Nickel plating solution and method for producing nickel or nickel alloy plating film

Abstract

Provided are a nickel plating solution and a method for manufacturing a nickel or nickel alloy plating coating with which it is possible to enhance the efficiency of deposition of SiC microparticles on a nickel or nickel alloy plating coating. The nickel plating solution contains a water-soluble nickel compound and SiC microparticles, the nickel plating solution further containing a dispersant comprising at least one substance selected from deoxycholic acid and deoxycholic acid derivatives.

Description

[Technical Field]

[0001] The present invention relates to a nickel plating solution containing a nickel component and SiC particles, and a method for producing a nickel or nickel alloy plating film. [Background technology]

[0002] Nickel or nickel alloy plating is used in the field of surface treatment technology for the purposes of circuit formation, decoration, and improving the wear resistance and corrosion resistance of machine parts. In particular, plating films in which fine particles of SiC (silicon carbide) are dispersed in nickel or nickel alloy plating films are used in parts requiring high wear resistance, such as sliding parts of shafts, cylinders, and bearings. One example of a method for forming such plating films is to perform electroplating or electroless plating using a plating solution containing a water-soluble nickel compound and fine SiC particles, thereby forming a plating film in which SiC is dispersed in a nickel matrix (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-105573 Summary of the Invention [Problem to be solved by the invention]

[0004] From the viewpoint of improving the wear resistance of the plating film, it is preferable that the SiC particles contained in the plating film are dispersed uniformly at a high concentration within the plating film. For example, the concentration of SiC particles in the plating film can be increased by increasing the concentration of SiC particles in the plating solution. However, as the concentration of SiC particles in the plating solution increases, excess SiC particles will settle to the bottom of the container containing the plating solution. Therefore, even if the concentration of SiC particles in the plating solution is excessively increased, the actual concentration of SiC particles in the plating solution near the workpiece to be plated will reach a plateau. As a result, the deposition efficiency of SiC particles on the nickel plating film decreases. [Means for solving the problem]

[0005] The nickel plating solution for solving the above problems contains a water-soluble nickel compound, SiC fine particles, and a dispersant made of at least one selected from deoxycholic acid and deoxycholic acid derivatives.

[0006] According to the above configuration, the dispersibility of SiC particles contained in the nickel plating solution can be improved by using a dispersant consisting of at least one selected from deoxycholic acid and deoxycholic acid derivatives. This allows the SiC particles to be uniformly precipitated in the nickel matrix of the plating film. In addition, it is possible to suppress the sedimentation of the SiC particles in the nickel plating solution, thereby increasing the precipitation efficiency of the SiC particles in the plating film.

[0007] In order to solve the above problems, a method for producing a nickel or nickel alloy plating film involves electrolytic plating or electroless plating using the above nickel plating solution. According to the above manufacturing method, the dispersant can improve the dispersibility of SiC particles contained in the nickel plating solution, thereby allowing the SiC particles to be uniformly precipitated in the nickel matrix of the plating film and increasing the efficiency of precipitation of the SiC particles in the plating film. [Effects of the Invention]

[0008] According to the present invention, the deposition efficiency of SiC fine particles on a nickel or nickel alloy plating film can be increased. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the nickel plating solution of the present invention will be described, with reference to the configuration of the electroless plating solution used in the electroless plating method and the configuration of the electrolytic plating solution used in the electrolytic plating method.

[0010] [Electroless plating solution] The electroless plating solution used in the electroless plating method contains a nickel component, a reducing agent, a complexing agent, a pH adjuster, SiC fine particles, and a dispersant.

[0011] [Nickel content] The nickel component is a water-soluble nickel compound that is soluble in the plating solution. The water-soluble nickel compound is, for example, at least one selected from the group consisting of nickel sulfate, nickel chloride, nickel sulfamate, and nickel hypophosphite. Nickel sulfate is particularly preferred because of its good solubility in the plating solution. The concentration of the nickel component is, for example, 0.5 g / L or more and 50 g / L or less.

[0012] [Reducing agent] The reducing agent is at least one selected from the group consisting of hypophosphorous acid, hypophosphites (sodium salts, potassium salts, and ammonium salts), boron hydride compounds such as dimethylamine borane, and hydrazine. The concentration of the reducing agent is, for example, 0.01 g / L or more and 100 g / L or less.

[0013] [Complexing agent] The complexing agent may be at least one selected from the group consisting of monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, aminopolycarboxylic acids, ethylenediaminediacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and their ammonium salts, potassium salts, and sodium salts. Examples of the monocarboxylic acid include acetic acid and formic acid. Examples of the dicarboxylic acid include malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid. Examples of the hydroxycarboxylic acid include malic acid, lactic acid, glycolic acid, gluconic acid, and citric acid. Examples of the aminopolycarboxylic acid include ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid. Other complexing agents that may be used include phosphonic acids and amino acids. The concentration of the complexing agent is, for example, 5 g / L or more and 180 g / L or less.

[0014] [pH adjuster] The pH adjuster is at least one selected from the group consisting of inorganic acids such as sulfuric acid and phosphoric acid, sodium hydroxide, and aqueous ammonia. The pH range of the electroless plating solution is usually from 2 to 9. The pH range of the electroless plating solution of this embodiment is from 4.0 to 6.0.

[0015] [SiC fine particles] The SiC particles disperse in the nickel matrix of a nickel or nickel alloy plating film, improving the wear resistance and corrosion resistance of the plating film. The SiC particles can be of any shape, including regular shapes such as platelets or spheres, as well as amorphous shapes. The particle size of the SiC particles is preferably 0.1 μm to 3.0 μm, more preferably 0.2 μm to 2.0 μm, in terms of 50% particle size (median size D50). The concentration of the SiC particles in the electroless plating solution is preferably 100 mg / L to 5000 mg / L, more preferably 300 mg / L to 3000 mg / L, and even more preferably 400 mg / L to 2800 mg / L.

[0016] [Dispersant] The dispersant improves the dispersibility of the SiC particles in the electroless plating solution, allowing them to deposit uniformly in the nickel matrix of the plating film. The dispersant also suppresses the settling of the SiC particles in the nickel plating solution, thereby increasing the deposition efficiency of the SiC particles in the plating film.

[0017] In the case of electroless plating, when SiC fine particles settle in the plating solution, a plating reaction occurs on the surface of the settled SiC fine particles, consuming the nickel components in the treatment solution. In this regard, by using a dispersant to suppress the settling of SiC fine particles in the nickel plating solution, it is possible to suppress the consumption of nickel components in the nickel plating solution due to the plating reaction occurring on the surface of the settled SiC fine particles.

[0018] The dispersant used is at least one selected from deoxycholic acid and deoxycholic acid derivatives. Deoxycholic acid derivatives are bile acids such as hyodeoxycholic acid, chenodeoxycholic acid, and cholic acid. These bile acids are added as a single substance or in the form of a salt with sodium or the like.

[0019] The total concentration of the dispersant comprising at least one selected from deoxycholic acid and deoxycholic acid derivatives is preferably 10 μg / L to 10,000 μg / L, more preferably 20 μg / L to 5,000 μg / L, and even more preferably 40 μg / L to 4,800 μg / L. When deoxycholic acid is used as the dispersant, the concentration of deoxycholic acid in the electroless plating solution is, for example, 40 μg / L to 280 μg / L. When hyodeoxycholic acid, an example of a deoxycholic acid derivative, is used as the dispersant, the concentration of hyodeoxycholic acid in the electroless plating solution is, for example, 600 μg / L to 4,800 μg / L.

[0020] If the dispersant concentration is below the lower limit, the effects of improving the uniform deposition and deposition efficiency of SiC particles are reduced. Furthermore, if the dispersant concentration exceeds the upper limit, the uniform deposition and deposition efficiency of SiC particles are less likely to improve relative to the amount of dispersant added, and tend to gradually decrease. Therefore, by controlling the dispersant concentration within the range from the lower limit to the upper limit, SiC particles can be more uniformly deposited in the nickel matrix of the plating film and the deposition efficiency of SiC particles in the plating film can be further improved. In addition, if the dispersant concentration is excessively high, the plating solution may easily foam, which may adversely affect the workability of the plating process. In this regard, by controlling the dispersant concentration to the upper limit or less, the workability of the plating process can be prevented from decreasing.

[0021] Furthermore, due to the manufacturing process, SiC microparticles often contain graphite, a residue of the raw material. If the graphite detaches from the SiC microparticles and diffuses into the nickel plating solution, it will adhere to the parts to be plated, causing poor appearance and poor plating adhesion. In this regard, deoxycholic acid and deoxycholic acid derivatives have the ability to disperse not only SiC microparticles but also graphite. Therefore, even if graphite diffuses into the nickel plating solution, deoxycholic acid and deoxycholic acid derivatives can stabilize the dispersion of the graphite, thereby avoiding the above-mentioned poor appearance and poor plating adhesion.

[0022] [Additives] Various additives may also be added to the electroless plating solution. Examples of additives include stabilizers, such as at least one selected from the group consisting of lead salts (e.g., lead nitrate and lead acetate), bismuth salts (e.g., bismuth nitrate and bismuth acetate), and sulfur compounds (e.g., thiodiglycolic acid and sodium thiosulfate). The amount of stabilizer added is, for example, 0.01 mg / L to 100 mg / L. Examples of additives include pH buffers, such as at least one selected from the group consisting of boric acid, phosphoric acid, phosphorous acid, carbonate, and their sodium, potassium, and ammonium salts. The amount of pH buffers added is, for example, 0.1 g / L to 200 g / L. Examples of additives include surfactants, such as at least one selected from the group consisting of nonionic, cationic, anionic, and amphoteric surfactants. The amount of surfactant added is, for example, 0.1 mg / L to 100 mg / L.

[0023] An example of an electroless plating solution contains 25 g / L of nickel sulfate hexahydrate, 25 g / L of sodium hypophosphite monohydrate, 20 g / L of malic acid, 10 g / L of sodium acetate, 10 g / L of sodium hydroxide, 100 mg / L to 5000 mg / L of SiC fine particles, and 10 μg / L to 10,000 μg / L of a dispersant. An optional stabilizer is also added to the electroless plating solution so that the bismuth ion concentration in the electroless plating solution is 0.5 mg / L.

[0024] [Electrolytic plating solution] In the case of electrolytic plating, an electrolytic plating solution such as a Watts bath or a nickel sulfamate bath is used. These electrolytic plating solutions all contain nickel components, SiC particles, and a dispersant. Metal components such as tungsten may be added to the plating solution to increase the hardness of the plating film.

[0025] [Nickel content] In the case of a Watts bath, the nickel component is, for example, at least one selected from the group consisting of water-soluble nickel compounds such as nickel sulfate hexahydrate, nickel chloride hexahydrate, and nickel carbonate tetrahydrate. Among water-soluble nickel compounds, nickel sulfate hexahydrate or nickel chloride hexahydrate is preferred due to its excellent deposition on the substrate, and a mixture of nickel sulfate hexahydrate and nickel chloride hexahydrate is more preferred. When a mixture of nickel sulfate hexahydrate and nickel chloride hexahydrate is used as the nickel component, the amount of nickel sulfate hexahydrate added is preferably 200 g / L or more and 500 g / L or less, and the amount of nickel chloride hexahydrate added is preferably 70 g / L or less. In the case of a nickel sulfamate bath, the nickel component is, for example, water-soluble nickel compounds such as nickel sulfamate or nickel chloride hexahydrate, or a mixture thereof.

[0026] [SiC fine particles] The SiC particles contained in the electrolytic plating solution do not differ significantly from the SiC particles used in the electroless plating solution in terms of shape, particle size, and concentration. That is, the SiC particles contained in the electrolytic plating solution can be of the same shape and at the same concentration as the SiC particles used in the electroless plating solution.

[0027] [Dispersant] The dispersant contained in the electrolytic plating solution may be of the same type and form as the dispersant used in the electroless plating solution, and the optimum concentration of the dispersant in the electrolytic plating solution is the same as the optimum concentration of the dispersant used in the electroless plating solution.

[0028] [Brightener] Various primary and secondary brighteners may also be added to the electrolytic plating solution. The primary brightener is at least one selected from the group consisting of saccharin, derivatives of benzene and naphthalene, such as sodium naphthalene sulfonate, sulfonates, and sulfonamides. The secondary brightener is at least one selected from the group consisting of butynediol, propargyl alcohol, and coumarin.

[0029] An example of an electrolytic plating solution for a Watts bath contains 240 g / L of nickel sulfate hexahydrate, 45 g / L of nickel chloride hexahydrate, 45 g / L of boric acid, 5 g / L of nickel oxalate dihydrate particles, 100 mg / L to 5,000 mg / L of SiC fine particles, and 10 μg / L to 10,000 μg / L of a dispersant. The solution may also contain 2 g / L or less of saccharin and 0.2 g / L or less of butynediol as brighteners. The pH range of the electrolytic plating solution for a Watts bath is 4.0 to 4.5.

[0030] An example of a nickel sulfamate plating solution contains 450 g / L of nickel sulfamate tetrahydrate, 15 g / L of nickel chloride hexahydrate, 30 g / L of boric acid, 5 g / L of nickel oxalate dihydrate particles, 100 mg / L to 5,000 mg / L of SiC fine particles, and 10 μg / L to 10,000 μg / L of a dispersant. The pH range of the nickel sulfamate plating solution is 4.0 to 4.5.

[0031] [Plating solution preparation method] The method for producing a nickel plating solution is not particularly limited for either an electroless plating solution or an electrolytic plating solution. In either case, the nickel plating solution can be prepared by diluting one or more of a mixture of multiple components with water, or by dissolving each of the individual raw materials in water. The method for adding the SiC microparticles is not particularly limited. To maximize the interaction with the dispersant, for example, the desired nickel plating solution may be obtained by adding the SiC microparticles to a dispersant diluted with water to prepare a dispersion in which the SiC microparticles are sufficiently dispersed, and then adding the dispersion to the nickel plating solution.

[0032] [Method for analyzing dispersants in plating solutions] Deoxycholic acid and deoxycholic acid derivatives can be identified and quantified by LC-MS / MS, which combines high-performance liquid chromatography (HPLC) with a triple quadrupole mass spectrometer (MS / MS). The above analytical method has extremely high measurement sensitivity even for nickel plating solutions containing multiple components, such as those in this embodiment, and specifically, has quantitative accuracy down to the order of approximately 1 μg / L.

[0033] [Effects of the embodiment] According to the above embodiment, the following effects can be obtained. (1) The dispersant consisting of at least one selected from deoxycholic acid and deoxycholic acid derivatives can enhance the dispersibility of SiC particles contained in the nickel plating solution. This allows the SiC particles to be uniformly precipitated in the nickel matrix of the plating film. The dispersant can also suppress the sedimentation of SiC particles in the nickel plating solution, thereby increasing the precipitation efficiency of SiC particles in the plating film.

[0034] (2) In the case of electroless plating, the dispersant suppresses the settling of SiC particles in the nickel plating solution, thereby preventing the plating reaction from occurring on the surface of the settled SiC particles, which would consume the nickel components in the nickel plating solution.

[0035] (3) The dispersant stabilizes the dispersion of graphite, which is a residue of the raw material for SiC particles, in the plating solution, thereby suppressing poor appearance and poor plating adhesion caused by graphite that has diffused into the nickel plating solution adhering to the parts to be plated.

[0036] (4) The concentration of SiC microparticles contained in the nickel plating solution is preferably 100 mg / L to 5000 mg / L, more preferably 300 mg / L to 3000 mg / L, and even more preferably 400 mg / L to 2800 mg / L. The concentration of dispersant contained in the nickel plating solution is preferably 10 μg / L to 10000 μg / L, more preferably 20 μg / L to 5000 μg / L, and even more preferably 40 μg / L to 4800 μg / L. By setting the concentrations of SiC microparticles and dispersant contained in the nickel plating solution within the above ranges, the dispersibility of the SiC microparticles contained in the nickel plating solution can be suitably improved. This allows the SiC microparticles to be more uniformly precipitated in the nickel matrix of the plating film and further increases the precipitation efficiency of the SiC microparticles on the plating film.

[0037] (5) By forming a nickel or nickel alloy plating film by electrolytic plating or electroless plating using the nickel plating solution of this embodiment, the dispersant can enhance the dispersibility of SiC particles contained in the nickel plating solution. This method for producing a nickel or nickel alloy plating film allows SiC particles to be uniformly precipitated in the nickel matrix of the plating film and enhances the precipitation efficiency of SiC particles in the plating film.

[0038] [Example] Hereinafter, examples 1 to 6 of the present invention and comparative examples 1 to 3 will be described. Note that the above-described embodiment is not limited to the examples and comparative examples.

[0039] [Base material and plating pretreatment] In Examples 1 to 6 and Comparative Examples 1 to 3, a cold-rolled steel plate SPCC-SB (manufactured by Paltec Co., Ltd.) measuring 100 mm × 50 mm × 1.0 mm in thickness was used as the substrate. In addition, prior to the plating treatment, the surface of the substrate was cleaned in the following order: alkaline degreasing, deionized water washing, electrolytic degreasing, deionized water washing, acid washing (17% hydrochloric acid), and deionized water washing.

[0040] [Preparation of SiC particle additives] To prepare nickel plating solutions, SiC fine particles were added to pure water to prepare SiC fine particle additives 1 to 5. Note that SiC fine particle additives 3 to 5 contain a dispersant in addition to pure water and SiC fine particles.

[0041] [SiC fine particle additive 1] Alpha-type SiC particles #40000 (manufactured by Fujimi Inc., particle diameter D50 = 0.27 μm) were added to pure water and stirred so that the SiC concentration was 100 g / L. Then, ultrasonic waves were irradiated for 10 minutes to crush the secondary particles of the SiC particles and to stir the SiC particles, and SiC particle additive 1 was obtained.

[0042] [SiC fine particle additive 2] GMF-12H (manufactured by Pacific Random Co., Ltd., particle size D50 = 0.7 μm) was added to pure water and stirred so that the SiC concentration was 100 g / L. Then, ultrasonic waves were irradiated for 10 minutes to obtain SiC fine particle additive 2.

[0043] [SiC fine particle additive 3] Sodium deoxycholate was dissolved in pure water to a concentration of 10 mg / L of deoxycholic acid. Furthermore, α-type SiC microparticles #40000 (manufactured by Fujimi Inc., particle size D50 = 0.27 μm) were added and stirred to a concentration of SiC of 100 g / L. Ultrasonic waves were then applied for 10 minutes to prepare SiC microparticle additive 3.

[0044] [SiC fine particle additive 4] Hyodeoxycholic acid was added to pure water to a concentration of 200 mg / L, and sodium hydroxide was added to dissolve the acid until the solution became neutral. GMF-12H (manufactured by Pacific Random Corporation; particle size D50 = 0.7 μm) was then added and stirred to a concentration of SiC of 100 g / L. Ultrasonic irradiation was then performed for 10 minutes to obtain SiC microparticle additive 4.

[0045] [SiC fine particle additive 5] Sodium deoxycholate was added to pure water to a concentration of 5 mg / L, and then cholic acid was added to a concentration of 200 mg / L. Sodium hydroxide was then added and dissolved until the solution became neutral. GMF-12H (manufactured by Pacific Random Corporation; particle size D50 = 0.7 μm) was then added and stirred to a concentration of SiC of 100 g / L. Ultrasonic irradiation was then performed for 10 minutes to obtain SiC microparticle additive 5.

[0046] [Example 1] Electroless plating was performed using an electroless nickel plating solution prepared by adding 4 mL / L of SiC microparticle additive 3 to the medium-high phosphorus electroless nickel plating solution "SEC-930" (manufactured by Japan Kanigen Co., Ltd.). In the electroless plating process, the substrate was immersed in the electroless plating solution while stirring with a stirrer, and electroless plating was performed at 90°C until the film thickness was approximately 5 μm, followed by rinsing with water and drying.

[0047] [Example 2] Electroless plating was carried out in the same manner as in Example 1 using an electroless nickel plating solution prepared by adding 28 mL / L of SiC microparticle additive 3 to a medium-high phosphorus electroless nickel plating solution "SEC-930" (manufactured by Japan Kanigen Co., Ltd.).

[0048] [Example 3] Electroless plating was carried out in the same manner as in Example 1 using an electroless nickel plating solution prepared by adding 3 mL / L of SiC microparticle additive 4 to a medium-high phosphorus electroless nickel plating solution "SEC-930" (manufactured by Japan Kanigen Co., Ltd.).

[0049] [Example 4] Electroless plating was carried out in the same manner as in Example 1 using an electroless nickel plating solution prepared by adding 24 mL / L of SiC microparticle additive 4 to a medium-high phosphorus electroless nickel plating solution "SEC-930" (manufactured by Japan Kanigen Co., Ltd.).

[0050] [Example 5] Electroless plating was carried out in the same manner as in Example 1 using an electroless nickel plating solution prepared by adding 10 mL / L of SiC microparticle additive 5 to a medium-high phosphorus electroless nickel plating solution "SEC-930" (manufactured by Japan Kanigen Co., Ltd.).

[0051] [Example 6] Electrolytic plating was performed using an electrolytic nickel plating solution containing 4 mL / L of SiC particle additive 3 in a Watts bath. The Watts bath contained 280 g / L of nickel sulfate, 40 g / L of nickel chloride, and 20 g / L of boric acid, and the pH was adjusted to 4.5. In the electrolytic plating, the substrate was immersed in the Watts bath while stirring with a stirrer, and the current density was adjusted to 2 A / dm at 50°C. 2 The plate was electroplated to a film thickness of about 5 μm using DC electrolysis, and then washed with water and dried.

[0052] [Comparative Example 1] Electroless plating was carried out in the same manner as in Example 1 using an electroless nickel plating solution prepared by adding 4 mL / L of SiC microparticle additive 1 to a medium-high phosphorus electroless nickel plating solution "SEC-930" (manufactured by Japan Kanigen Co., Ltd.).

[0053] Comparative Example 2 Electroless plating was carried out in the same manner as in Example 1 using an electroless nickel plating solution prepared by adding 22 mL / L of SiC microparticle additive 2 to a medium-high phosphorus electroless nickel plating solution "SEC-930" (manufactured by Japan Kanigen Co., Ltd.).

[0054] Comparative Example 3 Electrolytic plating was carried out in the same manner as in Example 6 using an electrolytic nickel plating solution prepared by adding 4 mL / L of SiC fine particle additive 1 to the same Watts bath as in Example 6.

[0055] [Evaluation 1: Plating solution stability] For Examples 1 to 5 and Comparative Examples 1 and 2 in which electroless plating was performed, the plating solution stability was evaluated based on the degree of settling of SiC particles at the bottom of the plating tank after plating. A sample in which almost no settling of SiC particles was observed was rated "Good," a sample in which a small amount of settling of SiC particles was observed was rated "Good," and a sample in which more settling of SiC particles than the "Good" level was observed was rated "Poor."

[0056] In electroless nickel plating, the SiC particles that settle to the bottom of the plating tank are gradually precipitated with nickel on their surfaces by the action of a reducing agent. This consumes the nickel component in the plating solution, necessitating the replacement of the plating solution. Note that, since electrolytic nickel plating solutions basically do not contain reducing agents, such a reaction does not occur in electrolytic nickel plating. Therefore, this evaluation was performed only on Examples 1 to 5 and Comparative Examples 1 and 2, which were subjected to electroless nickel plating.

[0057] [Evaluation 2: Dispersibility of SiC particles in plating film] The plating film was observed under a scanning electron microscope to evaluate the dispersibility of the SiC particles in the plating film. Films in which the SiC particles were uniformly dispersed and no aggregation was observed were rated "Good", films in which some aggregation of SiC particles was observed in the plating film were rated "Good", and films in which clear aggregation of SiC particles was observed in the plating film were rated "Poor".

[0058] [Evaluation 3: SiC particle content in plating film] Test pieces with a plating film formed on the substrate by plating treatment were immersed in 67.5% nitric acid for 40 minutes to remove the plating film. The amount of plating film was calculated from the area of ​​the test piece and the difference in mass before and after removal. Next, the SiC particles in the stripping solution were collected by filtration, washed with water, dried, and then the amount of SiC particles was measured. Finally, the SiC particle content in the plating film was calculated from the amount of plating film and the amount of SiC particles.

[0059] [Evaluation results] Tables 1 and 2 show the conditions for preparing the plating solutions, the compositions of the plating solutions, and the results of Evaluations 1 to 3 in Examples 1 to 6 and Comparative Examples 1 to 3.

[0060] [Table 1]

[0061] [Table 2]

[0062] As shown in Table 1, 300 40 mg / L or more and 2800 mg / L or less of SiC particles μg / L or more 4800μg In Examples 1 to 6 containing a dispersant of 40 / L or less, the effects of improving the uniform deposition of SiC particles and the deposition efficiency were confirmed. μg / L or more 280 μg In Examples 1, 2, and 6 containing deoxycholic acid at 600 / L or less, the effects of uniform deposition of SiC particles and improved deposition efficiency were confirmed. μg / L or more 4800 μg In the cases of Examples 3 and 4 containing hyodeoxycholic acid at 50 / L or less, the effects of uniform deposition of SiC particles and improved deposition efficiency were confirmed. μg / L deoxycholic acid and 2000 μg / L of cholic acid and dispersant, total concentration of dispersant is 2050 μg In the case of Example 5 where the SiC content was 1 / L, the effects of uniform deposition of SiC particles and improved deposition efficiency were confirmed.

[0063] As shown in Tables 1 and 2, in the case of electroless plating, when Example 1 and Comparative Example 1 are compared, where conditions other than the presence or absence of a dispersant are the same, Example 1, where the plating solution contains a dispersant, has better plating solution stability and SiC particle dispersibility in the plating film than Comparative Example 1. Furthermore, the SiC particle content in the plating film of Example 1 was significantly higher than that of Comparative Example 1. Therefore, adding a dispersant to the plating solution improved the deposition efficiency of SiC particles in the plating film. A similar trend was also confirmed when Example 4 and Comparative Example 2, where conditions other than the presence or absence of a dispersant are the same, were compared.

[0064] Furthermore, in the case of electrolytic plating, when Example 6 and Comparative Example 3, which are identical in conditions except for the presence or absence of a dispersant, are compared, Example 6, which contains a dispersant, has a superior dispersibility of SiC particles in the plating film compared to Comparative Example 3. Furthermore, the content of SiC particles in the plating film of Example 6 is significantly higher than that of Comparative Example 3. Therefore, it was confirmed that the addition of a dispersant to the plating solution can improve the deposition efficiency of SiC particles in the plating film not only in electroless plating but also in electrolytic plating.

[0065] [Example of change] The above embodiment can be modified as follows. The plating film produced using the nickel plating solution of this embodiment is not limited to a nickel plating film, and a nickel alloy plating film may be formed by adding a metal component to the components of the nickel plating solution of this embodiment.

[0066] Even when hyodeoxycholic acid is contained as a dispersant, the concentration of hyodeoxycholic acid may be less than 600 μg / L or more than 4800 μg / L, as long as the dispersibility of the SiC fine particles contained in the nickel plating solution is ensured.

[0067] Even when deoxycholic acid is contained as a dispersant, the concentration of deoxycholic acid may be less than 40 μg / L or more than 280 μg / L, as long as the dispersibility of the SiC fine particles contained in the nickel plating solution is ensured.

[0068] The total concentration of the components constituting the dispersant may be less than 10 μg / L as long as the dispersibility of the SiC particles contained in the nickel plating solution is ensured. Also, the total concentration of the components constituting the dispersant may be more than 10,000 μg / L as long as there is no adverse effect on the nickel plating solution or on the plating film produced using the nickel plating solution.

Claims

1. a water-soluble nickel compound; SiC fine particles, and a dispersant comprising at least one selected from deoxycholic acid and deoxycholic acid derivatives. A nickel plating solution characterized by:

2. Electrolytic plating or electroless plating is carried out using the nickel plating solution according to claim 1.

2. A method for producing a nickel or nickel alloy plating film, comprising:

Images