solution compositions and processing conditions of Examples 1 and 2 and Comparative Example 1. The test pieces used for plating were:
It was 5 cm square and 0.3 mm thick, and was subjected to pretreatment of generally used immersion degreasing, cathodic electrolytic degreasing, and acid plating with 5% hydrochloric acid, followed by plating.

[0011]

[Table 1]

Comparative Example 2 Kosaku Co., Ltd. plating solution (Stainy-Like, Black)
Use, temperature 40 ° C, cathode current density 0.5A / dm2
And treated for 10 minutes as Comparative Example 2. The test piece
And the pretreatment of the test piece was the same as in Examples 1 and 2 and Comparative Example 1.
did.

Comparative Example 3 Plating Solution of Kisai Co., Ltd. (Stanaroy, Neo Black)
At a temperature of 40 ° C. and a cathode current density of 0.5 A / dm 2
Was treated for 20 minutes as Comparative Example 3. In addition, test
The pretreatment of the test piece and the test piece is the same as in Examples 1, 2 and Comparative Example 1.
And

Examples 1 and 2 and Comparative Examples 1 to 3
Color, abrasion resistance, surface condition, film
Table 2 shows the results of the evaluation of the thickness and the coloring property. In addition, color
About Suga Test Machine Co., Ltd. SM Color Computer
Using SM-5-1S-2B, L
The evaluation was performed by value. As for the wear resistance, Ji
It was carried out based on sH8682.

[0015]

[Table 2]

[0016]

The skin obtained by using the plating solution of the present invention
The film is thicker than the film obtained by the comparative example.
Nevertheless, the color tone and coloration are good and the wear resistance
Excellent, uniform surface condition, well-balanced
It was.

[0017]

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C25D 1/00-7/12

Claims (1)

(57) [Claims] 1. A tin compound , a nickel salt and a fluoride compound.
A tin-nickel alloy electroplating solution composition comprising at least a substance or a sulfamate and an aromatic aldehyde.