JP2013014833A - Zinc-nickel alloy plating liquid and plating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a zinc-nickel electroplating liquid formable of a coating of a zinc-nickel alloy film on a metal member, the coating being high in the eutectoid ratio of Ni and excellent in appearance and corrosion resistance.SOLUTION: This zinc-nickel plating liquid includes: one or more reaction products produced by mixing amines having 4 or more nitrogen atoms in a molecule and a compound including an epoxy group and a halogen group together in a molecule; and a soluble polymer.

Description

  The present invention relates to zinc-nickel alloy plating, which is practically impossible with existing nickel complexing agents and brighteners / additives. And a plating solution. In addition, this plating solution makes it possible to deposit an excellent plating film having a nickel eutectoid rate that cannot be stably supplied by conventional zinc-nickel alloy plating, and it is possible to supply nickel with a method that can be supplied more stably than before. In addition to being able to provide nickel plating with a deposition rate, the plating solution according to the present invention has also succeeded in extending the life by a management method that is impossible with conventional plating solutions.

  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. In the conventional zinc-nickel alloy plating, as disclosed in JP-A-63-53285, the electrolytic plating is carried out in an alkaline electrogalvanizing bath containing nickel solubilized with a complexing agent, thereby forming a zinc plating film. It is carried out by a method of precipitating nickel. Polyalkene polyamines and alkanolamines are mentioned as complexing agents that can obtain a nickel eutectoid rate of 2% or more. As the brightener, a reaction product of amines and epihalohydrin is used as a primary brightener, an aromatic aldehyde is used as a secondary brightener, and a tellurium compound is used as a tertiary brightener. In addition, plating baths using reaction products of amine compounds and glycidyl ethers such as epihalohydrins as complexing agents are also disclosed in JP-A-6-173073 and JP-A-2007-2274. Yes. This is superior in running performance as compared with the case where amines are used as they are as complexing agents, and is therefore the most commonly used complexing agent in current zinc-nickel alloy plating.

JP-A-63-53285 JP-A-6-173073 JP 2007-2274 A

  However, the conventional zinc-nickel alloy plating solution has a very sensitive characteristic to temperature. If the plating line is kept moving at 25 ° C. or higher, the complexing agent and the primary brightener change due to the reaction, and the chelate becomes strong. Then, not only the nickel eutectoid rate is lowered but also the physical properties of the plating are lowered, and a symptom in which kogation occurs in the high current portion occurs. Furthermore, since the current efficiency is lower than that of galvanizing, the heat generation is very large, and a great deal of energy and temperature management are required to maintain a low temperature around 20 ° C. Therefore, it is a big problem in zinc-nickel alloy plating to provide a plating film that is the same as when plated at about 20 ° C. even at 25 ° C. or higher. Further, in the case of plating using a plating solution using a complexing agent and a brightener using a reaction product of a conventional amine and epihalohydrin, the nickel eutectoid rate that can be stably supplied is only 8 to 10%. This is inferior in corrosion resistance although it is superior in workability as compared with an alloy plating having a nickel eutectoid rate of 15% or more, which is known to be stably obtained by changing the complexing agent. Moreover, there has been no method for stably obtaining an alloy plating having a nickel eutectoid rate intermediate between the two. Also, in terms of concentration management, in the conventional zinc-nickel alloy plating, if the optimum nickel concentration and complexing agent concentration during the plating bath preparation are maintained, the complexing agent, brightener and additives are added along with running. There is a phenomenon that the nickel eutectoid rate decreases due to the change and the chelate becoming stronger. However, when the nickel concentration is increased, the nickel eutectoid rate can be maintained, but the appearance and physical properties are deteriorated. Therefore, he was forced to rebuild frequently, which was not only economical but also had a great negative impact on the environment.

（式中、Ｒ１、Ｒ２は水素、メチル、エチル、イソプロピル、ブチル、−ＣＨ₂ＣＨ₂（ＯＣＨ₂ＣＨ₂）_XＯＨ（Ｘは０〜５）又は−ＣＨ₂ＣＨ₂（ＯＣＣＨ₂ＣＨ₂）_XＯＨ（Ｘは０〜５）を表わし、ｎは１以上を表わす）で表されるポリマー、構造式（２）

（式中、Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれ水素、メチル、エチル、イソプロピル、２−ヒドロキシルエチル−ＣＨ₂ＣＨ₂（ＯＣＨ₂ＣＨ₂）xＯＨ（Ｘは０〜６）又は２−ヒドロキシルエチル−ＣＨ₂ＣＨ₂（ＯＣＣＨ₂ＣＨ₂）xＯＨ（Ｘは０〜６）を表わし、Ｒ５は（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₂、（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₂又はＣＨ₂−ＣＨＯＨ−ＣＨ₂−Ｏ−ＣＨ₂−ＣＨＯＨ−ＣＨ₂を表わし、ｎは１以上であり、ＹはＳ又はＯである）で表されるポリマー、構造式（３）

（式中、Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれ水素、メチル、エチル、イソプロピル、２−ヒドロキシルエチル−ＣＨ₂ＣＨ₂（ＯＣＨ₂ＣＨ₂）xＯＨ（Ｘは０〜６）又は２−ヒドロキシルエチル−ＣＨ₂ＣＨ₂（ＯＣＣＨ₂ＣＨ₂）xＯＨ（Ｘは０〜６）を表わし、Ｒ５は（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₂、（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₂又はＣＨ₂−ＣＨＯＨ−ＣＨ₂−Ｏ−ＣＨ₂−ＣＨＯＨ−ＣＨ₂を表わし、ｎは１以上を表わし、ＹはＳ又はＯを表わす）で表されるポリマー、構造式（４）

（式中、Ｒ１及びＲ２はそれぞれ水素、メチル、エチル、イソプロピル、ブチル、−ＣＨ₂ＣＨ₂（ＯＣＨ₂ＣＨ₂）_XＯＨ（Ｘは０〜５）又は−ＣＨ₂ＣＨ₂（ＯＣＣＨ₂ＣＨ₂）_XＯＨ（Ｘは０〜５）を表わし、ｎは１以上を表わし、ＹはＯ又はＳを表わす）をモノマーとするポリマー、構造式（５）

（式中、Ｒ１又はＲ２は水素、メチル、エチル、ブチル又はイソブチルを表し、Ｒ３はＣＨ₂、Ｃ₂Ｈ₄又はＣ₃Ｈ₆を表わす）で表されるポリマー、構造式（６）

（式中、Ｒ１及びＲ２はそれぞれ水素又は炭素数が１０以下のアルキルを表わす）で表されるポリマー、構造式（７）

（式中、Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれ水素又はＣが５以下のアルキルを表わし、Ｘは無機陰イオンを表わし、ＹはＳ又はＯを表わす）で表されるポリマー、構造式（８）

（式中、Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれ水素又は炭素数が５以下のアルキルを表わし、Ｘは無機陰イオンを表わし、ＹはＳ又はＯを表わす）で表されるポリマー、及び構造式（９）

（式中、Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれ水素、メチル、エチル、イソプロピル、２−ヒドロキシルエチル−ＣＨ₂ＣＨ₂（ＯＣＨ₂ＣＨ₂）xＯＨ（Ｘは０〜６）又は２−ヒドロキシルエチル−ＣＨ₂ＣＨ₂（ＯＣＣＨ₂ＣＨ₂）xＯＨ（Ｘは０〜６）を表わし、ｎは２〜４を表わす）で表されるポリマー、及び、（ａ）イミダゾール、（ｂ）エピハロヒドリンの水溶性反応生成物、及び、（ａ）ニコチン酸、（ｂ）エピハロヒドリンの水溶性反応生成物、及び、（ａ）尿素又はチオ尿素、（ｂ）ジアルキルアミノエチルアミン及び／又はジアルキルアミノプロピルアミン及び（ｃ）ジクロルアルキルエーテルの水溶性反応性生成物から成る群から選択される１種以上を用いることにより課題を解決した。 As a result of intensive studies by the present inventors, (A) conventionally, amines having 3 or less nitrogen atoms in the molecule have been used as amines for complexing agents, but amines having 4 or more nitrogen atoms are used ( B) Structural formula (1) as primary brightener and additive

(In the formula, R1 and R2 are hydrogen, methyl, ethyl, isopropyl, butyl, —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _X OH (X is 0 to 5) or —CH ₂ CH ₂ (OCCH ₂ CH ₂ ). A polymer represented by _X OH (where X represents 0 to 5 and n represents 1 or more), structural formula (2)

(Wherein, R1, R2, R3 and R4 are each hydrogen, methyl, ethyl, isopropyl, 2-hydroxyethyl _{-CH 2 CH 2 (OCH 2 CH} 2) xOH (X is 0-6) or 2-hydroxyethyl - _{CH 2 CH 2 (OCCH 2 CH} 2) xOH (X is 0-6) represents, R5 is _{(CH 2) 2 -O- (CH} 2) 2, (CH 2) 2 -O- (CH 2) 2 -O- (CH ₂ ) ₂ or CH ₂ -CHOH-CH ₂ -O-CH ₂ -CHOH-CH ₂ , n is 1 or more, and Y is S or O), Structural formula (3)

(Wherein, R1, R2, R3 and R4 are each hydrogen, methyl, ethyl, isopropyl, 2-hydroxyethyl _{-CH 2 CH 2 (OCH 2 CH} 2) xOH (X is 0-6) or 2-hydroxyethyl - _{CH 2 CH 2 (OCCH 2 CH} 2) xOH (X is 0-6) represents, R5 is _{(CH 2) 2 -O- (CH} 2) 2, (CH 2) 2 -O- (CH 2) 2 -O- (CH ₂₎ represents ₂ or _{CH 2 -CHOH-CH 2 -O-} CH 2 -CHOH-CH 2, n is 1 or more, Y is a polymer represented by the representative) S or O, Structural formula (4)

Wherein R1 and R2 are each hydrogen, methyl, ethyl, isopropyl, butyl, —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _X OH (X is 0 to 5) or —CH ₂ CH ₂ (OCCH ₂ CH ₂ ) _X OH (X represents 0 to 5), n represents 1 or more, Y represents O or S), a polymer having a monomer, structural formula (5)

Wherein R1 or R2 represents hydrogen, methyl, ethyl, butyl or isobutyl, and R3 represents CH ₂ , C ₂ H ₄ or C ₃ H ₆ , a structural formula (6)

(Wherein R1 and R2 each represent hydrogen or alkyl having 10 or less carbon atoms), structural formula (7)

Wherein R 1, R 2, R 3 and R 4 are each hydrogen or C is alkyl having 5 or less, X is an inorganic anion, and Y is S or O, a structural formula (8 )

(Wherein R1, R2, R3 and R4 each represent hydrogen or alkyl having 5 or less carbon atoms, X represents an inorganic anion, and Y represents S or O), and a structural formula (9)

(Wherein, R1, R2, R3 and R4 are each hydrogen, methyl, ethyl, isopropyl, 2-hydroxyethyl _{-CH 2 CH 2 (OCH 2 CH} 2) xOH (X is 0-6) or 2-hydroxyethyl - CH ₂ CH ₂ (OCCH ₂ CH ₂ ) x OH (X represents 0 to 6 and n represents 2 to 4), a water-soluble reaction of (a) imidazole and (b) epihalohydrin Products, and (a) water-soluble reaction products of nicotinic acid, (b) epihalohydrin, and (a) urea or thiourea, (b) dialkylaminoethylamine and / or dialkylaminopropylamine and (c) di The problem has been solved by using one or more selected from the group consisting of water-soluble reactive products of chloroalkyl ethers.

  Conventionally, when a reaction product of an amine having 4 or more nitrogen atoms in one molecule belonging to Group (A) and an epihalohydrin is used as a complexing agent, the gloss of the plating becomes weak. However, only the reaction product using 2 or 3 amines has been put into practical use.

  The addition of a substance belonging to group (B) as a primary brightener / additive was disclosed in JP-A-11-193488, JP-A-2001-226793, etc., but was actually added to zinc-nickel alloy plating. In this case, the current efficiency and the nickel eutectoid rate are lowered and the plating appearance is deteriorated when the addition of No. 3 sodium silicate is not performed. When No. 3 sodium silicate is added, current efficiency is reduced compared to conventional zinc-nickel alloy plating. Therefore, it is not used for zinc-nickel alloy plating, but has been used only for zinc plating. There is a background.

  As mentioned above, even if it applies to a zinc-nickel alloy plating solution alone, a plating situation deteriorates, and even if there is an effective interaction, the (A) group as a complexing agent and an additive ( It can be said that it is difficult for those skilled in the art to concomitantly use the substance of group B). However, when the bath composition is reexamined after actually using it together, a stable alloy plating film can be continuously obtained even at 25 ° C. or higher, and the appearance is equal to or more than that of the conventional zinc-nickel alloy plating. The film is an alloy plating with a nickel eutectoid rate of 10 to 13%, which is higher than any of the films with a nickel eutectoid rate of 8 to 10% or 15% or more that have been conventionally obtained stably. High corrosion resistance. Further, by changing the nickel concentration, it is possible to form an alloy plating with a nickel eutectoid rate of 15% or more, and a stable alloy plating film can be formed even at a high temperature of 25 ° C. or more. The current efficiency is not different from the conventional plating bath. Also in concentration control, when the nickel eutectoid rate decreases during running, the nickel eutectoid rate can be maintained by increasing the nickel concentration of the plating bath itself and decreasing the concentration of group (A) used as a complexing agent. In addition, the appearance and physical properties of the plating are not deteriorated, and as a result, the plating bath has been successfully extended in life, thereby reducing costs and reducing environmental impact.

According to the embodiments of the present invention, the following inventions are provided.
(1) Bath dissolution with one or more reaction products produced by mixing an amine having 4 or more nitrogen atoms in one molecule and a compound containing both an epoxy group and a halogen group in one molecule. Any one or more of the structural formulas (1) to (9) as a water-soluble polymer, or (a) a water-soluble reaction product of imidazole and (b) epihalohydrin, (a) a water-soluble reaction product of (b) epihalohydrin And one or more selected from the group consisting of (a) urea or thiourea, (b) a water-soluble reactive product of dialkylaminoethylamine and / or dialkylaminopropylamine and (c) dichloroalkyl ether And an electrolytic plating solution containing a metal ion source for zinc-nickel alloy plating.
(2) The plating solution according to the above (1), wherein the ratio of the addition amount of the reaction product and the bath-soluble polymer is 10: 1 or more.
(3) The plating solution according to (1) or (2), wherein a part or all of nickel is supplied from the group consisting of nickel chloride, nickel hydroxide and nickel carbonate as a nickel source.
(4) The plating solution according to any one of (1) to (3), which is used at a plating solution temperature of 25 ° C. or higher.
(5) The plating solution according to any one of (1) to (4), wherein the amine is a polyalkene polyamine.
(6) The plating solution according to any one of (1) to (4), wherein the compound is an epihalohydrin.
(7) Electrolytic plating characterized by applying a zinc-nickel alloy plating with a nickel eutectoid rate of 10 to 13% using the electrolytic plating solution according to any one of (1) to (6) above. Method.
(8) A member subjected to zinc-nickel alloy plating using the electrolytic plating solution according to any one of (1) to (6) above.

Hereinafter, the zinc-nickel alloy plating of the present invention will be described in detail.
As the amine used in the complexing agent component of group (A), triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, and the like can be used, but are not limited thereto. Not. A product obtained by reacting this with epihalohydrin is used as a complexing agent. Examples of the amine polymer used as the brightener / additive of the group (B) are “MIRAPOL ™ 100” commercially available from Rhone-Poulenc as an example of the polymer of (1), and examples of the polymer of the structural formula (2). As “MIRAPOL ™ WT”, examples of the polymer of the structural formula (3) as “MIRAPOL ™ AD-1”, and examples of the polymer of the structural formula (4) as “MIRAPOL ™ 550”. However, it is not limited to this. Examples of the compound (9) include aminoethylethanolamine and tetramethylethylenediamine, but are not limited thereto.

  The target member for plating is made of iron. The plating bath composition is as shown in Table 1 below, and is characterized in that the zinc concentration is low and the nickel concentration is high compared to the conventional plating bath.

  If the zinc ion concentration is too high, the required amount of brightener increases, which is uneconomical. Further, the uniformity of the film is lowered, and in a member having a complicated shape, the throwing power to the low current portion becomes weak. If it is too low, the plating rate will decrease. When nickel is too high or too low, the nickel eutectoid rate in the film does not become an appropriate value, the appearance of the plating film and the appearance after the chemical conversion film are deteriorated, and the necessary corrosion resistance cannot be obtained. In particular, red rust tends to occur more quickly. It is known that if the hydroxide ion is too high, it will destroy the brightener molecules and increase the amount of brightener required, which is uneconomical. If it is too low, the uniformity of the film and the plating coverage will deteriorate. If the concentration of the complexing agent is too high, the current efficiency is reduced and the amount of replenishment is increased, which increases the labor for wastewater treatment and is uneconomical. If it is too low, the uniformity of the film deteriorates, and not only the appearance of the plating film but also the appearance after the chemical conversion film treatment is deteriorated. (B) If the group concentration is too high, the effect is flat and uneconomical, and if it is too low, the plating film is not sufficiently glossy.

  There is no particular limitation on the nickel source. In actual production sites, nickel sulfate has been used for many years due to problems such as cost. However, other nickel compounds such as nickel chloride, nickel carbonate, and nickel hydroxide can be used in the present invention, and particularly when nickel carbonate and nickel hydroxide are used, compared to the case of using conventional nickel sulfate. This has the effect of extending the life of the plating solution.

  In addition to the above, a brightener component that can be used in conventional zinc-nickel alloy plating can be used. For example, aldehydes and tellurium compounds can be used.

Current density 1~6A / dm ² in a stationary plating for plating conditions, carried out in 0.5~1.5A / dm ² in barrel plating. The plating temperature can be in the range of 15 to 50 ° C., thereby significantly reducing the cost and energy required for cooling compared to conventional zinc-nickel alloy plating.

Hereinafter, the present invention will be described with reference to examples and comparative examples. After performing appropriate pretreatment on the test piece, plating was performed according to each of the examples shown below. In the following examples, unless otherwise specified, an iron plate (50 × 100 × 2 mm) was used as a test piece serving as a cathode, and a nickel plate was used as an anode. The plating conditions were a current density of 4 A / dm ² , a plating bath temperature of 25 ° C., and a plating time of 60 minutes. After plating, a trivalent chromium conversion coating was applied for corrosion resistance evaluation. Nickel sulfate was used as the nickel supply source. The trivalent chromium conversion coating treatment was performed under standard conditions using TRN-988 manufactured by Nippon Surface Chemical Co., Ltd.

I Change in plating bath composition and appearance of plating, nickel eutectoid rate, corrosion resistance Zinc, nickel, complexing agent, and (B) group substances were changed to evaluate appearance and corrosion resistance. Hereinafter, unless otherwise specified, a reaction product of triethylenetetramine and epichlorohydrin was used as the complexing agent, and “MIRAPOL ™ 100” was used as the group (B) substance. Appearance was evaluated for gloss and uniformity. Corrosion resistance measured the time until red rust generation. The results are shown in Table 2.

II Complexing Agent Component The complexing agent component of the present invention is provided by the reaction product of an amine having 4 or more nitrogen atoms and an epihalohydrin. Therefore, the products of a plurality of amines and epihalohydrins were plated under the same conditions as in Example 1, and the appearance, nickel eutectoid rate, and corrosion resistance were compared. The results are shown in Table 3.

III (B) Group Substances The results of plating with substances other than “MIRAPOL ™ 100” under the same conditions as in Example 1 are shown in Table 4 below.

IV Temperature A plating test was conducted under the same conditions as in Example 1 except for the temperature change during plating. The results are shown in Table 5.

V Nickel eutectoid rate change The plating solution of this invention can obtain stably the plating which changed nickel eutectoid rate by changing nickel concentration. The results are shown in Table 6.

  Furthermore, when a temperature change test is performed with the nickel concentration of Example 28, it is as shown in Table 7 below.

VI Barrel Plating Test After a suitable pretreatment was performed on the test piece, plating was performed according to each of the following examples.
The test piece used as the cathode was a bolt (M8 × 50 mm), and the anode was a nickel plate.
The plating conditions were a current density of 1 A / dm ² , a plating bath temperature of 25 ° C., a plating time of 90 minutes, and a trivalent chromium conversion coating treatment was applied after plating. The trivalent chromium conversion coating treatment was performed under standard conditions using TRN-988 manufactured by Nippon Surface Chemical Co., Ltd. The results are shown in Table 8.

Comparative Examples 1-4
Various tests were conducted using a reaction product of diethyltriamine and epichlorohydrin as a complexing agent component. The results are shown in Table 9.

Comparative Examples 5-12
Various tests were conducted using a reaction product of triethylenetetramine and epichlorohydrin as a complexing agent component. The results are shown in Table 10.

Comparative Examples 13-16
About the comparative example 1, it plated by changing temperature. The results are shown in Table 11.

Comparative Examples 17-21
The plating bath is constructed using the standard product Nihon Surface Chemical Co., Ltd. complexing agent and brightener ZN-204, which can stably supply high nickel plating with a nickel eutectoid rate of 15% or more. When the temperature change test was performed, the results were as shown in Table 12.

Comparative Examples 22-25
When ZN-204 was used at 20 ° C. and the nickel concentration in the plating bath was changed, the results shown in Table 13 below were obtained. Even if the nickel concentration was lowered, the plating film having a nickel concentration of 10 to 13% according to the present invention was obtained. It can be seen that can not be stably supplied.

  Each of the plating solutions of Example 1 and Comparative Example 1 was subjected to a running test for 1 month at 10 AH / L per day. In order to maintain the nickel eutectoid rate while appropriately replenishing the chemicals, the nickel concentration in the plating solution was gradually increased and the complexing agent concentration was gradually decreased. The results shown in Table 14 below were obtained. .

  When the running test of Comparative Example 1 was performed without changing the Ni concentration and the (A) group concentration, the results shown in Table 15 below were obtained.

  When the running test was conducted on Comparative Example 18, the results shown in Table 16 below were obtained.

  Moreover, when the running test of Comparative Example 18 was performed without changing the Ni concentration and the (A) group concentration, the results shown in Table 17 below were obtained.

  In Example 1 and the case where the nickel supply source was changed to nickel carbonate and nickel hydroxide, a three-month running test was performed. When nickel sulfate was used, the corrosion resistance did not change, but the appearance was uneven. It was. When nickel carbonate and nickel hydroxide were used, both the appearance and corrosion resistance were kept in good condition. Further, when nickel sulfate and nickel hydroxide were used in half each, the degree of unevenness in appearance was smaller than when the entire amount was replenished with nickel sulfate.

Claims (8)

One or more reaction products produced by mixing an amine having 4 or more nitrogen atoms in one molecule and a compound containing both an epoxy group and a halogen group in one molecule, and a structural formula ( 1)

(In the formula, R1 and R2 are hydrogen, methyl, ethyl, isopropyl, butyl, —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _X OH (X is 0 to 5) or —CH ₂ CH ₂ (OCCH ₂ CH ₂ ). A polymer represented by _X OH (where X represents 0 to 5 and n represents 1 or more), structural formula (2)

(Wherein, R1, R2, R3 and R4 are each hydrogen, methyl, ethyl, isopropyl, 2-hydroxyethyl _{-CH 2 CH 2 (OCH 2 CH} 2) xOH (X is 0-6) or 2-hydroxyethyl - _{CH 2 CH 2 (OCCH 2 CH} 2) xOH (X is 0-6) represents, R5 is _{(CH 2) 2 -O- (CH} 2) 2, (CH 2) 2 -O- (CH 2) 2 -O- (CH ₂ ) ₂ or CH ₂ -CHOH-CH ₂ -O-CH ₂ -CHOH-CH ₂ , n is 1 or more, and Y is S or O), Structural formula (3)

(Wherein, R1, R2, R3 and R4 each represent a hydrogen, methyl, an ethyl, isopropyl, 2-hydroxyethyl _{-CH 2 CH 2 (OCH 2 CH} 2) xOH (X is 0-6) or 2-hydroxyethyl - _{CH 2 CH 2 (OCCH 2 CH} 2) xOH (X is 0-6) represents, R5 is _{(CH 2) 2 -O- (CH} 2) 2, (CH 2) 2 -O- (CH 2) 2 -O- (CH ₂₎ represents ₂ or _{CH 2 -CHOH-CH 2 -O-} CH 2 -CHOH-CH 2, n is 1 or more, Y is a polymer represented by the representative) S or O, Structural formula (4)

Wherein R1 and R2 are each hydrogen, methyl, ethyl, isopropyl, butyl, —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _X OH (X is 0 to 5) or —CH ₂ CH ₂ (OCCH ₂ CH ₂ ) _X OH (X represents 0 to 5), n represents 1 or more, Y represents O or S), a polymer having a monomer, structural formula (5)

Wherein R1 or R2 represents hydrogen, methyl, ethyl, butyl or isobutyl, and R3 represents CH ₂ , C ₂ H ₄ or C ₃ H ₆ , a structural formula (6)

(Wherein R1 and R2 each represent hydrogen or alkyl having 10 or less carbon atoms), structural formula (7)

Wherein R 1, R 2, R 3 and R 4 are each hydrogen or C is alkyl having 5 or less, X is an inorganic anion, and Y is S or O, a structural formula (8 )

(Wherein R1, R2, R3 and R4 each represent hydrogen or alkyl having 5 or less carbon atoms, X represents an inorganic anion, and Y represents S or O), and a structural formula (9)

(Wherein, R1, R2, R3 and R4 each represent a hydrogen, methyl, ethyl, isopropyl, 2-hydroxyethyl _{-CH 2 CH 2 (OCH 2 CH} 2) xOH (X is 0-6) or 2-hydroxyethyl - CH ₂ CH ₂ (OCCH ₂ CH ₂ ) x OH (X represents 0 to 6 and n represents 2 to 4), and (a) water-soluble reaction product of (imidazole) and (b) epihalohydrin , (A) water-soluble reaction product of nicotinic acid and (b) epihalohydrin, and (a) urea or thiourea, (b) dialkylaminoethylamine and / or dialkylaminopropylamine and (c) dichloroalkyl ether An electroplating solution containing at least one selected from the group consisting of water-soluble reactive products and a metal ion source for zinc-nickel alloy plating.   The plating solution according to claim 1, wherein the ratio of the reaction product to the addition amount of the bath-soluble polymer is 10: 1 or more.   The plating solution according to claim 1 or 2, wherein a part or all of nickel is supplied from the group consisting of nickel chloride, nickel hydroxide and nickel carbonate as a nickel source.   The plating solution according to any one of claims 1 to 3, which is used at a plating solution temperature of 25 ° C or higher.   The plating solution according to claim 1, wherein the amine is a polyalkene polyamine.   The plating solution according to claim 1, wherein the compound is an epihalohydrin.   An electroplating method comprising applying a zinc-nickel alloy plating with a nickel eutectoid rate of 10 to 13% using the electroplating solution according to any one of claims 1 to 6.   The member which gave zinc-nickel alloy plating using the electrolytic plating solution of any one of Claims 1-6.