KR20220099367A - Additive for electrolytic plating solution and high current electrolytic nickel-plating solution comprising the same - Google Patents

Abstract

The present invention relates to an electroplating solution additive and an electroplating solution containing the electroplating solution additive, comprising a specific first brightening agent, a second brightening agent, a leveler, and a surfactant. An objective of the present invention is to provide the electroplating solution additive that can be universally applied to electrical nickel plating solutions and form a uniform plating film while shortening a nickel plating time.

Description

ADDITIVE FOR ELECTROLYTIC PLATING SOLUTION AND HIGH CURRENT ELECTROLYTIC NICKEL-PLATING SOLUTION COMPRISING THE SAME

The present invention relates to an additive added to an electroplating solution and an electronickel plating solution capable of high-speed plating under high current conditions by including the additive.

In general, metal plating on iron has been performed a lot for rust prevention, decoration, and the like. For example, electrical nickel plating has been developed to secure corrosion resistance and good appearance of a steel sheet, which is widely applied in fields such as home appliances, automobiles, and construction.

In order to continuously and efficiently perform nickel plating on the steel sheet (improving productivity), the quality of the plating surface obtained must be uniform, and plating is required within a relatively short time. Here, in order to perform nickel plating within a short period of time, a high current must be applied, which in the prior art has a problem in that a burnt nickel plating film is formed. That is, in order to perform nickel plating within a short time, a current density of 50 ASD or more must be applied. Since the allowable current density of a conventional electrolytic nickel plating solution is typically 0.5 to 10 ASD, when plating is performed using this, the surface A burnt nickel plating film is formed.

In order to solve the above problems, various additives to be added to the electrolytic nickel plating solution have been proposed. However, although it was possible to shorten the nickel plating time through the above additives, the plating film was not secured to a required level (plating film surface uniformity was lowered) or the compatibility with the conventional nickel plating solution was poor, so there was a limitation in application.

Accordingly, there is a need for a technique that can be universally applied to a conventional electronic nickel plating solution and can form a uniform plating film even when nickel plating is performed within a short time.

Korean Patent Publication No. 2008-0061458

An object of the present invention is to provide an electroplating solution additive that can be universally applied to an electroplating solution and can form a uniform plating film while shortening the nickel plating time.

Another object of the present invention is to provide an electroplating solution containing the electroplating solution additive.

In order to achieve the above object, the present invention provides a first brightening agent comprising an alkyne-based complex compound; a second brightener comprising a sulfur-containing compound; a leveler comprising a cation-substituted nitrogen-containing compound; and an electroplating solution additive comprising a surfactant.

The alkyne-based complex compound is N,N-diethyl-2-propyne-1-amine (N,N-Diethyl-2-propyne-1-amine), sodium propargyl sulfonate (Sodium propargyl sulfonate), Pargyl alcohol ethoxylate, Propargyl alcohol propoxylate, Propargyl alcohol, 1,1-dimethyl-2-propyn-1-amine (1 ,1-Dimethyl-2-propyne-1-amine), 3-hexyne-2,5-diol (3-Hexyne-2,5-diol), 2-butyne-1,4-diol (2-Butyne-1) ,4-diol), 2-butyne-1,4-diol propoxylate (2-Butyne-1,4-diol propoxylate), 2-butyne-1,4-diol ethoxylate (2-Butyne-1, 4-diol ethoxylate), butyne-1,4-diol-glycerol-ether and propargyl-3-sulfopropyl ether sodium salt) may be at least one selected from the group consisting of.

The sulfur-containing compound includes sodium vinyl sulfonate, sodium allylsulfonate, dibenzenesulfonamide, sodium p-toluenesulfonate, sodium benzene-1, 3-disulfonate (Sodium benzene-1,3-disulfonate), sodium benzenesulfonate (Sodium benzenesulfonate), N-(3-sulfopropyl)-saccharin sodium salt (N-(3-sulfopropyl)-saccharin sodium salt) , 1,2-benzisothiazolion-3-one-1,1-dioxide (1,2-Benzisothiazolin-3-one-1,1-dioxide) and saccharin sodium salt from the group consisting of It may be one or more selected.

The nitrogen-containing compound is carboxyethylisothiuronium betaine, 3-Pyridinium propyl sulfonate, 1-(2-hydroxy-3-sulfopropyl)-pyridinium beta Phosphorus (1-(2-hydroxy-3-sulfopropyl)-pyridinium betaine), 1-(3-propyl sulfonic acid-1)-2-vinyl pyridinium betaine (1-(3-propyl sulfonic acid-1)- 2-vinyl pyridinium betaine) may be at least one selected from the group consisting of.

The surfactant may be an anionic surfactant.

The anionic surfactant is one selected from the group consisting of dihexyl sodium sulfosuccinate, sodium 2-ethylhexyl sulfate and sodium lauryl sulfate may be more than

A mixing ratio of the first brightener, the second brightener, the leveler, and the surfactant may be in a weight ratio of 1 to 5:0.1 to 1:0.2 to 1:5 to 30.

On the other hand, the present invention is a nickel ion source; halide ion source; and an electroplating solution comprising the electroplating solution additive.

The concentration of the electroplating solution additive may be 5 to 20 g per 1 liter of the electroplating solution.

Since the electroplating solution additive according to the present invention contains a specific first brightener, a second brightener, a leveler, and a surfactant, when nickel plating is performed with an electroplating solution containing the same, good and uniform appearance within a relatively short time A nickel plating film showing (surface) can be formed. In addition, since the electroplating solution additive according to the present invention has excellent compatibility, it can be universally applied to a known electroplating solution.

Accordingly, the present invention can increase the efficiency of the nickel plating process for the steel sheet, thereby contributing to improving the productivity of home appliances, automobiles (electric vehicles), construction, and the like.

1 is an image for explaining Experimental Example 1 of the present invention.
2 is an image for explaining Experimental Example 2 of the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor should properly understand the concept of the term in order to best describe his invention. Based on the principle that it can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

The present invention relates to an electroplating solution additive capable of forming a plating film having a good appearance that is not burned or burned even when plating is performed under high current conditions to shorten the electroplating time, and an electroplating solution comprising the same, This will be described in detail as follows.

The electroplating solution additive according to the present invention comprises a first brightener, a second brightener, a leveler and a surfactant.

The first brightening agent included in the electroplating solution additive according to the present invention includes an alkyne-based complex compound. The alkyne-based complex compound acts as an electron donor in the additive, and thus the first brightener may serve to form a uniform and high-gloss plating film.

The alkyne-based complex compound may not be particularly limited as long as it is a compound having a carbon triple bond in a molecule. Specifically, the alkyne-based complex compound is N,N-diethyl-2-propyne-1-amine in consideration of the physical properties of the plating film and compatibility of additives. , Sodium propargyl sulfonate, Propargyl alcohol ethoxylate, Propargyl alcohol propoxylate, Propargyl alcohol, 1, 1-dimethyl-2-propyne-1-amine (1,1-Dimethyl-2-propyne-1-amine), 3-hexyne-2,5-diol (3-Hexyne-2,5-diol), 2 -Butyne-1,4-diol (2-Butyne-1,4-diol), 2-butyne-1,4-diol propoxylate (2-Butyne-1,4-diol propoxylate), 2-butyne-1 ,4-diol ethoxylate (2-Butyne-1,4-diol ethoxylate), butyne-1,4-diol-glycerol-ether (Butyne-1,4-diol-glycerol-ether) and propargyl-3 - It may be at least one selected from the group consisting of sulfopropyl ether sodium salt (propargyl-3-sulfopropyl ether sodium salt).

The second brightener included in the electroplating solution additive according to the present invention includes a sulfur-containing compound. The sulfur-containing compound acts to reduce internal stress during the formation of the plating film, and thus the second brightener may serve to form a plating film having a uniform structure.

The sulfur-containing compound is not particularly limited, but considering the properties of the plating film and compatibility of additives, sodium vinyl sulfonate, sodium allylsulfonate, dibenzenesulfonamide, Sodium p-toluenesulfonate, sodium benzene-1,3-disulfonate, sodium benzenesulfonate, N-(3-sulfopropyl) )-Saccharin sodium salt (N-(3-sulfopropyl)-saccharin sodium salt), 1,2-Benzisothiazolin-3-one-1,1-dioxide (1,2-Benzisothiazolin-3-one-1 ,1-dioxide) and may be at least one selected from the group consisting of saccharin sodium salt.

The leveler included in the electroplating solution additive according to the present invention includes a cation-substituted nitrogen-containing compound. The cation-substituted nitrogen-containing compound acts to suppress excessive precipitation of metals when a high current is applied during plating, whereby the leveler may serve to form a smooth and glossy plating film.

The cation-substituted nitrogen-containing compound is not particularly limited, but considering the smoothness of the plating film and compatibility of additives, carboxyethylisothiuronium betaine, 3-pyridinium propyl sulfonate (3-Pyridinium propyl sulfonate), 1-(2-hydroxy-3-sulfopropyl)-pyridinium betaine (1-(2-hydroxy-3-sulfopropyl)-pyridinium betaine) and 1-(3-propyl sulfonic acid-1) It may be at least one selected from the group consisting of -2-vinyl pyridinium betaine (1-(3-propyl sulfonic acid-1)-2-vinyl pyridinium betaine).

The surfactant included in the electroplating solution additive according to the present invention may help the release of hydrogen generated from the surface of the anode during plating, and may serve to form a smooth plating film. The surfactant may not be particularly limited as long as it is an anionic surfactant.

The anionic surfactant is not particularly limited, but considering the smoothness of the plating film and compatibility of additives, dihexyl sodium sulfosuccinate, sodium 2-ethylhexyl sulfate And it may be at least one selected from the group consisting of sodium lauryl sulfate.

The mixing ratio of the first brightener, the second brightener, the leveler and the surfactant included in the electroplating solution additive according to the present invention is not particularly limited, but the formation of a uniform and smooth plating structure, the formation of a glossy plating film, and compatibility Considering the like, it may be a weight ratio of 1 to 5:0.1 to 1:0.2 to 1:5 to 30, and specifically, a weight ratio of 1:0.3 to 0.5:0.5 to 0.6:7.5 to 24.

The present invention provides an electroplating solution comprising the electroplating solution additive described above. Specifically, the electroplating solution according to the present invention may include a nickel ion source, a halide ion source, and the above-described electroplating solution additive.

The nickel ion source included in the electronic nickel plating solution according to the present invention serves to supply nickel ions for forming the nickel plating film. Specifically, the nickel ion source may be at least one selected from the group consisting of nickel sulfate, nickel sulfamate, nickel carbonate, and nickel acetate.

The concentration of the nickel ion source is not particularly limited, but in consideration of the smooth formation of the nickel plating film, the nickel ion source may be included in an amount of 200 to 400 g, specifically, 250 to 350 g per 1 liter of the nickel plating solution.

The halide ion source included in the electrolytic nickel plating solution according to the present invention serves to dissolution the anode through the halide ion source. Specifically, the halide ion source may be at least one selected from the group consisting of nickel chloride and nickel bromide.

The concentration of the halide ion source is not particularly limited, but considering the smooth formation of the nickel plating film, the halide ion source may be included in an amount of 10 to 80 g, specifically, 20 to 60 g per 1 liter of the nickel plating solution.

The electroplating solution additive included in the electroplating solution according to the present invention serves to form a uniform, smooth, and glossy nickel plating film. A detailed description of the electroplating solution additive is the same as described above, and thus will be omitted.

The concentration of the electroplating solution additive is not particularly limited, but considering the smooth formation of the nickel plating layer, the electroplating solution additive may be included in an amount of 5 to 20 g, specifically, 8 to 15 g per 1 liter of the electroplating solution.

Such an electronickel plating solution according to the present invention may further include additives such as a commonly known pH buffer, a surface tension control agent, a pH control agent, and the like.

The electro nickel plating solution according to the present invention can form a nickel plating film that is not burned or burned even when a high current (50 ASD or more) as well as a low current (specifically, 0.5 to 10 ASD) is applied during plating. That is, as the electroplating solution according to the present invention includes the above-described electroplating solution additive, due to the interaction between each component in the additive, a wide range of current densities (specifically 0.5 to 70 ASD, or 40 to 70 ASD, or Even if 50 to 70 ASD) is applied, it is possible to form a nickel plating film having a good appearance (surface).

Therefore, when the plating process is performed with the electronic nickel plating solution according to the present invention, the plating process time can be shortened by applying a high current, so that the plating process efficiency (productivity improvement) can be improved.

On the other hand, when the plating process is performed with the electronic nickel plating solution according to the present invention, the plating process temperature may be 45 to 60 °C. As the plating process temperature is within the above range, current uniformity is ensured while preventing easy decomposition of components in the solution, thereby forming a uniform nickel plating film.

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are intended to illustrate the present invention, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention, and the scope of the present invention is not limited thereto.

[ Example 1 and 2]

Electroplating solution additives having the composition shown in Table 1 were prepared.

ingredient Example 1 Example 2 first polish Butyne-1,4-diol-glycerol-ether 10g/L 10g/L 2-Butyne-1,4-diol ethoxylate 10g/L 10g/L propargyl-3-sulfopropyl ether sodium salt 20g/L 10g/L second varnish Sodium vinyl sulfonate 20g/L 10g/L leveler 3-Pyridinium propyl sulfonate 10g/L 10g/L 1-(3-propyl sulfonic acid-1)-2-vinyl pyridinium betaine 10g/L - Carboxyethylisothiuronium betaine - 10g/L Surfactants Dihexyl sodium sulfosuccinate 300g/L 500g/L Sodium lauryl sulfate - 200g/L

[ comparative example 1 to 5]

Electroplating solution additives having the composition shown in Table 2 were prepared.

ingredient Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 first polish Butyne-1,4-diol-glycerol-ether - - - - 10g/L 2-Butyne-1,4-diol ethoxylate - - 10g/L 10g/L 10g/L propargyl-3-sulfopropyl ether sodium salt - - 10g/L 10g/L 10g/L 2-Butyne-1,4-diol - 10g/L - - - Propargyl alcohol ethoxylate, - - 10g/L 10g/L - second varnish Sodium vinyl sulfonate - - - 10g/L 10g/L leveler 3-Pyridinium propyl sulfonate - - - - 10g/L 1-(3-propyl sulfonic acid-1)-2-vinyl pyridinium betaine - - - - 10g/L Carboxyethylisothiuronium betaine - - - - - Surfactants Dihexyl sodium sulfosuccinate - - - - - Sodium lauryl sulfate - - - - -

[Preparation Examples 1 and 2 and Comparative Preparation Examples 1 to 5]

To 300 g/L of nickel sulfate, 40 g/L of nickel chloride, and 40 g/L of boric acid, 10 g/L of the additives prepared in Examples 1 and 2 and Comparative Examples 1 to 5 were each added to prepare an electrical nickel plating solution, respectively. (Comparative Preparation Example 1 means that no additives are added).

[ Experimental example One]

The electronic nickel plating solutions prepared in Preparation Examples 1 and 2 and Comparative Preparation Examples 1 to 5, respectively, were plated on a substrate (steel plate) under the conditions of Table 3 to form a plating film, and the formed plating film was visually confirmed.

Plating conditions Current density (ASD) 50 Temperature (℃) 50 Acidity (pH) 4.5 time (min) 5 Target plating thickness (㎛) 3-5

1 shows the appearance of the formed plating film, it was confirmed that Examples 1 and 2 in which plating was performed with the electroplating solution additive to which the electroplating solution additive according to the present invention was applied had good appearance. On the other hand, in Comparative Example 1, in which plating was performed with an electrical nickel plating solution to which no additives were applied, and Comparative Examples 2 to 4, in which plating was performed with an electrical nickel plating solution to which only a brightener was applied, it was confirmed that the entire surface of the plating film or the outer surface of the plating film was burnt. In addition, in Comparative Example 5, which was plated with an electronic nickel plating solution to which only a brightener and a leveler were applied, it was confirmed that burning occurred on the outer surface of the plating film.

[ Experimental example 2]

The electronic nickel plating solution prepared in Preparation Example 2 was adjusted to current densities of 10 ASD and 50 ASD (other conditions are the same as in Table 3) to form a plating film, and the formed plating film structure was confirmed with a scanning electron microscope.

2 is an image confirming the formed plating film structure, and as the electroplating solution additive according to the present invention was applied, it was confirmed that a uniform plating structure was formed not only when the current density was 10 ASD but also at a high current of 50 ASD.

Claims (9)

A first brightener comprising an alkyne-based complex compound;
a second brightener comprising a sulfur-containing compound;
a leveler comprising a cation-substituted nitrogen-containing compound; and
An electroplating solution additive comprising a surfactant. The method of claim 1,
The alkyne-based complex compound is N,N-diethyl-2-propyne-1-amine, sodium propargyl sulfonate, pro Pargyl alcohol ethoxylate, Propargyl alcohol propoxylate, Propargyl alcohol, 1,1-dimethyl-2-propyn-1-amine (1 ,1-Dimethyl-2-propyne-1-amine), 3-hexyne-2,5-diol (3-Hexyne-2,5-diol), 2-butyne-1,4-diol (2-Butyne-1) ,4-diol), 2-butyne-1,4-diol propoxylate (2-Butyne-1,4-diol propoxylate), 2-butyne-1,4-diol ethoxylate (2-Butyne-1, 4-diol ethoxylate), butyne-1,4-diol-glycerol-ether and propargyl-3-sulfopropyl ether sodium salt) of at least one selected from the group consisting of an electroplating solution additive. According to claim 1,
The sulfur-containing compound is sodium vinyl sulfonate, sodium allylsulfonate, dibenzenesulfonamide, sodium p-toluenesulfonate, sodium benzene-1, 3-disulfonate (Sodium benzene-1,3-disulfonate), sodium benzenesulfonate (Sodium benzenesulfonate), N-(3-sulfopropyl)-saccharin sodium salt (N-(3-sulfopropyl)-saccharin sodium salt) , 1,2-benzisothiazolion-3-one-1,1-dioxide (1,2-Benzisothiazolin-3-one-1,1-dioxide) and saccharin sodium salt from the group consisting of An electroplating solution additive that is at least one selected. The method of claim 1,
The nitrogen-containing compound is carboxyethylisothiuronium betaine, 3-Pyridinium propyl sulfonate, 1-(2-hydroxy-3-sulfopropyl)-pyridinium beta Phosphorus (1-(2-hydroxy-3-sulfopropyl)-pyridinium betaine) and 1-(3-propyl sulfonic acid-1)-2-vinyl pyridinium betaine (1-(3-propyl sulfonic acid-1)- 2-vinyl pyridinium betaine) of at least one selected from the group consisting of an electroplating solution additive. According to claim 1,
The electroplating solution additive wherein the surfactant is an anionic surfactant. 6. The method of claim 5,
The anionic surfactant is one selected from the group consisting of dihexyl sodium sulfosuccinate, sodium 2-ethylhexyl sulfate and sodium lauryl sulfate An electroplating solution additive that is more than one. According to claim 1,
The electroplating solution additive to which the mixing ratio of the first brightener, the second brightener, the leveler and the surfactant is from 1 to 5:0.1 to 1:0.2 to 1:5 to 30 by weight. a source of nickel ions;
halide ion source; and
An electrolytic nickel plating solution comprising the electroplating solution additive according to any one of claims 1 to 7. 9. The method of claim 8,
The electrolytic nickel plating solution, wherein the concentration of the electroplating solution additive is 5 to 20 g per 1 liter of the electroplating solution.

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