Method for quantifying non-volatile impurities, method for evaluating treatment liquid, method for managing treatment liquid, device for evaluating treatment liquid, and treatment device

Abstract

Provided is a method that allows quantification of non-volatile impurities in a liquid.　This method for quantifying non-volatile impurities is characterized by comprising: a first step for producing a calibration curve on the basis of measurement values obtained by measuring standard liquids each containing a standard substance at a known concentration by a charged particle detector; and a second step for quantifying non-volatile impurities using the calibration curve and a measurement value obtained by measuring a sample liquid containing non-volatile impurities by the charged particle detector. The method is characterized in that the standard substance is a substance in which the ratio (H / W) of the height (H) to the width (W) of a peak in a spectrum obtained by measuring a solution of the standard substance at a concentration of 1 mg / L by the charged particle detector is at least three.

Description

Method for quantifying nonvolatile impurities, method for evaluating processing liquid, method for managing processing liquid, device for evaluating processing liquid, and processing device

[0001] The present disclosure relates to a method for quantifying nonvolatile impurities, a method for evaluating a treatment liquid, a method for managing a treatment liquid, an apparatus for evaluating a treatment liquid, and a treatment apparatus.

[0002] In the analysis of impurities in liquids such as water and organic solvents, ICP-MS (inductively coupled plasma mass spectrometry) is generally used for the analysis of metals, and GC (gas chromatography) is generally used for the analysis of organic substances. LC (liquid chromatography) is sometimes used for the analysis of nonvolatile impurities such as nonvolatile organic substances, but the sensitivity varies depending on the type of nonvolatile impurity, making it difficult to quantify the nonvolatile impurities.

[0003] CHROMATGRAPHY, Journal of the Society of Chromatographic Science, Vol. 32, No. 3, pp. 161-170, 2011

[0004] Therefore, an object of the present disclosure is to enable the quantitative determination of non-volatile impurities in a liquid.

[0005] A method for quantifying non-volatile impurities according to one aspect of the present disclosure includes a first step of creating a calibration curve based on measurement values ​​obtained by measuring a standard solution having a known concentration of a standard substance using a charged particle detector, and a second step of quantifying the non-volatile impurities using the measurement values ​​obtained by measuring a sample solution containing non-volatile impurities using the charged particle detector and the calibration curve, wherein the standard substance is a substance such that the ratio (H / W) of the height (H) to the width (W) of a peak in a spectrum obtained by measuring a solution of the standard substance at a concentration of 1 mg / L using the charged particle detector is 3 or more.

[0006] In the method for quantifying non-volatile impurities, the solvent of the sample solution preferably contains at least one selected from the group consisting of water, isopropyl alcohol (IPA), methanol (MeOH), propylene glycol monomethyl ether (PGME), and propylene glycol monomethyl ether acetate (PGMEA).

[0007] A method for evaluating a treatment liquid according to one aspect of the present disclosure is characterized by including a measurement step of measuring non-volatile impurities in an ion exchange treatment liquid obtained by passing the treatment liquid through an ion exchanger filling device using a charged particle detector and quantifying the non-volatile impurities.

[0008] In the above-described method for evaluating a treated liquid, it is preferable that the measuring step includes passing the ion-exchange treated liquid through a liquid chromatography column, and introducing the treated liquid discharged from the liquid chromatography column into the charged particle detector.

[0009] In the above-described method for evaluating a treated liquid, it is preferable that the ion-exchange treated liquid is introduced directly into the charged particle detector without being passed through a liquid chromatography column.

[0010] In the above-mentioned method for evaluating a treatment liquid, it is preferable that the nonvolatile impurities in the treatment liquid are quantified by a calibration curve method.

[0011] Furthermore, a method for managing a treatment liquid according to one aspect of the present disclosure is characterized in that the operating conditions of the ion exchanger filling device are managed based on the amount of non-volatile impurities obtained by the method for evaluating the treatment liquid.

[0012] Furthermore, a method for managing a treatment liquid, which is one aspect of the present disclosure, is characterized in that it manages the treatment conditions of the ion exchange treatment liquid downstream of the ion exchanger filling device based on the amount of non-volatile impurities obtained by the method for evaluating the treatment liquid.

[0013] Furthermore, one aspect of the present disclosure is a treatment liquid evaluation device characterized by including a charged particle detector that measures non-volatile impurities in the ion exchange treatment liquid obtained by passing the treatment liquid through an ion exchanger filling device.

[0014] Furthermore, a treatment device according to one aspect of the present disclosure is characterized by comprising an ion exchanger packing device through which the liquid to be treated is passed, and a charged particle detector that measures non-volatile impurities in the ion exchange treatment liquid obtained by passing the liquid to be treated through the ion exchanger packing device.

[0015] According to the present disclosure, it is possible to quantify non-volatile impurities in a liquid.

[0016] 1 is a block diagram showing the configuration of a charged particle detector, and FIG. 2 is a diagram showing an example of a spectrum obtained by measuring a standard solution containing a standard substance with a charged particle detector, and FIG. 3 is a schematic diagram showing an example of a processing apparatus according to the present embodiment.

[0017] An embodiment of the present disclosure will be described below. The embodiment is an example, and the present disclosure is not limited to the embodiment.

[0018] The method for quantifying nonvolatile impurities in this embodiment includes a first step of creating a calibration curve based on measurement values ​​obtained by measuring a standard solution having a known concentration of a standard substance using a charged aerosol detector, and a second step of quantifying the nonvolatile impurities using the measurement values ​​obtained by measuring a sample solution containing nonvolatile impurities using the charged aerosol detector and the calibration curve.

[0019] First, a charged particle detector for measuring a standard solution containing a standard substance in the first step and a sample solution containing nonvolatile impurities in the second step will be described.

[0020] FIG. 1 is a block diagram showing the configuration of a charged particle detector. The configuration of the charged particle detector shown in FIG. 1 is an example, and is not limited thereto; conventionally known charged particle detectors can be used. The charged particle detector 16 shown in FIG. 1 includes a nebulizer 20, a drying tube 22, a mixing chamber 24, a collector 26, an electrometer 28, and a detection unit 30. Measurement of nonvolatile impurities using the charged particle detector 16 is performed, for example, as follows: A standard solution or sample solution is supplied to the nebulizer 20 through a piping (not shown). The nebulizer 20 nebulizes the standard solution or sample solution with a carrier gas (nitrogen or air) to form droplets. The droplets are sent to the drying tube 22, and as they pass through the drying tube 22, the solvent in the droplets evaporates, forming residual particles of the standard substance or nonvolatile impurities in the droplets. The residual particles are sent to the mixing chamber 24, where they collide with positively charged nitrogen gas and become positively charged. The stream of positively charged residual particles moves to collector 26, and the charge imparted to the residual particles in collector 26 is measured as a current value by electrometer 28. Then, detection unit 30 creates and stores a spectrum with the retention time on the horizontal axis and the current value (signal intensity) detected by electrometer 28 on the vertical axis. Since the current value measured by electrometer 28 is directly proportional to the amount of detected residual particles, i.e., the amount of standard substance or non-volatile impurities, the amount of standard substance or non-volatile impurities can be quantified using the current value at the apex of the peak or the area of ​​the peak in the spectrum created by detection unit 30.

[0021] <Step 1> A standard solution with a known concentration of the standard substance is prepared. For example, a plurality of standard solutions with different concentrations of the standard substance are prepared, such as standard solution I with standard substance concentration A, standard solution II with standard substance concentration B, and standard solution III with standard substance concentration C (concentrations: A<B<C). These standard solutions are then measured using a charged particle detector, and a calibration curve is created based on the obtained measured values. The measured values ​​are, for example, the current value at the apex of a peak or the area of ​​the peak in a spectrum with retention time on the horizontal axis and current value on the vertical axis. From the perspective of measurement accuracy, it is preferable to use the peak area in the spectrum as the measured value.

[0022] A calibration curve can be obtained, for example, by plotting the known concentrations of the standard substance in the standard solution and the measured values ​​of the standard solution (such as the area of ​​the peak or the current value at the apex) on a graph with the concentration (mg / L) on the horizontal axis and the measured values ​​(such as the area of ​​the peak or the current value at the apex) on the vertical axis. Specifically, (concentration A of standard solution I, measured value of standard solution I), (concentration B of standard solution II, measured value of standard solution II), (concentration C of standard solution III, measured value of standard solution III), and so on are plotted, and an approximate straight line is drawn based on the plotted points using, for example, the least squares method, to form the calibration curve.

[0023] FIG. 2 shows an example of a spectrum obtained by measuring a standard solution containing a standard substance using a charged particle detector. The standard substance used in this embodiment is a substance whose peak height (H) to width (W) ratio (H / W) is 3 or greater in the spectrum obtained by measuring a solution of the standard substance at a concentration of 1 mg / L using a charged particle detector. The peak height is the height from a current value of 0 to the apex of the peak, and the peak width is the width between the start and end points of the peak, which is the rising portion of the peak. Use of this standard substance can lower the detection limit and improve the accuracy of quantification.

[0024] The peak height (H) in the spectrum must be sufficiently higher than the height of the baseline noise, and therefore the detection limit (DL (mg / L)) in this embodiment is defined as the value calculated by the following formula: In the formula, N is the maximum absolute height of the baseline noise in the spectrum obtained by measuring a solution of a standard substance with a concentration of 1 mg / L using a charged particle detector, and H is the height of the peak in the same spectrum. DL (mg / L) = 3 × N × 1 / H

[0025] <Second Step> A sample liquid containing nonvolatile impurities is measured using a charged particle detector, and the nonvolatile impurities are quantified using the obtained measurement values ​​and the calibration curve created in the first step. The measurement values ​​are, for example, the current value at the apex of a peak or the area of ​​the peak in a spectrum with retention time on the horizontal axis and current value on the vertical axis. For example, the sample liquid containing nonvolatile impurities is measured using the charged particle detector 16, and the current value at the apex of the peak or the area of ​​the peak is determined in the spectrum. The determined current value at the apex of the peak or the area of ​​the peak is applied to the calibration curve created in the first step to calculate the concentration of the nonvolatile impurities in the sample. In this way, the nonvolatile impurities in the sample can be quantified. The quantification of the nonvolatile impurities may be performed by an operator or by a computing device.

[0026] A sample liquid suitable for quantifying non-volatile impurities in this embodiment is, for example, a sample liquid containing at least one solvent selected from the group consisting of water, isopropyl alcohol (IPA), methanol (MeOH), propylene glycol monomethyl ether (PGME), and propylene glycol monomethyl ether acetate (PGMEA).

[0027] When the amount of sample liquid is small, it is preferable to mix the sample liquid with an eluent that is highly miscible with the solvent of the sample liquid. For example, the sample liquid is added to a pipe that supplies liquid to a nebulizer while the eluent is flowing. The pipe preferably has a predetermined length, for example, a length of 5 m to 20 m. By lengthening the pipe, it is possible to lengthen the retention time of the peak measured by the charged particle detector.

[0028] When the nonvolatile impurities include nonvolatile organic substances and metal impurities, the sample liquid may be analyzed by ICP-MS to quantify the metal impurities in the sample liquid. By calculating the concentration of the metal impurities in the sample liquid through ICP-MS analysis, the concentration of the nonvolatile organic substances contained in the nonvolatile impurities can be estimated from the concentration of the nonvolatile impurities determined in the second step.

[0029] In this embodiment, the sample liquid may be introduced directly into the charged particle detector 16, or the sample liquid may be passed through a liquid chromatography column, and the treated liquid discharged from the liquid chromatography column may be sequentially introduced into the charged particle detector 16. In the former case, the total amount of nonvolatile impurities contained in the sample liquid can be measured. In the latter case, the components of the nonvolatile impurities are separated by the liquid chromatography column, and the amount of each component of the nonvolatile impurities contained in the sample liquid can be measured. The liquid chromatography column may be appropriately selected depending on the components of the nonvolatile impurities, and conventionally known columns such as a gel filtration column, a cation exchange column, or an anion exchange column can be used.

[0030] Fig. 3 is a schematic diagram showing an example of a treatment apparatus according to this embodiment. The treatment apparatus 1 shown in Fig. 3 includes an ion exchanger filling device 10 and a treatment liquid evaluation device 12. A pipe 14a is connected to the inlet of the ion exchanger filling device 10, and a pipe 14b is connected to the outlet of the ion exchanger filling device 10. The treatment liquid evaluation device 12 includes a charged particle detector 16, and a pipe 14c branching from the pipe 14b is connected to the charged particle detector 16.

[0031] The treatment process for a liquid to be treated using the treatment device 1 shown in Figure 3 will be described. The liquid to be treated contains ionic impurities. The liquid to be treated is passed through the ion exchanger packing device 10 via pipe 14a. During this process, the liquid to be treated comes into contact with the ion exchangers packed in the ion exchanger packing device 10, and the ionic impurities in the liquid to be treated are ion-exchanged and removed by the ion exchangers. The liquid to be treated from which the ionic impurities have been removed is discharged as a treated liquid (hereinafter referred to as the ion-exchanged treated liquid) from the ion exchanger packing device 10 to pipe 14b.

[0032] The liquid to be treated is not particularly limited, and examples thereof include water, sugar solutions, organic solvents, etc. Examples of organic solvents include alcohols such as isopropyl alcohol, methanol, and ethanol; ketones such as cyclohexanenone, methyl isobutyl ketone, acetone, and methyl ethyl ketone; alkene-based organic solvents such as 2,4-diphenyl-4-methyl-1-pentene and 2-phenyl-1-propene; N-methylpyrrolidone; and mixed organic solvents thereof. The organic solvent may be either a polar organic solvent or a nonpolar organic solvent. Furthermore, the polar organic solvent may be either a protic polar organic solvent or an aprotic polar organic solvent.

[0033] The ionic impurities contained in the liquid to be treated are not particularly limited, but examples thereof include cationic impurities such as monovalent ionic metal impurities such as Na, K, and Li, divalent or higher ionic metal impurities such as Cr, As, Ca, Cu, Fe, Mg, Mn, Ni, Pb, and Zn, and anionic impurities such as sulfate ions, nitrate ions, chloride ions, boron, fluorine, and organic acids such as formic acid and acetic acid.

[0034] Examples of the ion exchanger packed into the ion exchanger packing device 10 include granular ion exchange resins, non-particulate organic porous ion exchangers, activated carbon, carbonized resins, and zeolites. Examples of the granular ion exchange resins include cation exchange resins, anion exchange resins, and chelate exchange resins. Examples of the non-particulate organic porous ion exchangers include monolithic organic porous materials having a continuous framework phase and a continuous pore phase, to which ion exchange groups have been introduced. Examples of the ion exchange groups include anion exchange groups and cation exchange groups.

[0035] The ion exchange treatment liquid obtained from the ion exchanger packing device 10 may be contaminated with nonvolatile impurities. For example, when a granular ion exchange resin or a non-particulate organic porous ion exchanger is used as the ion exchanger, depending on the liquid to be treated passing through the ion exchanger packing device 10, the nonvolatile impurities may react with the nonvolatile organic material that is the matrix of the ion exchanger, resulting in the nonvolatile organic material being contaminated into the ion exchange treatment liquid. Furthermore, nonvolatile impurities may be contaminated into the ion exchange treatment liquid if the liquid to be treated contains a large amount of nonvolatile impurities or if the ion exchanger deteriorates. Therefore, quantifying the nonvolatile impurities in the ion exchange treatment liquid discharged from the ion exchanger packing device 10 is important in terms of managing the operating conditions of the ion exchanger packing device 10 and the treatment conditions of the ion exchange treatment liquid.

[0036] The following describes a method for evaluating the ion-exchange treated solution to quantify the amount of non-volatile impurities in the treated solution.

[0037] A portion of the ion exchange treatment liquid discharged from the ion exchanger filling device 10 passes through the pipe 14c and is introduced into the charged particle detector 16. The nonvolatile impurities in the ion exchange treatment liquid are measured by the charged particle detector 16, and the amount of nonvolatile impurities is quantified (measurement step). The frequency of measuring the nonvolatile impurities with the charged particle detector 16 may be, for example, about once a day to once a month.

[0038] FIG. 1 is a block diagram showing the configuration of a charged particle detector. The configuration of the charged particle detector shown in FIG. 1 is an example, and is not limited thereto; conventionally known charged particle detectors can be used. The charged particle detector 16 shown in FIG. 1 includes a nebulizer 20, a drying tube 22, a mixing chamber 24, a collector 26, an electrometer 28, and a detection unit 30. Measurement of nonvolatile impurities using the charged particle detector 16 is performed, for example, as follows: The ion exchange treatment liquid discharged from the ion exchanger filling device 10 is atomized by the nebulizer 20 with a carrier gas such as nitrogen or air to form droplets. The droplets are sent to the drying tube 22, and as they pass through the drying tube 22, the solvent in the droplets evaporates, forming residual particles of the nonvolatile impurities in the droplets. The residual particles are sent to the mixing chamber 24, where they collide with positively charged nitrogen gas and become positively charged. The stream of positively charged residual particles moves to collector 26, where the charge imparted to the residual particles is measured as a current value by electrometer 28. Then, detector 30 creates and stores a spectrum with retention time on the horizontal axis and the current value (signal intensity) detected by the electrometer on the vertical axis. The current value measured by the electrometer is directly proportional to the amount of detected residual particles, i.e., the amount of nonvolatile impurities, so the amount of nonvolatile impurities can be quantified from the area of ​​the peak in the spectrum created by detector 30.

[0039] The quantitative determination of nonvolatile impurities is preferably performed by a calibration curve method. An example of the calibration curve method is described below. (1) As described above, the peak area in the spectrum of nonvolatile impurities obtained by the charged particle detector 16 is determined. (2) Multiple standard solutions containing different concentrations of a substance soluble in the treated liquid are prepared. For example, when the treated liquid is isopropanol, a preferred example of the soluble substance is LiBr. That is, multiple isopropanol solutions containing different concentrations of LiBr are prepared. (3) The standard solutions are analyzed using the charged particle detector 16 in the same manner as described above, and a calibration curve showing the relationship between the peak area of ​​the obtained spectrum and the LiBr concentration is created. (4) Using the calibration curve created in (3), the peak area determined in (1) is converted to the concentration of nonvolatile impurities. The quantitative determination of nonvolatile impurities may be performed by an operator, or may be performed by a calculation device provided in the treatment liquid evaluation device 12.

[0040] The metal impurities in the treated solution may be quantified by analyzing the ion-exchanged solution discharged from the ion exchanger filling device 10 by ICP-MS. By calculating the concentration of the metal impurities in the treated solution through ICP-MS analysis, the concentration of nonvolatile organic substances contained in the nonvolatile impurities can be estimated from the concentration of the nonvolatile impurities.

[0041] In this embodiment, the ion exchange treatment liquid discharged from the ion exchanger filling device 10 may be directly introduced into the charged particle detector 16, or the ion exchange treatment liquid may be passed through a liquid chromatography column, and the treatment liquid discharged from the liquid chromatography column may be sequentially introduced into the charged particle detector 16. In the former case, the total amount of nonvolatile impurities contained in the ion exchange treatment liquid can be measured. In the latter case, the nonvolatile impurity components are separated by the liquid chromatography column, and the amount of each component of the nonvolatile impurity contained in the ion exchange treatment liquid can be measured. The liquid chromatography column may be appropriately selected depending on the components of the nonvolatile impurities, and conventionally known columns such as gel filtration columns, cation exchange columns, and anion exchange columns can be used.

[0042] The method for managing the treated solution in this embodiment is characterized by managing the operating conditions of the ion exchanger packing apparatus 10 based on the amount of non-volatile impurities in the ion exchanger treated solution obtained by the above-described method for evaluating the treated solution. Examples of managing the operating conditions include, for example, stopping the operation of the ion exchanger packing apparatus 10, regenerating the ion exchanger, or replacing the ion exchanger when the amount of non-volatile impurities in the ion exchanger treated solution exceeds a predetermined value as a result of quantifying the non-volatile impurities during actual operation of the ion exchanger packing apparatus 10. Managing the operating conditions also includes, for example, quantifying the non-volatile impurities in the ion exchanger treated solution during actual operation of the ion exchanger packing apparatus 10 and adjusting the flow rate of the treated water in accordance with the amount of non-volatile impurities. Managing the operating conditions also includes, for example, changing the material or amount of ion exchanger packed during the design stage of the ion exchanger packing apparatus 10, i.e., during test operation of the ion exchanger packing apparatus 10, when the amount of non-volatile impurities in the ion exchanger treated solution exceeds a predetermined value as a result of quantifying the non-volatile impurities.

[0043] The method for managing the treated liquid in this embodiment is characterized in that it manages the treatment conditions for the ion exchange treated liquid downstream of the ion exchanger packing device 10 based on the amount of nonvolatile impurities in the ion exchanger treated liquid obtained by the above-described method for evaluating the treated liquid. Examples of the management of the treatment conditions for the ion exchange treated liquid include, for example, installing equipment for treating nonvolatile impurities downstream of the ion exchanger packing device 10 when the amount of nonvolatile impurities in the ion exchanger treated liquid exceeds a predetermined value as a result of quantifying the nonvolatile impurities during test operation of the ion exchanger packing device 10, which is the design stage of the device. Examples of downstream equipment include equipment for coagulation sedimentation, biological treatment, photooxidation, wet contact oxidation, pressure flotation, activated carbon adsorption, microfiltration, and ultrafiltration. The management of the treatment conditions for the ion exchange treated liquid also includes, for example, changing the treatment conditions of the equipment installed downstream of the ion exchanger packing device 10 when the amount of nonvolatile impurities in the ion exchanger treated liquid exceeds a predetermined value as a result of quantifying the nonvolatile impurities during actual operation of the ion exchanger packing device 10.

[0044] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples.

[0045] <Selection of standard substances> The following standard solutions I to V were prepared. Standard solution I: Isopropyl alcohol solution with a LiBr concentration of 1 mg / L Standard solution II: Isopropyl alcohol solution with an Octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate concentration of 1 mg / L Standard solution III: Aqueous solution of sodium benzenesulfonate with a concentration of 1 mg / L Standard solution IV: Aqueous solution of KCl with a concentration of 1 mg / L Standard solution V: Aqueous solution of p-glucose with a concentration of 1 mg / L

[0046] Each of the standard solutions I to V was measured using a charged particle detector, and the ratio (H / W) of the peak height (H) to the width (W) in the obtained spectrum was determined. Furthermore, the detection limit (DL (mg / L)) was calculated from the obtained spectrum using the above formula. The results are shown in Table 1. The charged particle detector used was a Vanquish CAD H (Thermo Scientific ＴＭ Vanquish ＴＭ Flex UHPLC system).

[0047]

[0048] As shown in Table 1, the substances for which the ratio (H / W) of the spectral peak height (H) to the peak width (W) was 3 or more were LiBr in sample solution I, sodium benzenesulfonate in sample solution III, KCl in sample solution IV, and p-glucose in sample solution V. Furthermore, the detection limits for samples I, III, IV, and V were lower than those for sample II.

[0049] In the following, the non-volatile impurities were quantified using LiBr as a standard substance.

[0050] Example 1: Quantitation of non-volatile impurities Isopropyl alcohol solutions with LiBr concentrations of 0.0, 0.1, 0.2, 0.5, 1.0, and 2.0 mg / L were prepared, and each solution was measured using a charged particle detector to determine the peak area in the resulting spectrum. The LiBr concentrations in the isopropyl alcohol solutions and the resulting peak areas are summarized in Table 2.

[0051]

[0052] A calibration curve was created that defines the relationship between the LiBr concentration in the isopropyl alcohol solution and the obtained peak area. Next, a sample solution was prepared by dissolving a resin in isopropyl alcohol. The resin concentration in the sample solution was 1.4 mg / L. The sample solution was measured using a charged particle detector, and the peak area in the obtained spectrum was found to be 0.64 (pA*min). The resin concentration in the sample solution was calculated from the peak area obtained by measuring the calibration curve and the sample solution, and was found to be 1.4 mg / L. In other words, the value was close to the resin concentration in the prepared sample solution, resulting in a highly accurate measurement.

[0053] Example 2 Three samples (a sample with dissolved resin A, a sample with dissolved resin B, and a sample with dissolved resin C) were prepared by dissolving 100 mL each of resin A, resin B, and resin C in 500 mL of isopropanol. These samples were analyzed using a charged particle detector, and the peak areas of resins A, B, and C in the samples were determined. Measurement conditions Mobile phase: isopropanol / ultrapure water=50 / 50 Flow rate: 0.5 mL / min Charged particle detector: Vanquish CAD H (Thermo Scientific ＴＭ Vanquish ＴＭ Flex UHPLC system) Concentration measurement method: calibration curve method

[0054] Isopropanol standard solutions containing octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate at concentrations of 0.05, 0.1, 0.5, 1, 10, 50, and 100 μg / mL were prepared. Each standard solution was analyzed using a charged particle detector to determine the peak area of ​​octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate in each standard solution. A calibration curve was then created that defined the relationship between the octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate concentration and peak area. Using the resulting calibration curve, the peak areas of the resins A, B, and C described above were converted to their concentrations in the samples. The results were 1100 ppm for resin A, 2100 ppm for resin B, and 170 ppm for resin C. These values ​​were close to the concentrations of resins A, B, and C in the prepared samples, demonstrating high measurement accuracy.

[0055] [Note] (1) A method for quantifying nonvolatile impurities, comprising: a first step of preparing a calibration curve based on measurements obtained by measuring a standard solution having a known concentration of a standard substance using a charged aerosol detector; and a second step of quantifying the nonvolatile impurities using the measurements obtained by measuring a sample solution containing nonvolatile impurities using the charged aerosol detector and the calibration curve, wherein the standard substance is a substance whose peak height (H) to width (W) ratio (H / W) in a spectrum obtained by measuring a solution of the standard substance at a concentration of 1 mg / L using the charged aerosol detector is 3 or more. (2) The method for quantifying nonvolatile impurities according to (1), wherein the solvent of the sample solution includes at least one selected from the group consisting of water, isopropyl alcohol (IPA), methanol (MeOH), propylene glycol monomethyl ether (PGME), and propylene glycol monomethyl ether acetate (PGMEA). (3) A method for evaluating a treated liquid, comprising a measuring step of measuring non-volatile impurities in an ion-exchange treated liquid obtained by passing a liquid to be treated through an ion exchanger-packed device using a charged aerosol detector to quantify the non-volatile impurities. (4) The method for evaluating a treated liquid described in (3), wherein the measuring step includes passing the ion-exchange treated liquid through a liquid chromatography column and introducing the treated liquid discharged from the liquid chromatography column into the charged aerosol detector. (5) The method for evaluating a treated liquid described in (3), wherein the measuring step includes introducing the ion-exchange treated liquid directly into the charged aerosol detector without passing it through a liquid chromatography column. (6) The method for evaluating a treated liquid described in any one of (3) to (5), wherein the quantification of non-volatile impurities in the treated liquid is performed using a calibration curve method. (7) A method for managing a treated liquid, comprising managing the operating conditions of the ion-exchanger-packed device based on the amount of non-volatile impurities obtained by the method for evaluating a treated liquid described in any one of (3) to (6).(8) A method for managing a treatment liquid, which manages treatment conditions for the ion exchange treatment liquid downstream of the ion exchanger packing device based on the amount of nonvolatile impurities obtained by the treatment liquid evaluation method described in any one of (3) to (6). (9) A treatment liquid evaluation device comprising a charged particle detector that measures nonvolatile impurities in the ion exchange treatment liquid obtained by passing the liquid to be treated through the ion exchanger packing device. (10) A treatment device comprising: an ion exchanger packing device through which the liquid to be treated is passed; and a charged particle detector that measures nonvolatile impurities in the ion exchange treatment liquid obtained by passing the liquid to be treated through the ion exchanger packing device.

[0056] 1 Processing device, 10 Ion exchanger filling device, 12 Processing liquid evaluation device, 14a to 14c Piping, 16 Charged particle detector, 20 Nebulizer, 22 Drying tube, 24 Mixing chamber, 26 Collector, 28 Electrometer, 30 Detection unit

Claims

1. A method for quantifying non-volatile impurities, comprising: a first step of creating a calibration curve based on measurement values ​​obtained by measuring a standard solution having a known concentration of a standard substance using a charged aerosol detector; and a second step of quantifying the non-volatile impurities using the measurement values ​​obtained by measuring a sample solution containing non-volatile impurities using the charged aerosol detector and the calibration curve, wherein the standard substance is a substance whose peak height (H) to width (W) ratio (H / W) is 3 or more in the spectrum obtained by measuring a solution of the standard substance at a concentration of 1 mg / L using the charged aerosol detector.

2. The method for quantifying non-volatile impurities according to claim 1, characterized in that the solvent of the sample liquid contains at least one selected from the group consisting of water, isopropyl alcohol (IPA), methanol (MeOH), propylene glycol monomethyl ether (PGME), and propylene glycol monomethyl ether acetate (PGMEA).

3. A method for evaluating a treated liquid, comprising a measurement step of measuring non-volatile impurities in an ion exchange treated liquid obtained by passing the treated liquid through an ion exchanger filling device using a charged aerosol detector, and quantifying the non-volatile impurities.

4. A method for evaluating a treatment liquid as described in claim 3, characterized in that in the measurement process, the ion exchange treatment liquid is passed through a liquid chromatography column, and the treatment liquid discharged from the liquid chromatography column is introduced into the charged particle detector.

5. The method for evaluating a treatment liquid according to claim 3, wherein in the measuring step, the ion-exchange treatment liquid is introduced directly into the charged particle detector without being passed through a liquid chromatography column.

6. The method for evaluating a processing liquid according to any one of claims 3 to 5, characterized in that the non-volatile impurities in the processing liquid are quantified by a calibration curve method.

7. A method for managing a treatment liquid, comprising managing the operating conditions of the ion exchanger-filled device based on the amount of non-volatile impurities obtained by the method for evaluating a treatment liquid according to claim 3.

8. A method for managing a treatment liquid, which manages the treatment conditions of the ion exchange treatment liquid downstream of the ion exchanger filling device based on the amount of the non-volatile impurities obtained by the treatment liquid evaluation method described in claim 3.

9. A treatment liquid evaluation device comprising a charged particle detector for measuring non-volatile impurities in an ion-exchange treatment liquid obtained by passing the treatment liquid through an ion exchanger-packed device.

10. A treatment device comprising: an ion exchanger packing device through which a liquid to be treated is passed; and a charged particle detector for measuring non-volatile impurities in the ion exchange treatment liquid obtained by passing the liquid to be treated through the ion exchanger packing device.

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