JP7074197B2 - Electroplating bath, manufacturing method of electroplating products, and electroplating equipment - Google Patents

Description

The present invention relates to an electroplating bath, a method for manufacturing an electroplating product, and an electroplating apparatus.

As a form of the electric Co-plating method and the electric Co-Ni plating method, a method using a soluble anode and a method using an insoluble anode are known. The soluble anode is, for example, an ingot composed of a metal as a plating source, or a metal piece as a plating source and an insoluble container for storing the ingot (sometimes referred to as a basket-type anode). be. Considering workability, plating uniformity, and the like, it is said that a soluble anode composed of an insoluble container and a plating source is preferable. For example, Patent Document 1 describes a basket-type anode that houses plating raw material grains in a plating bath and is used for electrolytic plating of a steel strip, in which the basket-type anode is arranged so as to face the steel strip. Disclosed is a basket-type anode comprising a reticulated member made of steel, wherein the reticulated member contains a platinum group element.

As the Co plating bath used in the Co plating method using a soluble anode, a bath in which cobalt sulfate or cobalt sulfamic acid is used as a Co source and boric acid, cobalt chloride, sodium chloride or the like is added to them is often used. Further, it is also possible to add Ni to such a Co plating bath to perform Co—Ni alloy plating. In Non-Patent Document 1, a plating bath composed of Ni sulfate, Ni chloride, Co sulfate, and boric acid is used, and Ni—Co alloy plating is performed with an insoluble basket type soluble anode in which Ni pellets and Co pellets are filled in a Ti basket. It is shown. In Patent Document 2, a Ni-Co alloy plating can be performed with an insoluble basket-type soluble anode in which Ni pellets are filled in a Ti basket using a plating bath composed of Ni sulfate, Ni chloride, Co sulfate, boric acid, and sodium lauryl sulfate. It is shown.

Electric Co plating and electric Ni—Co alloy plating using a soluble anode have an advantage that an inexpensive metal piece can be used as a plating source instead of an expensive metal salt. However, in recent years, there has been a demand for further improvement in the production efficiency of plated products, and as a result, electroplating using a soluble anode has the problems described below.

One of the means for improving the production efficiency of Co-plated products and Co—Ni plated products is to increase the ion concentration of the plating source in the electroplating bath in order to improve the current density. However, if the Co concentration in the electroplating bath is increased, a black sludge reaction may proceed on the insoluble components constituting the soluble anode. The black sludge reaction is a reaction in which Co ²⁺ in an electroplating bath is oxidized to generate CoO (OH). Even if it is a soluble anode, such a reaction is unlikely to occur when a metal Co plate or an ingot or the like is directly used for the anode without using an insoluble container. The insoluble container of the soluble anode ideally has only the function of carrying the electron conduction between the plating source and the power source, and the electrochemical reaction such as the black sludge reaction should not occur on this surface. However, in reality, in a large-scale and high-speed plating process represented by a continuous surface treatment process for thin steel plates, a black sludge reaction occurs on the surface of an insoluble container. This is because, in the case of small-scale component plating, it is possible to arrange a large number of anodes around the material to be plated, and although it is possible to keep the current density of the anode low with respect to the plating current density, it is continuous. In a large-scale and high-speed plating process represented by a surface treatment process, one of the reasons is that a current density almost equal to that of the plating current density is also applied to the anode.

When continuous plating is performed in a state where black sludge can be generated, the characteristics of the plating bath are changed due to the black sludge contaminating the bath, and the electrolytic resistance is increased due to the anode surface being covered with black sludge, resulting in increased power consumption. In some cases, it may increase, and in some cases, a high voltage exceeding the capacity of the plating apparatus may be required. In such a case, the bath and the anode need to be replaced, which impairs the production efficiency of the plated product.

Another means of improving the production efficiency of Co-plated products and Co—Ni plated products is to include chloride ions in the electroplating bath in order to efficiently dissolve the metal Co of the soluble anode. Chloride ions have a function of promoting the dissolution of metal Co at the anode. By promoting the dissolution of the soluble anode, the ion concentration of the plating source in the electroplating bath can be increased and the current density can be improved. For example, the chloride ion concentration of a general Watt bath type Co plating bath is about 10 to 20 g / L. However, chlorine gas is generated in electroplating using an electroplating bath containing chloride ions. For example, when this electroplating bath is applied to electroplating with a current density of more than 10 A / dm ² , there is a possibility that the periphery of the electroplating apparatus will be filled with odor.

In the method for producing a Co-plated product and a Co-Ni-plated product in which a soluble anode having an insoluble container and an electroplating bath having a high Co concentration are combined, the generation of chlorine gas and black sludge becomes a problem. No means is known to solve these problems while keeping the current density high.

International Publication No. 2015/198958 Pamphlet JP-A-2007-122940

Toyo Kohan, vol. 39, p17

An object of the present invention is to provide an electroplating bath having a high Co ion concentration in order to increase the current density and capable of suppressing the generation of chlorine gas even when used in combination with a soluble anode. Furthermore, the present invention uses a combination of an electroplating bath having a high Co ion concentration and a soluble anode, and is capable of suppressing chlorine gas and black sludge reactions while increasing the current density, and a method for manufacturing an electroplating product and electricity. The subject is to provide a plating apparatus.

According to common wisdom, when trying to suppress the generation of chlorine gas from an electroplating bath, reduce the chloride ion concentration, reduce the current density, and consider other components that can replace the chloride ion in the electroplating bath. Etc. are expected to be effective. The present inventors have obtained findings that are completely different from this expectation. That is, as a result of diligent studies, the present inventors have found that it is effective to increase the chloride ion concentration of the electroplating bath in order to suppress the generation of chlorine gas from the electroplating bath. Specifically, it was found that when the chloride ion concentration in the electroplating bath was 70 g / L or more, almost no odor was generated during the electroplating. For example, the chloride ion concentration of a general Watt bath type Co plating bath is about 10 to 20 g / L, and the suitable chloride ion concentration found by the present inventors is three times or more of this. .. The present inventors have also found that an increase in the chloride ion concentration of the electroplating bath also contributes to the suppression of the black sludge reaction.

If the electroplating bath obtained based on the above findings is used, it has a high Co ion concentration in order to increase the current density, and even when combined with a soluble anode, it is possible to suppress the generation of chlorine gas and black sludge. .. However, the present inventors preferably do not make the current pattern during electroplating into a pulse shape, and preferably arrange both the electrically insulating region and the exposed region in the insoluble container having the soluble anode, thereby black sludge. It was also found that the reaction can be suppressed more efficiently.

The present invention has been made based on the above findings, and the gist thereof is as follows.
(1) The electroplating bath according to the present invention is an electroplating bath for producing electric Co plating or electric Co—Ni alloy plating, and has 20 to 200 g / L of Co ions and 131.5 to 250 g / g. The total molar concentration of the alkali metal ion, the alkaline earth metal ion, and the Al ion containing L Cl ion is 1.20 mol / L or less.
(2) The electroplating bath according to (1) above may further contain Ni ions of 100 g / L or less.
(3) In the electroplating bath according to (1) or (2) above, the mass concentration of the Cl ion / the mass concentration of the Co ion may be 1.5 or more.
(4) In the electroplating bath according to any one of (1) to (3) above, the molar concentration of K ions in the alkali metal ions is 1.0 mol / L or less, and the alkaline earth metal. The total molar concentration of the ion and the Al ion may be 0.35 mol / L or less.
(5) The electroplating bath according to any one of (1) to (4) above may contain 35 g / L or more of the Co ion.
(6) The electroplating bath according to any one of (1) to (5) above may contain 120 to 200 g / L of the Cl ion.
(7) In the electroplating bath according to any one of (1) to (6) above, the Co ion consists of a group consisting of cobalt sulfate, cobalt sulfamate, cobalt nitrate, cobalt chloride, and cobalt fluoride. It may be a Co ion of one or more water-soluble Co salts selected.
(8) In the electroplating bath according to any one of (1) to (6) above, the Co ion is Co, which is one or more halogen compounds selected from the group consisting of cobalt chloride and cobalt fluoride. It may be an ion.
(9) The method for manufacturing an electroplated product according to another aspect of the present invention comprises a step of immersing a soluble anode and a member connected to a cathode in an electroplating bath to energize, and in the energization, a current is generated. The electric plating bath is an electric plating bath for producing electric Co plating or electric Co—Ni alloy plating, in which the energization direction is one direction, and 20 to 200 g / L of Co ions and 70 to 250 g / L. The total molar concentration of alkali metal ion, alkaline earth metal ion, and Al ion is 1.20 mol / L or less, and the soluble anode is the plating source and the plating source is. An insoluble container made of one or more metals selected from titanium, zirconium, niobium, tantalum, and hasterloy, which is filled and electrically connected to the plating source, is provided, and the insoluble container is the insoluble container of the insoluble container. It has a liquid-passing portion configured so that the inside and the outside communicate with each other, the soluble anode is arranged so that the liquid-passing portion faces the member, and at least a part of the outer surface of the insoluble container is formed. The member and the soluble ion are arranged so that the entire region of the outer surface of the insoluble container facing the member is the electrically insulated region, and the insoluble container is provided. Has a square pillar shape.
(10) In the method for manufacturing an electroplated product according to (9) above, the entire surface of the inner surface of the insoluble container that comes into contact with the plating source may be exposed.
(11) In the method for manufacturing an electroplated product according to (9) or (10) above, the first outer surface of the insoluble container, the second outer surface and the third outer surface on both sides thereof, and the outer bottom surface thereof. However, the soluble anode may be arranged so that the first outer surface faces the member.
(12) In the method for manufacturing an electroplated product according to (11) above, the lower portion of the fourth outer surface opposite to the first outer surface of the insoluble container is defined as the electrically insulating region. The lower portion of the fourth outer surface opposite the first outer surface of the insoluble container is within 20% of the height of the fourth outer surface from the lower end of the fourth outer surface. There may be.
(13) In the method for manufacturing an electroplated product according to any one of (9) to (12) above, the portion of the inner surface of the insoluble container that does not come into contact with the plating source is the electrically insulating region. It may have been done.
(14) In the method for manufacturing an electroplated product according to any one of (9) to (13) above, a step of Ni-plating or Ni-alloy plating on the member may be provided as a pretreatment.
(15) In the method for manufacturing an electroplated product according to any one of (9) to (14) above, the plating source of the soluble anode is composed of a Co piece, a Ni piece, and a Co—Ni alloy piece. It may contain one or more selected from the group.
(16) In the method for manufacturing an electroplated product according to any one of (9) to (15) above, the shape of the member may be a plate shape.
(17) In the method for producing an electroplated product according to any one of (9) to (16) above, the electroplating bath may further contain Ni ions of 100 g / L or less.
(18) The electroplating device according to another aspect of the present invention includes a soluble ion, a cathode, an electroplating bath, and a control device, so that the control device has a current energization direction in one direction. The electroplating bath is an electroplating bath for producing electric Co plating or electric Co—Ni alloy plating, and contains 20 to 200 g / L of Co ions and 70 to 250 g / L of Cl ions. , And the total molar concentration of alkali metal ions, alkaline earth metal ions, and Al ions is 1.20 mol / L or less, and the soluble anode contains the plating source and the plating source. An insoluble container made of one or more metals selected from titanium, zirconium, niobium, tantalum, and hasterloy, which is electrically connected to the plating source, is provided, and the insoluble container is inside and outside the insoluble container. The cathode and the soluble ion are arranged so that the cathode and the liquid-passing portion face each other, and at least a part of the outer surface of the insoluble container is electrically operated. The cathode and the soluble ion are arranged so that the entire region of the outer surface of the insoluble container facing the cathode is the electrically insulating region, and the insoluble container is formed. It has a square column shape.
(19) In the electroplating apparatus according to (18) above, the electroplating bath may further contain Ni ions of 100 g / L or less.

The electroplating bath according to the present invention has an increased Co ion concentration in order to increase the current density, and can suppress the generation of chlorine gas even when used in combination with a soluble anode. The method for manufacturing an electroplating product according to the present invention and the electroplating apparatus according to the present invention use an electroplating bath having a high Co ion concentration in combination with a soluble anode, and chlorine gas and chlorine gas while increasing the current density. It is possible to suppress the black sludge reaction. Therefore, according to the present invention, a Co-plated product or a Co—Ni alloy-plated product can be manufactured with high efficiency.

It is a schematic diagram which shows an example of the electroplating apparatus. It is a schematic diagram which shows an example of an insoluble container. It is a side schematic diagram which shows an example of an insoluble container. FIG. 3A is a schematic top view of the insoluble container of FIG. 3A. It is a side schematic diagram which shows an example of an insoluble container. FIG. 4A is a schematic top view of the insoluble container of FIG. 4A. It is a side schematic diagram which shows an example of an insoluble container. FIG. 5A is a schematic top view of the insoluble container of FIG. 5A. It is a side schematic diagram which shows an example of an insoluble container. FIG. 6A is a schematic top view of the insoluble container of FIG. 6A. It is a side schematic diagram which shows an example of an insoluble container. FIG. 7A is a schematic top view of the insoluble container of FIG. 7A. It is a side schematic diagram which shows an example of an insoluble container. FIG. 8A is a schematic top view of the insoluble container of FIG. 8A. It is a side schematic diagram which shows an example of an insoluble container. 9A is a schematic top view of the insoluble container of FIG. 9A. It is a side schematic diagram which shows an example of an insoluble container. It is a schematic top view of the insoluble container of FIG. 10A.

The present inventors have made extensive studies on an electroplating bath that has a high Co ion concentration to increase the current density and can suppress the generation of chlorine gas and black sludge even when used in combination with a soluble anode. .. As a result, when the chloride ion concentration is 70 g / L or more by changing the electroplating bath to a total chloride bath or by adding chloride to the electroplating bath, chlorine gas is reached to a level where almost no chlorine odor is felt. It was found that the outbreak could be suppressed. It is not clear why the unexpected phenomenon that the increase in the amount of chloride ion, which is the source of chlorine gas, decreases the amount of chlorine gas generated. It is considered that the promotion of the dissolution reaction of the plating source of the soluble anode by increasing the amount of chloride ions may contribute to the suppression of the amount of chlorine gas generated.

It was also found that increasing the chloride ion concentration also contributes to the suppression of the oxidation reaction (black sludge reaction) from Co ²⁺ to CoO (OH). The black sludge reaction occurs mainly on the surface of the insoluble container of the soluble anode, but by increasing the chloride ion concentration, the dissolution reaction of the plating source of the soluble anode is prioritized and the black sludge reaction is inactivated. Is believed to be.

By using the electroplating bath having the above-mentioned features, it is possible to reduce the generation of chlorine gas and black sludge to a practical level without particularly limiting the type of the soluble anode. However, the present inventors have repeated further studies. As a result, it was found that providing an electrically insulating region in the insoluble container constituting the soluble anode is more effective in suppressing the black sludge reaction. This is because the black sludge reaction occurs mainly on the surface of the insoluble container, but this reaction does not occur in the electrically insulated region. In particular, when an electrically insulating region is provided in a region closer to the cathode (or a member connected to the cathode) than the plating source in the insoluble container, discoloration of the electrode due to the black sludge reaction can be prevented. We also found that pulsed energization to invert the cathode and anode should be avoided. The pulsed energization that inverts the cathode and anode reduces the plating adhesion efficiency by dissolving the plating, and may also cause plating defects that are presumed to be caused by plating entrainment of minute black sludge, and further, at the anode. It was also found to inhibit the dissolution of the metal Co.

However, the black sludge reaction could not be completely suppressed only by the above-mentioned means. The present inventors have found that it is preferable not to provide an electrically insulating region in the region that can come into contact with the plating source in the insoluble container in order to suppress black sludge. When the region where the insoluble container and the plating source can come into contact includes an electrically insulating region, non-uniformity of the current density and non-uniformity of the Co ion concentration occur, which is considered to promote the black sludge reaction.

The electroplating bath according to the present embodiment, the method for manufacturing the electroplating product according to the present embodiment, and the electroplating apparatus according to the present embodiment, which are obtained based on the above findings, will be described below.

1. 1. Electroplating bath The electroplating bath according to the present embodiment can be used, for example, for Co plating using a soluble anode and Co—Ni alloy plating. First, the electroplating bath according to the present embodiment will be described below.

As the electroplating bath according to the present embodiment, an electroplating bath using a water-soluble Co salt as a Co source can be used. The Co ion concentration in the electroplating bath is 20 to 200 g / L. When the Co ion concentration is insufficient, it becomes necessary to lower the cathode current density, so that the production efficiency of plating is reduced. On the other hand, if the Co ion concentration is too high, the stability of the electroplating bath may decrease and plating defects may occur. The Co ion concentration may be 25 g / L or more, 35 g / L or more, 40 g / L or more, or 60 g / L or more. The Co ion concentration may be 180 g / L or less, 150 g / L or less, or 120 g / L or less.

The type of the Co salt having high water solubility is not particularly limited, but is one or more selected from the group consisting of, for example, cobalt sulfate, cobalt sulfamic acid, cobalt nitrate, cobalt chloride, cobalt fluoride and the like. An electroplating bath using these as a Co source contains one or more selected from the group consisting of sulfate ion, sulfamic acid ion, nitrate ion, chloride ion, and fluoride ion. In order to promote the dissolution of soluble metals such as Co contained in the soluble anode, it is desirable to use a halogen compound such as cobalt chloride and cobalt fluoride as a Co source for electroplating. However, among the halides, iodide is inappropriate as a Co source for electroplating. This is because the iodide ion has a relatively low redox potential and is easily oxidized at the anode. As a result of the oxidation of the iodide ion at the anode, the dissolution of metals such as Co is suppressed, and the generated iodine adversely affects the bath stability and the plating properties.

Generally, in an electroplating bath, a so-called supporting electrolyte may be added in order to reduce the electric resistance of the solution. The supporting electrolyte is a water-soluble salt such as a cation that is difficult to electrodeposit in an aqueous solution, for example, an alkali metal ion, an alkaline earth metal ion, and an Al ion. Although Be and Mg may not be classified as alkaline earth metals, the alkaline earth metals are considered to contain Be and Mg in the electroplating bath according to the present embodiment. In the electroplating bath according to the present embodiment, the inclusion of these supporting electrolytes is permitted. However, in the electroplating bath according to the present embodiment, since the Co ion concentration in the plating bath is relatively high as described above, alkali metal ions, alkaline earth metal ions, and Al ions increase the viscosity of the plating bath. It is presumed to have an effect. As a result, the supporting electrolyte may inhibit the dissolution reaction at the soluble anode, causing chlorine gas generation and black sludge reaction. Therefore, it is desirable that the electroplating bath according to the present embodiment does not contain the supporting electrolyte in principle. When the supporting electrolyte is contained in the electroplating bath according to the present embodiment, it is necessary to limit the concentrations of the alkali metal ion, the alkaline earth metal ion, and the Al ion, which are the cationic components of the supporting electrolyte, as much as possible. Specifically, it is necessary to make the total molar concentration of alkali metal ion, alkaline earth metal ion, and Al ion 1.20 mol / L or less in order to suppress chlorine gas generation and black sludge reaction. be. Even if the total molar concentration of alkali metal ion, alkaline earth metal ion, and Al ion is 1.20 mol / L or less, 1.15 mol / L or less, 1.10 mol / L or less, or 1.00 mol / L or less. good.

Further, it is preferable to set an upper limit of the concentration for individual ions that can constitute the cationic component of the supporting electrolyte after satisfying the above-mentioned regulations. A specific study of the permissible range of individual ions is as follows. When the electroplating bath contains one or both of Li ion and Na ion as alkali metal ions, the total concentration of Li ion and Na ion is 1.20 mol / L or less, 1.15 mol / L or less, 1 It is preferably 10 mol / L or less, or 1.00 mol / L or less. When the electroplating bath contains K ions as alkali metal ions, the concentration of K ions is 1.20 mol / L or less, 1.10 mol / L or less, 1.00 mol / L or less, 0.95 mol / L or less. , Or 0.90 mol / L or less. Of the alkali metals, Rb ion and Cs ion are expensive and are not common as cations of the supporting electrolyte. Therefore, their concentrations should be suppressed to the impurity level. When the electroplating bath contains one or more selected from the group consisting of alkaline earth metal ions and Al ions, the total concentration thereof is 0.50 mol / L or less, 0.45 mol / L or less, 0.40 mol or less. It is preferably / L or less, or 0.35 mol / l or less.

The alkali metal ion, alkaline earth metal ion, and Al ion may be added to the electroplating not as the cation of the supporting electrolyte but as the chloride cation for adding the chloride ion described above. However, even in this case, the total concentration of the alkali metal ion, the alkaline earth metal ion, and the Al ion should be within the above range.

Further, the electroplating bath according to the present embodiment may further contain one or more selected from the group consisting of sulfate ion, sulfamic acid ion, nitrate ion, fluoride ion, borate ion and bromide ion. These are effective as a buffer for suppressing fluctuations in pH during plating. Among them, borate ion is easy to use in view of stability. Needless to say, the use of iodide ions among halogen anions should be avoided as described above. In addition, other known additives such as brighteners can also be added to the electroplating bath.

As the electroplating bath, a Co plating bath or a Ni—Co alloy plating bath is effective from the viewpoint of industrial use, but the electroplating bath is not necessarily limited to this.

The electroplating bath may contain Ni ions. According to such an electroplating bath, Co—Ni alloy plating can be formed. Further, it is considered that Ni ions do not cause problems such as promoting the black sludge reaction. Considering the stability of the electroplating bath, the concentration of Ni ions is preferably 0 to 100 g / L. The Ni ion concentration may be 5 g / L or more, 10 g / L or more, or 20 g / L or more. The Ni ion concentration may be 80 g / L or less, 50 g / L or less, or 40 g / L or less. The Ni source is not particularly limited, and examples thereof include nickel sulfate, nickel sulfamate, nickel nitrate, nickel chloride, and nickel fluoride. It is desirable to use a halogen compound such as nickel chloride to promote the dissolution of Ni and / or Co. Needless to say, in this case as well, the use of iodide as a halide should be avoided. When a trace amount of alloying element is added to Co-plating in order to improve various characteristics of Co-plating, ions of the alloying element can be further contained in the electroplating bath.

The electroplating bath according to this embodiment contains Cl ions. Cl ions have the effect of promoting the dissolution of the plating source of the soluble anode. When Cl ions are not contained, the progress rate of dissolution of the plating source such as Co slows down, so that the ion balance of the electroplating bath cannot be maintained.

The concentration of Cl ions in the electroplating bath according to this embodiment is 70 to 250 g / L. When the concentration of Cl ions is less than 70 g / L, a large amount of chlorine gas is generated during electroplating, and the periphery of the electroplating apparatus is filled with odor. In this case, it is indispensable to provide an exhaust facility or the like in the electroplating apparatus, which impairs the economic efficiency and workability of the electroplating. Therefore, the concentration of Cl ions is set to 70 g / L or more. It is considered that the reason why chlorine gas is generated due to the lack of Cl ions is that the progress rate of dissolution of the plating source such as Co is insufficient. The concentration of Cl ions may be 80 g / L or more, 90 g / L or more, 100 g / L or more, or 120 g / L or more. On the other hand, if the concentration of Cl ions is excessive, the corrosion of plating equipment such as insoluble containers becomes serious. Therefore, the concentration of Cl ions is set to 250 g / L or less. The concentration of Cl ions may be 200 g / L or less, 180 g / L or less, 160 g / L or less, 150 g / L or less, or 130 g / L or less.

As a more advantageous embodiment, it is preferable to control the ratio of the Cl ion concentration to the Co ion concentration to a predetermined value. As the Co ion concentration increases, it becomes a disadvantageous condition for suppressing the chlorine odor. Therefore, it is preferable to increase the Cl ion concentration as well. Specifically, it is preferable that the mass concentration of Cl ions / the mass concentration of Co ions (the value obtained by dividing the mass concentration of Cl ions by the mass concentration of Co ions) is 1.2 or more. For a total chloride bath in which all of the Co ion sources are chlorides, the mass concentration of Cl ions / the mass concentration of Co ions is 1.2, but by adding another chloride to this, Cl It is more preferable to increase the mass concentration of ions / the mass concentration of Co ions. The mass concentration of Cl ions / mass concentration of Co ions may be 1.3 or more, 1.5 or more, or 1.8 or more. The chloride ion constituting the chloride other than Co chloride is preferably ammonium ion, for example.

2. 2. About the manufacturing method (electroplating method) of the plating product Next, the manufacturing method of the electroplating product which concerns on this embodiment will be described. The electroplating method according to the present embodiment includes a step of immersing the soluble anode 11 and the member 12 connected to the cathode in the electroplating bath 10 to energize the electroplating bath 10, and the electroplating bath 10 according to the present embodiment. It is an electroplating bath. Since the electroplating bath 10 contains 20 g / L or more of Co ions, the method for manufacturing an electroplating product according to the present embodiment can perform a highly efficient plating operation with a high current density. Further, since the electroplating bath 10 contains 70 g / L or more of Cl ions, the method for producing an electroplated product according to the present embodiment can suppress the generation of chlorine gas.

The current density for electroplating is not particularly limited, but a higher current density is preferable in order to improve the productivity of the plating work. At least, a high current density of about 10 to 30 A / dm ² can be applied to the method for manufacturing a plated product according to the present embodiment. The upper limit of the current density is generally about 100 A / dm ² , but is not limited to these conditions.

It is desirable that the plating current is a normal direct current current. So-called pulsed energization should be avoided. In particular, pulsed energization that inverts the cathode and anode reduces the plating adhesion efficiency by dissolving the plating. Furthermore, the reversal of the energization direction may also cause plating defects, which are presumed to be caused by plating entrainment of minute black sludge. Inversion of the energization direction also inhibits the dissolution of the metal Co at the anode.

In view of the above circumstances, in the method for manufacturing a plated product according to the present embodiment, at least the current energization direction should be one direction, that is, a pulse current pattern that inverts the anode and the cathode should not be generated. is necessary. Pulse current patterns that increase or decrease the current value without inverting the anode and cathode are acceptable. However, even in this case, a pulse current pattern in which the minimum current value is 0 A is not preferable because it impairs the plating efficiency.

The apparatus for using the method for manufacturing an electroplating product according to the present embodiment is not particularly limited, and for example, the electroplating apparatus 1 illustrated in FIG. 1 can be used. The electroplating apparatus 1 of FIG. 1 includes an electroplating bath 10, a soluble anode 11, and a member 12 connected to the cathode. The soluble anode 11 has an insoluble container 100 and a plating source 101, and is insoluble. The container 100 has a liquid passing portion 111, preferably an electrically insulating region 112. In the method for manufacturing an electroplated product according to the present embodiment, the configuration of the soluble anode 11 and the arrangement of the soluble anode 11 with respect to the member 12 connected to the cathode are preferably defined as follows.

The soluble anode 11 is not particularly limited, but is, for example, one or more selected from titanium, zirconium, niobium, tantalum, and hasteloy, in which the plating source 101 and the plating source 101 are housed and electrically connected to the plating source 101. The insoluble container 100 made of metal may be provided, and the insoluble container 100 may have a liquid passing portion 111 configured so that the inside and the outside of the insoluble container 100 communicate with each other. On the other hand, an ingot made of a plating source 101 may be used as the soluble anode 11. In this case, the soluble anode 11 and the plating source 101 are equated, and the soluble anode 11 does not have the insoluble container 100.

The plating source 101 may be a Co piece when forming Co plating. The shape of the Co piece is, for example, a plate shape, a grain shape, or the like. When forming Co—Ni alloy plating, the plating source 101 may include one or more selected from the group consisting of Co pieces, Co—Ni alloy pieces, and Ni pieces. When a trace element is further contained in the plating in order to improve various characteristics of the plating, the plating source 101 may contain a metal piece of the trace element, an alloy piece containing the trace element, or the like.

The insoluble container 100, sometimes referred to as an insoluble basket, is provided to hold a plating source 101 such as a Co piece in the electroplating bath 10 and to electrically connect the plating source 101 and a power source. The insoluble container 100 needs to be made of a conductive material that does not dissolve in the electroplating bath 10 according to the present embodiment, and is made of one or more metals selected from, for example, titanium, zirconium, niobium, tantalum, and Hastelloy. can do. Considering the material cost, it is preferable to use Ti as the material of the insoluble container 100. Further, a corrosion-resistant Ti alloy obtained by adding a trace alloy element (for example, Pd, Ru, etc.) to Ti is also preferably used.

Further, the insoluble container 100 needs to have a liquid passing portion 111 configured so that the inside and the outside of the insoluble container 100 communicate with each other. During electroplating, the dissolved plating source 101 flows out from the inside of the insoluble container 100 to the outside through the liquid passing portion 111, and adheres to the member 12 connected to the cathode. In order not to obstruct the flow of the melted plating source 101, it is preferable to arrange the soluble anode 11 so that the liquid passing portion 111 faces the member 12. The entire insoluble container 100 may be used as the liquid passing portion 111, while a part thereof may be used as the liquid passing portion 111 as shown in FIG. It is preferable that the liquid passing portion 111 is formed in a net shape as shown in FIG. The net-like shape here also includes a lath-like shape and an expanded-like shape.

On the inner surface of the insoluble container 100, at least a part of the region where the insoluble container 100 and the plating source 101 come into contact with each other needs to be exposed so that the insoluble container 100 and the plating source 101 conduct with each other. Here, the term “exposure” means that the metal constituting the insoluble container 100 is exposed so that the insoluble container 100 and the electroplating bath 10 come into contact with each other and are energized. When the entire surface of the region where the insoluble container 100 and the plating source 101 come into contact with each other is set as the electrically insulating region 112 by using an insulating film or the like, the function of the insoluble container 100 of connecting the plating source 101 and the power supply is fulfilled. It disappears.

Preferably, the entire surface of the area where the insoluble container 100 and the plating source 101 come into contact is exposed. If a part of the region where the insoluble container 100 and the plating source 101 come into contact is the electrically insulating region 112 and the rest is the exposed region, black sludge may be generated in the exposed region. It is presumed that this is because the current density is locally increased by concentrating the current in the exposed region, and the oxidation reaction (black sludge reaction) from Co ²⁺ to CoO (OH) is likely to occur. In this case, it is presumed that the electroplating bath stays inside the insoluble container 100 and the concentration of Co ²⁺ locally increases, which also contributes to the promotion of the black sludge reaction. However, even if a part of the region where the insoluble container 100 and the plating source 101 come into contact with each other is a soluble anode 11 having an electrically insulating region 112, black sludge is used in combination with the electroplating bath according to the present embodiment. Can be maintained at a level where there is no practical inconvenience.

However, as will be described later, the portion of the inner surface of the insoluble container that does not come into contact with the plating source 101 may be an electrically insulating region 112 formed by using an insulating film or the like. This is because the electrically insulating region 112 in the portion that does not come into contact with the plating source 101 does not hinder the uniformity of the current flow and contributes to the suppression of the black sludge reaction described later.

Since it is considered that the local increase in the concentration of Co ²⁺ contributes to the promotion of the black sludge reaction as described above, it is possible to stir the plating bath to make the concentration of Co ²⁺ uniform. desirable. As a method of stirring, a method of forming a plating bath flow using a circulator or the like, a method of performing inert gas bubbling, or the like is used. It is not preferable to use a gas having an oxidizing action such as air as the bubbling gas because this promotes the black sludge reaction.

The outer surface of the insoluble container 100 preferably has an electrically insulating region 112 formed by using an insulating film or the like. In the electrically insulating region 112, the oxidation reaction from Co ²⁺ to CoO (OH) does not occur, so that the generation of black sludge is suppressed. However, even if the soluble anode 11 does not have an electrically insulating region 112 like the soluble anode 11 exemplified in FIGS. 3A and 3B, black sludge is used in combination with the electroplating bath according to the present embodiment. Can be maintained at a level where there is no practical inconvenience.

From the viewpoint of suppressing the generation of black sludge, it is preferable that the entire outside of the insoluble container 100 is an electrically insulating region 112 as in the soluble anode 11 exemplified in FIGS. 5A and 5B. On the other hand, from the viewpoint of cost, it may be preferable to arrange the electrically insulating region 112 only in the place where black sludge is particularly likely to occur from the viewpoint of the whole. An example of the arrangement of the electrically insulated region 112 will be described below.

The portion of the soluble anode 11 where the black sludge reaction is most likely to occur is the surface facing the cathode and the member 12. Therefore, it is preferable to configure and arrange the insoluble container 100 so that the region of the outer surface of the insoluble container 100 facing the member 12 is an electrically insulating region. For example , when the insoluble container 100 has a substantially quadrangular prism shape as shown in FIG. 2, as shown in FIGS. 4A and 4B, the first outer surface of the insoluble container 100 (viewed from the cathode side). The front surface) should be the electrically isolated area.

The current flows between the member 12 connected to the cathode and the plating source 101 in the electroplating bath. Therefore, it is preferable to configure and arrange the insoluble container 100 so that the entire region of the outer surface of the insoluble container 100 closer to the member 12 than the plating source 101 is an electrically insulating region. For example, when the insoluble container 100 has a substantially quadrangular prism shape as shown in FIG. 2, as shown in FIGS. 6A and 6B, the first outer surface of the insoluble container 100 (viewed from the cathode side). The front surface), the second outer surface and the third outer surface (side surface when viewed from the cathode side) on both sides of the first outer surface, and the outer bottom surface are set as an electrically insulating region, and the first with respect to the member 12. By arranging the soluble anode 11 so that the outer surfaces of the insoluble container 100 face each other, the region of the outer surface of the insoluble container 100 that is closer to the member 12 than the plating source 101 can be used as an electrically insulating region.

In addition to the above-mentioned regions, according to the experiments by the present inventors, it was found that black sludge is likely to be generated also in the lower part of the fourth outer surface opposite to the first outer surface of the insoluble container 100. .. Therefore, as shown in FIGS. 7A and 7B, in addition to the first to third outer surfaces and outer bottom surfaces of the insoluble container 100, the fourth outer surface opposite the first outer surface of the insoluble container 100. The lower portion (for example, a region within 20% of the height of the fourth outer surface from the lower end of the fourth outer surface) (the back surface when viewed from the cathode side) may also be an electrically insulating region 112.

Further, according to the experiments by the present inventors, it was found that black sludge is likely to be generated even in the portion of the inner surface of the insoluble container 100 that does not come into contact with the plating source 101. Therefore, as shown in FIGS. 8A and 8B, and FIGS. 9A and 9B, the portion of the inner surface of the insoluble container 100 that does not come into contact with the plating source 101 may be the electrically insulating region 112. The electrically insulating region 112 in the portion not in contact with the plating source 101 does not interfere with the uniformity of the current flow. The configurations shown in FIGS. 8A and 8B, as well as FIGS. 9A and 9B, are such that the plating source 101 is completely submerged in the electroplating bath 10, i.e., the plating source 101 is present only below the waterline. It is particularly effective when the soluble anode 11 is arranged. Of the portions of the inner surface of the insoluble container 100 that do not come into contact with the plating source 101, the portion close to the cathode tends to be relatively unlikely to generate black sludge. It is considered that this is due to the action of the electrically insulating region 112 facing the cathode of the insoluble container 100. Therefore, when it is desirable to reduce the area of the electrically insulated region, as shown in FIGS. 8A and 8B, the portion of the inner surface of the insoluble container 100 that does not come into contact with the plating source 101 and is far from the cathode (for example,). The electrical insulation region 112 may be provided only on the inner surface opposite to the fourth outer surface). On the other hand, as shown in FIGS. 10A and 10B, when the electrically insulating region 112 extends to the region where the insoluble container 100 and the plating source 101 come into contact with each other, the current density and the Co ion concentration become non-uniform as described above. May occur. However, even in this case, when used in combination with the electroplating bath according to the present embodiment, the amount of black sludge generated can be maintained at a level that does not cause any practical inconvenience.

Since the electrically insulating region 112 is for suppressing the oxidation reaction from Co ²⁺ to CoO (OH), it may be formed only in the draft region where Co ²⁺ is present. Therefore, the portion where the above-mentioned electrically insulating region 112 should be formed is the draft region of the insoluble container 100. On the other hand, an electrically insulating region 112 may be provided in the non-draft region of the insoluble container 100 in case the position of the water surface of the electroplating bath 10 is not constant.

The electrically insulating region can be formed by using an insulating film as described above. For example, it can be formed by thermal spraying of ceramics such as alumina, yttria, zirconia, titania, and chromia, or by coating with rubber or resin (for example, fluororesin or polyimide resin), but the present invention is not limited thereto. For example, the insoluble container 100 may be composed of a plurality of parts, and an insulating material may be inserted between the parts (for example, the parts may be connected by an insulating resin material such as a resin bolt) to form an electrically insulating region. 112 can be formed. However, when the electrically insulating region 112 is formed by such means, the inner surface of the insoluble container 100 also becomes the electrically insulating region 112, and as described above, the current density is locally increased and the concentration of Co ²⁺ is increased. There is a risk of local increase in the amount of electricity. Therefore, a suitable means for forming the electrically insulating region 112 is the formation of an insulating film.

The shape of the member 12 is not particularly limited. Regardless of the shape of the member 12, the method for manufacturing an electroplating product according to the present embodiment increases the current density and improves the plating efficiency while suppressing the generation of chlorine gas and black sludge. can do. On the other hand, the shape of the member 12 may be a plate shape. This is because when the shape of the member 12 is a plate shape, the uniformity of the plating thickness is maintained even if the current density is improved. The uniformity of plating is further improved by using the member 12 as a steel plate, at least the portion of the insoluble container 100 facing the steel plate as a flat surface, and arranging both so that the steel plate and the portion of the insoluble container 100 are parallel to each other. be able to.

The material of the member 12 is not particularly limited, and a solid metal, a Ni-plated steel material, a Ni alloy-plated steel material, and a Co material for electrolytic refining of Co can be used. In particular, when the steel material plated with Ni or a Ni alloy is used as the member 12, the dissolution of the metal from the steel material into the electroplating bath 10 can be suppressed, which is preferable. Therefore, the method for manufacturing an electroplated product according to the present embodiment may include a step of Ni-plating or Ni-alloy plating on the member 12 as a pretreatment.

3. 3. About the electroplating device The electroplating device for carrying out the above-mentioned electroplating method is, for example, an electroplating device 1 including an electroplating bath 10, a soluble anode 11, and a cathode configured to be connectable to a member 12. Is. The electroplating bath 10 is the electroplating bath 10 according to the present embodiment, and can be filled in, for example, the plating cell 13. The soluble anode 11 and the cathode are connected to a power source, which may be included in the electroplating device 1 or may be installed outside the electroplating device 1. The electroplating device 1 may further include a control device for controlling voltage and current. This control device is configured so that the current energization direction is unidirectional, that is, it does not generate a pulse current pattern that inverts the anode and cathode.

In the electroplating apparatus 1, the soluble anode 11 is one or more selected from titanium, zirconium, niobium, tantalum, and hasteroi, in which the plating source 101 and the plating source 101 are housed and electrically connected to the plating source 101. The metal insoluble container 100 of the above may be provided. The plating source 101 may be one or more selected from the group consisting of Co pieces, Co—Ni alloy pieces, and Ni pieces.

In the electroplating apparatus 1, the insoluble container 100 has a liquid passing portion 111 configured so that the inside and the outside of the insoluble container 100 communicate with each other, and the cathode and the liquid passing portion 111 face each other. The soluble anode 11 may be arranged.

In the electroplating apparatus 1, the entire surface of the inner surface of the insoluble container 100 that comes into contact with the plating source 101 may be exposed. When the insoluble container 100 has a substantially quadrangular prism shape, the first outer surface of the insoluble container 100, the second outer surface and the third outer surface on both sides thereof, and the outer bottom surface are the electrically insulating regions 112, and the insoluble container 100 has an electrically insulating region 112. The soluble anode 11 may be arranged so that the first outer surface faces the cathode. According to this, the entire region closer to the cathode than the plating source 101 is the electrically insulating region 112.

In the electroplating apparatus 1, the lower portion of the fourth outer surface opposite to the first outer surface of the insoluble container 100 may be the electrically insulating region 112. Further, in the electroplating apparatus 1, the portion of the inner surface of the insoluble container 100 that does not come into contact with the plating source 101 may be the electrically insulating region 112.

Other ancillary equipment may be appropriately provided in the electroplating apparatus 1. For example, as a device for replacing the electroplating bath while continuing the plating work, another melting tank connected to the plating cell 13, a circulator for circulating the electroplating bath 10, and the like are provided in the electroplating device 1. be able to. Further, a measuring means capable of measuring the pH of the electroplating bath 10, the plating source concentration, the amount of the plating source 101 in the insoluble container 100, the plating source 101, and the like can be supplied into the electroplating bath 10 and the insoluble container 100. The electroplating apparatus 1 can be provided with a supply means and a control means or the like capable of controlling the composition of the electroplating bath 10 within a certain range by using these measuring means and the supply means.

(Experimental result 1: Relationship between composition of electroplating bath and chlorine odor)
Various electroplating baths were prepared with the blending amounts shown in Table 1-1. Co ion concentration (g / L), Ni ion concentration (g / L), chloride ion concentration (g / L), and other types and concentrations of metal cations (g / L and mol /) calculated based on the blending amount. L) and the ratio of the mass concentration of chloride ion to the mass concentration of Co ion: Cl / Co ratio are shown in Table 1-2. The unit of concentration is mass concentration in principle, but for the concentration of other metal cations, the mass concentration and the molar concentration are listed side by side (the numbers in parentheses are the molar concentration). Using these electroplating baths, electroplating work was performed under the following experimental conditions.
-Member to be plated connected to the cathode: Cold-rolled steel plate-Anode: A Ti basket (Table 2 Experimental Example A to be described later) is filled with a metal Co plate (length and width of about 10 mm, thickness of about 5 mm). A Ti lath plate (vertical opening 3.2 mm, horizontal opening 6 mm, thickness 1 mm), side surface, back surface, and bottom surface are joined by welding with a Ti plate (thickness 2 mm). The size is 50 mm in width, 30 mm in thickness, and 120 mm in height (the bath-immersed part is 100 mm).
-Bath temperature: 60 ° C
-Current density: 20A / dm ² (current density based on the apparent projected area of the anode)
The "apparent projected area of the anode" means the projected area of the anode on the virtual surface including the cold-rolled steel plate that is the cathode-power supply: normal DC power supply (current density is constant at the above value).
-Bath flow between anode and cathode: Yes (overflow)
-Polar distance: 20 mm
-Plating time: 30 seconds-Plating liquid amount: 10L

Atmospheric gas was sucked from the entire opening surface (about 80 mm × 70 mm) of the plating solution being electroplated under the above conditions at a rate of about 2 liters / min, and the odor sensory test and chlorine gas concentration measurement of this gas were carried out. The evaluation results are shown in Table 1-2. If the chlorine odor is "medium" or "strong", it is not preferable because it is necessary to install an exhaust facility.
Chlorine odor "weak" = atmospheric chlorine concentration less than 0.20 ppm Chlorine odor "medium" = atmospheric chlorine concentration 0.20 ppm or more and 0.50 ppm or less Chlorine odor "strong" = atmospheric chlorine concentration more than 0.50 ppm

The electroplating baths used in Experimental Examples A1 to A16 contain the requirements of the present invention, that is, 20 to 200 g / L of Co ions and 70 to 250 g / L of Cl ions, and alkali metal ions. The total molar concentration of alkaline earth metal ions and Al ions was 1.2 mol / L or less. In these Experimental Examples A1 to A16, the chlorine concentration in the atmosphere was less than 0.20 ppm, and there was no or very little chlorine odor.

On the other hand, in Experimental Examples B1 to B4, the chloride ion concentration of the electroplating bath was less than 70 g / L. In these Experimental Examples B1 to B4, the chlorine concentration in the atmosphere was more than 0.20 ppm, and the chlorine odor could not be suppressed. Further, in Experimental Examples B5 and B6, although the chloride ion concentration of the electroplating bath was 70 to 250 g / L, the total molar concentration of alkali metal ion, alkaline earth metal ion, and Al ion was 1. It was more than .2 mol / L. In Experimental Examples B5 and B6 as well, as in Experimental Examples B1 to B4, the chlorine concentration in the atmosphere was more than 0.20 ppm, and the chlorine odor could not be suppressed.

Comparing Experimental Examples A1 and A11 here, the Co ion concentration and the chloride ion concentration of both electroplating baths were the same, but the Na ion concentration was higher in A1. In A1, where the Na ion concentration was high, the chlorine concentration in the atmosphere was 0.20 ppm, which was within the acceptable range, but it was higher than the chlorine concentration in the atmosphere in A11.

Further, when the experimental examples A11 and A12 are compared here, the Co ion concentration and the chloride ion concentration of both electroplating baths are the same, but the Mg ion concentration due to the supporting electrolyte is larger in A12. In A12, where the Mg ion concentration was high, the chlorine concentration in the atmosphere was 0.20 ppm, which was within the acceptable range, but it was higher than the chlorine concentration in the atmosphere in A11. That is, according to the comparison between Experimental Examples A1 and A11 and Experimental Examples A11 and A12, it was shown that the smaller the amount of cations such as Na and Mg in the electroplating bath, the smaller the chlorine concentration in the atmosphere.

Further, when Experimental Examples A2, A13, and A14 were compared, the Co ion concentration and the other metal cation concentration of these electroplating baths were at the same level, but the Cl / Co ratio was different. In all of Experimental Examples A2, A13, and A14, the chlorine concentration in the atmosphere was 0.20 ppm, which was within the acceptable range, but the chlorine concentration in the atmosphere decreased as the Cl / Co ratio increased. That is, according to the comparison of Experimental Examples A2, A13, and A14, the ratio of the mass concentration of chloride ions / the mass concentration of Co ions can be increased by further adding chloride to the total chloride bath. It was shown that it is more preferable from the viewpoint of reducing the chlorine concentration in the atmosphere.

(Experimental result 2: Relationship between electrically insulated region and black sludge in Co plating)
Electroplating was performed under the following conditions using various insoluble containers (Ti baskets) with different arrangements of the electrically insulating regions, and the state of discoloration due to the black sludge reaction was confirmed. Except for the following description, it is the same as the example on the left.
-Composition of electroplating bath: Same as the composition of Experimental Example 1 shown in Table 1-1 and Table 1-2-Power supply and current density: Shown in Table 2-Continuous plating time: 1 hour-Electrical insulation region at anode Arrangement: Described in Table 2 (in the present invention, the electrically insulating region can be provided on a part or all of each surface, but in Table 2, "Yes" means that the electrically insulating region is arranged on all the surfaces. Means that)
-Insulation region formation method: Alumina spraying-Evaluation criteria After checking whether the plated plate after the test has an abnormal appearance due to black sludge, and after removing the metal Co in the Ti basket, there is an abnormality on the Ti basket surface (inner and outer surfaces). We confirmed that there was no such thing and evaluated it according to the following criteria.
0: There is an abnormality in the plating appearance, there is a clear discoloration in both the plating solution and the Ti basket 1: There is no abnormality in the plating appearance, there is a clear discoloration in both the plating solution and the Ti basket 2: There is no abnormality in the plating appearance, in the plating solution and the Ti basket There is a slight discoloration 3: There is no abnormality in the plating appearance and plating solution, and there is a slight discoloration in the Ti basket 4: There is no abnormality in the plating appearance, plating solution and Ti basket. The "apparent projected area of the anode" is the cathode. It means the projected area of the anode on the virtual surface including the cold-rolled steel plate, and here, it is assumed that the electrically insulating region of the insoluble container is also included in the anode.

In Experimental Example A in which the electrically insulating region was not provided, the outside of the front surface of the insoluble container was significantly discolored. Further, in Experimental Example A, discoloration was also observed on the outside of each of the side surface, the bottom surface, and the back surface. Further, in Experimental Example A, the color of the electroplating bath, which was initially pale red and translucent, changed to brown. However, the amount of black sludge generated was not so great that it was difficult to continue the plating, and no abnormality was observed in the appearance of the plating.
In Experimental Example B in which the electrically insulating region was provided on the outside of the front surface, slight discoloration was observed on the outer sides of the side surface, the bottom surface, and the back surface of the insoluble container, but the color of the electroplating bath was changed. No change was seen.
In Experimental Example C in which an electrically insulating region was provided on the outside of each of the front surface, the side surface, and the bottom surface, extremely slight discoloration was observed in a very small part of the lower end of the back surface of the insoluble container, but the color of the electroplating bath was changed. No change was seen.
In Experimental Example D in which electrically insulating regions were provided on the outside of the front surface, the side surface, the bottom surface, and the back surface, no discoloration was observed in any of the insoluble container and the electroplating bath.
Electrically insulated regions are provided on the outside of each of the front surface, side surface, bottom surface, and back surface, and on the inside of the front surface. Discoloration was seen. Further, in Experimental Example E, the electroplating bath was slightly discolored to brown.
Experimental Example F had the same conditions as Experimental Example A except that the power supply was different. In Experimental Example F, black sludge was remarkably generated as compared with Experimental Example A due to the fact that the inverting current was generated by using the pulse power supply.

(Experimental result 3: Evaluation of black sludge in Co—Ni alloy plating)
Electroplating was performed under the following conditions using various soluble anodes with different plating source configurations, and the state of discoloration due to the black sludge reaction was confirmed.
-Composition of electroplating bath: same as the composition of Experimental Example 10 shown in Table 1-1 and Table 1-2-Bath temperature: 60 ° C.
-Current density: 20A / dm ² (current density based on the apparent projected area of the anode)
-Continuous plating time: 1 hour-Member to be plated connected to the cathode: Cold-rolled steel plate-Anode: The Ti basket of Table 2 Experimental Example D is filled with the plating source shown in Table 3-Electrical insulation region in the anode. Arrangement: Same as Experimental Example D in Table 2-Bath flow between anode and cathode: Yes (overflow)
-Evaluation criteria 1: There is an abnormality in the plating appearance 2: There is no abnormality in the plating appearance, but there is discoloration in the plating bath or Ti basket 3: There is no abnormality in the plating appearance, plating bath, Ti basket, but the plating bath concentration fluctuation is large 4 : There is no abnormality in the plating appearance, plating bath, and Ti basket, and there is almost no fluctuation in the plating bath concentration.

In Experimental Example a, no discoloration occurred in both the Ti basket and the electroplating bath. In Experimental Example a, the Co concentration in the electroplating bath increased and the Ni concentration decreased as the plating progressed, but it was within the range that did not adversely affect the quality of the alloy plating.
In Experimental Example b, no discoloration occurred in both the Ti basket and the electroplating bath. In Experimental Example b, the Co concentration in the electroplating bath decreased and the Ni concentration increased as the plating progressed, but it was within the range that did not adversely affect the quality of the alloy plating.
In Experimental Example c, no discoloration occurred in both the Ti basket and the electroplating bath. Further, in Experimental Example c, the Co concentration and the Ni concentration in the electroplating bath hardly changed.

The electroplating bath according to the present invention has an increased Co ion concentration in order to increase the current density, and can suppress the generation of chlorine gas even when used in combination with a soluble anode. The method for manufacturing an electroplating product according to the present invention and the electroplating apparatus according to the present invention use an electroplating bath having a high Co ion concentration in combination with a soluble anode, and chlorine gas and chlorine gas while increasing the current density. It is possible to suppress the black sludge reaction. Therefore, the present invention can produce a Co-plated product or a Co—Ni alloy-plated product with high efficiency, and thus has a high possibility of industrial reason.

1 Electroplating device 10 Electroplating bath 11 Soluble anode 12 Member 13 Plating cell 100 Insoluble container 101 Plating source 111 Liquid passing part 112 Electrical insulation area

Claims (19)

An electroplating bath for producing electric Co-plating or electric Co-Ni alloy plating.
With 20-200 g / L Co ion,
With 131.5-250 g / L Cl ion,
Including
An electroplating bath characterized in that the total molar concentration of alkali metal ions, alkaline earth metal ions, and Al ions is 1.20 mol / L or less. The electroplating bath according to claim 1, further comprising 100 g / L or less of Ni ions. The electroplating bath according to claim 1 or 2, wherein the mass concentration of the Cl ion / the mass concentration of the Co ion is 1.5 or more. In the alkali metal ion, the molar concentration of K ion is 1.0 mol / L or less.
The electroplating bath according to any one of claims 1 to 3, wherein the total molar concentration of the alkaline earth metal ion and the Al ion is 0.35 mol / L or less. The electroplating bath according to any one of claims 1 to 4, wherein the Co ion is contained in an amount of 35 g / L or more. The electroplating bath according to any one of claims 1 to 5, wherein the Cl ion is contained in an amount of 120 to 200 g / L. Claims 1 to 1, wherein the Co ion is a Co ion of one or more water-soluble Co salts selected from the group consisting of cobalt sulfate, cobalt sulfamate, cobalt nitrate, cobalt chloride, and cobalt fluoride. The electroplating bath according to any one of 6. The electroplating bath according to any one of claims 1 to 6, wherein the Co ion is a Co ion of one or more halogen compounds selected from the group consisting of cobalt chloride and cobalt fluoride. .. A step of immersing the soluble anode and a member connected to the cathode in an electroplating bath to energize the solution is provided.
In the above-mentioned energization, the energization direction of the current is set to one direction.
The electroplating bath is an electroplating bath for producing electric Co plating or electric Co—Ni alloy plating.
With 20-200 g / L Co ion,
70-250 g / L Cl ion and
Including
The total molar concentration of alkali metal ions, alkaline earth metal ions, and Al ions is 1.20 mol / L or less.
The soluble anode is
With the plating source,
An insoluble container made of one or more metals selected from titanium, zirconium, niobium, tantalum, and Hastelloy, filled with the plating source and electrically connected to the plating source.
Equipped with
The insoluble container has a liquid passing portion configured so that the inside and the outside of the insoluble container communicate with each other.
The soluble anode is arranged so that the liquid passing portion faces the member.
At least a part of the outer surface of the insoluble container is an electrically insulating region.
The member and the soluble anode are arranged so that the entire region of the outer surface of the insoluble container facing the member is the electrically insulating region.
A method for manufacturing an electroplated product, wherein the insoluble container has a quadrangular prism shape. The method for manufacturing an electroplated product according to claim 9, wherein the entire inner surface of the insoluble container that comes into contact with the plating source is exposed. The first outer surface of the insoluble container, the second outer surface and the third outer surface on both sides thereof, and the outer bottom surface are the electrically insulating regions.
The method for manufacturing an electroplated product according to claim 9, wherein the soluble anode is arranged so that the first outer surface faces the member. The lower part of the fourth outer surface opposite to the first outer surface of the insoluble container is defined as the electrically insulating region.
The lower portion of the fourth outer surface opposite the first outer surface of the insoluble container is a region within 20% of the height of the fourth outer surface from the lower end of the fourth outer surface. The method for manufacturing an electroplated product according to claim 11, wherein the method is characterized by the above. The manufacture of the electroplating product according to any one of claims 9 to 12, wherein the portion of the inner surface of the insoluble container that does not come into contact with the plating source is the electrically insulating region. Method. The method for manufacturing an electroplated product according to any one of claims 9 to 13, wherein the member is provided with a step of plating Ni plating or Ni alloy as a pretreatment. The invention according to any one of claims 9 to 14, wherein the plating source of the soluble anode contains one or more selected from the group consisting of Co pieces, Ni pieces, and Co—Ni alloy pieces. How to manufacture electroplated products. The method for manufacturing an electroplated product according to any one of claims 9 to 15, wherein the member has a plate shape. The method for producing an electroplated product according to any one of claims 9 to 16, wherein the electroplating bath further contains 100 g / L or less of Ni ions. An electroplating device including a soluble anode, a cathode, an electroplating bath, and a control device.
The control device is configured so that the current energizing direction is one direction.
The electroplating bath is an electroplating bath for producing electric Co plating or electric Co—Ni alloy plating.
With 20-200 g / L Co ion,
70-250 g / L Cl ion and
Including
The total molar concentration of alkali metal ions, alkaline earth metal ions, and Al ions is 1.20 mol / L or less.
The soluble anode comprises a plating source and one or more metallic insoluble containers selected from titanium, zirconium, niobium, tantalum, and hastelloy that contain the plating source and are electrically connected to the plating source. , Equipped with
The insoluble container has a liquid passing portion configured so that the inside and the outside of the insoluble container communicate with each other.
The cathode and the soluble anode are arranged so that the cathode and the liquid passing portion face each other.
At least a part of the outer surface of the insoluble container is an electrically insulating region.
The cathode and the soluble anode are arranged so that the entire region of the outer surface of the insoluble container facing the cathode is the electrically insulating region.
An electroplating apparatus characterized in that the insoluble container has a quadrangular prism shape. The electroplating apparatus according to claim 18, wherein the electroplating bath further contains 100 g / L or less of Ni ions.

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