TW202009330A - Plating solution production and regeneration process and device for insoluble anode acid copper electroplating - Google Patents

Abstract

A production method for the electroplating solution or the electroplating supplement solution in an insoluble anode acid copper electroplating process, comprising the following steps: (1) providing an electrolytic cell and using an electrolytic cell membrane to separate the electrolytic cell into an electrolytic anode area and an electrolytic cathode area; (2) respectively preparing an anode electrolyte and a cathode electrolyte; (3) adding the anode electrolyte to the electrolytic anode area, and adding the cathode electrolyte into the electrolytic cathode area; (4) immersing an electrolytic anode into the anode electrolyte, and immersing an electrolytic cathode into the cathode electrolyte; and (5) connecting the electrolytic anode and the electrolytic cathode to a positive electrode and a negative electrode of an electrolytic power supply, connecting the electrolytic power supply to perform an electrolytic reaction, and extracting the anode electrolyte when the concentration of a copper ion in the anode electrolyte reaches a predetermined value. Also disclosed is a device for implementing the production method suitable for the electroplating solution or the electroplating supplement solution in an insoluble anode acid copper electroplating process.

Description

Method and device for producing electroplating solution or electroplating replenishing solution of insoluble anode acidic copper plating process

The invention relates to the field of acid copper electroplating process, in particular to a method and device for producing an electroplating solution or electroplating replenishment solution for an insoluble anode acid copper electroplating process.

Electroplating is the process of plating a thin layer of other metals or alloys on the metal surface using the principle of the electrolytic cell. The existing acid copper sulfate copper electroplating process can be divided into two processes: soluble anode and insoluble anode.

The soluble anode electroplating copper process, as the name implies, refers to the type of process in which the anode will gradually dissolve during the electroplating electrochemical reaction. The common soluble anode material is phosphor copper. During the electroplating process, the copper ions in the plating solution are reduced to metallic copper on the surface of the cathode plating to achieve electroplating. The copper ions in the plating solution are continuously consumed; at the same time, the copper metal on the phosphor copper as the anode dissolves into copper ions. Therefore, the copper ions in the plating solution are replenished.

Phosphorus copper is used as the soluble anode in the current soluble anode electroplated copper, because the surface of the metal copper anode is easily oxidized by the oxidizing substances in the plating solution to copper oxide or cuprous oxide during the electroplating process, resulting in metallic copper The dissolution rate of the anode is not uniform, which makes the composition of the plating solution unstable, which in turn affects the quality of the plating. Although the use of phosphorous copper as a soluble anode can improve the defect of uneven anode dissolution rate to a certain extent, when using phosphorous copper anodes, it is prone to problems such as anode polarization and uneven current distribution, which lead to unstable plating quality; another On the other hand, the price of phosphorous copper is relatively high, and toxic phosphorous wastewater will be produced during its production and use, and it will be extremely harmful to the liver and other organs when entering the human body. In order to achieve the wastewater discharge standard, the treatment cost of electroplating waste liquid needs to be increased.

The insoluble anode electroplating copper process is just the opposite. It refers to the electroplating process in which the anode does not occur or a very small amount of dissolution occurs during the electroplating reaction. Common insoluble anodes include precious metal oxide coated titanium, conductive graphite, platinum and lead alloys.

The first common acidic copper plating process using an insoluble anode uses an aqueous solution of copper sulfate and sulfuric acid as the main plating solution. The water reacts at the anode to generate hydrogen ions and oxygen. The copper ions in the plating solution are reduced to metal at the cathode. copper. With the electroplating of copper, the concentration of sulfuric acid in the plating solution is getting higher and higher. Therefore, copper oxide needs to be continuously added during the plating process. On the one hand, it reacts with the sulfuric acid in the plating solution to supplement the copper ions lost in the plating solution. On the other hand, the equivalent amount of sulfuric acid is consumed accordingly to suppress the increasing concentration of sulfuric acid in the plating solution.

陰極上的電化學反應：

硫酸銅電鍍液再生的反應：

。The specific reaction formula is as follows: Electrochemical reaction on the anode:

Electrochemical reaction on the cathode:

Reaction of copper sulfate plating solution regeneration:

.

The disadvantage of using this method to replenish copper ions is that during the electroplating process, copper oxide, which is more expensive than metal copper, must be continuously added to dissolve it into the plating solution to supplement the copper ion concentration of the plating solution. This electroplating process continues, resulting in increased production costs.

Another common acidic copper plating process that uses an insoluble anode is to add iron ions based on an electroplating solution composed of copper sulfate and sulfuric acid aqueous solution. The electrochemical reaction on the anode is the oxidation of ferric iron ions to ferric iron ions, copper The ions are reduced to metallic copper at the cathode. In the electroplating process, ferric ions are used to continuously corrode the copper metal outside the electroplating system, so that the copper ion concentration of the electroplating solution is supplemented.

陰極上的電化學反應：

三價鐵離子對陰極上的金屬銅進行返蝕的反應：

The specific reaction formula is as follows: Electrochemical reaction on the anode:

Electrochemical reaction on the cathode:

The reaction of ferric ions to etch back the metallic copper on the cathode:

This process can reduce the amount of oxygen dissolved in the electroplating solution, and avoid the degradation of electroplating quality caused by oxygen. However, due to the presence of ferric ions in the plating solution, the metal copper on the cathode plating can be etched back, destroying the plating layer that has been formed, and thus affecting the plating quality.

In the above two common insoluble anodized copper plating processes, although different methods are used to supplement the copper ions in the plating solution with decreasing concentration in the production line, both methods bring actual production due to their respective defects. Because of many inconveniences, it is necessary to improve the method of supplementing the copper ion in the plating solution in the insoluble anode copper plating process.

The first object of the present invention is to provide a method for producing an electroplating solution or electroplating replenishing solution for an insoluble anode acid copper electroplating process. The cost of the production method is low, and the prepared solution can be used as an electroplating solution or electroplating replenishing solution or finished copper sulfate Solution to suit many different needs.

The second object of the present invention is to provide an apparatus for realizing the production method of the plating solution or plating replenishment solution suitable for the above-mentioned insoluble anode acidic copper plating process.

The first object of the present invention is achieved by the following technical solutions:

A method for producing an electroplating solution or electroplating replenishing solution for an insoluble anode acid copper electroplating process includes the following steps:

(1) An electrolytic cell is provided, and the electrolytic cell diaphragm is used to separate the electrolytic cell into an electrolytic anode area and an electrolytic cathode area. The electrolytic cell diaphragm is used to prevent the passage of cations to prevent cations from being between the electrolytic anode area and the electrolytic cathode area Free exchange between

(2) Prepare anolyte and catholyte separately; wherein, the anolyte is composed of an aqueous solution of at least one of sulfuric acid and copper sulfate, and the composition according to the mass percentage is: 0.001%-45% sulfuric acid or/and 0.001% to 21% copper sulfate; the rest is water, and the total mass percentage of solute in the anolyte is not less than 0.03%;

(3) Add anolyte to the electrolytic anode area, and add catholyte to the electrolytic cathode area;

(4) A metal electrode containing copper element is used as an electrolytic anode, and the electrolytic anode is immersed in the anolyte; an electrical conductor is used as an electrolytic cathode, and the electrolytic cathode is immersed in the cathode electrolysis In liquid

(5) Connect the electrolysis anode and electrolysis cathode to the positive and negative poles of the electrolysis power supply respectively, turn on the electrolysis power supply, and start the electrolysis reaction when energized. When the concentration of copper ions in the anolyte reaches a predetermined value, The anolyte is taken out to obtain the electroplating solution or electroplating replenishing solution or the finished copper sulfate solution of the insoluble anode acidic copper electroplating process or the raw material used to prepare the insoluble anode acidic copper electroplating solution.

The present invention provides a plating solution or plating replenishing solution suitable for the insoluble anode acid copper electroplating process to provide the plating solution required for the production of insoluble anode acid copper electroplating, and/or by adding the plating solution in the copper electroplating production in a timely manner The method of electroplating replenishment to maintain the concentration of copper ions in the electroplating solution that can continue to plate copper, not only can ensure good plating quality, but also simple operation, no need to use complex and large-scale equipment, nor expensive chemicals as raw materials, making the The cost of copper electroplating is reduced, which significantly improves the processability and cost performance of the copper electroplating production.

The role of the electrolyzer membrane in step (1) of the present invention is to prevent the passage of cations, so as to prevent the free exchange of cations between the electrolysis anode area and the electrolysis cathode area, and at the same time, it can allow the charge in the electrolysis process during the electrolysis Transfer between the anode zone and the electrolytic cathode zone. Preferably, the membrane of the electrolytic cell may use an anion exchange membrane and/or a bipolar membrane.

When the membrane of the electrolytic cell uses an anion exchange membrane: the catholyte is composed of an aqueous solution of at least one of sulfuric acid, sulfate, carbonic acid and inorganic base, and the total mass percentage of the solute in the catholyte is 0.1 %-40%, at least one of the anolyte and the catholyte contains sulfuric acid.

When the membrane of the electrolytic cell is a bipolar membrane: the catholyte is water or an aqueous solution of an electrolyte, the electrolyte may be any electrolyte, and the anolyte needs to contain sulfuric acid.

The anolyte prepared in step (2) of the present invention may be prepared using component raw materials, or it may be an electroplating solution derived from an insoluble anode acid electroplating copper process production line.

According to different actual needs of the present invention, the copper ion concentration in the anolyte can reach different predetermined values to obtain solutions for different purposes such as electroplating solution, electroplating replenishment solution or finished copper sulfate solution:

1. The predetermined value is equal to the concentration of copper ions in the plating solution required on the production line of the insoluble anode acid copper electroplating process. The resulting solution can be used directly as the initial plating solution in the insoluble anode acid copper electroplating process, or as a plating solution. Add directly to the plating solution during the plating process to quickly replenish the copper ions lost during the plating process;

2. The predetermined value is any value other than zero, and the resulting solution can be used as one of the raw materials of the initial plating solution for preparing the insoluble anode acidic copper plating process;

3. The predetermined value is greater than the concentration of copper ions in the plating solution required on the production line of the insoluble anode acidic copper electroplating process. The resulting solution can be used as a plating replenisher to be directly added to the plating solution during the plating process to quickly supplement the plating process Copper ions lost in

4. The predetermined value is equal to the concentration of copper ions in the finished copper sulfate solution, and the resulting solution can be used as the finished copper sulfate solution.

陰極上的電化學反應：

The working principle of the present invention: in the electrolytic cell, the metallic copper on the anode becomes copper ions and dissolves in the anolyte, and the hydrogen ions on the cathode becomes hydrogen to escape from the electrolytic cell. The specific electrochemical reactions that occur are as follows : Electrochemical reaction on the anode:

Electrochemical reaction on the cathode:

When the present invention uses an anion exchange membrane as the membrane of the electrolytic cell, with the generation of hydrogen in the electrolysis cathode zone, hydroxide ions are continuously generated in the cathode electrolyte.

When only the anolyte contains sulfuric acid, the hydroxide ions generated by the cathodic electrochemical reaction and/or the carbonate ions in the catholyte and/or the inorganic base anions in the catholyte can enter the electrolytic anode through the anion exchange membrane The zone combines with the hydrogen ions in the anolyte to produce water to consume the sulfuric acid in the anolyte, while the sulfate radicals originally belonging to the sulfuric acid in the anolyte form copper sulfate with the copper ions electrochemically generated by the anode.

When the catholyte contains sulfuric acid, the hydroxide ions generated by the cathodic electrochemical reaction combine with the hydrogen ions in the catholyte to form water to consume the sulfuric acid in the catholyte, which originally belongs to the sulfate ion of sulfuric acid It can enter the electrolytic anode area through the anion exchange membrane and form copper sulfate with the copper ions electrochemically generated by the anode.

In addition, when an anion exchange membrane is used as the membrane of the electrolytic cell and the catholyte contains sulfate, the anolyte can also be prepared by first using water as the electrolyte and then applying an electrolytic voltage higher than the working setting Electrolysis, the sulfate in the catholyte passes through the anion exchange membrane and copper ions generated on the anode to form a copper sulfate electrolyte to complete. Since water itself has a weaker ionization ability, ion transfer can also occur to achieve an electrochemical reaction at a higher electrolysis voltage.

When the invention adopts a bipolar membrane as the membrane of an electrolytic cell, since the bipolar membrane is a special ion exchange membrane, it is a composite cathode and anode membrane made of a cation exchange membrane and an anion exchange membrane. In the DC electric field, anion and cation exchange water (H ₂ O) between the film composite layer dissociates into hydrogen ions (H ⁺⁾ and hydroxide ions (OH ^-), and each exchange membrane by the anion exchange membrane and a cation , As a source of H ⁺ and OH ^- ions. As the electrolysis reaction progresses, the hydrogen ions generated on the bipolar membrane enter the electrolytic cathode area and become hydrogen precipitates, and the hydroxide ions generated on the bipolar membrane enter the electrolytic anode area. Sulfate ions generated by ionization of sulfuric acid in the anolyte and copper ions generated by the electrochemical reaction of metallic copper on the anode form copper sulfate, and the remaining hydrogen ions generated by ionization of sulfuric acid combine with the above-mentioned hydroxide ions to form water.

When the invention adopts the bipolar membrane as the membrane of the electrolytic cell, the bipolar membrane can be hydrolyzed into H ⁺ and OH ^- under the action of a DC electric field, and water can be directly used as the catholyte. The aqueous solution of the electrolyte can also be used as the catholyte, which can effectively improve the electrical efficiency and reduce the electrolytic voltage. Since the solutions on both sides of the bipolar membrane are not connected, the selected electrolyte can be dissolved in water to generate ions. There is no limit.

The sulfate in the catholyte of the present invention is a strong electrolyte salt of sulfuric acid, that is, water-soluble sulfate, including potassium sulfate, sodium sulfate, copper sulfate, iron sulfate, aluminum sulfate, ferrous sulfate, titanium sulfate, ammonium sulfate , Cadmium sulfate, magnesium sulfate, manganese sulfate, potassium bisulfate, sodium bisulfate, nickel sulfate and zinc sulfate one or more, the ratio of multiple sulfates is not limited.

The inorganic base according to the present invention has at least one of hydroxide, carbonate and bicarbonate, including sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate , One or more of ammonium carbonate and ammonium bicarbonate, there is no limit to the ratio between the various inorganic bases.

As a preferred embodiment of the present invention, the electrolytic cathode is an acid and alkali resistant electrical conductor, preferably composed of metal and/or graphite. The metal may be titanium, platinum, gold, silver, copper, iron Any one, or an alloy containing at least one of the above metals, may be a bare metal, or a metal electrode coated with an electrode coating or plated with an inert metal on the surface, or may be stainless steel. The inert metals include but are not Limited to platinum and gold, the inert metals that can be used when the catholyte does not contain sulfuric acid also include titanium and silver.

Although the electrolytic anode according to the present invention contains metal elements other than copper and/or insoluble impurities, it can still achieve the purpose of electrolytically generating copper sulfate. However, it will cause the anolyte obtained by electrolysis to contain other metal ion impurities and/or insoluble solid impurities. When it is used as an electroplating solution or electroplating replenisher for electroplating, it may cause power consumption and make the plating layer contain metals other than copper Impurities, resulting in uneven plating unevenness, etc., affect production efficiency or plating quality, usually need to increase filtration or other means to reduce impurities in the resulting anolyte to ensure that it can achieve better plating quality when used in electroplating, Thereby increasing the complexity of the process and the possibility of unstable plating quality. Therefore, the metal anode and/or insoluble impurities other than copper contained in the electrolytic anode used are as small as possible. Therefore, in the present invention, it is preferable to use a copper electrode for the electrolytic anode.

As an embodiment of the present invention, the present invention is associated with an insoluble anode acidic copper electroplating process production line, and adjusts the size of the electrolysis current according to step (5) of the present invention according to the dynamic change of the process parameters of the insoluble anode acidic copper electroplating process production line , Or control the on or off of the electrolytic power supply of the present invention; or according to the dynamic change of the electrolysis process parameters in step (5) of the present invention, or adjust the size of the plating current on the production line of the insoluble anode acidic copper plating process, or control The electroplating power of the insoluble anode acid copper electroplating process production line is turned on/off, so that the process parameters of the electroplating replenishing solution obtained by the present invention can be adapted to the process parameters of the insoluble anode acid copper electroplating process production line, or can make the production line The copper ions in the plating solution can be replenished in a timely manner. The process parameters include copper ion concentration, sulfuric acid concentration, working time, and workload.

As a preferred embodiment of the present invention, when the present invention is associated with an insoluble anode acidic copper electroplating process production line, that is, the anolyte described in the present invention is directly derived from the plating solution and/or from the insoluble anode acidic copper electroplating process production line Electroplating waste liquid, after the step (5) is connected to the electrolysis power supply to start the electrolysis reaction, the copper ion concentration of the anolyte according to the present invention and/or the copper ion concentration of the electroplating solution on the production line of the insoluble anode acidic copper electroplating process And adjust the electrolysis current and/or the electroplating current on the production line according to the detection result, or turn on/off the electrolysis power and/or the electroplating power on the production line of the invention, the specific operations are as follows:

When the copper ion concentration of the anolyte and/or the electroplating solution on the production line of the present invention is less than or equal to the set value, increase the electrolysis current or turn on the electrolysis power supply to promote the electrolysis reaction of the present invention and/or reduce the electroplating on the production line The current is used to reduce the copper ion consumption rate of the electroplating solution until the copper ion concentration of the anolyte and/or the copper ion concentration of the electroplating solution on the production line returns to the set value according to the present invention, reducing the electrolytic current or shutting down the electrolytic power supply , And/or increase the plating current.

In the process of detecting the copper ion concentration of the anolyte and/or the electroplating solution on the production line according to the present invention, it can be indirectly detected by detecting the specific gravity value and/or photoelectric colorimetric value and/or redox potential of the anolyte The copper ion concentration of the anolyte and/or the copper ion concentration of the plating solution. The larger the measured specific gravity of the anolyte and/or the plating solution on the production line, or the darker the color, or the higher the redox potential, the higher the concentration of copper ions.

As another embodiment of the present invention, after the step (5) is turned on the electrolysis power to start the electrolysis reaction, the concentration of sulfuric acid and/or sulfate and/or carbonic acid and/or inorganic base in the catholyte is detected, And adding sulfuric acid and/or sulfate and/or water and/or carbon dioxide to the electrolytic cathode area according to the detection result, so as to adjust the sulfuric acid and/or sulfate and/or carbonic acid and/or inorganic alkali in the catholyte The concentration is maintained within the set value range:

When the inorganic alkali concentration of sulfuric acid and/or sulfate and/or carbonic acid and/or carbonate or bicarbonate in the catholyte is less than or equal to the set value, add sulfuric acid or Aqueous solution and/or sulfate or its aqueous solution and/or carbon dioxide, or when the concentration of the catholyte is greater than or equal to the set value due to evaporation of water, add fresh water to the electrolysis cathode area until the catholyte The concentration of sulfuric acid and/or sulfate and/or inorganic base returns to the set value.

In the process of detecting the sulfuric acid concentration of the catholyte, the sulfuric acid concentration of the catholyte can be indirectly detected by detecting the acidity value and/or specific gravity value of the catholyte; During the concentration of sulfate and/or carbonic acid and/or inorganic base, the pH and/or specific gravity of the catholyte can be detected to indirectly detect the sulfate and/or carbonic acid and/or of the catholyte Inorganic base concentration; in the process of detecting the inorganic base and/or carbonic acid concentration of the carbonic acid and/or bicarbonate of the catholyte, the carbonic acid of the catholyte can be indirectly detected by detecting the electrolytic cell pressure of the present invention The inorganic alkali component and/or carbonic acid of the root and/or bicarbonate.

When the catholyte contains the inorganic alkali component of carbonate and/or bicarbonate and/or carbonic acid, and the membrane is an anion exchange membrane, as the electrolytic reaction proceeds, part of the carbonate and/or Bicarbonate ions enter the electrolytic anode area through the diaphragm and react with the hydrogen ions in the anolyte to produce water and carbon dioxide. At the same time, the pH value of the catholyte also rises due to the increase in hydroxide ion concentration , And as the concentration of hydroxide ions in the catholyte increases, the proportion of hydroxides in the anions passing through the anion exchange membrane becomes larger and larger. The copper ions in the anolyte react to precipitate copper sludge on the anion exchange membrane, causing the pressure of the electrolytic cell to rise. At this time, carbon dioxide is added to the electrolytic cathode area, which reacts with hydroxide ions in the catholyte to generate carbonate and/or bicarbonate and water, which can effectively stabilize the carbonic acid in the catholyte The root and/or bicarbonate concentration and the pH and electrolyzer pressure of the catholyte. When the diaphragm is a bipolar membrane and the catholyte is water, in step (5) after the electrolytic power is turned on to start the electrolysis reaction, the level of the catholyte can be detected, and the Determine whether to add water to the electrolytic cathode area to maintain the volume of catholyte within the set value range.

As a preferred embodiment of the present invention, the present invention feeds oxygen into the anolyte, and the oxygen may be derived from the oxygen generated at the electrolysis anode and/or an external oxygen source and/or air . The function of introducing oxygen into the anolyte is to accelerate the increase of the copper ion concentration in the anolyte. The principle is that oxygen oxidizes part of the metal copper in the electrolytic anode to copper oxide, and the generated copper oxide and sulfuric acid The reaction produces copper sulfate, which increases the concentration of copper ions and does not affect the progress of the electrolytic reaction. The greater the amount of oxygen introduced, the faster the copper ion concentration increases, so the amount of oxygen introduced is not particularly limited.

As another preferred embodiment of the present invention, the electrolytic anode according to the present invention contains copper oxide. Similar to the above principle, copper oxide in the electrolytic anode reacts with sulfuric acid to produce copper sulfate, which accelerates the increase of the copper ion concentration in the anode electrolyte.

，從而將固體的銅泥轉化為銅離子溶解至陽極電解液中。當落在不溶性電解陽極表面的金屬銅較少或沒有時，所述不溶性電解陽極則會發生氧氣的生成反應，2H₂ O+2e^- →O₂ +4H⁺ ，達到向所述的陽極電解液中通入氧氣和氣浮攪拌的效果。只要是電解過程中耐硫酸或硫酸銅的導電體都可以作為所述的不溶性電解陽極，如常見的塗覆貴金屬氧化物的鈦、導電石墨、鉑金、黃金、鍍有鉑金或黃金的金屬等不溶電解陽極。In order to solve the problem that the copper powder peeled off by the electrolytic anode during the electrolysis process accumulates at the bottom of the electrolytic anode area to form copper sludge, an insoluble electrolytic anode may be provided at the bottom of the electrolytic anode area. When the metallic copper sinks to the bottom of the electrolytic anode area, it will fall to the surface of the insoluble electrolytic anode, and the metallic copper reacts directly by the current on the insoluble electrolytic anode.

, So that the solid copper mud is converted into copper ions and dissolved into the anolyte. Falls when the amount of insoluble metallic copper electrolysis anode surface or not, the insoluble anode electrolytic oxygen generation reaction will ^{_{occur, 2H 2 O + 2e - →}} O 2 + 4H +, to reach the anolyte The effect of mixing oxygen and air floatation. As long as it is a conductor resistant to sulfuric acid or copper sulfate in the electrolysis process, it can be used as the insoluble electrolytic anode, such as common noble metal oxide coated titanium, conductive graphite, platinum, gold, platinum or gold-plated metals, etc. Electrolytic anode.

Preferably, the electrolytic current of the electrolytic anode is higher than the electrolytic current of the insoluble electrolytic anode at the bottom of the electrolytic anode area, so as to reduce unnecessary power consumption when there is little or no metallic copper falling on the surface of the insoluble electrolytic anode.

Preferably, the anode electrolyte with the copper ion concentration higher than the plating solution is added to the plating tank on the production line by detecting the copper ion concentration and/or acid concentration in the plating solution and/or according to the time setting. The concentration of copper ions in the plating solution may be correspondingly reflected by its specific gravity value and/or oxidation-reduction potential value and/or colorimetric value, and the acid concentration in the plating solution may be correspondingly reflected by its acidity value and/or pH value .

Preferably, by monitoring the liquid level of the electroplating tank on the production line and/or the electrolytic anode zone and/or electrolytic cathode zone of the present invention, the electroplating tank on the production line and/or the electrolytic anode zone of the present invention and And/or the electrolytic cathode area is added with fresh water or the corresponding aqueous solution of the components contained in the plating solution or electrolyte. The present invention can also make the following improvements: when using an anion exchange membrane as the membrane, the membrane can also use two layers of anion exchange membrane, or when using a bipolar membrane as the membrane, the membrane can use a layer of bipolar The combination of a membrane and a layer of anion exchange membrane, wherein the layer of anion exchange membrane is located on the side of the anion exchange membrane in the bipolar membrane, the two layers of anion exchange membrane or a layer of bipolar membrane and an anion exchange membrane The combination makes an electrolytic buffer zone formed between the electrolytic anode zone and the electrolytic cathode zone, so as to avoid hydroxide ions generated on the electrolytic cathode and/or anions of the original inorganic base of the catholyte through the anion exchange membrane and the anode The copper ions of the electrolyte contact, or the hydroxide ions generated on the bipolar membrane directly contact the copper ions of the anolyte, thereby avoiding the problem that the separator is easily blocked by the generated copper sludge without this electrolytic buffer. The electrolytic buffer contains buffer electrolyte, and the buffer electrolyte is an aqueous solution containing no copper ions but containing sulfuric acid.

The reason why the electrolytic buffer is not provided in the electrolytic cell is easy to cause copper mud to block the diaphragm is that when the diaphragm uses an anion exchange membrane and the catholyte is neutral or alkaline, the hydroxide ions and/or generated on the electrolytic cathode The anion of the original inorganic base of the catholyte can enter the electrolytic anode area through the anion exchange membrane; when the diaphragm is a bipolar membrane, the hydroxide ions generated on the bipolar membrane directly enter the electrolytic anode area. Once the hydroxide ion or the anion of the inorganic base enters the electrolysis anode area, it will react with copper ions and generate copper sludge deposits such as copper hydroxide on the diaphragm, thereby accumulating copper sludge and causing the diaphragm to block, affecting the progress of the electrolytic reaction. When a large area of the diaphragm is blocked by the copper mud, the diaphragm must be replaced. It can be seen that the problem of the copper mud blocking the diaphragm will cause the service life of the diaphragm to decrease, which virtually increases the production cost.

Therefore, an electrolysis buffer zone is provided between the electrolysis anode zone and the electrolysis cathode zone, so that hydroxide ions and/or anions of the inorganic base react with sulfuric acid in the buffer electrolyte before entering the electrolysis anode zone Water, the sulfate radical originally belonging to the sulfuric acid in the buffer electrolyte, enters the electrolysis anode area through the anion exchange membrane under the attraction of the electric field, and forms copper sulfate with the copper ions electrochemically generated on the electrolysis anode. Therefore, it can effectively reduce the direct contact of hydroxide ions and/or inorganic alkali ions with the copper ions in the electrolysis anode area, thereby avoiding the formation of copper sludge clogging on the diaphragm, which can stabilize the electrolysis reaction on the one hand, and Helps save production costs.

When the separator is a combination of a bipolar membrane and an anion exchange membrane and the anion exchange membrane is on the side of the anion exchange membrane in the bipolar membrane, if the buffer electrolyte is free of free hydrogen ions The aqueous solution can also achieve the purpose of the present invention, that is, it can still produce electroplating replenishment, etc., but it does not function as the electrolytic buffer, that is, there may still be a phenomenon of copper mud blocking the diaphragm. This is because the buffer electrolyte does not contain free hydrogen ions, and the hydroxide ions generated on the bipolar membrane are not consumed in the electrolytic buffer, and will continue to enter the electrolytic anode area through the anion exchange membrane, and will also be The copper ions react and form copper sludge deposits such as copper hydroxide on the anion exchange membrane.

The invention detects the pH value and/or acidity value and/or specific gravity value of the buffer electrolyte after the electrolytic power is turned on in the step (5) and starts electrolysis to the buffer electrolysis according to the detection result Add sulfuric acid and/or copper ion-free but sulfuric acid to the solution:

When the pH value and/or acidity value and/or specific gravity value of the buffer electrolyte are less than or equal to the set value, sulfuric acid and/or an aqueous solution containing no copper ions but containing sulfuric acid is added to the buffer electrolyte until The pH value and/or acidity value and/or specific gravity value of the buffer electrolyte are restored to the set value or greater than the set value.

The invention can be further improved as follows:

The invention is connected with a copper electroplating production line and combined into a whole production, that is, the electrolytic cell of the invention forms a controllable loop flow system with the solution in the electroplating tank on the electroplating production line, wherein the preferred method is in the electroplating copper production process After the anode electrolyte in the electrolytic cell of the present invention is detected to reach or exceed the set value, and the plating solution on the electroplating production line needs to supplement the copper ion content, the anode can be electrolyzed by relevant equipment. The liquid is directly added to the electroplating tank, and at the same time, the medium amount of electroplating liquid in the electroplating tank is transferred to the electrolytic anode area of the electrolysis cell of the present invention as an anolyte to increase the copper ion concentration, thus forming a plating and electrolytic regeneration loop Use the system.

However, when the anolyte of the present invention forms a loop flow system with the electroplating solution of the copper electroplating production line, and the membrane of the electrolytic cell uses an anion exchange membrane, if the catholyte contains sulfate, as the electrolytic reaction Proceeding, the sulfate ions in the catholyte will pass through the anion exchange membrane and enter the electrolytic anode zone, resulting in a continuous decrease in the concentration of sulfate ions in the catholyte, while the sulfate ions in the anolyte The concentration continues to rise. The reduction of sulfate ions in the catholyte means the reduction of conductive ions, which increases the resistance of the electrolyte, which in turn reduces the electrical efficiency. In order to avoid this, it is necessary to supplement the sulfate ion in the catholyte. At this time, if the amount of sulfate ions is supplemented by directly adding sulfuric acid/sulfate to the catholyte, the total amount of sulfate ions in the entire electrolysis and electroplating system will be increased, thereby destroying the overall balance of electrolysis and electroplating reactions.

In order to solve the above balance problem, it is necessary to set up an acidity balance electrolysis system: that is, an acidity balance cathode area is separated in the electrolysis anode area, and the acidity balance cathode area faces the direction of the electrolysis cathode area using a separator as a partition, the The acidity balanced cathode zone contains an acidity balanced catholyte. When the membrane of the acidity balanced cathode zone uses an anion membrane, the acidity balanced catholyte is an inorganic alkaline aqueous solution with a mass percentage of 0.5% to 35%; When the diaphragm of the acidity balance cathode region uses a bipolar membrane, the acidity balance catholyte is an aqueous solution with a mass percentage of water and/or electrolyte; the acidity balance electrolysis system includes the acidity balance cathode region The acidity balance cathode, and the acidity balance anode provided in the electrolytic cathode area, and the acidity balance power supply, the acidity balance cathode and the acidity balance anode are respectively connected to the negative and positive poles of the acidity balance power supply. The acidity balance anode and the acidity balance cathode are both insoluble electrodes, preferably composed of metal and/or graphite, the metal surface of the insoluble electrode may be covered with a protective coating or an inert metal, and the metal is preferably titanium or platinum , Gold, silver, copper, iron, an alloy containing at least one of the above metals, or at least one of stainless steel, the inert metal includes but is not limited to platinum, gold, when the solution contacted by the acidity balance electrode does not contain sulfuric acid Inert metals that can be used also include titanium and silver. The acid balance electrolysis system will cause the water in the electrolyte of the present invention to undergo an electrolytic reaction, generating hydrogen gas at the acid balance cathode, and generating oxygen and hydrogen ions at the acid balance anode. Sulfate ions in the anolyte will pass through the anion exchange membrane and enter the electrolysis cathode area under the influence of the electric field attraction of the acidity balance anode, and combine with hydrogen ions generated by water electrolysis to form sulfuric acid, thereby improving the sulfate in the catholyte concentration. In this way, the concentration of sulfate ions in the catholyte can be increased without increasing the total concentration of sulfate ions in the entire electrolysis and electroplating system, while maintaining the stability of the electrolyte components, reducing electrolysis Resistance of liquid. In addition, after the acid balance electrolysis system is installed, when the membrane in step (2) of the present invention is an anion exchange membrane, the preparation of the catholyte may also be: after preparing the anolyte and adding it to the electrolytic cell, the The cathodic electrolysis zone first uses water as the electrolyte, and then applies an acid balance electrolysis voltage higher than the working set to the acid balance electrolysis system to electrolyze, so that the sulfate in the anode electrolyte passes through the anion exchange membrane and the acidity balance generated on the anode Hydrogen ions form sulfuric acid to complete. Since water itself has a weaker ionization ability, ion transfer can also occur to achieve an electrochemical reaction at a higher electrolysis voltage.

Preferably, when the membrane of the acidity balance cathode region uses an anion membrane, the present invention can also detect the concentration of the inorganic base of the acidity balance catholyte and perform inorganic base and/or the acidity balance catholyte according to the detection result Adding carbon dioxide, or replacing it with a new acid balance catholyte; when the diaphragm of the acid balance cathode zone uses a bipolar membrane, the level of the acid balance catholyte can be detected and the acidity can be adjusted according to the test results Balance the catholyte to add water, or replace with a new acidity balanced catholyte:

When the membrane of the acidity balance cathode area adopts an anion membrane and the concentration of the inorganic base in the acidity balance cathode liquid is lower than the initial value, inorganic base and/or carbon dioxide is added to the acidity balance cathode liquid until the acidity balance The concentration of each component in the catholyte is restored to the initial value, or a new acidity balance catholyte is replaced. The detection of the concentration of the inorganic base in the acidity balance catholyte can also be reflected by detecting the pH value and/or acidity value and/or specific gravity value of the acidity balance catholyte.

When the diaphragm of the acidity balanced cathode region uses a bipolar membrane and the liquid level in the acidity balanced catholyte is lower than the initial value, water is added to the acidity balanced catholyte until the acidity balanced catholyte liquid level Restore to the initial value, or replace with a new acid balance catholyte.

The second object of the present invention is achieved by the following technical solutions:

An insoluble anode acid copper electroplating process electroplating solution or electroplating replenishment liquid production device, characterized in that it includes an electrolysis device, the electrolysis device is mainly composed of an electrolytic cell, an electrolytic anode, an electrolytic cathode and an electrolytic power supply, the electrolytic anode and The electrolytic cathode is respectively connected to the positive electrode and the negative electrode of the electrolytic power supply, wherein:

The electrolytic cell is provided with an electrolytic cell diaphragm, and the electrolytic cell is divided into an electrolytic anode area and an electrolytic cathode area, and the electrolytic anode area and the electrolytic cathode area are respectively used to contain an anolyte and a catholyte;

The electrolysis anode is a soluble electrolysis anode, the electrolysis anode contains copper element (corresponding to the method sovereignty), and the electrolysis anode is provided in the electrolysis anode area, and the electrolysis anode Copper electrolysis is copper ions, used to increase the concentration of copper ions in the anode electrolyte;

The electrolytic cathode is a conductor, and the electrolytic cathode is disposed in the electrolytic cathode area.

The present invention can further make the following improvements:

In the present invention, a current regulator can be added to the electrolytic power supply, or the current regulator included in the power supply itself can be used to adjust the output current of the electrolytic power supply, or to control the on/off of the electrolytic power supply. The output current of the electrolytic power supply can affect the rate of increase of the copper ion concentration in the anolyte during the electrolysis reaction. The larger the output current, the faster the copper ion concentration increases; otherwise, the smaller the output current, the copper ion concentration The slower the rate of increase. Connect the current regulator to the electrolyte or electroplating liquid detection device and set the setting value of the relevant detection index, which can realize the automatic control of the current regulator to the electrolytic power supply according to the dynamic index of the electrolyte or electroplating liquid detected by the detection device in real time Output current adjustment operation.

The membrane of the electrolytic cell of the present invention uses an anion exchange membrane and/or a bipolar membrane.

The electrolytic anode containing a copper element according to the present invention may be an electrolytic anode containing metallic copper or an electrolytic anode containing both metallic copper and copper oxide.

In order to distribute the components of the electrolyte evenly in the present invention, an electrolyte stirring device may be added in the electrolytic anode area and/or the electrolytic cathode area; the electrolyte stirring device may use electrolyte reflux liquid stirring Device, leaf stirring device, pneumatic stirring device, or any combination thereof. The electrolyte reflux liquid stirring device includes a discharge tube, a pump, and a reflux tube. The pneumatic stirring device is a A device that allows gas to flow through the electrolyte to make the electrolyte flow.

In the present invention, a hydrogen evacuation system can also be provided above the electrolysis cathode area for absorbing hydrogen generated in the electrolysis cathode area due to the electrolysis reaction to avoid potential safety hazards caused by hydrogen accumulation. The hydrogen exhaust system may use a general exhaust system or a simple exhaust pipe.

As a recommended embodiment of the present invention, the electrolytic anode area of the present invention is connected to the electroplating tank of the insoluble anode acid copper electroplating process by pipes, so that when the copper ion concentration of the anolyte reaches a predetermined value, or electroplating When the copper ion concentration of the solution is lower than the set value of the insoluble anode acidic copper plating process, the anolyte can be directly added as a plating solution to the plating bath of the insoluble anode acidic copper plating process, or the plating bath The electroplating solution flows into the electrolytic anode zone. Preferably, the electrolytic anode zone is connected to the electroplating tank through pumps and pipes and/or overflow ports, and a diaphragm and/or a filtering device are provided at the connection between the electrolytic anode zone and the electroplating tank to remove the electroplating solution and And/or copper sludge that may be present in the electrolyte and/or impurities brought during the use of the electrode.

Preferably, a liquid level meter, a specific gravity meter, an acidity meter, a redox potentiometer, a photoelectric colorimetric meter are provided in the electroplating tank on the production line and/or the electrolytic anode zone and/or electrolytic cathode zone according to the present invention One or more detection devices in the reagent and the pH meter to detect the corresponding parameters in the plating solution in the plating bath and/or the anolyte and/or catholyte of the present invention.

More preferably, the electrolyte detection device is connected to an automatic feeding controller, and the automatic feeding controller can be based on time and/or the detection result of the plating solution and/or electrolyte detection device and/or the present invention The electrolytic cell pressure control adds anolyte to the electroplating solution, and/or adds electroplating solution and/or raw materials and/or water to the anolyte, and/or electrolyzes to the cathode Add raw materials and/or carbon dioxide and/or water to the liquid.

In order to prevent the diaphragm from being easily clogged with copper mud, preferably, the diaphragm adopts a two-layer anion exchange membrane or a combined membrane composed of a bipolar membrane and an anion exchange membrane between the electrolytic anode zone and the electrolytic cathode zone An electrolytic buffer zone is provided, and the electrolytic buffer zone contains an aqueous solution containing no copper ions and containing sulfuric acid as an electrolytic buffer solution.

The present invention may also provide a stirring device and/or a buffer detection device in the electrolytic buffer, and the buffer detection device includes one or more of a pH meter, an acidity meter, and a specific gravity meter. The buffer in the electrolytic buffer is used to detect one or more indicators.

The present invention may further connect the buffer detection device with an automatic feeding controller, and the automatic feeding controller can control the replenishment of sulfuric acid and/or sulfuric acid to the electrolytic buffer according to the detection result of the buffer detection device Or a solution containing sulfuric acid.

When the electrolyzer diaphragm adopts an anion exchange membrane and the catholyte contains sulfate, as a preferred embodiment of the present invention, an acidity balance cathode area is separated in the electrolysis anode area, and the acidity balance The cathode area faces the direction of the electrolysis cathode area using an anion exchange membrane as a partition, and an acidity balance electrolysis system is provided at the same time, so that when the electrolysis cell of the present invention is connected to the electroplating cell on the production line to form a loop flow system in electroplating production, it can be Without increasing the total amount of sulfate ions in the electroplating and electrolytic regeneration loop recycling system, resulting in disrupting the overall balance of the system, the concentration of sulfate ions in the catholyte is increased, while maintaining the stability of the electrolyte composition At the same time, reduce the resistance of the electrolyte. The acidity balance electrolysis system is mainly composed of the acidity balance cathode area, the acidity balance cathode provided in the acidity balance cathode area, the acidity balance anode provided in the electrolysis cathode area, and an acidity balance The power source is composed of the acidity balanced cathode and the acidity balanced anode connected to the negative electrode and the positive electrode of the acidity balanced power supply, respectively.

Preferably, the present invention may also be provided with a variety of detection devices such as a stirring device and/or a pH meter and/or an acidity meter and/or a specific gravity meter in the acidity balance cathode area, which are used for the acidity balance cathode area The acidity balance in the catholyte is tested for one or more indicators.

More preferably, in order to stabilize the components of the acidity balance catholyte in the present invention, a supplementary liquid addition tank and/or a carbon dioxide source and an automatic feeding controller may be further added, wherein the supplementary liquid addition tank and the acidity The pipeline in the balanced cathode area is connected and a supplementary liquid pump is provided on the pipeline. The carbon dioxide source is connected to the pipeline in the acidity balanced cathode area and a gas valve is provided on the pipeline between the two to control the flow of carbon dioxide gas. Or open or close; the automatic feeding controller is respectively connected to the detection device, the supplementary liquid pump and/or the carbon dioxide source gas valve in the acidity balance cathode area, and controls the supplement according to the detection result of the detection device The flow rate of the liquid pump and/or carbon dioxide source gas valve is either open/closed.

According to the present invention, a hydrometer and/or acidity meter and/or pH meter can be provided in the electrolytic cathode zone, and the acidity balance can be controlled according to the detection results of the hydrometer and/or acidity meter and/or pH meter. The current of the power supply and/or electrolytic power supply may be turned on or off.

Compared with the prior art, the present invention has the following beneficial effects:

1. The present invention provides the plating solution required for the production of insoluble anode acid copper electroplating by separately producing a plating solution or plating replenisher suitable for the insoluble anode acid copper electroplating process, and/or by providing the plating in the copper electroplating production in a timely manner The method of adding electroplating replenishment solution to maintain the copper ion concentration in the electroplating solution that can continue to plate copper, not only can ensure good plating quality, but also simple operation, no need to use complex and large-scale equipment, nor expensive chemicals as raw materials, making The cost of the copper electroplating is reduced, thereby overcoming the defects of the prior art, and the processability and cost performance of the copper electroplating production are significantly improved, which is beneficial to the application in actual production;

2. The present invention can produce electroplating replenishing solution for addition to the electroplating solution added to the insoluble anode acid copper electroplating production line to supplement the copper ion concentration in the electroplating solution, and can also produce the initial electroplating solution or produce the electroplating solution The raw materials can also be used to produce finished copper sulfate solutions for direct sale, with various uses;

3. The invention can be connected with the production line of insoluble anode acidic copper electroplating process to form electroplating and electrolytic regeneration loop recycling system, and control the produced electroplating replenisher according to the process requirements and immediate situation of insoluble anode acidic copper electroplating process production line The added amount can automatically control the replenishment rate of copper ions in the electroplating solution, thereby ensuring that a high-quality copper layer is obtained by electroplating;

4. In the present invention, the electrolytic buffer zone can be provided between the electrolysis anode area and the electrolysis cathode area of the electrolysis reaction to avoid the problem of clogging of the diaphragm caused by copper sludge generated on the diaphragm and improve the service life of the diaphragm;

5. When the membrane of the present invention uses an anion exchange membrane, the acidity balance electrolysis system is provided in the electrolytic cell, so that the sulfate ion in the catholyte can be made without increasing the total concentration of sulfate ion in the electrolyte Increased concentration reduces the resistance of the electrolyte while maintaining the stability of the electrolyte components;

6. When the present invention is connected to the production line of insoluble anode acidic electroplating copper process, the parameters of the electrolyte or/and the electroplating solution on the production line of the present invention can be detected, and the electroplating or/and cost of the production line can be adjusted according to the results of the detection. The current size of the electrolysis of the invention, or the control of the electroplating on the production line and/or the electrolysis power supply of the invention, is turned on or off, so that the electrolysis production of the electroplating replenishment liquid of the invention is coordinated with the production line of the insoluble anode acidic copper plating process, so as to achieve continuous Stable electroplating production.

The present invention will be further described below through specific examples.

In the following embodiments, the copper sulfate used is preferably copper sulfate produced by Changzhou Hairun Chemical; the sulfuric acid, copper oxide, potassium sulfate, iron sulfate, aluminum sulfate, ferrous sulfate, ammonium sulfate, cadmium sulfate, sulfuric acid Magnesium, manganese sulfate, potassium bisulfate, sodium bisulfate, nickel sulfate, zinc sulfate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, carbonic acid The ammonium hydrogen is preferably a product produced by Guangzhou Chemical Reagent Factory; the metallic copper used is preferably the metallic copper produced by Changsha Tianjiu Metal Materials Co., Ltd.; the sodium sulfate used is preferably the sodium sulfate produced by Jiuzhong Chemical Company; the titanium sulfate used It is preferably titanium sulfate produced by Sinopharm Group Co., Ltd.; the electroplating anode used is preferably a noble metal oxide-coated titanium anode plate produced by Yegao Electronic Plastic Material Factory; the electroplating cathode used is preferably a commercially available pure copper plate ; The anion exchange membrane used is preferably an anion exchange membrane produced by Membrane International; the bipolar membrane used is preferably a bipolar membrane produced by Guochu Technology; the microscope used is preferably a computer microscope produced by Guangzhou Optical Instrument Factory. In addition to those listed above, those skilled in the art can also choose other products with similar performance to the above-mentioned products listed in the present invention according to conventional choices, all of which can achieve the purpose of the present invention.

Example 1

As shown in FIG. 1, it is a basic embodiment of a production apparatus of a plating solution or plating replenishment solution suitable for an insoluble anode acid copper plating process, which is an electrolysis device, mainly composed of an electrolytic cell, an electrolytic anode 4, an electrolytic cathode 5 and The electrolytic power supply 6 and the electrolytic cell diaphragm 3 are composed of the electrolytic anode 4 and the electrolytic cathode 5 respectively connected to the positive electrode and the negative electrode of the electrolytic power supply 6, wherein: the electrolytic cell diaphragm 3 divides the electrolytic cell into an electrolytic anode region 2 and The electrolytic cathode zone 1, the electrolytic anode zone 2 and the electrolytic cathode zone 1 are respectively used to contain anolyte and catholyte; the electrolytic cell membrane 3 uses an anion exchange membrane.

It is suitable for the production method of electroplating solution or electroplating replenishing solution of insoluble anode acid copper electroplating process, including the following steps:

Step 1: Use an anion exchange membrane to divide the electrolytic cell into an electrolytic anode zone 2 and an electrolytic cathode zone 1;

Step 2: Prepare anolyte and catholyte separately;

Step 3: Pour the anolyte prepared in step 2 into electrolytic anode zone 2 and prepare catholyte and pour into electrolytic cathode zone 1;

Step 4: Connect the electrolytic anode 4 to the positive electrode of the electrolytic power supply 6 and immerse in the anolyte, and connect the electrolytic cathode 5 to the negative electrode of the electrolytic power supply 6 and immerse into the catholyte;

Step 5: Turn on the electrolysis power supply 6 for electrolysis, set a predetermined value of copper ions with the required copper ion concentration of the plating solution, and remove the anolyte when the concentration of copper ions in the anolyte reaches a predetermined value , Used as the initial acid copper sulfate plating solution in the ordinary plating tank 12 without diaphragm;

Step 6: After electroplating using the initial acid copper sulfate electroplating solution described in Step 5, remove the electroplating cathode 14 (ie, cathode plating); clean the electroplating cathode 14 with clean water and blow dry with hot air; and use a computer The surface of the plating layer was observed with a microscope, and the observation results were recorded in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4 and electrolytic cathode 5 described in Example 1 are shown in Table 1 below.

Example 2

Example 2 is also a production device of the present invention suitable for an insoluble anode acid copper electroplating process of electroplating solution or electroplating replenishment solution. The composition of the electrolysis device is the same as that of Example 1, except for the difference between the anolyte and catholyte The ratio is different.

It is suitable for the production method of electroplating solution or electroplating replenishing solution of insoluble anode acid copper electroplating process, including the following steps:

Step 1: Set up three electrolytic cells as shown in Fig. 1, and the electrolytic cell diaphragm 3 uses an anion exchange membrane to divide the electrolytic cell into an electrolytic anode zone 2 and an electrolytic cathode zone 1;

Step 2: Prepare anolyte and catholyte separately;

Step 3: Pour the anolyte prepared in step 2 into electrolytic anode zone 2 and prepare catholyte and pour into electrolytic cathode zone 1;

At the same time, prepare the plating solution and pour it into the ordinary plating tank 12 without diaphragm;

Step 4: Connect the electrolytic anode 4 to the positive electrode of the electrolytic power supply 6 and immerse in the anolyte, and connect the electrolytic cathode 5 to the negative electrode of the electrolytic power supply 6 and immerse into the catholyte;

The insoluble electroplating anode 13 and the electroplating cathode 14 are respectively connected to the positive electrode and the negative electrode of the electroplating power source and immersed in the electroplating solution;

Step 5: Turn on the electrolysis power supply 6 to perform the electrolysis operation of the present invention, and start the production operation of copper electroplating at the same time, wherein the electroplating test time is set to 5 hours. During the process of simultaneous electroplating and electrolysis of the present invention, this According to the invention, when the copper ion concentration in the anolyte is equal to or higher than the copper ion concentration required by the electroplating solution, and the copper ion concentration of the electroplating solution is lower than the set value, the anolyte is added to the electroplating tank 12 as a plating solution In the process, the copper ion concentration of the plating solution is restored or exceeds the set value, thereby stabilizing the copper ion concentration of the plating solution;

Step 6: Take out the electroplating cathode 14 after the set electroplating time is completed; rinse the electroplating cathode 14 with clean water and dry it with hot air; and observe the surface of the plating layer using a computer microscope, and record the observation results in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4 and electrolytic cathode 5 described in Example 2 are shown in Table 1 below.

Example 3

FIG. 2 shows one of the embodiments in which the electroplating solution or/and electroplating replenishment production device of the present invention is connected to an insoluble anode acidic electroplating copper process production line. The electroplating solution or/and electroplating replenishment production device of the present invention uses an electrolysis device. The electrolysis device is composed of an electrolysis cell, 2 electrolysis anodes 4, 2 electrolysis cathodes 5, 3 electrolysis cell diaphragms 3, an electrolysis power supply 6, an electrolyte stirring device 16 and 2 hydrogen discharge systems 11. An electrolytic anode 4 and two electrolytic cathodes 5 are respectively connected to the positive and negative electrodes of the electrolytic power supply 6, wherein: three electrolytic cell diaphragms 3 divide the electrolytic cell into four electrolytic zones, the electrolytic anode 4 and the electrolytic cathode 5 Placed in the four electrolysis zones respectively to form two electrolysis anode zones 2 and two electrolysis cathode zones 1, and the electrolysis anode zone 2 is arranged adjacent to the electrolysis cathode zone 1, the electrolysis anode zone 2 and the electrolysis cathode zone 1 is used to contain anolyte and catholyte respectively; the electrolytic cell diaphragm 3 uses an anion exchange membrane; the electrolyte stirring device 16 uses an electrolyte reflux liquid stirring device, which includes a discharge pipe and a pump 1. The return pipe; the hydrogen exhaust system 11 uses a common exhaust system, and the two exhaust ports are respectively arranged above the two electrolytic cathode regions 1.

This embodiment is associated with an electroplating tank 12 produced by insoluble anode acid copper electroplating. The electroplating tank 12 is provided with an insoluble electroplating anode 13 and a electroplating cathode 14 (that is, a cathode plating part), and an exhaust fan is provided directly above the electroplating anode 13 System 15, the outlet of the exhaust pipe of the system is introduced into the anolyte of the present invention, so as to introduce the oxygen generated in the electroplating process into the anolyte, so as to supplement the anolyte as an oxygen source in.

It is suitable for the production method of electroplating solution or electroplating replenishing solution of insoluble anode acid copper electroplating process, including the following steps:

Step 1: As shown in FIG. 2, the electrolytic cell is divided into an electrolytic anode area 2 and an electrolytic cathode area 1 using an electrolytic cell diaphragm 3. The electrolytic anode area 22 is provided with an electrolyte reflux liquid stirring device, and the electrolytic cathode 5 A hydrogen discharge system 11 is provided above to lead the hydrogen generated on the electrolysis cathode 5 out of the electrolysis system;

Step 2: Prepare the anolyte and catholyte separately; prepare the electroplating solution and pour it into the ordinary electroplating tank 12 without diaphragm;

Step 3: Pour the anolyte prepared in step 2 into electrolytic anode zone 2 and prepare catholyte and pour into electrolytic cathode zone 1;

Step 4: Connect the electrolytic anode 4 to the positive electrode of the electrolytic power supply 6 with a current regulator and immerse in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power supply 6 and immerse into the catholyte; The anode 13 and the electroplating cathode 14 are respectively connected to the positive electrode and the negative electrode of the electroplating power supply and immersed in the electroplating solution. An exhaust fan system 15 is provided directly above the electroplating anode 13, and an air outlet of the exhaust pipe of the exhaust fan system 15 Introduced into the anolyte;

Step 5: Connect the electrolysis power supply 6 to conduct the electrolysis operation at the same time, and start the electroplating operation at the same time; set the electroplating test time to 5 hours. During the electroplating process, the copper ion concentration and sulfuric acid concentration of the anolyte are manually detected, based on the obtained anode Liquid copper ion concentration adjusts the electrolysis current, adds supplemental sulfuric acid to the electrolytic anode area 2 according to the measured anolyte sulfuric acid concentration, and adds 5% of the electrolytic solution volume to the electroplating bath 12 every 1 hour;

Step 6: Take out the electroplating cathode 14 after the set electroplating time is completed; rinse the electroplating cathode 14 with clean water and dry it with hot air; and observe the surface of the plating layer using a computer microscope, and record the observation results in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4 and electrolytic cathode 5 described in Example 3 are shown in Table 1 below.

Example 4

As shown in FIG. 3, it is one of the embodiments in which the electroplating solution or/and electroplating replenishment production device of the present invention is connected to an insoluble anode acidic electroplating copper process production line. The electroplating solution or/and electroplating replenishment production device of the present invention uses an electrolysis device , Mainly composed of an electrolytic cell, an electrolytic anode 4, an electrolytic cathode 5, an electrolytic power supply 6, a stirring device 16, and an electrolytic cell diaphragm 3, the electrolytic anode 4 and the electrolytic cathode 5 are respectively connected to the positive and negative electrodes of the electrolytic power supply 6, Wherein: the electrolytic cell membrane 3 divides the electrolytic cell into an electrolytic anode zone 2 and an electrolytic cathode zone 1, the electrolytic anode zone 2 and the electrolytic cathode zone 1 are respectively used to contain anolyte and catholyte; the electrolysis The tank diaphragm 3 uses an anion exchange membrane; the stirring device 16 is placed in the electrolytic anode zone 2 and the electrolytic cathode zone 1, and the stirring device 16 placed in the electrolytic anode zone 2 adopts a paddle stirrer and is placed in the electrolytic cathode zone 1 The internal stirring device 16 uses a reflux liquid stirring device.

A hydrogen discharge system 11 for discharging hydrogen generated on the cathode out of the electrolysis system is also provided above the electrolytic cathode zone 1.

This embodiment is associated with an electroplating tank 12 produced by insoluble anode acid copper electroplating. The electroplating tank 12 is provided with an insoluble electroplating anode 13 and a electroplating cathode 14 (ie, cathode plating); the electroplating tank 12 has an overflow port 20 and Connected to the transfer slot 19.

An automatic feeding controller 17 is connected to the electrolytic anode zone 2, the electrolytic cathode zone 1 and the electroplating tank 12 to detect the parameters in the anolyte, catholyte and electroplating baths; the automatic feeding controller 17 is also connected to the electrolytic power supply 6 To control the size of the electrolytic current and the on/off of the electrolytic power supply 6.

Two replenishing liquid addition tanks 18 are connected to the electrolytic cathode area 1, and the pump connected to the replenishing liquid addition tank 18 is connected to an automatic feeding controller 17, and the automatic feeding controller 17 controls the opening/closing of the pump , So as to realize automatic feeding.

It is suitable for the production method of electroplating solution or electroplating replenishing solution of insoluble anode acid copper electroplating process, including the following steps:

Step 1: As shown in FIG. 3, the electrolytic cell is divided into an electrolytic anode zone 2 and an electrolytic cathode zone 1 using an electrolytic cell diaphragm 3, and a stirring device 16 is provided at the bottom of the electrolytic anode zone 2, and the stirring device 16 uses paddle stirring The electrolysis cathode zone 1 is also provided with a stirring device 16, which uses a reflux liquid stirring device, and a hydrogen discharge system 11 is provided above the electrolysis cathode zone 1 to lead the hydrogen generated on the cathode out of the electrolysis system;

Step 2: Prepare the anolyte and pour into the electrolytic anode zone 2, prepare the catholyte and pour into the electrolytic cathode zone 1, prepare the electroplating solution and pour into the ordinary electroplating tank 12 without diaphragm, the electroplating tank 12 has There is an overflow port 20 and is connected with the transfer slot 19;

Step 3: Connect the electrolytic anode 4 to the positive electrode of the electrolytic power supply 6 with a current regulator and immerse in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power supply 6 and immerse into the catholyte; The anode 13 and the plating cathode 14 are respectively connected to the positive electrode and the negative electrode of the plating power supply with a current regulator and immersed in the plating solution;

Step 4: Using the automatic feeding controller 17, the parameters of the specific gravity of the electroplating solution, the photoelectric colorimetric value of the anolyte, the acidity of the catholyte, and the specific gravity of the catholyte are measured and set according to the obtained values. The electrolysis process Automatically adjust the current of the electroplating tank 12 and the electrolytic tank according to the specific gravity value of the electroplating solution obtained by the detection and the photoelectric colorimetric value of the anolyte, or shut down, according to the acidity of the catholyte obtained by the detection to the electrolytic cathode area 1 Add supplemental sulfuric acid, add supplemental sulfate aqueous solution to the electrolysis cathode area 1 according to the specific gravity value of the catholyte obtained by the test; turn on the power, energize the electrolysis operation, and start the electroplating operation;

Step 5: Set the electroplating test time to 5 hours. During the electroplating process, the acidity of the electroplating solution is manually tested, and the anode electrolyte is added to the electroplating bath 12 according to the acidity of the electroplating solution obtained by the test;

Step 6: Take out the electroplating cathode 14 after the set electroplating time is completed; rinse the electroplating cathode 14 with clean water and dry it with hot air; and observe the surface of the plating layer using a computer microscope, and record the observation results in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4 and electrolytic cathode 5 described in Example 4 are shown in Table 1 below.

Example 5

As shown in FIG. 4, it is one of the embodiments in which the electroplating liquid or/and electroplating replenishment liquid production device of the present invention is connected to an insoluble anode acid copper electroplating process production line. The difference between embodiment 5 and embodiment 4 is that it is placed in an electrolytic anode The stirring device 16 in the zone 2 uses a reflux liquid stirring device; a supplementary liquid addition tank 18 is connected to the electrolytic cathode zone 1; another supplementary liquid addition tank 18 is connected to the electrolytic anode zone 2; the electrolytic anode zone 2 Connected to the electroplating tank 12, a pump is also provided between the electrolysis anode area 2 and the electroplating tank 12, the pump is connected to the automatic feeding controller 17; the electroplating tank 12 is provided with an overflow port 20, which is connected to the overflow port 20 A transfer slot 19 is connected.

It is suitable for the production method of electroplating solution or electroplating replenishing solution of insoluble anode acid copper electroplating process, including the following steps:

Step 1: As shown in FIG. 4, an anion exchange membrane is used to divide the electrolytic cell into an electrolytic anode zone 2 and an electrolytic cathode zone 1. The anode zone and the cathode zone of the electrolytic cell are provided with an electrolyte reflux liquid stirring device. A hydrogen evacuation system 11 is provided above the cathode of the electrolytic cell to lead the hydrogen generated on the cathode out of the electrolytic system. The electrolysis anode zone 2 is connected to a pump by a pipe, and the pump liquid outlet is a pipe and a common diaphragmless The electroplating tank 12 is connected with an overflow port 20 and connected with the transfer tank 19;

Step 2: Prepare anolyte and pour into electrolytic anode zone 2, prepare catholyte and pour into electrolytic cathode zone 1, prepare electroplating solution and pour into electroplating tank 12;

Step 3: Connect the electrolytic anode 4 to the positive electrode of the electrolytic power supply 6 with a current regulator and immerse in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power supply 6 and immerse into the catholyte; The anode 13 and the plating cathode 14 are respectively connected to the positive electrode and the negative electrode of the electroplating power source and immersed in the plating solution;

Step 4: Using the automatic feeding controller 17, the specific gravity of the plating solution, the redox potential of the plating solution, the photoelectric colorimetric value of the plating solution, the specific gravity value of the anolyte, the level of the anolyte, and the cathode electrolysis The pH value of the solution is measured and set according to the obtained value. During the electrolysis process, an anode electrolyte is automatically added to the plating tank 12 according to the specific gravity value, redox potential value and photoelectric colorimetric value of the electroplating solution obtained by the detection. The specific gravity value of the anolyte obtained by the test is used to adjust the current of the electrolytic cell or shut down. According to the level of the anolyte obtained by the test, a supplementary sulfuric acid aqueous solution is added to the electrolytic anode zone 2 according to the The pH value is added to the electrolytic cathode area 1 to add a mixed aqueous solution of sulfate and sulfuric acid; turn on the power, energize to perform the electrolysis operation, and start the electroplating operation at the same time, set the electroplating test time to 5 hours;

Step 5: Remove the electroplating cathode 14 after the set electroplating time is completed; rinse the electroplating cathode 14 with clean water and dry it with hot air; and observe the surface of the plating layer using a computer microscope, and record the observation results in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4 and electrolytic cathode 5 described in Example 5 are shown in Table 1 below.

Example 6

As shown in FIG. 5, it is one of the embodiments of the present invention associated with an insoluble anode acid copper electroplating process production line. The difference between embodiment 6 and embodiment 5 is that: an insolubilization connected to a power source is provided at the bottom of electrolytic anode zone 2 Electrolytic anode 23; electroplating bath 12 is divided into electroplating bath anode area and electroplating bath cathode area by electroplating diaphragm 21; electroplating bath anode area and electroplating bath cathode area of electroplating bath 12 are respectively connected to a clean water source 25, and clean water source 25 and electroplating bath A pump is connected between the anode area and between the fresh water source 25 and the cathode area of the electroplating tank. Both pumps are connected to the automatic feeding controller 17 so that the automatic feeding controller 17 controls the anode area and electroplating of the electroplating tank The cathode area of the tank is supplemented with fresh water; the supplementary liquid addition tank 18 connected to the electrolytic anode area 2 is replaced by a clean water source 25; a filter device 22 is also connected between the electroplating tank 12 and the anode area; the electrolytic cathode area 1 is connected to a carbon dioxide source 26 , A gas valve 27 is connected between the carbon dioxide source 26 and the electrolytic cathode area 1, and the gas valve 27 is connected to an automatic feeding controller 17, so that the automatic feeding controller 17 controls the addition of carbon dioxide; the plating tank cathode area of the plating tank 12 An overflow port 20 is also provided. The overflow port 20 allows electroplating and overflow in the cathode area of the electroplating bath to the electrolytic anode area 2. A diaphragm 24 is also provided between the overflow port 20 and the electrolytic anode area 2.

It is suitable for the production method of electroplating solution or electroplating replenishing solution of insoluble anode acid copper electroplating process, including the following steps:

Step 1: As shown in FIG. 5, the electrolytic cell membrane 3 of the present invention uses an anion exchange membrane to divide the electrolytic cell into an electrolytic anode zone 2 and an electrolytic cathode zone 1. At the same time, the electroplating copper production line uses an electroplating cell 12 with a diaphragm 24. The electrolytic anode zone 2 and the electrolytic cathode zone 1 of the present invention are respectively equipped with an electrolyte reflux liquid stirring device, and a hydrogen discharge system 11 is provided above the electrolytic cathode 5 in the electrolytic cathode zone 1 to lead the hydrogen generated on the cathode out of the electrolytic system The electrolysis anode zone 2 is connected to a pump by a pipe, the pump outlet is connected by a pipe, the pipe outlet is placed in the cathode zone of the electroplating tank, and the pipe is provided with a filter device 22; The cathode area of the electroplating bath is provided with an overflow port 20 and is connected to the electrolytic anode area 2 by a pipe, and a diaphragm 24 is installed on the pipe;

Step 2: Prepare anolyte and pour into electrolytic anode zone 2, prepare catholyte and pour into electrolytic cathode zone 1, prepare electroplating solution and pour into the electroplating bath anode zone and electroplating bath cathode zone;

Step 3: Connect the anode of electrolysis anode 4 to the electrolysis power supply 6 with current regulator and immerse in the anolyte, connect the cathode of electrolysis cathode 5 to the anode of electrolysis power supply 6 and immerse in the catholyte, the electrolysis The bottom of the anode area 2 is provided with a titanium anode and is connected to the positive electrode of the electrolysis power supply 6; the insoluble electroplating anode 13 and the electroplating cathode 14 are respectively connected to the positive electrode and the negative electrode of the electroplating power supply and immersed in the electroplating solution;

Step 4: Using the automatic feeding controller 17, the acidity of the cathodic plating solution, the specific gravity value of the anolyte, the pH of the catholyte, the liquid level of the anode area of the electroplating bath, and the liquid level of the cathode area of the electroplating bath 1. The liquid level of the electrolytic anode zone 2, the liquid level of the electrolytic cathode zone 1, and the pressure of the electrolytic cell are measured and set according to the obtained data. During the electrolysis process, the acidity value of the cathode electroplating solution obtained automatically is automatically sent to the electroplating tank Anode electrolyte is added in the cathode area, the current of the electrolytic cell is adjusted or shut down automatically according to the specific gravity value of the anolyte obtained by the detection, and the anode area of the electroplating bath anode area automatically obtained according to the detection is automatically added to the anode area of the electroplating bath Add fresh water, automatically add fresh water to the cathode area of the electroplating tank according to the liquid level of the cathode area of the electroplating tank obtained by the detection, automatically add fresh water to the electrolytic anode area 2 according to the level of the electrolysis anode area 2 obtained by the detection, automatically according to The liquid level of the electrolysis cathode area 1 obtained by the detection automatically adds an inorganic alkaline aqueous solution to the electrolysis cathode area 1, and automatically adds carbon dioxide to the electrolysis cathode area 1 according to the electrolytic cell pressure of the electrolysis cell; At the same time start the electroplating operation and set the electroplating test time to 5 hours;

Step 5: Remove the electroplating cathode 14 after the set electroplating time is completed; rinse the electroplating cathode 14 with clean water and dry it with hot air; and observe the surface of the plating layer using a computer microscope, and record the observation results in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4 and electrolytic cathode 5 described in Example 6 are shown in Table 1 below.

Example 7

As shown in FIG. 6, it is one of the embodiments associated with the insoluble anode acidic copper electroplating process production line of the present invention. The difference between embodiment 7 and embodiment 5 is that the electrolytic cell is divided into electrolytic anode area 2 by electrolytic cell diaphragm 3. Cathode zone 1 and electrolysis buffer zone 7, and the electrolysis buffer zone 7 is located between the electrolysis anode zone 2 and the electrolysis cathode zone 1; there is no supplementary liquid addition tank 18 connected to the electrolysis cathode zone 1 and the electrolysis anode zone 2 Instead, a clean water source 25 is connected to the electrolytic cathode area 1, and a gas valve 27 is also provided between the clean water source 25 and the electrolytic cathode area 1, and the automatic feeding controller 17 is connected to the gas valve 27, so that automatic feeding The controller 17 controls adding fresh water to the electrolytic cathode zone 1; the overflow port 20 of the electroplating tank 12 is connected to the electrolytic anode zone 2; the electrolytic anode zone 2 is also connected to an oxygen source 28.

It is suitable for the production method of electroplating solution or electroplating replenishing solution of insoluble anode acid copper electroplating process, including the following steps:

Step 1: As shown in Fig. 6, the electrolysis cell is divided into an electrolysis anode zone 2, an electrolysis buffer zone 7 and an electrolysis cathode zone 1 by using an anion exchange membrane. The anode zone and the cathode zone of the electrolysis cell are respectively provided with electrolyte reflux A liquid agitation device. A hydrogen discharge system 11 is provided above the cathode of the electrolytic cell to lead the hydrogen generated on the cathode out of the electrolytic system. The electrolysis anode zone 2 is connected to a pump by a pipe. The pump outlet is connected by a pipe and A common electroplating tank 12 without a diaphragm is connected. The electroplating tank 12 has an overflow port 20 and is connected to the electrolytic anode zone 2 to form a closed loop between the electrolytic anode zone 2 and the electroplating tank 12;

Step 2: Prepare anolyte and pour into electrolytic anode zone 2, prepare catholyte and pour into electrolytic cathode zone 1, prepare buffer electrolyte and pour into electrolytic buffer zone 7, prepare plating solution and pour into plating tank 12 in

Step 3: Connect the electrolytic anode 4 to the positive electrode of the electrolytic power supply 6 with a current regulator and immerse in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power supply 6 and immerse into the catholyte; The anode 13 and the plating cathode 14 are respectively connected to the positive electrode and the negative electrode of the electroplating power source and immersed in the plating solution;

Step 4: Use the automatic feeding controller 17 to set and detect the specific gravity of the plating solution, the specific gravity value of the anolyte, and the specific gravity value of the catholyte, and automatically transfer to the electroplating according to the specific gravity value of the plating solution obtained by the detection Anode electrolyte is added to the tank 12, and the current of the electrolytic cell is adjusted or shut down automatically according to the specific gravity value of the anolyte obtained by the detection, and automatically added to the electrolytic cathode area 1 according to the specific gravity value of the catholyte obtained by the detection. Clean water; turn on the power, energize the electrolysis operation, and start the electroplating operation at the same time, set the electroplating test time to 5 hours; continue to add oxygen to the electrolysis anode area 2, and check the acid value of the buffer electrolyte every 1 hour Add sulfuric acid to the electrolytic buffer 7 to supplement the sulfuric acid component in the buffer electrolyte;

Step 5: Remove the electroplating cathode 14 after the set electroplating time is completed; rinse the electroplating cathode 14 with clean water and dry it with hot air; and observe the surface of the plating layer using a computer microscope, and record the observation results in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4, electrolytic cathode 5, and buffer electrolyte described in Example 7 are shown in Table 1 below.

Example 8

As shown in FIG. 7, it is one of the embodiments associated with the insoluble anode acid copper electroplating process production line of the present invention. The difference between embodiment 8 and embodiment 7 is that: the electrolytic buffer 7 is further provided with a stirring device 16, which is 16. A paddle stirrer is used; a carbon dioxide source 26 is used to replace the clean water source 25 connected to the electrolytic cathode area 1; a supplementary liquid addition tank 18 connected to the electrolytic buffer 7 is provided. The electrolytic buffer 7 and the supplementary liquid addition tank 18 A pump is also connected between the pumps and the pump is connected to the automatic feeding controller 17, so that the automatic feeding controller 17 controls the addition of the replenishing liquid into the electrolytic buffer 7 according to the parameters detected by the electrolytic buffer 7.

It is suitable for the production method of electroplating solution or electroplating replenishing solution of insoluble anode acid copper electroplating process, including the following steps:

Step 1: As shown in FIG. 7, the electrolysis cell is divided into an electrolytic anode zone 2, an electrolytic buffer zone 7 and an electrolytic cathode zone 1 using an anion exchange membrane, the electrolytic anode zone 2, the electrolytic cathode zone 1 and the electrolytic buffer zone 7 Stirring devices 16 are provided respectively. The stirring device 16 uses an electrolyte reflux liquid stirring device. A hydrogen discharge system 11 is provided above the electrolysis cathode 5 to lead the hydrogen generated on the electrolysis cathode 5 out of the electrolysis system. The electrolysis anode area 2 is connected to a pump by a pipe, and the pump outlet is connected by a pipe to a common electroplating tank 12 without a diaphragm, the electroplating tank 12 has an overflow port 20 and is connected to the electrolytic anode area 2, Making the electrolytic anode area 2 and the electroplating tank 12 form a closed loop;

Step 2: Prepare anolyte and pour into electrolytic anode zone 2, prepare catholyte and pour into electrolytic cathode zone 1, prepare buffer electrolyte and pour into electrolytic buffer zone 7, prepare plating solution and pour into plating tank 12 in

Step 3: Connect the electrolytic anode 4 to the positive electrode of the electrolytic power supply 6 with a current regulator and immerse in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power supply 6 and immerse into the catholyte; The anode 13 and the plating cathode 14 are respectively connected to the positive electrode and the negative electrode of the electroplating power source and immersed in the plating solution;

Step 4: Use the automatic feeding controller 17 to set and test the specific gravity of the electroplating solution, the specific gravity value of the anolyte, the pH of the catholyte, the pH and the specific gravity of the buffer electrolyte, and automatically obtain based on the detection The specific gravity value of the electroplating solution automatically adds anolyte to the electroplating tank 12, and automatically adjusts or shuts down the current of the electrolytic regeneration tank according to the specific gravity value of the anolyte obtained by the detection, and automatically adjusts the current value of the catholyte obtained according to the detection. Adding supplementary carbon dioxide to the electrolysis cathode area 1 by pH value, automatically adding a mixed solution of sulfuric acid and sodium sulfate to the electrolysis buffer 7 according to the pH value and specific gravity value of the buffer electrolyte obtained by the detection; turning on the power and energizing for electrolysis operations , At the same time start the electroplating operation, set the electroplating test time to 5 hours;

Step 5: Remove the electroplating cathode 14 after the set electroplating time is completed; rinse the electroplating cathode 14 with clean water and dry it with hot air; and observe the surface of the plating layer using a computer microscope, and record the observation results in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4, electrolytic cathode 5, and buffer electrolyte described in Example 8 are shown in Table 1 below.

Example 9

As shown in Figures 8 and 9 is one embodiment of the present invention associated with an insoluble anode acid copper electroplating process production line. The electroplating solution or/and electroplating replenishing solution production device of the present invention uses an electrolysis device, which is mainly composed of an electrolytic cell and an electrolytic anode 4. The electrolytic cathode 5, the electrolytic power supply 6, the stirring device 16 and the electrolytic cell diaphragm 3, the electrolytic anode 4 and the electrolytic cathode 5 are respectively connected to the positive electrode and the negative electrode of the electrolytic power supply 6, wherein: the electrolytic cell diaphragm 3 will The electrolysis cell is divided into an electrolysis anode area 2 and an electrolysis cathode area 1, the electrolysis anode area 2 and the electrolysis cathode area 1 are respectively used to contain anolyte and catholyte; the electrolysis cell diaphragm 3 uses an anion exchange membrane; The stirring device 16 is placed in the electrolysis anode area 2 and the electrolysis cathode area 1, and the stirring device 16 adopts a uniform reflux liquid stirring device; a hydrogen discharge system 11 is provided above the electrolysis cathode area 1 to lead out the hydrogen generated on the cathode Outside the electrolysis system; an electrolytic cell diaphragm 3 is also used in the electrolytic anode zone 2 to separate an acidity balanced cathode zone 8, the acidity balanced cathode zone 8 is provided with an acidity balanced cathode 10, and the electrolytic cathode zone 1 is provided with an acidity balance Anode 9, the acid balance anode 9 and the acid balance cathode 10 are respectively connected to the positive electrode and the negative electrode of another electrolysis power supply 6; the automatic feeding controller 17 detects the electroplating tank 12, the electrolytic anode area 2, and the acid balance cathode area 8 respectively Value in order to control the adding and dropping action and the size of the electrolysis current and the on/off of the electrolysis power supply 6; the electrolysis anode area 2 is connected to the electroplating tank 12 in which the electroplating anode 13 and the electroplating cathode 14 are provided, and the electrolysis A pump is provided between the anode area 2 and the electroplating tank 12, and the pump is connected to the automatic feeding controller 17, so that the automatic feeding controller 17 controls the opening/closing of the pump; the electroplating tank 12 is provided with an overflow port 20, and the overflow port 20 is connected to the electrolysis anode region 2; a carbon dioxide source 26 is connected to the acidity balance cathode region 8, and a gas valve 27 is also connected between the carbon dioxide source 26 and the acidity balance cathode region 8 27 is connected to the automatic feeding controller 17, so that the automatic feeding controller 17 controls the addition of carbon dioxide.

It is suitable for the production method of electroplating solution or electroplating replenishing solution of insoluble anode acid copper electroplating process, including the following steps:

Step 1: As shown in FIGS. 8 and 9, the anion exchange membrane is used to divide the electrolytic cell into an electrolytic anode zone 2, an acidity balance cathode zone 8 and an electrolytic cathode zone 1. The electrolytic anode zone 2 and the electrolytic cathode zone 1 are respectively provided There is an electrolyte reflux liquid stirring device. A hydrogen discharge system 11 is provided above the electrolysis cathode 5 to lead the hydrogen generated on the cathode out of the electrolysis system. The electrolysis anode area 2 is connected to a pump by a pipe, and the pumped liquid The port is connected with a common electroplating tank 12 without a diaphragm, the electroplating tank 12 has an overflow port and is connected to the electrolytic anode zone 2, so that the electrolytic anode zone 2 and the electroplating tank 12 are formed Closed loop

Step 2: Prepare anolyte and pour into electrolytic anode zone 2, prepare catholyte and pour into electrolytic cathode zone 1, prepare acidity balanced catholyte and pour into acidity balanced cathode zone 8, prepare electroplating solution and pour into In the plating tank 12;

Step 3: Connect the electrolytic anode 4 to the positive electrode of the electrolytic power supply 6 with current regulator and immerse in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power supply 6 and immerse into the catholyte; balance the acidity The anode 9 is connected to the positive electrode of the acid balance power supply and immersed in the catholyte, the acid balance cathode is connected to the negative electrode of the acid balance power supply and immersed in the acid balance cathode liquid; the insoluble plating anode 13 and the plating cathode 14 are respectively connected to the plating power supply Positive electrode and negative electrode are connected and immersed in the plating solution;

Step 4: Use the automatic feeding controller 17 to set and test the redox potential of the electroplating solution, the specific gravity value of the anolyte, and the specific gravity of the catholyte with acid balance, and automatically determine the redox of the electroplating solution according to the detection Potential value automatically adds anolyte to the electroplating tank 12, automatically adjusts or shuts down the current of the electrolytic tank according to the specific gravity value of the anolyte obtained by the test, and automatically balances the specific gravity value of the catholyte according to the acidity obtained by the test. Add supplementary carbon dioxide to the acidity balance cathode area 8; turn on the power, turn on the electrolysis electrode and the acid balance electrode to perform electrolysis, and at the same time start the electroplating operation, set the electroplating test time to 5 hours;

Step 5: Remove the electroplating cathode 14 after the set electroplating time is completed; rinse the electroplating cathode 14 with clean water and dry it with hot air; and observe the surface of the plating layer using a computer microscope, and record the observation results in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4, electrolytic cathode 5, acid balance catholyte, acid balance anode 9, and acid balance cathode 10 described in Example 9 are shown in Table 1 below.

Example 10

As shown in FIGS. 9 and 10, it is one of the embodiments of the present invention associated with the insoluble anode acid copper electroplating process production line. The difference between embodiment 10 and embodiment 9 is that: plating tank 12 is not provided with overflow port 20; automatic feeding control The device 17 detects the values in the electroplating tank 12 and the electrolysis anode area 2 respectively, so as to control the adding and dropping action and the size of the electrolysis current and the on/off of the electrolysis power supply 6; no carbon dioxide source 26 is provided; the electrolysis anode area 2 and the electroplating tank 12 The connection forms a loop circuit, and the two pumps between the electrolytic anode zone 2 and the electroplating tank 12 are connected to the automatic feeding controller 17.

It is suitable for the production method of electroplating solution or electroplating replenishing solution of insoluble anode acid copper electroplating process, including the following steps:

Step 1: As shown in FIGS. 9 and 10, the anion exchange membrane is used to divide the electrolytic cell into an electrolytic anode zone 2, an electrolytic cathode zone 1 and an acidity balance cathode zone 8, the electrolytic anode zone 2 and the electrolytic cathode zone 1 are respectively provided There is an electrolyte reflux liquid stirring device. A hydrogen discharge system 11 is provided above the electrolysis cathode 5 to lead the hydrogen generated on the cathode out of the electrolysis system. The electrolysis anode area 2 and a common diaphragmless plating tank 12 are composed of two pipes Connected, the pipes are respectively provided with pumps with opposite fluid directions, so that the electrolytic anode area 2 and the electroplating tank 12 form a closed loop;

Step 2: Prepare anolyte and pour into electrolytic anode zone 2, prepare catholyte and pour into electrolytic cathode zone 1, prepare acidity balanced catholyte and pour into acidity balanced cathode zone 8, prepare electroplating solution and pour into In the plating tank 12;

Step 3: Connect the electrolytic anode 4 to the positive electrode of the electrolytic power supply 6 with current regulator and immerse in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power supply 6 and immerse into the catholyte; balance the acidity The anode 9 is connected to the positive electrode of the acid balance power supply and immersed in the catholyte, the acid balance cathode 10 is connected to the negative electrode of the acid balance power supply and immersed in the acid balance cathode liquid; the insoluble electroplating anode 13 and the electroplating cathode 14 are respectively electroplated The positive and negative poles of the power supply are connected and immersed in the plating solution;

Step 4: Use the automatic feeding controller 17 to set and detect the photoelectric colorimetric value of the plating solution and the specific gravity value of the anolyte, and automatically send the electroplated colorimetric value of the plating solution to the plating tank 12 automatically according to the detection Add the anolyte and start the pump to add the electroplating solution to the electrolysis anode zone 2 automatically adjust the current of the electrolytic cell or shut down according to the specific gravity value of the anolyte obtained by the detection; turn on the power and take turns Conduct electrolysis on the electrolysis electrode and acid balance electrode, and start electroplating at the same time, set the electroplating test time to 5 hours;

Step 5: Remove the electroplating cathode 14 after the set electroplating time is completed; rinse the electroplating cathode 14 with clean water and dry it with hot air; and observe the surface of the plating layer using a computer microscope, and record the observation results in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4, electrolytic cathode 5, acid balance catholyte, acid balance anode 9, and acid balance cathode 10 described in Example 10 are shown in Table 1 below.

Example 11

As shown in FIGS. 11 and 12, it is one of the embodiments of the present invention associated with the insoluble anode acid copper electroplating process production line. The difference between embodiment 11 and embodiment 9 is that the electrolytic anode zone 2 is also separated by an electrolytic cell membrane 3 An acidity balanced cathode region 8 is provided, and the electrolytic anode region 2 is placed between the electrolytic cathode region 1 and the acidity balanced cathode region 8, and the stirring device 16 is provided in the electrolytic anode region 2, the electrode cathode region, and the acidity balanced cathode region 8 In addition, the stirring devices 16 all use an electrolyte reflux liquid stirring device; the acidity balance cathode area 8 is also connected with a supplementary liquid addition tank 18, and a supplementary liquid addition tank 18 and an acidity balance cathode area 8 are provided with a The pump is connected to the automatic feeding controller 17 to control the addition of the supplementary liquid through the automatic feeding controller 17; the acidity balance cathode area 8 is also provided with an overflow port 20, which is connected to a relay The tank 19 is connected; the automatic feeding controller 17 detects the values in the electroplating tank 12, the electrolytic anode zone 2, the electrolytic cathode zone 1, and the acidity balance cathode zone 8, respectively, thereby controlling the addition action and the size of the electrolytic current and the opening of the electrolytic power supply 6 /Or off.

It is suitable for the production method of electroplating solution or electroplating replenishing solution of insoluble anode acid copper electroplating process, including the following steps:

Step 1: As shown in FIGS. 11 and 12, an anion exchange membrane is used to divide the electrolytic cell into an electrolytic anode zone 2, an electrolytic cathode zone 1 and an acidity balance cathode zone 8, the electrolytic anode zone 2, the electrolytic cathode zone 1 and the acidity The balanced cathode area 8 is respectively provided with an electrolyte reflux liquid stirring device. The acidity balanced cathode area 8 is provided with an overflow port 20 and the overflow port 20 is connected to a transfer tank 19 by a pipe. The electrolytic cathode 5 A hydrogen evacuation system 11 is provided to lead the hydrogen generated on the cathode out of the electrolysis system. The electrolysis anode area 2 is connected to a pump by a pipe, and the pump outlet is a pipe and a common electroplating tank 12 without a diaphragm Connected, the electroplating tank 12 has an overflow port 20 and is connected to the electrolytic anode region 2, so that the electrolytic anode region 2 and the electroplating tank 12 form a closed loop;

Step 2: Prepare anolyte and pour into electrolytic anode zone 2, prepare catholyte and pour into electrolytic cathode zone 1, prepare acidity balanced catholyte and pour into acidity balanced cathode zone 8, prepare electroplating solution and pour into In the plating tank 12;

Step 3: Connect the electrolytic anode 4 to the positive electrode of the electrolytic power supply 6 with current regulator and immerse in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power supply 6 and immerse into the catholyte; balance the acidity The anode 9 is connected to the positive electrode of the acid balance power supply and immersed in the catholyte, the acid balance cathode 10 is connected to the negative electrode of the acid balance power supply and immersed in the acid balance cathode liquid; the insoluble electroplating anode 13 and the electroplating cathode 14 are respectively electroplated The positive and negative poles of the power supply are connected and immersed in the plating solution;

Step 4: Use the automatic feeding controller 17 to set and test the specific gravity of the electroplating solution, the specific gravity value of the anolyte, the acidity value of the catholyte, and the pH value of the acidity balance catholyte. The specific gravity value of the electroplating solution automatically adds anolyte to the electroplating tank 12, automatically adjusts or shuts down the current of the electrolysis cell according to the specific gravity value of the anolyte obtained by the detection, and automatically adjusts the acidity value of the catholyte obtained according to the detection Control the opening and closing of the acid balance power supply; automatically add fresh acidity balance catholyte to supplement the inorganic alkali raw materials according to the pH value of the acid balance catholyte obtained by the detection, and add carbon dioxide at the same time; connect the power supply for electrolysis, At the same time start the electroplating operation and set the electroplating test time to 5 hours;

Step 5: Remove the electroplating cathode 14 after the set electroplating time is completed; rinse the electroplating cathode 14 with clean water and dry it with hot air; and observe the surface of the plating layer using a computer microscope, and record the observation results in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4, electrolytic cathode 5, acid balance catholyte, acid balance anode 9, and acid balance cathode 10 described in Example 11 are shown in Table 1 below.

Example 12

As shown in FIGS. 11 and 12, the apparatus of Example 12 and the production method of the plating solution or plating replenishment solution applicable to the insoluble anode acidic copper plating process are the same as those of Example 11.

Step 5: When the set plating time is completed, remove the electroplating cathode 14; clean the electroplating cathode 14 with clean water and dry it with hot air; and observe the surface of the plating layer using a computer microscope, and record the observation results in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4, electrolytic cathode 5, acid balance catholyte, acid balance anode 9, and acid balance cathode 10 described in Example 12 are shown in Table 1 below.

Examples 13-14

As shown in FIG. 1, the apparatuses of Example 13 and Example 14 and the production methods of the plating solution or plating replenishment solution applicable to the insoluble anode acidic copper plating process are the same as those of Example 1.

Among them, in the electrolysis process of step 4, the acidity and specific gravity of the catholyte are manually detected every 15 minutes, and the electrolytic cathode zone 1 is supplemented with a 50 wt% sulfuric acid aqueous solution according to the measured results, and the anode obtained after the electrolysis is completed The electrolyte becomes copper sulfate product after concentration and drying.

The components or materials of the anolyte, catholyte, electrolytic anode 4 and electrolytic cathode 5 described in Example 13 and Example 14 are shown in Table 1 below.

Examples 15 to 16

As shown in FIGS. 9 and 10, the apparatuses of Examples 15 and 16 and the production methods of the plating solution or plating replenishment solution applicable to the insoluble anode acidic copper plating process are the same as those of Example 10.

Wherein, the acidity balanced cathode area 8 is composed of a bipolar membrane; an automatic feeding controller 17 is used to parameterize the photoelectric colorimetric value of the plating solution, the specific gravity value of the anolyte, and the liquid level of the acidity balanced catholyte Set and test, automatically add anolyte to the electroplating tank 12 according to the photoelectric colorimetric value of the electroplating solution obtained by the test and start the pump to add the electroplating solution into the electrolysis anode zone 2 at the same time, automatically according to the anode electrolysis obtained by the test The specific gravity value of the liquid adjusts the current size of the electrolytic cell or shuts down, and automatically adds fresh water to the acidity balanced cathode area 8 according to the liquid level of the acidity balanced cathode liquid obtained by the detection; The acid balance electrode was energized for electrolysis, and the electroplating operation was started at the same time. The electroplating test time was set to 5 hours.

When the set electroplating time is completed, the electroplating cathode 14 is taken out; the electroplating cathode 14 is washed with clean water and dried with hot air; and the surface of the plating layer is observed using a computer microscope, and the observation results are recorded in Table 1.

The components or materials of the anolyte, catholyte, electrolytic anode 4, electrolytic cathode 5, acidity balanced catholyte, acidity balanced anode 9, acidity balanced cathode 10 described in Example 15 and Example 16 are shown in Table 1 below.

Example 17

As shown in FIG. 2, the apparatus of Example 17 and the production method of the plating solution or plating replenishment solution applicable to the insoluble anode acidic copper plating process are the same as those of Example 3.

Among them, the bipolar membrane is used to divide the electrolytic cell into an electrolytic anode zone 2 and an electrolytic cathode zone 1; during the electroplating process, the copper ion concentration and sulfuric acid concentration of the anolyte and the level of the catholyte are manually detected, according to the obtained The anolyte copper ion concentration adjusts the electrolysis current, adds supplemental sulfuric acid to the electrolytic anode zone 2 according to the measured anolyte sulfuric acid concentration, and supplements the electrolytic cathode zone 1 according to the measured level of the catholyte water.

The components or materials of the anolyte, catholyte, electrolytic anode 4 and electrolytic cathode 5 described in Example 17 are shown in Table 1 below.

Example 18

As shown in FIG. 6, the apparatus of Example 18 and the production method of the plating solution or plating replenishment solution applicable to the insoluble anode acidic copper plating process are the same as those of Example 7.

Among them, the electrolytic cell is divided into an electrolytic anode zone 2, an electrolytic buffer zone 7 and an electrolytic cathode zone 1, the electrolytic anode zone 2 and the electrolytic buffer zone 7 are separated by an anion exchange membrane, the electrolytic buffer zone 7 and the electrolytic cathode Zone 1 is separated by a bipolar membrane.

The components or materials of the anolyte, catholyte, electrolytic anode 4, electrolytic cathode 5, and buffer electrolyte described in Example 18 are shown in Table 1 below.

[Table 1]

As can be seen from Table 1, after the electroplating solution or electroplating solution obtained in the above Examples 1 to 18 is used for electroplating, the quality of the plating layer is bright, uniform and smooth, so it can be seen that the electroplating solution or electroplating solution obtained by the present invention can meet The use of insoluble anode acid copper plating process.

It should be noted that the above-mentioned embodiments are only a further illustration of the present invention, not a limitation. Any adjustment or change within the meaning and scope equivalent to the technical solutions of the present invention by those skilled in the art should be considered as included in this Within the scope of protection of the invention.

1‧‧‧Electrolytic cathode area 2‧‧‧Electrolysis anode area 3‧‧‧Electrolyzer diaphragm 4‧‧‧Electrolytic anode 5‧‧‧Electrolytic cathode 6‧‧‧Electrolysis power supply 7‧‧‧Electrolysis buffer 8‧‧‧Acidity balanced cathode area 9‧‧‧acidity balance anode 10‧‧‧acid balance cathode 11‧‧‧Hydrogen Emission System 12‧‧‧plating bath 13‧‧‧ Electroplating anode 14‧‧‧plating cathode 15‧‧‧Exhaust fan system 16‧‧‧Mixing device 17‧‧‧Automatic feeding controller 18‧‧‧Replenishment liquid adding tank 19‧‧‧Transit slot 20‧‧‧Overflow 21‧‧‧ Electroplated diaphragm 22‧‧‧Filter device 23‧‧‧Insoluble electrolytic anode 24‧‧‧ Diaphragm 25‧‧‧ water source 26‧‧‧CO2 source 27‧‧‧ gas valve 28‧‧‧Oxygen source P‧‧‧Pump

The present invention will be further described below with reference to the drawings. FIG. 1 is a schematic diagram of a production apparatus for an electroplating solution or an electroplating replenishment process of the insoluble anode acid copper electroplating process of Examples 1-2 and Examples 13-14 of the present invention. 2 is a schematic diagram of the electroplating and electrolytic regeneration loop recycling system of the insoluble anode acidic copper electroplating process of Example 3 and Example 17 of the present invention. 3 is a schematic diagram of the electroplating and electrolytic regeneration loop recycling system of the insoluble anode acidic copper electroplating process of Example 4 of the present invention. 4 is a schematic diagram of the electroplating and electrolytic regeneration loop recycling system of the insoluble anode acidic copper electroplating process in Example 5 of the present invention. FIG. 5 is a schematic diagram of the electroplating and electrolytic regeneration loop recycling system of the insoluble anode acid copper electroplating process in Example 6 of the present invention. 6 is a schematic diagram of the electroplating and electrolytic regeneration loop recycling system of the insoluble anode acidic copper electroplating process of Example 7 of the present invention. FIG. 7 is a schematic diagram of the electroplating and electrolytic regeneration loop recycling system of the insoluble anode acidic copper plating process of Example 8 of the present invention. 8 is a schematic diagram of the electroplating and electrolytic regeneration loop recycling system of the insoluble anode acid copper electroplating process of Example 9 of the present invention. 9 is a schematic view of the structure of the electrolytic cell used in Example 9, Example 10, Example 15, and Example 16 of the present invention. 10 is a schematic diagram of the electroplating and electrolytic regeneration loop recycling system of the insoluble anode acid copper electroplating process of Example 10 of the present invention. 11 is a schematic diagram of the electroplating and electrolytic regeneration loop recycling system of the insoluble anode acidic copper electroplating process of Example 11 and Example 12 of the present invention. FIG. 12 is a schematic diagram of the structure of electrolytic cells used in Example 11 and Example 12 of the present invention.

1‧‧‧Electrolytic cathode area

2‧‧‧Electrolysis anode area

3‧‧‧Electrolyzer diaphragm

4‧‧‧Electrolytic anode

5‧‧‧Electrolytic cathode

6‧‧‧Electrolysis power supply

Claims (20)

A production method of electroplating solution or electroplating replenishing solution for insoluble anode acid copper electroplating process, including: (1) An electrolytic cell is provided, and an electrolytic cell diaphragm is used to divide the electrolytic cell into an electrolytic anode area and an electrolytic cathode area, and the electrolytic cell diaphragm is used to prevent the passage of cations to prevent cations from being in the electrolytic anode area and the electrolytic cathode area Free exchange between (2) Prepare anolyte and catholyte separately, Wherein, the anolyte is composed of an aqueous solution of at least one of sulfuric acid and copper sulfate, and the composition according to the quality percentage is: 0.001%～45% sulfuric acid or/and 0.001%～21% copper sulfate; The rest is water, and the total mass percentage of solute in the anolyte is not less than 0.03%; (3) Add the anolyte to the electrolytic anode area, and add the catholyte to the electrolytic cathode area; (4) A metal electrode containing copper element is used as an electrolytic anode, and the electrolytic anode is immersed in the anolyte; a conductor is used as an electrolytic cathode, and the electrolytic cathode is immersed in the catholyte; (5) Connect the electrolysis anode and the electrolysis cathode to the positive electrode and the negative electrode of the electrolysis power supply respectively, turn on the electrolysis power supply, and start the electrolysis reaction when energized, when the concentration of copper ions in the anode electrolyte reaches a predetermined value , The anolyte is taken out to obtain an electroplating solution or electroplating replenishment solution or a finished copper sulfate solution of an insoluble anode acidic copper electroplating process or a raw material for preparing an insoluble anode acidic electroplating copper electroplating solution. The method for producing an electroplating solution or an electroplating replenishing solution of an insoluble anode acid copper electroplating process as described in item 1 of the patent application range, wherein the electrolytic cell membrane may use an anion exchange membrane and/or a bipolar membrane. The production method of the electroplating solution or electroplating replenishing process of the insoluble anode acid copper electroplating process as described in item 2 of the patent scope, wherein when the electrolyzer diaphragm adopts the anion exchange membrane, the catholyte is made of sulfuric acid, sulfuric acid An aqueous solution of at least one of salt, carbonic acid and inorganic base, and the total mass percentage of solute in the catholyte is 0.1% to 40%, at least one of the anolyte and the catholyte contains sulfuric acid . A method for producing an electroplating solution or electroplating replenishment process for an insoluble anode acid copper electroplating process as described in item 2 of the patent scope, wherein when the electrolytic cell diaphragm is the bipolar membrane, the catholyte is water or electrolyte The electrolyte may be any electrolyte, and the anolyte needs to contain sulfuric acid. The production method of the electroplating solution or electroplating replenishment process of the insoluble anode acidic copper electroplating process as described in item 2 of the patent scope, which is associated with the insoluble anode acidic copper electroplating process production line, according to the process parameters of the insoluble anode acidic electroplating copper process production line Dynamic changes to adjust the size of the electrolysis current in step (5), or control the on or off of the electrolysis power supply; or according to the dynamic changes in the electrolysis process parameters in step (5), or adjust the The size of the electroplating current on the production line of the insoluble anode acidic copper electroplating process, or controlling the on/off of the electroplating power on the production line of the insoluble anode acidic copper electroplating process, so that the process parameters of the resulting electroplating replenisher can be in line with the insoluble anode acidic electroplating The process parameters of the copper process line can be adapted to each other, or the copper ions in the plating solution on the insoluble anode acidic copper electroplating process line can be replenished in a timely manner. The process parameters include copper ion concentration, sulfuric acid concentration, and working time Length and workload. The method for producing an electroplating solution or an electroplating replenishing solution for an insoluble anode acid copper electroplating process as described in item 5 of the patent application scope, wherein the step (5) is connected to the electrolysis power source to start an electrolysis reaction The concentration of sulfuric acid and/or sulfate and/or carbonic acid and/or inorganic base in the mixture is detected, and sulfuric acid and/or sulfate and/or water and/or carbon dioxide are added to the electrolytic cathode area according to the detection result, so that Adjust the concentration of sulfuric acid and/or sulfate and/or carbonic acid and/or inorganic base in the catholyte to maintain within the set value range: When the inorganic alkali concentration of sulfuric acid and/or sulfate and/or carbonic acid and/or carbonate or bicarbonate in the catholyte is less than or equal to the set value, add sulfuric acid or its aqueous solution to the electrolytic cathode area And/or sulfate or its aqueous solution and/or carbon dioxide, or when the concentration of the catholyte is greater than or equal to the set value due to evaporation of water, add fresh water to the electrolytic cathode area until the catholyte The concentration of sulfuric acid and/or sulfate and/or inorganic base returns to the set value. The production method of the electroplating solution or electroplating replenishing solution of the insoluble anode acid copper electroplating process as described in item 5 of the patent application scope, wherein by detecting the copper ion concentration and/or acid concentration in the electroplating solution and/or setting The anolyte with a higher copper ion concentration than the electroplating solution is added to the electroplating tank on the production line of the insoluble anode acidic copper electroplating process. The production method of the electroplating solution or electroplating replenishment process of the insoluble anode acidic copper electroplating process as described in item 5 of the patent scope, wherein when the anion exchange membrane is used as the membrane, the membrane uses a two-layer anion exchange membrane, or when When the bipolar membrane is used as a diaphragm, the diaphragm uses a combination of a bipolar membrane and an anion exchange membrane, wherein the anion exchange membrane is located on the side of the anion exchange membrane in the bipolar membrane , The combination of the two layers of anion exchange membranes or the one layer of bipolar membranes and the one layer of anion exchange membranes forms an electrolytic buffer zone between the electrolytic anode zone and the electrolytic cathode zone to avoid the electrolytic cathode The hydroxide ions generated on the electrode and/or the original inorganic base anions of the catholyte are in contact with the copper ions of the anolyte through the anion exchange membrane, or the hydroxide generated on the bipolar membrane The root ions directly contact the copper ions of the anolyte. A method for producing an electroplating solution or electroplating replenishment process for an insoluble anode acid copper electroplating process as described in item 8 of the patent application range, wherein the electrolytic buffer contains buffer electrolyte, which contains no copper ions but contains Sulfuric acid in water. The production method of the electroplating solution or electroplating replenishing solution of the insoluble anode acid copper electroplating process as described in item 9 of the patent scope, wherein after the step (5) is turned on the electrolysis power supply to start the electrolysis reaction, the buffer electrolysis The pH value and/or acidity value and/or specific gravity value of the liquid are detected, and sulfuric acid and/or an aqueous solution containing no sulfuric acid but containing sulfuric acid is added to the buffer electrolyte according to the detection result, When the pH value and/or acidity value and/or specific gravity value of the buffer electrolyte is less than or equal to the set value, sulfuric acid and/or an aqueous solution containing no copper ions but containing sulfuric acid is added to the buffer electrolyte until all The pH value and/or acidity value and/or specific gravity value of the buffer electrolyte return to the set value or greater than the set value. The production method of the electroplating solution or electroplating replenishment process of the insoluble anode acid copper electroplating process as described in item 5 of the patent application scope, in which during the electroplating copper production process, the anolyte in the electrolytic cell is detected to reach Or after the set value is exceeded, and the electroplating solution on the insoluble anode acid copper electroplating process production line needs to supplement the copper ion content, the anode electrolyte is directly added to the electroplating tank through relevant equipment control, and at the same time An amount of the electroplating solution in the electroplating tank is transferred to the electrolysis anode area of the electrolysis tank as the anolyte to increase the concentration of copper ions, thus forming an electroplating and electrolysis regeneration loop recycling system. The production method of the electroplating solution or electroplating replenishing solution of the insoluble anode acid copper electroplating process as described in item 11 of the patent application scope, wherein an acidity balance electrolysis system is also provided, that is, an acidity balance cathode area is separated in the electrolysis anode area , The acidity-balanced cathode area faces the direction of the electrolytic cathode area using a separator as a partition, the acidity-balanced cathode area contains an acidity-balanced cathode liquid, and when the acidity-balanced cathode area uses the anion exchange membrane, The acidity balanced catholyte is an inorganic alkali aqueous solution with a mass percentage of 0.5% to 35%; when the diaphragm of the acidity balanced cathode region uses the bipolar membrane, the acidity balanced catholyte is a water and/or mass percentage Or an aqueous solution of an electrolyte; the acidity balance electrolysis system includes an acidity balance cathode disposed in the acidity balance cathode region, and an acidity balance anode disposed in the electrolysis cathode region, and an acidity balance power supply, the acidity balance The cathode and the acid balance anode are respectively connected to the negative electrode and the positive electrode of the acid balance power supply. The production method of the electroplating solution or electroplating replenishing process of the insoluble anode acid copper electroplating process as described in item 12 of the patent application range, wherein the acidity balance cathode is detected when the membrane of the acidity balance cathode region uses the anion exchange membrane The inorganic alkali concentration of the liquid and add the inorganic alkali and/or carbon dioxide to the acidity balance catholyte according to the detection result, or replace the acidity balance catholyte with a new one; when the diaphragm of the acidity balance cathode zone uses the In the case of a bipolar membrane, the liquid level of the acidity balanced catholyte can be detected and water can be added to the acidity balanced catholyte according to the detection result, or a new acidity balanced catholyte can be replaced: When the membrane of the acidity balance cathode zone uses the anion exchange membrane and the concentration of the inorganic base in the acidity balance catholyte is lower than the initial value, the inorganic base and/or carbon dioxide is added to the acidity balance catholyte until The concentration of each component in the acidity balance catholyte is restored to the initial value, or a new one of the acidity balance catholyte is replaced. The detection of the concentration of the inorganic base in the acidity balance catholyte can also be performed by detecting the pH value of the acidity balance catholyte And/or acidity value and/or specific gravity value to reflect accordingly; When the diaphragm of the acidity balance cathode area uses the bipolar membrane and the liquid level in the acidity balance cathode liquid is lower than the initial value, water is added to the acidity balance cathode liquid until the acidity balance cathode liquid The liquid level of the liquid is restored to the initial value, or a new acidity balance catholyte is replaced. An insoluble anode acid copper electroplating process electroplating solution or electroplating replenishment liquid production device, including an electrolysis device, the electrolysis device is mainly composed of an electrolytic cell, an electrolytic anode, an electrolytic cathode and an electrolytic power supply, the electrolytic anode and the electrolytic cathode Respectively connected to the positive electrode and the negative electrode of the electrolytic power supply, wherein, An electrolytic cell diaphragm is provided in the electrolytic cell, and the electrolytic cell is divided into an electrolytic anode area and an electrolytic cathode area, and the electrolytic anode area and the electrolytic cathode area are respectively used to contain an anolyte and a catholyte; The electrolysis anode is a soluble electrolysis anode, the electrolysis anode contains copper element, and the electrolysis anode is disposed in the electrolysis anode area, and the copper on the electrolysis anode is electrolyzed into copper ions by electrolysis to improve The concentration of copper ions in the anolyte; The electrolytic cathode is a conductor, and the electrolytic cathode is disposed in the electrolytic cathode area. The production equipment of electroplating solution or electroplating replenishment process of insoluble anode acid copper electroplating process as described in item 14 of the patent application scope, wherein a current regulator is added to the electrolytic power supply, or a current regulator provided by the power supply itself is used to adjust the The output current of the electrolytic power supply, or control the on/off of the electrolytic power supply. The production device of the electroplating solution or electroplating replenishment process of the insoluble anode acidic copper electroplating process as described in item 14 of the patent application range, wherein the electrolytic cell diaphragm adopts an anion exchange membrane and/or a bipolar membrane. The production equipment for the electroplating solution or electroplating replenishment process of the insoluble anode acid copper electroplating process as described in item 16 of the patent scope, wherein the electrolytic anode area is connected to the electroplating tank of the insoluble anode acid copper electroplating process by pipes, so that When the copper ion concentration of the anolyte reaches a predetermined value, or when the copper ion concentration of the electroplating solution is lower than the set value required by the insoluble anode acidic copper plating process, the anolyte can be used as the electroplating solution directly It is added to the electroplating bath of the insoluble anode acid copper electroplating process, or the electroplating solution in the electroplating bath flows into the electrolytic anode zone. The production device of the electroplating solution or electroplating replenishment process of the insoluble anode acidic copper electroplating process as described in item 14 of the patent application scope also includes an electrolyte detection device, the electrolyte detection device is connected to an automatic feeding controller, and the automatic feeding The controller can control the addition of the anolyte to the plating solution according to the time and/or the detection result of the plating solution and/or the electrolyte detection device and/or the electrolytic cell pressure, and/or The anolyte is added with a plating solution and/or raw materials and/or water, and/or the catholyte is added with raw materials and/or carbon dioxide and/or water. The production equipment of electroplating solution or electroplating replenishment process of insoluble anode acid copper electroplating process as described in item 14 of the patent scope, in which two layers of anion exchange membrane or a combined membrane composed of a bipolar membrane and an anion exchange membrane are used An electrolytic buffer zone is formed between the electrolytic anode zone and the electrolytic cathode zone, and the electrolytic buffer zone contains an aqueous solution containing no copper ions and containing sulfuric acid as an electrolytic buffer solution. A production device for an electroplating solution or electroplating replenishment process for an insoluble anode acid copper electroplating process as described in item 16 of the scope of the patent application, wherein an acidity balanced cathode region is separated in the electrolytic anode region, and the acidity balanced cathode region faces the The direction of the electrolysis cathode area uses the anion exchange membrane as a partition, and an acidity balance electrolysis system is provided at the same time, so that in the electroplating production, when the electrolyzer is connected to the electroplating tank on the production line to form a loop flow system, the electroplating can be increased without increasing the electroplating. And the total amount of sulfate ions in the electrolysis regeneration loop recycling system leads to the destruction of the overall balance of the system, the concentration of sulfate ions in the catholyte is increased, while maintaining the stability of the electrolyte components , To reduce the resistance of the electrolyte; the acidity balance electrolysis system is mainly composed of the acidity balance cathode zone, the acidity balance cathode provided in the acidity balance cathode zone and the acidity balance anode provided in the electrolytic cathode zone , And an acidity balance power supply, the acidity balance cathode and the acidity balance anode are connected to the anode and anode of the acidity balance power supply, respectively.

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