JP5861176B2 - Zinc-nickel alloy plating solution and plating method - Google Patents

Description

  The present invention relates to zinc-nickel alloy plating, precipitation of plating solution, generation of sludge-like foreign matters in the anode back, generation of deposits on the plating tank, deposits on a filtration device (filtration membrane), pipe piping The present invention provides a plating solution and a plating method capable of addressing various problems such as clogging, dramatically improving productivity and manageability, and greatly reducing the defect occurrence rate.

  Zinc alloy plating is widely performed for the purpose of improving the corrosion resistance of galvanization. Among them, zinc-nickel alloy plating is widely used for automobile parts, particularly engine parts placed in a high temperature environment, parts requiring high corrosion resistance, and the like. Conventional zinc-nickel alloy plating is performed in an electrogalvanizing bath containing nickel solubilized with an amine complex such as polyalkene polyamines and alkanolamines as disclosed in JP-A-63-53285. It is carried out by a method of depositing nickel in the galvanized film by plating. Various types of complexing agents have since been developed depending on the purpose. For example, JP-A-6-173073 and JP-A-2007-2274 disclose a zinc-nickel alloy plating method using an alkaline electrogalvanizing bath using a reaction product of an amine compound and an epoxy group-containing compound such as epihalohydrin as a complexing agent. . This method is a method of obtaining a reaction product as a complexing agent by mixing an amine compound and glycidyl ethers, and this reaction product is currently most widely used as a complexing agent for zinc-nickel alloy plating. Other than the corrosion resistance, there is a special table 2009-541580 using a specific soluble polymer and a pyridinium compound for the purpose of an improved film thickness distribution. In addition, all the alkaline zinc nickel alloy platings that have been invented and put to practical use, such as plating solution discoloration, plating layer thickness unevenness, and reduced productivity as described in the background art of JP-T-2008-539329. I have a problem. In addition, alkaline zinc-nickel alloy plating generates plating solution precipitation, generation of sludge-like foreign matter in the anode back (adhesion on the anode), generation of deposit on the plating tank, filtration device (filtration membrane) There are many problems in producing deposits on pipes and clogging of pipes. If the invention described in Special Table 2008-539329 is not applied, all the inventions up to now, for example, the above Special Table 2009-541580 have the same problem. Yes. However, the invention of Special Table 2008-539329 requires a large amount of capital investment, and the product is damaged by contact with the equipment during the plating operation, so that the repair cost is increased and the filter membrane is frequently clogged. There is no improvement in the point of inefficiency in terms of cost and maintenance described in the problem to be solved, such as the fact that the line must be stopped for maintenance, and the practical cost is high.

JP-A-63-53285 JP-A-6-173073 JP 2007-2274 A Special table 2009-541580 Special table 2008-539329

  An object of the present invention is to solve the above-mentioned problems, and in particular, a plating solution, a plating method, and a plating solution that are highly effective in reducing costs by improving the stability of the plating solution and improving the productivity and reducing the defect rate. To provide a management method. In particular, productivity improvements such as curbing the reduction in current efficiency and shortening maintenance time are many times more economical than reducing drug costs. In addition, the ease of maintenance is effective not only for simple cost reduction but also for improving the working environment such as shortening working hours.

The present inventor has been researching and developing in order to solve the above-mentioned problem, but has found a method for solving this problem by an innovative means based on an idea completely different from the conventional idea. In the inventions so far, based on a chemical idea, the productivity and quality have been improved by improving the electrodeposition speed or current efficiency by improving the complexing agent and brightening agent. When such liquid is exposed to instability of the liquid due to industrial operation, physical measures such as adsorption or dilution to activated carbon or the like for liquid purification, or separation according to EP 1369505A2, separation membranes such as WO00 / 06807 Isolation and separation by filtration membranes described in JP-A-2008-539329 and physical, mechanical, and device measures have been proposed. In other words, chemical measures are considered clogged, and as a result of taking physical, mechanical, and device measures, the number of problems has increased as the number of facilities has increased, and the number of items to be maintained has increased. In view of the situation of falling into a dilemma that could not be fulfilled, we came back to the starting point and came up with a method that does not take physical, mechanical, and device measures.
Many inventions of zinc-nickel alloy plating have been made so far, and many complexing agents and organic compounds such as carboxylic acids, aliphatic carboxylic acids and their reaction products have been proposed. Despite being considered to be due to the decomposition product of the organic compound (Special Table 2008-539329), the first idea different from the conventional one of the inventor is that the problem is generated by the decomposition of the organic compound. This is not due to the product but to the opposite of the product due to the synthesis. In other words, if it is decomposition, it can be considered as a reaction of the organic compound itself, but if it is synthesis, synthesis with other than the organic compound can be considered and addition of a new functional group can be considered.

  According to the results of investigations of drug manufacturers all over the world by analyzing the obtained drugs or using MSDS, etc., the present inventors have found that zinc-nickel alloy plating solutions that are currently in practical use and industrially used include aldehydes. , Pyridinium compound, organic sulfur compound, aromatic sulfonic acid, aromatic sulfonamide, aromatic sulfonimide, acetylene compound, allyl compound, nitrile compound, sulfate ester, one or more are used, nickel supply All sources were nickel sulfate.

  The inventor's second idea different from the conventional one is that the conventional invention pays attention to the reaction (decomposition, conversion, etc.) of the complexing agent and tries to suppress it (Special Tables 2008-539329, p5, 35-35). (Line 37). In contrast to this, the focus is on components such as brighteners, not complexing agents. As described in JP 2008-539329, p3, line 11, since the change in the color of the liquid indicates the change in the complexing state of nickel, the inventions so far considered to suppress the change in the complexing agent. This is natural for those skilled in the art.

  The third idea of the present inventor, which is different from the conventional one, is that these components are considered to be removed. These components were invented by the predecessors to improve glossiness and physical properties of the film (secondary workability, stress), uniformity of the film, adhesion of the film, corrosion resistance, etc. It is insane not only for a person skilled in the art to remove it even though its effect is recognized by use.

  Among these components, regarding the nickel supply source, Japanese Patent Application No. 63-149088 describes the adverse effects of sulfate radicals. However. As far as the examples of the present invention are concerned, 4 to 6 g / L of brightener (IZ-260) is added. When investigated on the homepage, IZ-260 is a brightener for alkaline zinc-nickel alloy plating manufactured by Dipsol, the inventor of Japanese Patent Application No. 63-149088. When the patent relating to the alkaline zinc-nickel alloy plating applied for by Dippsor thereafter was examined, the components pointed out in the present application such as pyridinium compounds were included (Japanese Patent Application 2000-22298, Example 5). Therefore, according to Japanese Patent Application No. 63-149088, the effects of the present application cannot be obtained even if sulfate ions, chloride ions, carbonate ions, etc. are removed.

  Japanese Patent Application No. Sho 63-149088 proposes a method of melting and replenishing metallic nickel in a separate tank, but it is possible to install another plating facility such as newly installing not only a melting tank but also a power supply device. It was not practical because of the great investment required and the difficulty in adjusting the nickel concentration. Compared to other nickel compounds, nickel sulfate has the advantage that it is cheap and easily available, and for example, when nickel chloride is used, the chlorine concentration in the alloy plating layer increases due to the increase in the chlorine concentration in the plating solution. The increase in corrosion resistance is expected to decrease, and nickel acetate or nickel sulfamate may cause a deterioration of the plating state due to unintended chelate. In addition, when a poorly soluble nickel source is used, there is a problem that the nickel compound itself is poorly soluble in water, so the nickel complex cannot be efficiently synthesized. Nickel sulfate has been used as a source.

  Contrary to the history of the development of such alkaline zinc-nickel alloy plating, the present inventors have solved the problem by removing these.

More specifically, technical means for solving the problems of the present invention are as follows.
(1) containing a complexing agent of zinc, nickel, a conductive salt and nickel, the nickel source being at least one selected from nickel monohydroxide, nickel chloride, nickel carbonate, nickel sulfamate, and nickel acetate; An alkaline zinc-nickel alloy plating solution that does not contain a compound group consisting of aromatic sulfonic acid, aromatic sulfonamide, aromatic sulfonimide, acetylene compound, allyl compound, nitrile compound, and sulfate ester.
(2) The alkaline zinc-nickel alloy plating solution according to the above (1), wherein the molar ratio represented by nickel / sulfuric acid ions exceeds 1 when sulfate ions are present in the plating solution.
(3) The alkaline zinc-nickel alloy plating solution according to (1) or (2) above, wherein the molar ratio represented by nickel / halogen ions exceeds 0.5 when halogen ions are present in the plating solution.
(4) The alkaline zinc-nickel alloy plating solution according to any one of (1) to (3) above, which does not contain sulfate ions.
(5) The alkaline zinc-nickel alloy plating solution according to any one of (1) to (4), wherein the complexing agent is a reaction product of an amine and an epoxy group-containing compound.
(6) The alkaline zinc-nickel alloy plating solution according to the above (5), wherein the amine used as the complexing agent raw material has 4 or more nitrogen atoms in one molecule.
(7) A part or all of a nickel supply source is nickel carbonate, nickel hydroxide, or nickel chloride, and further contains a nickel complexing agent, according to any one of (1) to (6) above Nickel replenisher for alkaline zinc-nickel alloy plating solution.
(8) The nickel replenisher for alkaline zinc-nickel alloy plating solution according to (7) above, wherein the complexing agent is a reaction product of an amine and an epoxy group-containing compound.
(9) A method of performing electrolytic zinc-nickel alloy plating with the plating solution according to any one of (1) to (6) above.
(10) A nickel replenishing method using the replenisher according to (7) or (8) in the plating solution according to any one of (1) to (6) above.
(11) Alkaline effected by using the plating solution according to any one of (1) to (6) above without adding any of an aldehyde, a pyridinium compound, an organic sulfur compound, a polyalcohol, or a polycarboxylic acid. Zinc-nickel alloy plating method.
(12) An alkaline zinc-nickel alloy plating solution management method in which any one or more components of the compound group described in (11) above are periodically added and each component is controlled at a concentration of 0.0005 mol / L or less. .
(13) An alkaline zinc-nickel alloy plating solution management method in which the compound group according to (11) is not periodically added.
(14) An alkaline zinc-nickel alloy plating method characterized by using an alkaline zinc-nickel alloy plating solution managed by the management method described in (12) or (13) above.
(15) A zinc-nickel alloy plated product produced by the method of (9) or (14).

Hereinafter, the zinc-nickel alloy plating of the present invention will be described in detail.
The basic bath composition of plating may be the composition of conventional alkaline zinc-nickel alloy plating. For example, zinc is 3 to 30 g / L, preferably 5 to 15 g / L, and conductive such as sodium hydroxide or potassium hydroxide. The salt contains 50 to 200 g / L, preferably 80 to 160 g / L, nickel contains 0.5 to 15 g / L, preferably 1 to 8 g / L, and contains appropriate amounts of complexing agent and brightener.

As the complexing agent, carboxylic acid, amine compound and the like can be used.
There are no particular restrictions on the carboxylic acid, but polycarboxylic acids such as malic acid, succinic acid, malonic acid, tartaric acid, oxalic acid and citric acid, and salts thereof, hydroxycarboxylic acids such as gluconic acid and glyceric acid, and salts, etc. Can be mentioned. These concentrations are preferably 0.001-1 mol / L, more preferably 0.005-0.1 mol / L. The amine compound is not particularly limited, but is preferably a polyalkylene polyamine, specifically, an aliphatic amine such as dialkylaminoethylamine or dialkylaminopropylamine. For example, triethanolamine, ethylenediamine, pentaethylenehexamine, diaminopropane, diethylenetriamine, ethyl Aminoethanol, aminopropylethylenediamine, bisaminopropylpiperazine, triethylenetetramine, hexamethylenetetramine, isopropanolamine, amino alcohol, imidazole, picoline, piperazine, methylpiperazine, morpholine, hydroxyethylaminopropylamine, tetramethylpropylenediamine, dimethylamino Propylamine, amino alcohol, dimethylaminoethylamine, di Tilaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, especially ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Tripropylenetetramine is preferred. Preferably, these and an epoxy group-containing compound are reacted in the presence of a nickel compound. As the epoxy group-containing compound, glycidyl ethers and epihalohydrins are preferable, but not limited thereto. If the epoxy group-containing compound contains an epoxy group, the nickel complex of the present invention can be synthesized.

  When a reaction product of an amine having 4 or more nitrogen atoms and epihalohydrin is used as a complexing agent, a stable alloy plating film can be continuously obtained even at 25 ° C. or higher, and conventional zinc-nickel alloy plating Compared to the above, the coating is an alloy plating with a nickel eutectoid rate of 10 to 13%, and a nickel eutectoid rate of 8 to 10% or 15 which has been conventionally obtained stably. Corrosion resistance is higher than any of the above-described coatings. Further, by changing the nickel concentration, it is possible to form an alloy plating having a nickel eutectoid rate of 15% or more, and it has a distinct feature that a stable alloy plating film can be formed even at a high temperature of 25 ° C. or more.

  Regarding nickel compounds as a nickel supply source, any nickel compound that can avoid the presence of sulfate ions can suppress reactions such as sulfonation and esterification of sulfuric acid, but nickel acetate and nickel sulfamate can be used. However, nickel chloride, nickel carbonate, and nickel hydroxide are more preferable because there is a concern about deterioration of the plating state due to an unintended chelate before the reaction. Nickel chloride is the most preferable because nickel chloride is concerned about a decrease in corrosion resistance due to chlorine, and nickel carbonate is likely to accelerate the accumulation of sodium carbonate during operation. Japanese Patent Application No. 63-149088 describes that nickel hydroxide other than nickel sulfate is directly added to the plating solution to produce nickel hydroxide, resulting in poor plating. However, the zinc-nickel alloy plating apparatus has a zinc concentration control. Therefore, a zinc dissolution tank is provided, and a system for supplying zinc to the plating solution from there through a filter is usually used. Nickel hydroxide is sparingly soluble, but as described in Japanese Patent Application No. 63-149088, nickel hydroxide precipitation is a temporary formation, so it is replenished by using this zinc dissolution tank instead of direct addition. It is possible. However, from a management point of view, such as suppressing fluctuations in the plating composition due to the time lag between addition and dissolution, nickel chloride, nickel carbonate, nickel hydroxide, etc. must be supplied in a dissolved state. Is desirable. As in this case, if the solution is a solution in which nickel is dissolved in the complexing agent, precipitation does not occur even if it is added to the plating solution. It is possible for a person skilled in the art to mix and dissolve the nickel supply source of the present invention in the complexing agent, but in order to save time, a nickel source is added at the stage of the complexing agent synthesis, and the complexing agent is complexed with the complexing agent. It is more preferable to provide a nickel supplement.

  Sulfate ions are mainly supplied from nickel sulfate, and halogen ions are mainly supplied from nickel chloride and epihalohydrin, but in order to solve the problem and stabilize the corrosion resistance, the molar ratio expressed by nickel / sulfate ions exceeds 1. It is preferable to manage with a small amount of sulfate ions so that the molar ratio represented by nickel / halogen ions exceeds 0.5. Halogen is difficult to contain as long as it uses epihalohydrin, but it is desirable to stop using nickel sulfate and intentionally contain no sulfate.

  As the brightener for the plating solution, all the existing zinc plating or zinc-nickel alloy plating described in Japanese Patent Application Nos. 2000-22298, 2009-515571, 9-368645, etc. can be used. There is no particular limitation.

The optimum plating conditions of the present invention vary depending on the type and concentration of the amine and epoxy group-containing compound as the complexing agent raw material, or the type and concentration of the brightener used, but the current density is usually an average current density of 1 to 1 for static plating. ^{6A / dm 2, 0.5~1.5A / dm} 2 in barrel plating, plating temperature is performed in the range of 15 to 50 ° C., as determined by plating thickness plating time is obtained.

  A preferred form of the present invention contains a complexing agent of zinc, nickel, a conductive salt and nickel, and an aldehyde, a pyridinium compound, an organic sulfur compound, an aromatic sulfonic acid, an aromatic sulfonamide, an aromatic sulfonimide, an acetylene compound, An alkaline zinc-nickel alloy plating solution that does not contain an allyl compound, a nitrile compound, or a sulfate ester, and more preferably further controls sulfate ions and chloride ions, and (1) the molar ratio represented by nickel / sulfate ions is 1. (2) Alkaline zinc-nickel alloy plating solution that satisfies both or one of the molar ratios expressed by nickel / halogen ions exceeding 0.5, and the most preferable form contains sulfate ions and / or chloride ions There is no alkaline zinc-nickel alloy plating solution, but it is irregular in industrial operation. -Occurrence of negative conditions cannot be denied, so aldehydes, pyridinium compounds, aromatic sulfonic acids, aromatic sulfonamides, aromatic sulfonamides, acetylene compounds, allyl compounds, nitrile compounds, sulfate esters, sulfate ions are added irregularly There are things to do. For example, various troubles such as unexpected changes in bath composition due to the introduction of impurities from outside, incorrect addition / replenishment of workers, dissolution of parts due to machine failure / breakage, use of unclean water, etc. Various problems such as appearance, film thickness, non-uniformity, abnormal eutectoid rate and poor physical properties may occur. In such a case, in the initial stage until returning to a normal state or immediately after starting, the aldehyde, pyridinium compound, aromatic sulfonic acid, aromatic sulfonamide, aromatic sulfonimide, acetylene compound, allyl compound, Nitrile compounds, sulfate esters, and sulfate ions can be temporarily added. The problem to be solved by the present invention is not a laboratory-level problem but a solution to a problem that occurs after industrial operation. Therefore, the addition itself is not completely denied. In an industrial operation, the plating solution is constantly exchanged by bringing it in and out, so if it is temporarily added, it can be added because it gradually decreases. The amount of addition is suitably less than the amount shown in the examples of the invention so far, and if it is large, the risk of problems is increased, so that it is preferably as small as possible. More specifically, in the case of a pyridinium compound, it is 50 to 100 mg / L or less although it depends on the kind of the pyridinium compound. Whether it is an occasional temporary addition or a periodic addition, the management of complexing agents and brighteners in the normal alkaline zinc-nickel alloy plating solution is based on the amount of electricity, the processing area, the concentration of conductive salts, etc. Therefore, additions linked to these management items should be done regularly, and additions that are not linked should be irregular.

  The present inventor considers that the cause of the problem is a synthetic reaction, and this reaction is considered to depend on the concentration, temperature, amount of electricity, etc. of each reaction component, aldehyde, pyridinium compound, aromatic sulfonic acid, aromatic In the present invention which does not intend to contain sulfonamide, aromatic sulfonimide, acetylene compound, allyl compound, nitrile compound, sulfate ester, sulfate ion or chloride ion, the concentration factor is the concentration of these components. Whether or not the problem develops (whether the problem progresses to an industrially problematic level) is considered to be due to the ratio between the normal component and the synthetic product.

  When there are many fluctuation factors due to aging of the equipment and it is difficult to maintain the most favorable condition, the ratio between normal components and synthetic products is minimized while regular addition is performed to cope with some fluctuation. It is also possible to suppress the onset of problems. In this case, the amount of addition must be less than that shown in the examples of the present invention, and is preferably 1/3 or less, more preferably 1/5 or less. If there are many, the risk of problem generation increases, so a small amount is preferable. More specifically, in the case of a pyridinium compound, although it depends on the kind of the pyridinium compound, it is 20 to 50 mg / L or less, more preferably 5 to 20 mg / L or less. Although it cannot be generally said about all substances not intended to be contained only by the difference in molecular weight, it is 0.001 mol / L or less, preferably 0.0005 mol / L, more preferably 0.0001 mol / L or less.

Hereinafter, the present invention will be described with reference to examples and comparative examples. After performing an appropriate pretreatment on the test piece, plating was performed using the following conditions as standard conditions. In the experiment, a plating solution having a zinc concentration of 8 g / L, a nickel concentration of 1.6 g / L, sodium hydroxide of 110 g / L, and a complexing agent of 15 g / L was used. Used a nickel plate and the complexing agent used was a reaction product of triethylenetetramine and epichlorohydrin. Either a commercially available alkaline zinc-nickel alloy plating brightener (ZN-204A: manufactured by Nippon Surface Chemical Co., Ltd.) or a commercially available zinc plating brightener (9000A: manufactured by Nippon Surface Chemical Co., Ltd.) as a brightener The stated standard amounts were used. Nickel hydroxide was used as a nickel supply source. To facilitate replenishment, nickel hydroxide was added to the reaction system of the complexing agent, and the solution was adjusted and replenished with a solution in which nickel was previously dissolved in the complexing agent. The plating conditions were a current density of 3 A / dm ² , a plating bath temperature of 25 ° C., and a plating time of 25 minutes. After plating, a trivalent chromium conversion coating was applied for corrosion resistance evaluation. Trivalent chromium chemical conversion film treatment was performed under standard conditions using a TRIN-988SC made by Nippon Surface Chemical Co., Ltd. The overall appearance was evaluated comprehensively, paying particular attention to the graying out of the low electrical area. The current efficiency was measured by plating an iron 0.1 dm ² circular cathode plate at 2 A / dm ² and calculating the plating adhesion amount by measuring the film thickness. The film thickness and the Ni eutectoid rate were measured using FISCHER SCOPE X-RAY XDLM-C4 manufactured by FISCHER. Precipitation, presence of tank deposits, and discoloration of the liquid were determined visually. In the running test, each item was evaluated after 100 AH / L electrolysis was performed under the above-described conditions.

評価： 良 ○＞△＞× 劣 Examples 1 to 6 and Comparative Examples 1 and 2
ZN-204A as a brightener was added at 4 mL / L, and nickel source was nickel hydroxide (Example 1), nickel carbonate (Example 2), nickel chloride (Example 3), nickel sulfate (Comparative Example 1), As a brightener, 9000A was added at 12 mL / L, and nickel supply sources were nickel hydroxide (Example 4), nickel carbonate (Example 5), nickel chloride (Example 6), and nickel sulfate (Comparative Example 2).
The results of 100 AH / L running are shown in Table 1 below. It can be seen that when nickel hydroxide, nickel carbonate, and nickel chloride are used, excellent results are obtained in many respects as compared with nickel sulfate (Comparative Examples 1 and 2).

Evaluation: Good ○ ＞ △ ＞ × Poor

評価： 良 ○＞△＞× 劣 Examples 7 to 12 and Comparative Examples 3 and 4
Zinc concentration is 12 g / L, nickel concentration is 3.5 g / L, ZN-204A as a brightener is added at 4 mL / L, nickel supply source is nickel hydroxide (Example 7), nickel carbonate (Example 8), Nickel chloride (Example 9), nickel sulfate (Comparative Example 3), 9000A as a brightener was added at 12 mL / L, nickel supply source was nickel hydroxide (Example 10), nickel carbonate (Example 11), nickel chloride (Example 12) Nickel sulfate (Comparative Example 4) was used. Table 2 shows the results of 100 AH / L running. It can be seen that when nickel hydroxide, nickel carbonate, and nickel chloride are used, excellent results are obtained in many respects as compared with nickel sulfate (Comparative Examples 3 and 4).

Evaluation: Good ○ ＞ △ ＞ × Poor

評価： 良 ○＞△＞× 劣 Examples 13-16 and Comparative Examples 5-8
ZN-204A as a brightener was added at 4 mL / L, vanillin 30 mg / L (Example 13), 1-benzyl-3-carbamoylpyridinium chloride 15 mg / L (Example 14), saccharin 40 mg / L (Example) 15), 2-butyne-1,4-diol 20 mg / L (Example 16), or vanillin 200 mg / L (Comparative Example 5), 1-benzyl-3-carbamoylpyridinium chloride 100 mg / L (Comparative Example 6) Saccharin 200 mg / L (Comparative Example 7) and 2-butyne-1,4-diol 300 mg / L (Comparative Example 8) were added to perform a running test. Table 3 shows the results of 100 AH / L running. This result does not deny the use of these conventionally known additives, but indicates that the present invention should be suppressed to a small amount.

Evaluation: Good ○ ＞ △ ＞ × Poor

評価： 良 ○＞△＞× 劣 Comparative Examples 9-12
9000A as a brightener is added at 12 mL / L, nickel source is nickel sulfate, vanillin is 200 mg / L (Comparative Example 9), 1-benzyl-3-carbamoylpyridinium chloride 100 mg / L (Comparative Example 10), saccharin 200 mg / L (Comparative Example 11) and 2-butyne-1,4-diol 300 mg / L (Comparative Example 12) were added to perform a running test.
Table 4 shows the results of 100 AH / L running. When nickel sulfate is employed as the nickel supply source, it can be seen that the basic composition of the present invention does not provide the desired effect and requires a large amount of additive.

Evaluation: Good ○ ＞ △ ＞ × Poor

評価： 良 ○＞△＞× 劣 Examples 17-18 and Comparative Examples 13-17
ZN-204A as a brightening agent was added at 4 mL / L, and the running test was performed by changing the complexing agent to 50 g / L (Example 17) and tetraethylenepentamine (Example 18) in which the amine of the complexing agent was diethylenetriamine. went.
100 mg / L of 1-benzyl-3-carbamoylpyridinium chloride (Comparative Example 14) and 300 mg / L of saccharin (Comparative Example 15) were added to Comparative Example 13 and Example 18 in which the nickel supply source of Example 18 was nickel sulfate. The plating solution and the nickel supply source of Example 18 were changed to nickel sulfate, and 1-benzyl-3-carbamoylpyridinium chloride 100 mg / L (Comparative Example 16) or saccharin 200 mg / L (Comparative Example 17) was added. A running test was conducted with the liquid. The results are shown in Table 5. When nickel sulfate is employed as the nickel supply source, a large amount of various additives unnecessary in the present invention is necessary.

Evaluation: Good ○ ＞ △ ＞ × Poor

Claims (14)

Containing a complexing agent of zinc, nickel, a conductive salt and nickel, the nickel source being at least one selected from NiOH, Ni (OH) ₂ , nickel chloride, nickel carbonate, nickel sulfamate, and nickel acetate; And the complexing agent does not contain a compound group consisting of aromatic sulfonic acid, aromatic sulfonamide, aromatic sulfonimide, acetylene compound, allyl compound, nitrile compound, and sulfate ester, and does not contain sulfate ion. An alkaline zinc-nickel alloy plating solution , which is a reaction product of an amine and an epoxy group-containing compound, and the amine used as the complexing agent raw material has 4 or more nitrogen atoms in one molecule . Containing a complexing agent of zinc, nickel, a conductive salt and nickel, the nickel source being at least one selected from NiOH, Ni (OH) ₂ , nickel chloride, nickel carbonate, nickel sulfamate, and nickel acetate; And does not contain a compound group consisting of aromatic sulfonic acid, aromatic sulfonamide, aromatic sulfonimide, acetylene compound, allyl compound, nitrile compound, sulfate ester,
Further, an alkaline zinc-nickel alloy plating solution containing a halogen ion and having a molar ratio expressed by nickel / halogen ion exceeding 0.5.   3. The alkaline zinc-nickel alloy plating solution according to claim 2, wherein sulfate ions are present in the plating solution, and a molar ratio represented by nickel / sulfate ions exceeds 1. 4. The alkaline zinc-nickel alloy plating solution according to claim 2 or 3 , wherein the complexing agent is a reaction product of an amine and an epoxy group-containing compound.   The alkaline zinc-nickel alloy plating solution according to claim 4, wherein the amine used as the complexing agent raw material has 4 or more nitrogen atoms in one molecule. A nickel replenisher,
The nickel replenisher is nickel carbonate, Ni (OH) ₂ And a nickel source selected from nickel chloride,
And does not contain a compound group consisting of aromatic sulfonic acid, aromatic sulfonamide, aromatic sulfonimide, acetylene compound, allyl compound, nitrile compound, sulfate ester,
The nickel replenisher is used for the alkaline zinc-nickel alloy plating solution according to any one of claims 2 to 5,
The nickel replenisher, wherein the molar ratio represented by nickel / halogen ions in the alkaline zinc-nickel alloy plating solution exceeds 0.5 when the nickel replenisher is replenished. A nickel replenisher,
The nickel replenisher is nickel carbonate, Ni (OH) ₂ And a nickel source selected from nickel chloride,
And does not contain a compound group consisting of aromatic sulfonic acid, aromatic sulfonamide, aromatic sulfonimide, acetylene compound, allyl compound, nitrile compound, sulfate ester,
And it does not contain sulfate ions,
The nickel replenisher, which is used for the alkaline zinc-nickel alloy plating solution according to claim 1. The nickel replenisher according to claim 6 or 7,
The nickel supplement further includes a complexing agent,
The nickel replenisher , wherein the complexing agent is a reaction product of an amine and an epoxy group-containing compound.   The method to perform electrolytic zinc-nickel alloy plating with the plating solution of any one of Claims 1-5. The nickel replenishment method which uses the replenisher of any one of Claims 6-8 for the plating solution of any one of Claims 1-5. Any claim to use a plating solution according to any one of claim 1 to 5, aldehyde, pyridinium compounds, any one or more components of the organic sulfur compounds or al a compound selected group periodically while adding An alkaline zinc-nickel alloy plating solution management method in which the component is controlled at a concentration of 0.0005 mol / L or less.   An alkaline zinc-nickel alloy plating solution management method that uses the plating solution according to any one of claims 1 to 5 and does not periodically add a compound group selected from an aldehyde, a pyridinium compound, and an organic sulfur compound. . An alkaline zinc-nickel alloy plating method, wherein the alkaline zinc-nickel alloy plating solution managed by the management method according to claim 11 or 12 is used. Claim 9 or 13 the method by the rear lead - method of producing a nickel alloy plated products.