JP2010243200A - Measuring method of hydrogen peroxide concentration in hydrogen peroxide-containing aqueous solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and a system for measuring a hydrogen peroxide concentration in a hydrogen peroxide-containing aqueous solution not requiring much time, capable of saving a space, reducing a maintenance work, and reducing an analysis sample waste liquid amount, in measurement of the hydrogen peroxide concentration in the hydrogen peroxide containing aqueous solution. <P>SOLUTION: In the measuring method, titanium sulfate is added into the hydrogen peroxide-containing aqueous solution to form a complex compound between hydrogen peroxide and titanium, and a UV absorption spectrum of the complex compound is measured as an absorbance. The measuring system includes a sampling device for sampling a sample to be measured from the hydrogen peroxide-containing aqueous solution, a reagent supply device for introducing titanium sulfate, a mixing tank for preparing an analyte to be measured by mixing the sampled sample to be measured with the supplied titanium sulfate, and a UV absorption spectrum measuring device for detecting hydrogen peroxide for measuring the UV absorption spectrum in the analyte to be measured from the mixing tank. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for measuring a hydrogen peroxide concentration in a hydrogen peroxide-containing aqueous solution, and more particularly to a method and a system for measuring a hydrogen peroxide concentration in a hydrogen peroxide-containing aqueous solution.

  Aqueous solutions containing hydrogen peroxide are used in various applications such as cleaning agents, disinfectants, bleaches, oxidizing agents, catalysts and the like. For example, an aqueous solution containing hydrogen peroxide as an oxidizing agent is widely used for etching metal members.

  In an etching system for metal parts using hydrogen peroxide and sulfuric acid (hereinafter sometimes referred to as “overwater-sulfuric acid etching”), the composition of the etching solution is monitored by various analyzes in order to maintain a good etching state. It has been known. As a method for measuring or managing the composition of the etching solution, potential measurement, current measurement, and titration method are used, which are reported in Patent Documents 1 to 3, for example.

  Patent Document 1 discloses a copper or copper alloy etching method using an aqueous solution containing at least sulfuric acid and hydrogen peroxide as an etching solution, and detects a variation in the etching rate of the copper or copper alloy, and the etching rate is determined. A method of etching copper or copper alloy, wherein the etching rate is controlled at a constant rate (Claim 1); The method of etching copper or copper alloy according to claim 1, wherein the etching rate is controlled to be constant. A method for etching copper or copper alloy, comprising controlling a replenishment amount of hydrogen peroxide water using a measured value of an immersion potential of a material to be etched in the etchant or the same composition as the material to be etched as a control index ( (2) In the method of etching copper or copper alloy according to claim 1, when the etching rate is controlled to be constant, A method for etching copper or copper alloy, characterized in that hydrogen peroxide solution having a concentration corresponding to the halide ion concentration is replenished using the measured value of the halide ion concentration in the etching solution as a control index. 2) The method for etching copper or copper alloy according to claim 1, wherein when the etching rate is controlled to be constant, the immersion potential of the material to be etched or the same material as the material to be etched in the etching solution is controlled. A copper or copper alloy etching method characterized in that halide ions are removed (Claim 4); in the copper or copper alloy etching method according to claim 1, wherein the etching rate is controlled to be constant. , Using the measured value of halide ion concentration in the etching solution as a control index, Copper or etching process of the copper alloy, characterized by removing the response to halide ions (Claim 5) is disclosed.

  Patent Document 2 discloses that automatic potentiometric titration using potassium permanganate or sodium hydroxide is used to measure hydrogen peroxide concentration and sulfuric acid and copper concentration in a sulfuric acid / hydrogen peroxide etching solution. Has been.

  In Patent Document 3, the end point of titration analysis with an indicator that causes a color change in each of the three components of hydrogen peroxide, sulfuric acid, and copper is detected with an optical sensor to detect the concentration. From the obtained concentration and the concentration, A method for replenishing deficient components using the calculated specific gravity as an index is disclosed.

  Non-Patent Document 1 describes a chelate titration method for titanium in the presence of hydrogen peroxide, and discloses a photometric titration method utilizing the color development of a complex compound of hydrogen peroxide and titanium.

Japanese Patent Laid-Open No. 6-240474 JP-A-7-134112 JP 2004-361180 A

Ueno Keihei Chelate Titration Method Nanedo (1972) 393

  However, the method of measuring the potential and current of the etching solution is not suitable for multi-component concentration management. Since the titration method takes time for analysis, the state of the etching solution cannot be monitored in real time. Moreover, since the titration method measures each component individually, a plurality of analyzers must be incorporated in the etching system, and there is a problem that the amount of waste liquid of the analysis sample is large. A method using cobalt sulfate is also known, but this is a long reaction time and is not suitable for real-time monitoring.

  Therefore, the object of the present invention is to save time and save space in measuring the hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution, reducing maintenance work and reducing the amount of waste liquid for analysis samples. It is an object of the present invention to provide a method and system for measuring the hydrogen peroxide concentration in a hydrogen peroxide-containing aqueous solution.

  As a result of repeated studies, the present inventors have found that the hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution can be measured by measuring the UV absorption spectrum of the hydrogen peroxide-containing aqueous solution using titanium sulfate as an indicator. The invention has been reached.

  That is, the present invention provides a method for measuring the concentration of hydrogen peroxide in a hydrogen peroxide-containing aqueous solution by adding titanium sulfate to the hydrogen peroxide-containing aqueous solution to form a complex compound of hydrogen peroxide and titanium. An object of the present invention is to provide a method for measuring the concentration of hydrogen peroxide in an aqueous solution containing hydrogen peroxide, wherein the UV absorption spectrum of the compound is measured as absorbance.

  The present invention also provides a sampling device for sampling a sample to be measured from a hydrogen peroxide-containing aqueous solution, a reagent supply device for introducing titanium sulfate, and mixing the sampled sample to be measured and the supplied titanium sulfate. Hydrogen peroxide comprising: a mixing tank for preparing a sample to be measured; and a UV absorption spectrum measuring device for hydrogen peroxide detection for measuring a UV absorption spectrum in the sample to be measured from the mixing tank. An object of the present invention is to provide a measurement system for the hydrogen peroxide concentration in an aqueous solution.

  Further, the present invention relates to a method for controlling the concentration of hydrogen peroxide in a hydrogen peroxide-containing aqueous solution, by collecting a sample to be measured from the hydrogen peroxide-containing aqueous solution and adding titanium sulfate to the sample to be measured. A sample to be measured containing a complex compound of hydrogen and titanium is formed, and the UV absorption spectrum of the complex compound in the sample to be measured is measured as absorbance with a UV absorption spectrum measuring device for hydrogen peroxide detection. The measured result is sent to the arithmetic unit, and the hydrogen peroxide containing aqueous solution is compared with the preset hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution. Another object of the present invention is to provide a method for managing the concentration of hydrogen peroxide in a hydrogen peroxide-containing aqueous solution, wherein the hydrogen peroxide aqueous solution is replenished from the supply device to the hydrogen peroxide-containing aqueous solution.

  The present invention also provides a sampling device for sampling a sample to be measured from a hydrogen peroxide-containing aqueous solution, a reagent supply device for introducing titanium sulfate, and mixing the sampled sample to be measured and the supplied titanium sulfate. A mixing tank for preparing a sample to be measured, a UV absorption spectrum measuring device for hydrogen peroxide detection for measuring a UV absorption spectrum in the sample to be measured from the mixing tank, a preset in an aqueous solution containing hydrogen peroxide A computing device for comparing the hydrogen peroxide concentration and the measurement result, and a hydrogen peroxide aqueous solution supply device for replenishing the hydrogen peroxide aqueous solution to the hydrogen peroxide-containing aqueous solution by a signal from the computing device. An object of the present invention is to provide a management system for the concentration of hydrogen peroxide in an aqueous solution containing hydrogen peroxide.

  Furthermore, the present invention relates to a method for controlling the hydrogen peroxide concentration and sulfuric acid concentration in an aqueous solution containing hydrogen peroxide, by collecting a sample to be measured from the aqueous solution containing hydrogen peroxide and adding titanium sulfate to the sample to be measured. Then, a sample to be measured containing a complex compound of hydrogen peroxide and titanium is formed, and the UV absorption spectrum of the complex compound in the sample to be measured is measured as absorbance with a UV absorption spectrum measuring device for hydrogen peroxide detection. The measurement result obtained is sent to the arithmetic unit, and the hydrogen peroxide concentration in the aqueous solution containing hydrogen peroxide is compared with the measurement result. If the hydrogen peroxide concentration is lower than the set value, The hydrogen peroxide aqueous solution is replenished to the aqueous solution containing hydrogen peroxide from the hydrogen oxide aqueous solution supply device, and the UV absorption spectrum of the metal sulfate in the sample to be measured is used for detecting the metal sulfate. Absorbance is measured by the spectrum analyzer and the measurement result is sent to the arithmetic unit. The sulfuric acid concentration is lower than the set value by comparing the measurement result with the sulfuric acid concentration preset in the hydrogen peroxide-containing aqueous solution. In this case, an object of the present invention is to provide a method for managing the hydrogen peroxide concentration and the sulfuric acid concentration in the hydrogen peroxide-containing aqueous solution, wherein the sulfuric acid aqueous solution is replenished from the sulfuric acid aqueous solution supply device to the hydrogen peroxide-containing aqueous solution.

  The present invention also provides a sampling device for sampling a sample to be measured from a hydrogen peroxide-containing aqueous solution, a reagent supply device for introducing titanium sulfate, and mixing the sampled sample to be measured and the supplied titanium sulfate. Of a mixing tank for preparing a sample to be measured, a UV absorption spectrum measuring apparatus for hydrogen peroxide detection for measuring a UV absorption spectrum in the sample to be measured from the mixing tank, and a UV absorption spectrum measuring apparatus for hydrogen peroxide detection From the UV absorption spectrum measurement device for metal sulfate detection provided on the downstream side, the calculation device for comparing the measurement result with the hydrogen peroxide concentration and sulfuric acid concentration set in advance in the hydrogen peroxide-containing aqueous solution, from the calculation device A signal from a hydrogen peroxide aqueous solution supply device and a computing device for replenishing the hydrogen peroxide aqueous solution to the hydrogen peroxide containing aqueous solution by a signal. It is intended to provide a management system for hydrogen peroxide concentration and sulfuric acid concentration in a hydrogen peroxide-containing aqueous solution, characterized by comprising a sulfuric acid aqueous solution supply device for replenishing the sulfuric acid aqueous solution to the hydrogen peroxide-containing aqueous solution .

  According to the present invention, when measuring the concentration of hydrogen peroxide in a hydrogen peroxide-containing aqueous solution, analysis can be performed in a short time, and the analysis site can be saved in space, maintenance work can be reduced, and the amount of analysis sample waste liquid can be reduced. Can be applied to control the concentration of hydrogen peroxide in an aqueous solution containing hydrogen peroxide.

1 shows one embodiment of a system for measuring the concentration of hydrogen peroxide in a hydrogen peroxide-containing aqueous solution of the present invention. 1 shows one embodiment of a management system for the concentration of hydrogen peroxide in a hydrogen peroxide-containing aqueous solution of the present invention. It is one embodiment of the system which incorporated the measuring system of the copper sulfate concentration in the measuring system of the hydrogen peroxide concentration in the hydrogen peroxide containing aqueous solution of the present invention. It is one embodiment of the system which incorporated the management system of sulfuric acid concentration into the management system of hydrogen peroxide concentration in the hydrogen peroxide containing aqueous solution of the present invention.

First, a method for measuring the concentration of hydrogen peroxide in the hydrogen peroxide-containing aqueous solution of the present invention will be described.
The method for measuring the hydrogen peroxide concentration in a hydrogen peroxide-containing aqueous solution according to the present invention measures the UV absorption spectrum of a complex compound produced by the reaction between titanium sulfate and hydrogen peroxide. The reaction between hydrogen peroxide and titanium sulfate proceeds quickly without being inhibited even in the presence of titanium ions or other metal ions under acidic conditions, and forms a stable complex compound. Therefore, an excess amount of titanium sulfate is supplied in excess of the theoretical reaction equivalent of hydrogen peroxide present in the hydrogen peroxide-containing aqueous solution (sample to be measured), whereby all the hydrogen peroxide in the sample to be measured is replaced with titanium sulfate. Then, the UV absorption spectrum of the obtained aqueous solution containing the complex compound is detected as absorbance with a UV detector. In addition, the setting of the usage-amount of titanium sulfate can be adjusted with a titanium sulfate density | concentration, supply amount, and the supply amount of a sample to be measured. Further, when hydrogen peroxide is present at a high concentration in the sample to be measured, the sample to be measured can be diluted with a diluent and measured.

  Here, the complex compound of titanium sulfate and hydrogen peroxide exhibits a UV absorption spectrum of λmax 407 nm in the range of 350 nm to 600 nm in the aqueous solution. The absorbance in this wavelength range is quantitatively dependent only on the concentration of the complex compound, that is, the concentration of hydrogen peroxide, without being affected by the concentration of sulfuric acid or metal ions (copper ions, titanium ions, etc.). Therefore, if the absorbance at a predetermined hydrogen peroxide concentration is calibrated in advance using a device used for measurement and a UV absorption spectrum measuring device and a calibration equation is obtained, the measured absorbance is converted to the concentration of hydrogen peroxide. Can be converted to With respect to the measured absorbance and the concentration of the complex compound, that is, the concentration of hydrogen peroxide, the calibration equation obtained is a linear equation, and shows a correlation coefficient of 0.97 or more in the temperature range of 10 ° C to 30 ° C. This correlation coefficient tends to decrease when the temperature of the sample to be measured becomes high.

  For example, when the temperature of the sample to be measured is 18.5 to 21.5 ° C., the hydrogen peroxide concentration of any 10 concentrations between 2 g / liter and 25 g / liter is 2 A proportional correlation was obtained between the absorbance at 500 nm of the solution to which double the titanium sulfate was added and the aqueous hydrogen peroxide solution, and the correlation coefficient was 0.9914. When the same experiment was performed at 23.5 to 26.5 ° C., the correlation coefficient was 0.9902, and when performed at 28.5 to 31.5 ° C., the correlation coefficient was 0.9731. . Therefore, the temperature of the sample to be measured is preferably controlled to 30 ° C. or lower.

  In the method for measuring the concentration of hydrogen peroxide in the hydrogen peroxide-containing aqueous solution of the present invention, the concentration of hydrogen peroxide that can be quantified depends on the accuracy of the UV absorption spectrum measuring apparatus and the absorption wavelength used for the measurement, but is generally commercially available. When the liquid chromatography detector used is used, if the absorbance at 350 to 600 nm is used, a highly reliable measurement result is obtained in the range of 0.001 to 60% by mass.

  In the method for measuring the hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution of the present invention, the amount of titanium sulfate used for forming the complex compound is 1 to 10 equivalents, preferably 1 equivalent to 1 equivalent of hydrogen peroxide. 1.1 to 5 equivalents. In addition, the usage-amount of titanium sulfate can be adjusted with a titanium sulfate density | concentration, supply amount, and the supply amount of a sample to be measured. In addition, when the hydrogen peroxide is present at a high concentration in the sample to be measured, or depending on the standard of the UV spectrum measuring device for detecting hydrogen peroxide, the sample to be measured can be diluted with a diluting solution and measured. . It is preferable to use water or a sulfuric acid aqueous solution as the diluent.

  The method for measuring the hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution of the present invention is to sample a sample to be measured in a small amount and mix it with a small amount of titanium sulfate, and the reaction between hydrogen peroxide and titanium sulfate proceeds promptly. In addition, since it does not take time to detect absorbance, real-time continuous (always) monitoring of hydrogen peroxide concentration in aqueous solution containing hydrogen peroxide by continuously supplying a small amount of sample to be measured and titanium sulfate to the measurement system There is an advantage that can be realized.

  The system for measuring the concentration of hydrogen peroxide in a hydrogen peroxide-containing aqueous solution of the present invention is a system that can carry out the above-described method for measuring the concentration of hydrogen peroxide in a hydrogen peroxide-containing aqueous solution. A sampling device for sampling a sample, a reagent supply device for introducing titanium sulfate, a mixing vessel for preparing a sample to be measured by mixing the sample to be measured and the supplied titanium sulfate, and passing the sample to be measured from the mixing vessel A hydrogen peroxide concentration measurement system comprising a supply device for introduction into a UV absorption spectrum measurement device for hydrogen oxide detection and a UV absorption spectrum measurement device for hydrogen peroxide detection, in a sample to be measured from a mixing tank It is equipped with a diluting liquid supply device for diluting the complex compound to a concentration suitable for the measurement of the UV absorption spectrum and cleaning the measurement system. Good.

Next, one embodiment of the measurement system for the hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution of the present invention will be described with reference to FIG.
In the measurement system shown in FIG. 1, the reagent supply apparatus for introducing titanium sulfate includes a titanium sulfate supply line (1), a liquid pump (4), and a titanium sulfate supply line (1 ′). It is supplied from the titanium supply line (1) to the mixing tank (5) through the titanium sulfate supply line (1 ') by the liquid pump (4).
A sampling device for sampling a sample to be measured from a hydrogen peroxide-containing aqueous solution is composed of a sample to be measured supply line (2), a liquid pump (4), and a sample to be measured supply line (2 '), and contains hydrogen peroxide. The sample to be measured is supplied from the sample supply line (2) to the mixing tank (5) via the sample supply line (2 ′) by the liquid pump (4).
The diluting liquid supply device includes a diluting liquid supply line (3), a liquid pump (4), and a diluting liquid supply line (3 ′). The diluting liquid is supplied from the diluting liquid supply line (3) to the liquid pump (4). ) To the mixing tank (5) via the diluent supply line (3 ′).
In the mixing tank (5), titanium sulfate, the sample to be measured, and the diluent are mixed. The diluted solution is appropriately used in consideration of the hydrogen peroxide concentration of the sample to be measured, the standards of the UV spectrum measuring device (7) for detecting hydrogen peroxide, etc. used.
Moreover, although the liquid pump (4) is illustrated as a type in which three systems of titanium sulfate, a sample to be measured, and a dilution liquid are fed by one liquid pump, the titanium sulfate, the sample to be measured, and the dilution liquid are illustrated. It is also possible to install one liquid pump for each supply system. The titanium sulfate supply line (1 ′), the sample supply line (2 ′) to be measured, and the diluent supply line (3 ′) are connected to the mixing tank (5), respectively. It can also be set as the form connected to a mixing tank (5), after merging each line in an upstream. Furthermore, in the mixing tank (5), liquid stirring / mixing means, temperature control means for performing heating / cooling of the liquid, and the like can be appropriately installed.

  The liquid pump (4) can be appropriately selected depending on the amount of liquid to be fed, the type of liquid, and the like, and examples thereof include metering pumps such as a tube pump, a plunger pump, and a diaphragm pump. A tube pump is preferred when the concentration is continuously monitored by continuous flow.

  A sample to be measured containing a complex compound formed by the reaction of hydrogen peroxide and titanium sulfate in the sample to be measured is for hydrogen peroxide detection from the mixing tank (5) through the sample supply line (6). It is sent to the UV spectrum measuring device (7), and the absorbance at a predetermined wavelength in the wavelength region of 350 to 600 nm is measured. The hydrogen peroxide detection UV spectrum measuring device (7) is configured to output the absorbance measurement result as an electrical signal or to monitor the absorbance. The measured sample after measurement is configured to be discharged out of the system through the measured sample drain (8).

Next, the concentration management method for the aqueous hydrogen peroxide solution of the present invention will be described.
The hydrogen peroxide concentration control method of the present invention is such that the hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution obtained by the above-described method for measuring the hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution is hydrogen peroxide and titanium sulfate. The amount of hydrogen peroxide to be replenished to the hydrogen peroxide-containing aqueous solution is calculated from the obtained absorbance data, and the calculated hydrogen peroxide to be replenished is peroxidized. This is a method of supplying a hydrogen-containing aqueous solution. The concentration measurement can be performed by measuring the concentration constantly or every desired time and supplying a necessary amount of hydrogen peroxide.

Next, the concentration management system of the hydrogen peroxide solution of the present invention will be described.
A concentration management system for an aqueous hydrogen peroxide solution according to the present invention is a system capable of implementing the above-described concentration management method for an aqueous hydrogen peroxide solution, and the concentration of hydrogen peroxide from the absorbance obtained by the concentration measurement system, It is comprised from the calculating device which calculates the hydrogen peroxide amount which should be replenished obtained from the density | concentration, and the apparatus which supplies the hydrogen peroxide calculated by the said calculating device to a use point.

Next, one embodiment of the concentration management system of the aqueous hydrogen peroxide solution of the present invention will be described with reference to FIG.
In the hydrogen peroxide concentration management system shown in FIG. 2, the concentration measurement system (9) includes the liquid pump (4) shown in FIG. 1 to the UV absorption spectrum measurement device (7) for hydrogen peroxide detection. The sample to be measured, which is a hydrogen peroxide-containing aqueous solution, is introduced from the hydrogen peroxide-containing aqueous solution tank (18) such as an etching tank into the concentration measurement system (9) through the sample-to-be-measured supply line (2), and is peroxidized. The hydrogen concentration is measured as the absorbance of a complex compound of hydrogen peroxide and titanium sulfate. The obtained absorbance data is sent as a signal to the arithmetic unit (10), where it is converted into a hydrogen peroxide concentration and a supply amount by calculation. This amount of aqueous hydrogen peroxide solution is supplied to the use point by the liquid pump (12). Here, the liquid pump (12) can be appropriately selected depending on the amount of liquid to be fed, and examples thereof include metering pumps such as a tube pump, a plunger pump, and a diaphragm pump. That is, when compared with the set concentration of hydrogen peroxide in the hydrogen peroxide-containing aqueous solution tank (18) and the hydrogen peroxide concentration in the sample to be measured is lower than the set concentration value, the calculation device (10) In response to this signal, the liquid pump (12) is operated, and the hydrogen peroxide aqueous solution tank (11) is supplied to the hydrogen peroxide containing aqueous solution tank (18) via the hydrogen peroxide aqueous solution supply line (13). It is configured to be able to supply a fixed amount.

  Here, the titanium sulfate supplied through the titanium sulfate supply line (1) added to the sample to be measured is usually used as an aqueous solution. For example, taking as an example the case where the hydrogen peroxide-containing aqueous solution tank (18) is an etching solution for metal members, the hydrogen peroxide concentration (setting value) in the etching solution is 5 to 50 g / liter, preferably 5 to 30 g / liter. Within the liter range. Since titanium sulfate is used in excess with respect to hydrogen peroxide in the sample to be measured, an aqueous solution of 5 to 30% by mass, preferably 5 to 25% by mass is suitable for use. In addition, for the UV absorption spectrum measurement, the concentration of the complex compound of hydrogen peroxide and titanium sulfate in the sample to be measured can be diluted according to the standard of the UV absorption spectrum measuring apparatus for hydrogen peroxide detection. In this case, it is preferable to dilute the sample to be measured with dilution water before the UV absorption spectrum measurement. The concentration of the aqueous hydrogen peroxide solution supplied through the hydrogen peroxide aqueous solution supply line (13) is selected according to the concentration range of the hydrogen peroxide concentration setting value in the hydrogen peroxide-containing aqueous solution tank (18). . In the case of an etching solution for a metal member, the concentration of the aqueous hydrogen peroxide solution is in the range of 1 to 50% by mass, preferably 5 to 30% by mass.

  The measurement method and measurement system of the hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution of the present invention, the management method and management system of the hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution, for example, etching of metal members, sterilization process, Applicable to washing process, bleaching process, wastewater management, etc. Further, since the hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution of the present invention is highly sensitive, it can be applied to the measurement of hydrogen peroxide in environmental water.

  Next, an embodiment in which a measurement system for the concentration of metal sulfate is incorporated in the measurement system for the concentration of hydrogen peroxide in the hydrogen peroxide-containing aqueous solution of the present invention will be described. By incorporating a measurement system for metal sulfate concentration, it is possible to control the metal sulfate concentration at the same time in the same manner as hydrogen peroxide. For example, when the metal sulfate is copper sulfate, the metal sulfate concentration measurement system can be shared with the hydrogen peroxide concentration measurement system by using copper sulfate as an index for control.

The measurement of the metal sulfate concentration utilizes the UV absorption spectrum of the metal sulfate, and the UV wavelength used for measuring the UV absorption spectrum of the metal sulfate is contained in the aqueous solution containing hydrogen peroxide. Of UV absorption spectrum of metal sulfates, which are quantitative, even in the presence of hydrogen peroxide, sulfuric acid, and titanium ions, and the influence of absorption by titanium sulfate or a complex compound of hydrogen peroxide and titanium sulfate It is sufficient to select a range without any.

  For example, when the metal ion contained in the hydrogen peroxide-containing aqueous solution is a copper ion, the metal sulfate is copper sulfate. Copper sulfate exhibits a UV absorption spectrum of λmax 820 nm in a range exceeding 600 nm without being affected by the concentration of sulfuric acid and metal ions in an aqueous solution. The absorbance of this absorption is quantitatively dependent only on the concentration of copper sulfate without being affected by the concentrations of sulfuric acid, hydrogen peroxide and titanium ions. Therefore, when measuring the concentration of copper sulfate, it is preferable to calibrate the absorbance and copper sulfate concentration within this range. The concentration of copper sulfate in the hydrogen peroxide-containing aqueous solution that can be quantified by this method is 0.10 to 25% by mass.

Next, an embodiment in which a measurement system for metal sulfate concentration is incorporated into the measurement system for hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution of the present invention will be described with reference to FIG.
The system shown in FIG. 3 is a system in which a UV absorption spectrum measuring device (7 ′) for detecting metal sulfate is installed downstream of the UV absorption spectrum measuring device (7) for detecting hydrogen peroxide in the system shown in FIG. Yes, for example, for copper sulfate, the absorbance at a predetermined wavelength in the wavelength region from 600 nm to 900 nm is measured with a metal sulfate detection UV absorption spectrum measurement apparatus (7 ′), and the metal sulfate detection UV spectrum measurement apparatus ( 7 ') is configured to output the absorbance measurement result as an electrical signal or to monitor the absorbance. The sample to be measured after measurement is configured to be discharged out of the system through the measured drain (8).

Next, an embodiment in which the hydrogen peroxide concentration management system and the copper sulfate concentration management system are incorporated in a perwater-sulfuric acid etching system will be described with reference to FIG.
In FIG. 4, the concentration measurement system (9 ′) includes the liquid pump (4) shown in FIG. 3 to the metal sulfate detection UV absorption spectrum measurement device (7 ′). A sample to be measured is introduced into the concentration measurement system (9 ′) from the etching tank (17) through the sample supply line (2), and the hydrogen peroxide concentration is the absorbance of the complex compound of hydrogen peroxide and titanium sulfate. As measured. The obtained absorbance data is sent as a signal to the arithmetic unit (10), where it is converted into a supply amount of the aqueous hydrogen peroxide solution by calculation. The supply amount of hydrogen peroxide solution from the hydrogen peroxide solution tank (11) is supplied to the etching tank (17) by the liquid pump (12). The metal sulfate concentration is measured as the absorbance of the metal sulfate. The obtained absorbance data is sent as a signal to the calculation device (10), where it is converted into a supply amount of sulfuric acid by calculation. A sulfuric acid aqueous solution is supplied to the etching tank (17) by the liquid pump (14) for this supply amount. Here, the liquid pump (14) can be appropriately selected depending on the amount of liquid to be fed, and examples thereof include metering pumps such as a tube pump, a plunger pump, and a diaphragm pump.

  That is, the hydrogen peroxide concentration data is compared with the set concentration of hydrogen peroxide in the etching tank (17), and when the hydrogen peroxide concentration in the sample to be measured is lower than the set concentration value, the arithmetic unit In response to the signal from (10), the liquid pump (12) is operated, and the aqueous hydrogen peroxide solution (11) is transferred from the aqueous hydrogen peroxide solution tank (11) to the etching tank (17) through the hydrogen peroxide aqueous solution supply line (13). It is configured to be able to supply a fixed amount. Also, the metal sulfate concentration data is compared with the sulfuric acid concentration in the hydrogen peroxide-containing aqueous solution in the etching tank (17), and the supply amount of sulfuric acid to be replenished from the consumed sulfuric acid is calculated. The amount of the sulfuric acid aqueous solution thus obtained can be supplied from the sulfuric acid aqueous solution tank (14) to the etching tank (17) via the liquid pump (15). Thereby, the concentration control of hydrogen peroxide and sulfuric acid can be performed simultaneously. The density | concentration of the sulfuric acid aqueous solution supplied to an etching tank (17) is 5-60 mass%, Preferably it exists in the range of 10-50 mass%.

  The metal material processed by this metal member etching system is not particularly limited as long as etching using hydrogen peroxide as an oxidizing agent is applicable, but copper-containing materials represented by copper and copper alloys are suitable. . Examples of copper alloys include copper-aluminum alloys.

  In addition to the concentration management system of the present invention, this etching system may be provided with another chemical management system such as a management system using specific gravity, potential difference, titration, etc. as an index for adjusting the concentration of the etching solution. A water supply device may be provided.

  This etching system can be used for surface treatment (surface roughening, soft etching) and patterning of a metal material. Specifically, a printed wiring board, a package substrate, COF, TAB, etc. can be used. .

Hereinafter, the present invention will be described in more detail with examples, evaluation examples, and comparative examples. However, it should be understood that the present invention is not limited by the following examples.
Example 1
With the measurement system of hydrogen peroxide and metal sulfate concentration shown in FIG. 3, the continuous flow measurement of UV absorbance of a mixed aqueous solution of hydrogen peroxide, sulfuric acid and copper sulfate was performed under the following conditions. The change with time in absorbance at each concentration was observed. The results are shown in Table 1.
(UV absorbance measurement conditions)
Titanium sulfate aqueous solution concentration: 10% by mass, flow rate: 0.8 ml / min (1.2 to 3.5 times the reaction equivalent of titanium sulfate to hydrogen peroxide)
Mixed aqueous solution flow rate: 0.6 ml / minute Diluted water flow rate: 1.2 ml / minute Sample flow rate to be measured: 2.6 ml / minute Sample liquid temperature to be measured: 24 ° C.
UV absorption spectrum measuring device for hydrogen peroxide detection: 875-UV manufactured by JASCO Corporation
Cell optical path length and measurement wavelength of measuring device: optical path length 0.1 mm, wavelength 500 nm
UV absorption spectrum measuring apparatus for metal sulfate detection: UV-2070 manufactured by JASCO Corporation
Cell optical path length and measurement wavelength of measuring apparatus: optical path length 1.0 mm, wavelength 800 nm

  From the above, it was confirmed that the concentration measurement system of the present invention retained stable UV absorption, and thereby quantitative concentration measurement was possible.

Example 2
The hydrogen peroxide concentration measurement system shown in FIG. 1 was attached to a copper wet etching apparatus, and the UV absorbance of the etching solution during the copper etching process was continuously measured under the following conditions. Separately, the etching solution was sampled at a specific time, and hydrogen peroxide was analyzed by potentiometric titration using potassium permanganate. Table 2 shows the absorbance at the time of sampling for concentration analysis by titration and the concentration of hydrogen peroxide obtained by titration.
(UV absorbance measurement conditions)
Titanium sulfate aqueous solution concentration: 10% by mass Flow rate: 0.6 ml / min (2.1 times the reaction equivalent to the initial hydrogen peroxide concentration of titanium sulfate)
Mixed aqueous solution flow rate: 0.6 ml / minute Diluted water flow rate: 0.6 ml / minute Sample flow rate: 1.8 ml / minute Sample liquid temperature: 22-26 ° C
UV absorption spectrum measuring device for hydrogen peroxide detection: 875-UV manufactured by JASCO Corporation
Cell optical path length and measurement wavelength of measuring device: optical path length 0.1 mm, wavelength 500 nm
(Etching conditions)
Initial composition of etching solution: hydrogen peroxide concentration: 18.3 g / liter, sulfuric acid concentration: 39 g / liter, cupric sulfate pentahydrate 98.2 g / liter Etching method: liquid holding amount of spray type etching tank: 350 liter Effective etching distance: 1700mm
Etching solution temperature: 30 ° C
Spray pressure: 0.1 MPa
Conveyor speed: 2-3 m / weight etching area: 400 m ²
Etching rate: 2 μm / min

  From the above results, it was confirmed that the hydrogen peroxide concentration in copper wet etching can be continuously monitored by the method for measuring the hydrogen peroxide concentration of the present invention. An etching system comprising an etching solution concentration management system by calculating the hydrogen peroxide concentration in the etching solution and the amount of hydrogen peroxide to be replenished to the etching solution based on the obtained absorbance and supplying the calculated amount to the etching solution. It becomes.

  The method for measuring the concentration of hydrogen peroxide in the hydrogen peroxide-containing aqueous solution of the present invention can be widely used for the management of hydrogen peroxide-containing aqueous solutions such as cleaning agents, disinfectants, bleaches, oxidizing agents, catalysts, and etching solutions. it can.

1, 1 ′: titanium sulfate supply line, 2, 2 ′: sample supply line to be measured, 3, 3 ′: dilution liquid supply line, 4: pump for liquid, 5: mixing tank, 6: sample supply line to be measured 7: UV absorption spectrum measurement device for hydrogen peroxide detection, 7 ′: UV absorption spectrum measurement device for metal sulfate detection, 8: Sample drain to be measured, 9: Concentration measurement system, 10: Arithmetic device, 11: Hydrogen peroxide Aqueous solution tank, 12: liquid pump, 13: hydrogen peroxide aqueous solution supply line, 14: sulfuric acid aqueous solution tank, 15: liquid pump, 16: sulfuric acid aqueous solution supply line, 17: etching tank, 18: hydrogen peroxide containing aqueous solution tank.

Claims (13)

  In the method for measuring the hydrogen peroxide concentration in a hydrogen peroxide-containing aqueous solution, a complex compound of hydrogen peroxide and titanium is formed by adding titanium sulfate to the hydrogen peroxide-containing aqueous solution, and the UV absorption spectrum of the complex compound is measured. A method for measuring a hydrogen peroxide concentration in an aqueous solution containing hydrogen peroxide, characterized by measuring the absorbance.   The method for measuring a hydrogen peroxide concentration in an aqueous solution containing hydrogen peroxide according to claim 1, wherein a UV absorption spectrum of a complex compound of hydrogen peroxide and titanium in the range of 350 to 600 nm is measured.   The method for measuring a hydrogen peroxide concentration in an aqueous solution containing hydrogen peroxide according to claim 1 or 2, wherein the aqueous solution containing hydrogen peroxide is an etching solution for a metal member.   The method for measuring the hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution according to claim 3, wherein the metal member is copper or a copper alloy.   A sampling device for sampling a sample to be measured from an aqueous solution containing hydrogen peroxide, a reagent supply device for introducing titanium sulfate, and mixing the sampled sample to be measured and the supplied titanium sulfate to prepare a sample to be measured And a hydrogen peroxide-containing aqueous solution comprising a UV absorption spectrum measuring device for detecting hydrogen peroxide for measuring a UV absorption spectrum in a sample to be measured from the mixing tank. Hydrogen concentration measurement system.   The system for measuring the concentration of hydrogen peroxide in an aqueous solution containing hydrogen peroxide according to claim 5, comprising a diluent supply device for diluting the sample to be measured.   Furthermore, the measurement system of the hydrogen peroxide concentration in the hydrogen peroxide containing aqueous solution of Claim 5 or 6 provided with the UV absorption-spectrum measuring apparatus for a metal sulfate detection.   In the method for controlling the concentration of hydrogen peroxide in a hydrogen peroxide-containing aqueous solution, a sample to be measured is taken from the hydrogen peroxide-containing aqueous solution, and titanium sulfate is added to the sample to be measured, whereby the complex of hydrogen peroxide and titanium is obtained. A sample to be measured containing a compound is formed, the UV absorption spectrum of the complex compound in the sample to be measured is measured as absorbance with a UV absorption spectrum measuring device for hydrogen peroxide detection, and the obtained measurement result is an arithmetic unit Compare the measured hydrogen peroxide concentration in the hydrogen peroxide-containing aqueous solution with the measurement result. A method for managing the concentration of hydrogen peroxide in a hydrogen peroxide-containing aqueous solution, comprising replenishing the aqueous solution containing hydrogen peroxide with an aqueous solution.   A sampling device for sampling a sample to be measured from an aqueous solution containing hydrogen peroxide, a reagent supply device for introducing titanium sulfate, and mixing the sampled sample to be measured and the supplied titanium sulfate to prepare a sample to be measured A mixing tank for measuring, a UV absorption spectrum measuring device for detecting hydrogen peroxide in a sample to be measured from the mixing tank, a pre-set hydrogen peroxide concentration and measurement in an aqueous solution containing hydrogen peroxide A hydrogen peroxide-containing aqueous solution comprising an arithmetic device for comparing the results, and a hydrogen peroxide aqueous solution supply device for replenishing the hydrogen peroxide aqueous solution to the hydrogen peroxide-containing aqueous solution by a signal from the arithmetic device Management system of hydrogen peroxide concentration in the inside.   The management system of the hydrogen peroxide concentration in the hydrogen peroxide containing aqueous solution of Claim 9 provided with the diluent supply apparatus for diluting a to-be-measured sample.   In the method for controlling the hydrogen peroxide concentration and sulfuric acid concentration in a hydrogen peroxide-containing aqueous solution, a sample to be measured is taken from the hydrogen peroxide-containing aqueous solution, and titanium sulfate is added to the sample to be measured. The sample for measurement containing the complex compound is measured, and the UV absorption spectrum of the complex compound in the sample for measurement is measured as the absorbance with a UV absorption spectrum measuring device for hydrogen peroxide detection, and the measurement results obtained And compare the measurement result with the hydrogen peroxide concentration preset in the hydrogen peroxide-containing aqueous solution. If the hydrogen peroxide concentration is lower than the set value, The aqueous solution containing hydrogen peroxide is replenished with an aqueous solution containing hydrogen peroxide, and the UV absorption spectrum of the metal sulfate in the sample to be measured is measured using the UV absorption spectrum for detecting the metal sulfate. When the absorbance is measured by the device, the measurement result obtained is sent to the arithmetic unit, and the sulfuric acid concentration is lower than the set value by comparing the measurement result with the preset sulfuric acid concentration in the hydrogen peroxide-containing aqueous solution. A method for managing hydrogen peroxide concentration and sulfuric acid concentration in a hydrogen peroxide-containing aqueous solution, comprising replenishing the hydrogen peroxide-containing aqueous solution with a sulfuric acid aqueous solution from a sulfuric acid aqueous solution supply device.   A sampling device for sampling a sample to be measured from an aqueous solution containing hydrogen peroxide, a reagent supply device for introducing titanium sulfate, and mixing the sampled sample to be measured and the supplied titanium sulfate to prepare a sample to be measured Provided on the downstream side of the mixing tank, the UV absorption spectrum measuring apparatus for hydrogen peroxide detection for measuring the UV absorption spectrum in the sample to be measured from the mixing tank, and the UV absorption spectrum measuring apparatus for hydrogen peroxide detection UV absorption spectrum measuring device for metal sulfate detection, arithmetic unit for comparing measurement result with hydrogen peroxide concentration and sulfuric acid concentration preset in hydrogen peroxide-containing aqueous solution, hydrogen peroxide aqueous solution by signal from arithmetic device Aqueous sulfuric acid solution by signals from hydrogen peroxide aqueous solution supply device and arithmetic unit to replenish hydrogen peroxide containing aqueous solution Management system of hydrogen peroxide concentration and sulfuric acid concentration of the hydrogen peroxide-containing aqueous solution characterized in that it comprises a sulfuric acid aqueous solution supply device for replenishing the hydrogen peroxide-containing aqueous solution.   The management system of the hydrogen peroxide concentration and sulfuric acid concentration in the hydrogen peroxide containing aqueous solution of Claim 12 provided with the diluent supply apparatus for diluting a to-be-measured sample.

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