Reagent for detecting mercaptosulfonate compound in copper foil plating solution, and application and detection method thereof

Abstract

The present application relates to the technical field of organic matter content determination in copper foil electroplating solution, and discloses a detection reagent for mercapto sulfonate compounds in copper foil electroplating solution, application and detection method thereof.The detection reagent is a mixed solution comprising a detection additive and a basic blank solution, wherein the detection additive is selected from electroplating solution additives other than mercapto sulfonate compounds.The method determines the depolarization area A0 of the detection reagent to shield the interference of the detection additive, wherein the detection additive is selected from electroplating solution additives other than mercapto sulfonate compounds.The present application is simple, fast, convenient, reproducible, accurate, has a relative error of about ±4%, a relative standard deviation of about 0.1-5%, and a minimum detection limit of about 0.5mg / L, is suitable for online liquid taking and rapid detection in copper foil production line, and is suitable for real-time monitoring of the content of mercapto sulfonate compounds in copper foil electroplating solution, thereby stabilizing product quality.

Description

Technical Field

[0001] This invention relates to the field of organic matter content determination in copper foil electroplating solutions, specifically to a reagent for detecting mercaptosulfonate compounds in copper foil electroplating solutions, its application, and a detection method. Background Technology

[0002] With the rapid development of the copper foil industry, copper foil electroplating solutions have become the mainstream production method. The quality of copper foil hinges on the selection and formulation of additives in the electroplating solution. Appropriate additives can significantly regulate the growth and performance of the coating, improving its microstructure and properties. Mercaptosulfonate compounds, as typical and commonly used electroplating additives, can be combined with other additives in the actual electroplating process to improve the gloss of the copper foil surface while simultaneously forming a smooth, fine-grained surface, reducing surface roughness. Therefore, mercaptosulfonate compounds can significantly affect coating quality and improve the microstructure and properties of copper foil.

[0003] Because organic additives in copper foil plating solutions are unstable and prone to consumption, failure, and deterioration, routine inspection of these additives is crucial for ensuring product quality. Currently, conventional methods for determining mercaptosulfonate compounds in aqueous solutions are mostly HPLC or ion chromatography. However, these methods require expensive equipment, involve complex and cumbersome procedures, and are particularly problematic in high-acid, high-copper plating solutions, where the solutions corrode the chromatographic column, causing instrument wear and increasing testing costs. Existing conventional methods cannot achieve mg / L level detection. The high copper sulfate and sulfuric acid content in copper foil plating solutions not only causes corrosion and damage to instruments but also results in a large background value due to the high acidity and copper content, making additive detection difficult.

[0004] Therefore, there is an urgent need to develop a simple, rapid, accurate, and repeatable method for detecting mercaptosulfonate compounds in copper foil electroplating solutions. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of existing methods for detecting mercaptosulfonate compounds in copper foil electroplating solutions, such as complex operation, high cost, and insufficient detection effect. This invention provides a reagent for detecting mercaptosulfonate compounds in copper foil electroplating solutions, its application, and a detection method.

[0006] To achieve the above objectives, the first aspect of the present invention provides a detection reagent for mercaptosulfonate compounds in copper foil electroplating solutions, wherein the detection reagent is a mixed solution comprising a detection additive and a basic blank solution, wherein the detection additive is selected from electroplating solution additives other than mercaptosulfonate compounds.

[0007] A second aspect of the present invention provides the application of the aforementioned detection reagent in the detection of mercaptosulfonate compounds in copper foil electroplating solutions.

[0008] A third aspect of the present invention provides a method for detecting mercaptosulfonate compounds in copper foil electroplating solution using the aforementioned detection reagent, wherein the method measures the depolarization area A0 of the detection reagent to shield the interference of detection additives, wherein the detection additives are selected from electroplating solution additives other than mercaptosulfonate compounds.

[0009] The beneficial technical effects achieved by the present invention through the above technical solution are as follows:

[0010] (1) The detection reagent provided by the present invention is simple to prepare and can improve the detection effectiveness when used to detect mercaptosulfonate compounds in copper foil electroplating solution.

[0011] (2) The detection method provided by the present invention can effectively detect mercaptosulfonate compounds in copper foil electroplating solution, eliminate the interference of other additives on the test results, and as a systematic detection method, it is more in line with the detection requirements of copper foil processing enterprises for additive components, and effectively avoids the problem of additive interference in the actual application of conventional single additive detection.

[0012] (3) The present invention is simple to operate, fast and convenient, has good repeatability and high accuracy. The relative error is about ±4%, the relative standard deviation is about 0.1-5%, and the minimum detection limit is about 0.5 mg / L. It is suitable for rapid detection of copper foil in online liquid sampling in copper foil production line and is applicable to real-time monitoring of the content of mercaptosulfonate compounds in copper foil electroplating solution, thus stabilizing product quality. Attached Figure Description

[0013] Figure 1 This is the depolarization curve of the mixed solution of mercaptosulfonate compound and basic blank solution in this invention;

[0014] Figure 2 This is a standard curve of the (A-A0)-concentration of mercaptosulfonate compounds in this invention. Detailed Implementation

[0015] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0016] The first aspect of the present invention provides a detection reagent for mercaptosulfonate compounds in copper foil electroplating solution, wherein the detection reagent is a mixed solution comprising a detection additive and a basic blank solution, wherein the detection additive is selected from electroplating solution additives other than mercaptosulfonate compounds.

[0017] In this invention, the detection reagent for mercaptosulfonate compounds in copper foil electroplating solution is a mixed solution comprising detection additives and a basic blank solution. Therefore, the preparation of the detection reagent is relatively simple and convenient. When used to detect mercaptosulfonate compounds in copper foil electroplating solution, it can improve the detection effectiveness and accuracy, and is suitable for real-time monitoring of additives in production lines.

[0018] Conventional detection methods, such as ultraviolet-visible spectrophotometry or liquid chromatography, rely on a one-to-one correspondence between the detection principle, reagents, and methods selected and the specific additive being tested. The reagent must exhibit a characteristic reaction with the desired additive. However, copper foil plating solutions often contain a combination of multiple additives, and in actual plating processes, a single additive is insufficient to meet performance requirements. Therefore, conventional detection methods, when applied to copper foil plating solutions, suffer from inter-additive interference issues.

[0019] The present invention selects other additives in the electroplating solution that interfere with the test additives as the detection additives, thereby eliminating interference from other additives during the testing process.

[0020] In this invention, the detection additive can be selected by those skilled in the art based on the types of additives in the electroplating solution to be tested, such as alcohol-based additives and / or adhesive additives. The basic blank solution can be selected by those skilled in the art according to actual needs, and this invention does not limit it.

[0021] According to some embodiments of the present invention, the mercaptosulfonate compound is selected from at least one of sodium 3-mercapto-1-propanesulfonate, sodium polydithiopropanesulfonate, sodium thiopropanesulfonate, and sodium phenyldithiopropanesulfonate.

[0022] According to some preferred embodiments of the present invention, the concentration of the detection additive is 1-100 mg / L, for example, 1 mg / L, 10 mg / L, 20 mg / L, 30 mg / L, 40 mg / L, 50 mg / L, 60 mg / L, 70 mg / L, 80 mg / L, 90 mg / L, 100 mg / L, and any value within any range of any two of the above values, preferably 1-50 mg / L. In the present invention, controlling the concentration of the detection additive in the detection reagent within the above-mentioned specific range can achieve the concentration shielding effect of most interference-resistant components in the test solution.

[0023] According to some preferred embodiments of the present invention, the concentration of the detection additive is an effective threshold concentration.

[0024] In this invention, the effective threshold concentration refers to the concentration value at which the inhibitory or promoting effect of the detection additive on copper electrodeposition reaches a stable value, that is, further increasing the concentration of the detection additive cannot further enhance the inhibitory or promoting effect. This concentration value is the effective threshold concentration.

[0025] In this invention, the interference shielding effect on the additive components is best when the concentration of the detection additive in the detection reagent is at the effective threshold concentration.

[0026] If the concentration of the detection additive in the test reagent does not reach the effective threshold concentration, the standard curve needs to be tested multiple times during the testing process to determine the accuracy of the test solution. In this case, if the content of the detection additive in the test solution is low, it will not significantly affect the detection accuracy. However, if the content of the detection additive in the test solution is higher than that in the test reagent, interfering components may not be completely shielded, leading to the inability to detect thiosulfonates or poor detection accuracy.

[0027] According to some preferred embodiments of the present invention, the detection additive includes alcohol-based additives and / or gum-based additives.

[0028] According to some preferred embodiments of the present invention, the alcohol-based additive is selected from at least one of polyethylene glycol, polypropylene glycol, polyalkylene glycol and polyvinyl alcohol.

[0029] According to some preferred embodiments of the present invention, the concentration of the alcohol-based additive in the detection reagent is 5-30 mg / L, for example 5 mg / L, 10 mg / L, 15 mg / L, 20 mg / L, 25 mg / L, 30 mg / L, and any value within the range of any two of the above values, preferably 10-20 mg / L.

[0030] According to some preferred embodiments of the present invention, the gelatinous additive is selected from at least one of gelatin, collagen, bone glue and fish glue.

[0031] According to some preferred embodiments of the present invention, the concentration of the gel additive in the detection reagent is 2-40 mg / L, for example 2 mg / L, 8 mg / L, 15 mg / L, 20 mg / L, 25 mg / L, 30 mg / L, 35 mg / L, 40 mg / L, and any value within the range of any two of the above values, preferably 10-25 mg / L.

[0032] According to some embodiments of the present invention, the basic blank solution comprises Cu 2+ SO4 2+ and Cl- .

[0033] According to some preferred embodiments of the present invention, Cu in the basic blank solution 2+ The concentration is 5-150 g / L, for example 5 g / L, 10 g / L, 20 g / L, 40 g / L, 60 g / L, 80 g / L, 100 g / L, 120 g / L, 130 g / L, 150 g / L, and any value within the range of any two of the above values, preferably 20-120 g / L.

[0034] According to some preferred embodiments of the present invention, the basic blank solution contains SO4 2+ The concentration is 10-150 g / L, for example 10 g / L, 20 g / L, 50 g / L, 80 g / L, 100 g / L, 130 g / L, 150 g / L, and any value within the range of any two of the above values, preferably 50-120 g / L.

[0035] According to some preferred embodiments of the present invention, the basic blank solution contains Cl - The concentration is 5-100 mg / L, for example 5 mg / L, 10 mg / L, 20 mg / L, 50 mg / L, 80 mg / L, 100 mg / L, and any value within the range of any two of the above values, preferably 10-30 mg / L.

[0036] According to some preferred embodiments of the present invention, the raw materials for preparing the basic blank solution include hydrochloric acid and / or soluble chloride, copper sulfate, and concentrated sulfuric acid, preferably hydrochloric acid, copper sulfate, and concentrated sulfuric acid. In the present invention, the soluble chloride may be selected from at least one of sodium chloride, potassium chloride, and magnesium chloride.

[0037] In this invention, the basic blank solution can be prepared according to the following method: weigh copper sulfate pentahydrate into pure water, stir with a glass rod, slowly add concentrated sulfuric acid to completely dissolve the copper sulfate, add hydrochloric acid at the same time, stir with a glass rod to make it evenly dispersed in the copper sulfate solution, and make up to volume with pure water.

[0038] A second aspect of the present invention provides the application of the aforementioned detection reagent in the detection of mercaptosulfonate compounds in copper foil electroplating solutions.

[0039] A third aspect of the present invention provides a method for detecting mercaptosulfonate compounds in copper foil electroplating solution using the aforementioned detection reagent, wherein the method measures the depolarization area A0 of the detection reagent to shield the interference of detection additives, wherein the detection additives are selected from electroplating solution additives other than mercaptosulfonate compounds.

[0040] The detection method described in this invention is characterized by its simple operation, speed and convenience, good repeatability and high accuracy. It can realize online liquid sampling in copper foil production lines and is suitable for real-time monitoring of complex plating solution composition in copper foil enterprises, thus stabilizing product quality.

[0041] According to some embodiments of the present invention, the method includes the following steps:

[0042] (1) Prepare a mixed solution of the detection additive and the basic blank solution as a detection reagent;

[0043] (2) Prepare a mixed solution of mercaptosulfonate compound and detection reagent as a standard solution, and then use the standard solution to prepare mercaptosulfonate compound solutions of different concentrations;

[0044] (3) Plot a (A-A0)-concentration standard curve of mercaptosulfonate compounds with the concentration of mercaptosulfonate compounds as the abscissa and the difference between the depolarization area A of the mercaptosulfonate compound solutions of different concentrations and the depolarization area A0 of the detection reagent as the ordinate.

[0045] (4) Mix the test solution with the detection reagent to obtain a mixed solution, and determine the depolarization area A of the mixed solution. 待测 The concentration of mercaptosulfonate compounds in the test solution is obtained by comparing the difference between the depolarization area A0 of the detection reagent and the (A-A0)-concentration standard curve of the mercaptosulfonate compounds obtained in step (3).

[0046] According to some embodiments of the present invention, the operating temperature of the method is 15-40°C, for example 15°C, 20°C, 30°C, 40°C, and any value within the range of any two of the above values, preferably 20-30°C.

[0047] According to some preferred embodiments of the present invention, the concentration of the mercaptosulfonate compound in the standard solution is 100-300 mg / L, for example 100 mg / L, 150 mg / L, 200 mg / L, 250 mg / L, 300 mg / L, and any value within the range of any two of the above values, preferably 150-220 mg / L.

[0048] According to some preferred embodiments of the present invention, in step (2), different volumes of standard solutions are taken into equal volumes of detection reagents to obtain solutions of mercaptosulfonate compounds of different concentrations.

[0049] According to some preferred embodiments of the present invention, in the mixed solution of step (4), the volume ratio of the test solution to the detection reagent is 0.03-0.3:1, for example 0.03:1, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, and any value within the range of any two of the above values, preferably 0.05-0.2:1.

[0050] According to some preferred embodiments of the present invention, the depolarization area is measured using an electrochemical workstation.

[0051] According to some preferred embodiments of the present invention, the electrochemical workstation includes a working electrode, an auxiliary electrode, and a reference electrode.

[0052] According to some preferred embodiments of the present invention, the working electrode is selected from a platinum electrode, a gold electrode, and a glassy carbon electrode.

[0053] According to some preferred embodiments of the present invention, the auxiliary electrode is selected from one of a saturated copper wire electrode, a platinum sheet electrode, and a platinum wire electrode.

[0054] According to some preferred embodiments of the present invention, the reference electrode is selected from one of a mercurous sulfate electrode, a silver chloride electrode, and a calomel electrode.

[0055] According to some embodiments of the present invention, the method further includes: before step (1), preparing a solution of each of the detection additives by mixing it with a basic blank solution, taking different volumes of the solution in an equal volume of basic blank solution, and measuring the depolarization curves of the resulting series of solutions to obtain the effective threshold concentration of each detection additive.

[0056] In this invention, the detection additive can be selected by those skilled in the art based on the type of additive in the electroplating solution to be tested, such as alcohol-based additives and / or adhesive additives.

[0057] In this invention, different volumes of the above-mentioned solution are dissolved in a basic blank solution, and the depolarization curves of the resulting series of solutions are measured using an electrochemical workstation. Based on the depolarization curves, the effective threshold concentration of a certain detection additive in the basic blank solution is obtained, which guides the preparation of detection reagents.

[0058] According to some preferred embodiments of the present invention, the method further includes: before step (1), preparing a mixed solution of alcohol-based additive and basic blank solution and / or a mixed solution of colloidal additive and basic blank solution, taking different volumes of the mixed solution into an equal volume of basic blank solution, and measuring the depolarization curves of the resulting series of solutions to obtain the effective threshold concentration of alcohol-based additive and / or colloidal additive. The method for measuring the depolarization curve is as described above.

[0059] According to some preferred embodiments of the present invention, the concentration of the alcohol-based additive in the mixed solution of the alcohol-based additive and the basic blank solution is preferably 1-100 mg / L, for example 1 mg / L, 10 mg / L, 30 mg / L, 50 mg / L, 80 mg / L, 100 mg / L, and any value within the range of any two of the above values, and more preferably 5-30 mg / L.

[0060] According to some preferred embodiments of the present invention, the concentration of the adhesive additive in the mixed solution of the adhesive additive and the basic blank solution is preferably 1-100 mg / L, for example 1 mg / L, 10 mg / L, 30 mg / L, 50 mg / L, 80 mg / L, 100 mg / L, and any value within the range of any two of the above values, and more preferably 2-40 mg / L.

[0061] According to some preferred embodiments of the present invention, the method further includes: before step (1), preparing a mixed solution of a mercaptosulfonate compound and a basic blank solution, taking different volumes of the mixed solution in an equal volume of basic blank solution, and measuring the depolarization curves of the resulting series of solutions to obtain the effective threshold concentration of the mercaptosulfonate compound. The method for measuring the depolarization curve is as described above, and the depolarization curve of the mixed solution of the mercaptosulfonate compound and the basic blank solution can be obtained as follows: Figure 1 As shown. In this invention, based on the above depolarization curve, the effective threshold concentration of thiosulfonate compounds for copper electrodeposition can be obtained. Therefore, the concentration of thiosulfonate compounds in the standard curve should be selected below the effective threshold concentration. This depolarization curve can guide the selection of the concentration point in the standard curve.

[0062] According to some preferred embodiments of the present invention, the concentration of the mercaptosulfonate compound in the mixed solution of the mercaptosulfonate compound and the basic blank solution is 100-300 mg / L, for example 100 mg / L, 150 mg / L, 200 mg / L, 250 mg / L, 300 mg / L, and any value within the range of any two of the above values, preferably 200-300 mg / L.

[0063] In practice, the electrodes used in the electrochemical workstation can be cleaned in advance to improve the accuracy of the measurements. For example, the electrodes can be cleaned with an acid cleaning solution or an alkaline cleaning solution. The acid cleaning solution can be sulfuric acid with a volume fraction of 3-5%; the alkaline cleaning solution can be sodium hydroxide solution with a concentration of 1-3 mol / L.

[0064] According to a particularly preferred embodiment of the present invention, a method for detecting mercaptosulfonate compounds in copper foil electroplating solution using a detection reagent, the method comprising the following steps:

[0065] (1') Prepare mixed solutions of alcohol-based additives and basic blank solutions and mixed solutions of colloid additives and basic blank solutions. Take different volumes of mixed solutions into equal volumes of basic blank solutions and measure the depolarization curves of the obtained series of solutions to obtain the effective threshold concentrations of alcohol-based additives and colloid additives respectively.

[0066] (1”) Prepare a mixed solution of mercaptosulfonate compound and basic blank solution, take different volumes of the mixed solution into an equal volume of basic blank solution, and measure the depolarization curves of the obtained series of solutions to obtain the effective threshold concentration of mercaptosulfonate compound.

[0067] (1) Prepare a mixed solution of alcohol-based additive, colloidal additive and basic blank solution as a detection reagent according to the depolarization curve in step (1'); wherein, the concentrations of alcohol-based additive and colloidal additive are their respective effective threshold concentrations;

[0068] (2) Prepare a mixed solution of mercaptosulfonate compound and detection reagent as a standard solution, and take different volumes of standard solution into an equal volume of detection reagent to obtain mercaptosulfonate compound solutions of different concentrations; the maximum value of the different concentrations is lower than the effective threshold concentration of mercaptosulfonate compound.

[0069] (3) Plot a (A-A0)-concentration standard curve of mercaptosulfonate compounds with the concentration of mercaptosulfonate compounds as the abscissa and the difference between the depolarization area A of the mercaptosulfonate compound solutions of different concentrations and the depolarization area A0 of the detection reagent as the ordinate.

[0070] (4) The test solution and the detection reagent are mixed to obtain a mixed solution, wherein the volume ratio of the test solution to the detection reagent is 0.05-0.2:1. Based on the depolarization area A of the mixed solution... 待测 The concentration of mercaptosulfonate compounds in the test solution is obtained by comparing the difference between the depolarization area A0 of the detection reagent and the (A-A0)-concentration standard curve of the mercaptosulfonate compounds obtained in step (3).

[0071] The detection method provided by this invention can effectively detect mercaptosulfonate compounds in copper foil electroplating solution, eliminate the interference of other additives on the test results, and as a systematic detection method, it is more in line with the detection requirements of copper foil processing enterprises for additive components, effectively avoiding the problem of additive interference in the actual application of conventional single additive detection.

[0072] The present invention will be described in detail below through embodiments.

[0073] Unless otherwise specified in the following examples and comparative examples, all conditions were performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments used, unless otherwise specified, are all commercially available products.

[0074] Example 1

[0075] The mercaptosulfonate compounds in the copper foil electroplating solution were detected according to the operating conditions and reagent parameters in Table 1. The detection method includes the following steps:

[0076] (1) Prepare a basic blank solution using copper sulfate pentahydrate, concentrated sulfuric acid and hydrochloric acid;

[0077] (2) Prepare a mixed solution of alcohol-based additive and basic blank solution. Take 0 mL, 20 mL, 30 mL and 50 mL of the mixed solution into 20 mL of basic blank solution respectively, and measure the depolarization curves of the obtained series of solutions.

[0078] (3) Prepare a mixed solution of adhesive additives and basic blank solution. Take 0 mL, 10 mL, 20 mL and 30 mL of the mixed solution into 20 mL of basic blank solution respectively, and measure the depolarization curve of the obtained series of solutions.

[0079] (4) Prepare mixed solutions of mercaptosulfonate compounds and basic blank solutions. Take 0 mL, 0.01 mL, 0.02 mL, 0.03 mL, 0.04 mL, 0.09 mL, 0.19 mL, 0.39 mL, and 0.79 mL of the mixed solution respectively into 20 mL of basic blank solution, and determine the depolarization curves of the resulting series of solutions, such as... Figure 1 As shown;

[0080] (5) Based on the depolarization curves in steps (2) and (3), obtain the effective threshold concentrations of alcohol-based additives and gum additives, and prepare a detection reagent including alcohol-based additives and gum additives, wherein the concentrations of alcohol-based additives and gum additives are both effective threshold concentrations; based on the depolarization curves in step (4), obtain the effective threshold concentrations of mercaptosulfonate compounds, and prepare a standard solution including mercaptosulfonate compounds and detection reagents.

[0081] (6) Take different volumes of standard solution and add them to an equal volume of test reagent to obtain mercaptosulfonate compound solutions of different concentrations. Plot a (A-A0)-concentration standard curve of mercaptosulfonate compounds with the concentration of mercaptosulfonate compounds as the abscissa and the difference between the depolarization area A of the different concentrations of mercaptosulfonate compound solutions and the depolarization area A0 of the test reagent as the ordinate. Figure 2 As shown;

[0082] (7) Mix the test solution with the detection reagent to obtain a mixed solution, and determine the depolarization area A of the mixed solution. 待测 The concentration of mercaptosulfonate compounds in the test solution is obtained by comparing the difference between the depolarization area A0 of the detection reagent and the standard curve of the mercaptosulfonate compounds obtained in step (6).

[0083] Examples 2-5

[0084] The mercaptosulfonate compounds in the copper foil electroplating solution were detected according to the operating conditions and reagent parameters in Table 1.

[0085] The detection method includes the following steps:

[0086] (1) Prepare a basic blank solution using copper sulfate pentahydrate, concentrated sulfuric acid and hydrochloric acid;

[0087] (2) Prepare a mixed solution of mercaptosulfonate compound and basic blank solution. Take 0 mL, 0.01 mL, 0.02 mL, 0.03 mL, 0.04 mL, 0.09 mL, 0.19 mL, 0.39 mL and 0.79 mL of the mixed solution into 20 mL of basic blank solution, and measure the depolarization curves of the resulting series of solutions.

[0088] (3) Prepare a test reagent including alcohol-based additives and gum additives; prepare a standard solution including mercaptosulfonate compounds and test reagents according to the depolarization curve in step (4);

[0089] (4) Take different volumes of standard solutions into equal volumes of test reagents to obtain solutions of mercaptosulfonate compounds of different concentrations. Plot the (A-A0)-concentration standard curve of mercaptosulfonate compounds with the concentration of mercaptosulfonate compounds as the abscissa and the difference between the depolarization area A of the solutions of mercaptosulfonate compounds of different concentrations and the depolarization area A0 of the test reagent as the ordinate.

[0090] (5) Mix the test solution with the detection reagent to obtain a mixed solution, and determine the depolarization area A of the mixed solution. 待测 The concentration of mercaptosulfonate compounds in the test solution is obtained by comparing the difference between the depolarization area A0 of the detection reagent and the standard curve of the mercaptosulfonate compounds obtained in step (4).

[0091] Example 6

[0092] The mercaptosulfonate compounds in the copper foil electroplating solution were detected according to the detection method in Example 1, except that steps (2) and (3) were not performed, and the concentration of polyethylene glycol in the detection reagent was 20 mg / L and the concentration of collagen was 10 mg / L.

[0093] Table 1

[0094]

[0095]

[0096] Test Example 1

[0097] The concentrations of mercaptosulfonate compounds in electroplating solutions of different concentrations (10 mg / L, 8 mg / L, 5 mg / L, 3 mg / L, 2 mg / L, 1 mg / L, 0.5 mg / L) were measured in five parallel tests according to the methods in Examples 1 and 6, and the relative error and relative standard deviation were calculated. The results are shown in Tables 2 and 3, respectively.

[0098] Table 2

[0099]

[0100] Table 3

[0101]

[0102]

[0103] As shown in Tables 2 and 3, the relative error of the method for detecting the content of mercaptosulfonate compounds in electroplating solution provided by the present invention is about ±4%, the relative standard deviation is about 0.1-5%, and the limit of detection is about 0.5 mg / L.

[0104] The comparison between Tables 2 and 3 shows that the relative error of the detection method in Example 6 is greater than that of the detection method in Example 1. This indicates that when the concentration of the detection additive in the detection reagent is at the effective threshold concentration, the interference shielding effect on the additive components is the best, and the detection accuracy is higher.

[0105] Test Example 2

[0106] The concentration of mercaptosulfonate compounds in the electroplating solution at different electroplating times was detected according to the method in Example 1, and the results are shown in Table 4.

[0107] Table 4

[0108]

[0109] As shown in Table 4, the method for detecting the content of mercaptosulfonate compounds in electroplating solution provided by the present invention can realize online liquid sampling in copper foil production line and is suitable for real-time monitoring of complex plating solution composition in copper foil enterprises.

[0110] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A reagent for detecting mercaptosulfonate compounds in copper foil electroplating solution, characterized in that, The detection reagent is a mixed solution comprising a detection additive and a basic blank solution. The detection additive is selected from electroplating solution additives other than mercaptosulfonate compounds. The mercaptosulfonate compound is selected from at least one of sodium 3-mercapto-1-propanesulfonate, sodium polydithiopropanesulfonate, sodium thiopropanesulfonate, and sodium phenyldithiopropanesulfonate. The concentration of the detection additive is 1-100 mg / L. The concentration of the detection additive is an effective threshold concentration. The detection additive includes alcohol-based additives and adhesive additives. The alcohol-based additive is selected from at least one of polyethylene glycol, polypropylene glycol, polyalkylene glycol, and polyvinyl alcohol; the concentration of the alcohol-based additive in the detection reagent is 5-30 mg / L; The gelatinous additive is selected from at least one of gelatin, collagen, bone glue, and fish glue; the concentration of the gelatinous additive in the test reagent is 2-40 mg / L; The basic blank solution contains Cu 2+ SO4 2+ and Cl - Cu in the basic blank solution 2+ The concentration of SO4 in the basic blank solution is 5-150 g / L; 2+ The concentration is 50-120 g / L; the basic blank solution contains Cl - The concentration is 5-100 mg / L; The raw materials for preparing the basic blank solution include hydrochloric acid, copper sulfate, and concentrated sulfuric acid.

2. The detection reagent according to claim 1, wherein, The concentration of the detection additive is 1-50 mg / L; And / or, the concentration of the alcohol-based additive in the detection reagent is 10-20 mg / L; And / or, the concentration of the gelatinous additive in the test reagent is 10-25 mg / L.

3. The detection reagent according to claim 1 or 2, wherein, Cu in the basic blank solution 2+ The concentration is 20-120 g / L; and / or, the SO4 content in the basic blank solution is... 2+ The concentration is 50-120 g / L; and / or, the basic blank solution contains Cl - The concentration is 10-30 mg / L.

4. The use of the detection reagent according to any one of claims 1-3 in detecting mercaptosulfonate compounds in copper foil electroplating solution.

5. A method for detecting mercaptosulfonate compounds in copper foil electroplating solution using the detection reagent according to any one of claims 1-3, characterized in that, The method measures the depolarization area A0 of the detection reagent to shield the interference of the detection additive, wherein the detection additive is selected from electroplating solution additives other than mercaptosulfonate compounds. The method includes the following steps: Prepare solutions by mixing each of the detection additives with a basic blank solution, take different volumes of the solutions in an equal volume of basic blank solution, and measure the depolarization curves of the resulting series of solutions to obtain the effective threshold concentration of each detection additive. (1) Prepare a mixed solution of the detection additive and the basic blank solution as a detection reagent; (2) Prepare a mixed solution of mercaptosulfonate compound and detection reagent as a standard solution, and then use the standard solution to prepare mercaptosulfonate compound solutions of different concentrations; (3) Plot the (A-A0)-concentration standard curve of mercaptosulfonate compounds with the concentration of mercaptosulfonate compounds as the abscissa and the difference between the depolarization area A of the mercaptosulfonate compound solutions of different concentrations and the depolarization area A0 of the detection reagent as the ordinate. (4) Mix the test solution with the detection reagent to obtain a mixed solution, and determine the depolarization area A of the mixed solution. 待测 The concentration of mercaptosulfonate compounds in the test solution is obtained by comparing the difference between the depolarization area A0 of the detection reagent and the (A-A0)-concentration standard curve of the mercaptosulfonate compounds obtained in step (3). In the mixed solution of step (4), the volume ratio of the test solution to the detection reagent is 0.03-0.3:

1.

6. The method according to claim 5, wherein, The operating temperature of the method is 15-40℃; And / or, the concentration of mercaptosulfonate compounds in the standard solution is 100-300 mg / L; And / or, in step (2), different volumes of standard solutions are taken into equal volumes of detection reagents to obtain solutions of mercaptosulfonate compounds of different concentrations; And / or, in the mixed solution of step (4), the volume ratio of the test solution to the detection reagent is 0.05-0.2:

1.

7. The method according to claim 6, wherein, The operating temperature of the method is 20-30℃; And / or, the concentration of mercaptosulfonate compounds in the standard solution is 150-220 mg / L.

8. The method according to any one of claims 5-7, wherein, The depolarization area was measured using an electrochemical workstation.

9. The method according to claim 8, wherein, The electrochemical workstation includes a working electrode, an auxiliary electrode, and a reference electrode.

10. The method according to claim 9, wherein, The working electrode is selected from one of a platinum electrode, a gold electrode, and a glassy carbon electrode; And / or, the auxiliary electrode is selected from one of a saturated copper wire electrode, a platinum sheet electrode, and a platinum wire electrode; And / or, the reference electrode is selected from one of a mercurous sulfate electrode, a silver chloride electrode, and a calomel electrode.

11. The method according to any one of claims 5-7 and 9-10, wherein, The method further includes: before step (1), preparing a mixed solution of alcohol-based additive and basic blank solution and a mixed solution of gum additive and basic blank solution, taking different volumes of mixed solution in an equal volume of basic blank solution, and measuring the depolarization curves of the resulting series of solutions to obtain the effective threshold concentrations of alcohol-based additive and gum additive.

12. The method according to claim 11, wherein, The concentration of the alcohol-based additive in the mixed solution of the alcohol-based additive and the basic blank solution is 1-100 mg / L; And / or, the concentration of the adhesive additive in the mixed solution of the adhesive additive and the base blank solution is 1-100 mg / L.

13. The method according to claim 12, wherein, The concentration of the alcohol-based additive in the mixed solution of the alcohol-based additive and the basic blank solution is 5-30 mg / L; And / or, the concentration of the adhesive additive in the mixed solution of the adhesive additive and the basic blank solution is 2-40 mg / L.

14. The method according to claim 8, wherein, The method further includes: before step (1), preparing a mixed solution of alcohol-based additive and basic blank solution and a mixed solution of gum additive and basic blank solution, taking different volumes of mixed solution in an equal volume of basic blank solution, and measuring the depolarization curves of the resulting series of solutions to obtain the effective threshold concentrations of alcohol-based additive and gum additive.

15. The method according to claim 14, wherein, The concentration of the alcohol-based additive in the mixed solution of the alcohol-based additive and the basic blank solution is 1-100 mg / L; And / or, the concentration of the adhesive additive in the mixed solution of the adhesive additive and the base blank solution is 1-100 mg / L.

16. The method according to claim 15, wherein, The concentration of the alcohol-based additive in the mixed solution of the alcohol-based additive and the basic blank solution is 5-30 mg / L; And / or, the concentration of the adhesive additive in the mixed solution of the adhesive additive and the basic blank solution is 2-40 mg / L.

17. The method according to any one of claims 5-7, 9-10, and 12-16, wherein, The method further includes: before step (1), preparing a mixed solution of mercaptosulfonate compound and basic blank solution, taking different volumes of the mixed solution in an equal volume of basic blank solution, and measuring the depolarization curves of the resulting series of solutions to obtain the effective threshold concentration of mercaptosulfonate compound.

18. The method according to claim 17, wherein, The concentration of the mercaptosulfonate compound in the mixed solution of the mercaptosulfonate compound and the basic blank solution is 100-300 mg / L.

19. The method according to claim 18, wherein, The concentration of the mercaptosulfonate compound in the mixed solution of the mercaptosulfonate compound and the basic blank solution is 200-300 mg / L.

20. The method according to claim 8, wherein, The method further includes: before step (1), preparing a mixed solution of mercaptosulfonate compound and basic blank solution, taking different volumes of the mixed solution in an equal volume of basic blank solution, and measuring the depolarization curves of the resulting series of solutions to obtain the effective threshold concentration of mercaptosulfonate compound.

21. The method according to claim 20, wherein, The concentration of the mercaptosulfonate compound in the mixed solution of the mercaptosulfonate compound and the basic blank solution is 100-300 mg / L.

22. The method according to claim 21, wherein, The concentration of the mercaptosulfonate compound in the mixed solution of the mercaptosulfonate compound and the basic blank solution is 200-300 mg / L.

23. The method according to claim 11, wherein, The method further includes: before step (1), preparing a mixed solution of mercaptosulfonate compound and basic blank solution, taking different volumes of the mixed solution in an equal volume of basic blank solution, and measuring the depolarization curves of the resulting series of solutions to obtain the effective threshold concentration of mercaptosulfonate compound.

24. The method according to claim 23, wherein, The concentration of the mercaptosulfonate compound in the mixed solution of the mercaptosulfonate compound and the basic blank solution is 100-300 mg / L.

25. The method according to claim 24, wherein, The concentration of the mercaptosulfonate compound in the mixed solution of the mercaptosulfonate compound and the basic blank solution is 200-300 mg / L.

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