JP6814074B2 - Cleaning liquid contamination monitoring method, cleaning liquid contamination monitoring system and cleaning liquid purification equipment - Google Patents

Description

The present invention relates to a cleaning liquid contamination monitoring method, a cleaning liquid contamination monitoring system, and a cleaning liquid purification device.

The high frequency inductively coupled plasma mass spectrometer can detect trace metals in liquid samples with high sensitivity, and can analyze trace metals in ultrapure water to a level of one digit ng / L or less. It is known. The high-frequency inductively coupled plasma mass spectrometer has a sample introduction device (autosampler) for sucking a sample to be analyzed (see, for example, Patent Documents 1 and 2).
The sample introduction device usually has a holder for holding a plurality of sample containers for accommodating samples, and a nozzle (needle) for sucking a sample in the sample container held in the holder. The nozzle is held by the arm. The arm immerses the nozzle in the sample in the sample container. As a result, the nozzle sucks the sample from the sample container. (See, for example, Patent Documents 1 and 2.).

The sample sucked from the sample container may remain in the nozzle and affect the analysis result of the subsequent sample. This is called the memory effect. In particular, if a sample in another sample container is inhaled while the sample remains in the nozzle, a plurality of samples will be mixed. Therefore, the sample introduction device described in Patent Document 2 includes a cleaning liquid tank containing a cleaning liquid for cleaning the nozzle.

The cleaning liquid tank cleans the nozzle by immersing the nozzle in the pumped cleaning liquid. Every time the nozzle is immersed in the cleaning liquid, samples and impurities adhering to the nozzle are mixed in the cleaning liquid, and the cleaning liquid is mixed. Is gradually contaminated. Therefore, the cleaning liquid needs to continuously flow in the cleaning liquid tank and be exchanged. Patent Document 2 describes a cleaning liquid tank using pure water that continuously flows and exchanges liquid. In such a cleaning liquid tank, the nozzle is washed with the pure water of the cleaning liquid tank, and the sample remaining in the flow path is washed by continuously sucking the pure water of the cleaning liquid tank.

The pure water in the cleaning liquid tank is easily and automatically managed online by using a conductivity meter or a resistivity meter in the same manner as an analyzer generally used for pure water management.

Japanese Unexamined Patent Publication No. 8-505601 Japanese Unexamined Patent Publication No. 2015-144992 Japanese Unexamined Patent Publication No. 2013-023441

However, when performing analysis using an organic solvent (hereinafter, also simply referred to as "solvent") as a sample using a high-frequency inductively coupled plasma mass spectrometer, a solvent having low polarity is insoluble in water, so pure water is added to the cleaning solution. May not be available. In such a case, alcohol or the like is used as the cleaning liquid instead of water. For example, isopropyl alcohol (hereinafter, also referred to as IPA) is purified as necessary to remove trace metals, etc., and then used as a cleaning solution for cleaning nozzles, cleaning the flow path of the sample introduction device, and cleaning solution in the cleaning solution tank. It can be used for replacement. Even if the solvent (alcohol) is of reagent grade or higher, impurities include water, ionic metal, fine particle metal, acid and the like. Since the high-frequency inductively coupled plasma mass spectrometer is used for ng / L level trace metal analysis, it is necessary to reduce trace metals among impurities in order to use it as a cleaning liquid.

To reduce trace metals in the cleaning solution, a distillation method, a non-boiling distillation method, or a purification method that combines an ultrafiltration membrane with a metal removal filter, an ion exchange filter, an ion exchange fiber, or an ion exchange resin is effective. Is. Due to the difference in liquid properties between water and alcohol, it is difficult to easily manage the purified liquid by conductivity like pure water. Of the alcohols, IPA can be continuously controlled by resistivity, but cannot be used to control trace metals at the ng / L level.

When using purified alcohol as a cleaning solution for cleaning the inside of a high-frequency inductively coupled plasma mass spectrometer or cleaning a nozzle, put the purified alcohol in a container such as fluororesin that has been cleaned until trace metals are sufficiently reduced. It is common to separate and use it as a cleaning solution. Even when it is used in a cleaning solution in which the trace metal concentration is sufficiently reduced in this way, if cleaning is performed before and after analyzing the sample, the sample is gradually mixed in the cleaning solution. Therefore, the quality of the cleaning liquid is controlled by replacing the cleaning liquid in the cleaning liquid tank with a cleaning liquid containing no sample before the detection signal does not decrease even if the cleaning liquid is inhaled or the detection signal increases. Can be done. However, it was troublesome for the analyst to constantly monitor the detection signal of the cleaning liquid and manually replace the cleaning liquid.

When performing ng / L level trace metal analysis in a cleaning solution using a high-frequency inductively coupled plasma mass spectrometer, when the purified cleaning solution is used as the cleaning solution for the sample introduction part, the degree of purification of the cleaning solution can be easily confirmed. There is no means. If the sample introduction part of the high-frequency inductively coupled plasma mass spectrometer is cleaned with a cleaning solution having a low degree of purification, there is a concern that the analysis accuracy may decrease due to the influence of impurities. A simple method for monitoring the degree of purification of the cleaning solution before sample analysis is required to routinely monitor the performance of the cleaning solution purification device at startup and during use and to prevent accidental use of the cleaning solution with a low degree of purification. It becomes.

The present invention is a cleaning liquid contamination monitoring method and a cleaning liquid contamination monitoring method, which can easily confirm (monitor) the degree of purification of a cleaning liquid in an analysis using an analyzer with desired high sensitivity without requiring a special device. An object of the present invention is to provide a system and a cleaning liquid purification apparatus used for these.

In the present invention, a cleaning solution for cleaning a sampling tool that sucks an analysis sample is analyzed by an analyzer that analyzes the analysis sample, and the cleaning solution is monitored based on a contaminant detection signal obtained by the analysis. It ’s a pollution monitoring method .
The detection signal is detected for a set time, and it is determined whether or not the value obtained from the detection signal deviates from the preset reference value range by a specified time or more to determine the suitability of the cleaning solution. Provide a method for monitoring the contamination of the cleaning liquid .

The present invention includes a cleaning liquid purification device for purifying a cleaning liquid, and a cleaning liquid purification device.
A cleaning liquid tank to which the cleaning liquid purified from the cleaning liquid purification device is sent, and
A sampling tool that sucks the cleaning liquid stored in the cleaning liquid tank, and
A liquid feeding pipe that sends the cleaning liquid taken into the sampling tool to the analyzer that analyzes the analytical sample, and
It has a determination unit for determining the suitability of the cleaning liquid based on the detection signal of the cleaning liquid obtained by the analysis by the analyzer.
The determination unit detects the detection signal of the cleaning liquid for a set time, and determines whether or not the value obtained from the detection signal deviates from the preset reference value range by a specified time or more. to, is intended to determine the appropriateness of the washing solution, when propriety of the washing liquid of the washing liquid tub is negative, indicates the replacement of the cleaning solution of the cleaning solution tank, and / or further purification of the cleaning solution before Symbol cleaning liquid purifying device Provide a cleaning liquid contamination monitoring system that directs the above.

The present invention includes a cleaning liquid purification device for purifying a cleaning liquid, and a cleaning liquid purification device.
A cleaning liquid tank to which the cleaning liquid purified from the cleaning liquid purification device is sent, and
A sampling tool from which the analysis sample is sucked and
A liquid feeding pipe that sends the analytical sample sucked into the sampling tool to the analyzer,
A purification device pipe that is connected to a three-way valve arranged in the liquid delivery pipe and sends the cleaning liquid in the cleaning liquid purification device to the analyzer via the three-way valve and the liquid supply pipe.
It has a determination unit for determining the suitability of the cleaning liquid based on the detection signal of the cleaning liquid obtained by the analysis by the analyzer.
The determination unit provides a cleaning liquid contamination monitoring system that further instructs the cleaning liquid purification device to purify the cleaning liquid when the suitability of the cleaning liquid of the cleaning liquid purification device is unacceptable.

The present invention is a cleaning liquid purification apparatus for purifying a cleaning liquid for cleaning a sampling tool that sucks an analytical sample .
A route that guides the cleaning liquid purified by the cleaning liquid purification device to the analyzer in which the analysis sample is analyzed , and
A signal path for transmitting a detection signal indicating the analysis result of the cleaning liquid by the analyzer to the cleaning liquid purification device, and
The detection signal is detected for a set time, and it is determined whether or not the value obtained from the detection signal deviates from the preset reference value range by a specified time or more to determine the suitability of the cleaning solution. providing a cleaning liquid purifying device for chromatic and a determination unit for.

According to the method for monitoring contamination of the cleaning liquid of the present invention, the degree of purification of the cleaning liquid for cleaning the sampling tool that sucks the analysis sample can be easily confirmed by using an analyzer that analyzes the analysis sample.
According to the cleaning liquid contamination monitoring system of the present invention, the degree of purification of the cleaning liquid for cleaning the sampling tool that sucks the analysis sample can be easily confirmed by using an analyzer that analyzes the analysis sample.
The cleaning liquid purification apparatus of the present invention can easily confirm the degree of purification of the cleaning liquid.

It is a schematic block diagram of the contamination monitoring system of the cleaning liquid which showed one preferable embodiment for carrying out the contamination monitoring method of the cleaning liquid of this invention. The test container is shown by a cross section, and a part of the piping is shown by an arrow. It is a schematic block diagram of the contamination monitoring system of the cleaning liquid which showed another preferable embodiment for carrying out the contamination monitoring method of the cleaning liquid of this invention. The test container is shown by a cross section, and a part of the piping is shown by an arrow. It is a graph which showed an example of the detection result of the ion which passed through the analyzer tube measured by the secondary electron multiplier tube, the vertical axis represents a signal strength, and the horizontal axis represents a mass charge ratio. It is a flowchart which showed one preferable embodiment for carrying out the contamination monitoring method of the cleaning liquid of this invention.

A cleaning liquid contamination monitoring system 1 (1A and 1B) showing a preferred embodiment for carrying out the cleaning liquid contamination monitoring method according to the present invention will be described with reference to FIGS. 1 and 2.

<Cleaning liquid contamination monitoring system>
As shown in FIG. 1, the cleaning liquid contamination monitoring system 1A of the present invention includes a cleaning liquid purification device 11 for purifying the cleaning liquid. A cleaning liquid tank 13 in which the cleaning liquid purified by the cleaning liquid purification device 11 is sent and stored is connected to the cleaning liquid purification device 11 via a cleaning liquid feed pipe 12. The cleaning liquid feed pipe 12 is provided with a sluice valve (not shown). Further, a cleaning liquid return pipe 14 for returning the cleaning liquid used for cleaning in the cleaning liquid tank 13 to the cleaning liquid purification device 11 is connected between the cleaning liquid purification device 11 and the cleaning liquid tank 13. The cleaning liquid return pipe 14 is provided with a sluice valve (not shown). Therefore, the circulatory system of the cleaning liquid 70 is formed by the cleaning liquid feeding pipe 12 and the cleaning liquid returning pipe 14 between the cleaning liquid purification device 11 and the cleaning liquid tank 13.

Further, a sample introduction device 21 that sucks the cleaning liquid 70 stored in the cleaning liquid tank 13 and the analysis sample 32 of the liquid in the sample container 31 and sends them to the analysis device 40 is arranged. Hereinafter, the analysis sample 32 is also simply referred to as a sample 32. The sample introduction device 21 is provided with a sampling tool 23 for sucking the sample 32 and the cleaning liquid 70 via the arm 22, and the sampling tool 23 is connected to the analyzer 40 by the liquid feeding pipe 24.

Further, it has a determination unit 51 for determining the suitability of the cleaning liquid 70 based on the detection signal S of the cleaning liquid obtained by the analysis by the analyzer 40. When the suitability of the cleaning liquid 70 in the cleaning liquid tank 13 is unacceptable, the determination unit 51 instructs the replacement of the cleaning liquid 70 in the cleaning liquid tank 13. In the case propriety of the washing liquid of the washing liquid purification apparatus 11 (not shown) is negative, and further instructs the purification of washing liquid to the washing liquid purification apparatus 11.

The sample 32 is placed in the sample container 31, and the sample container 31 is supported by the sample table 33. The sample table 33 can support a plurality of sample containers 31.

Next, a cleaning liquid contamination monitoring system 1 (1B) showing another preferred embodiment for carrying out the cleaning liquid contamination monitoring method according to the present invention will be described with reference to FIG.
In the cleaning liquid contamination monitoring system 1B, in addition to the configuration of the cleaning liquid contamination monitoring system 1A, a purification device pipe 27 connected from the cleaning liquid purification device 11 to the three-way valve 26 arranged in the liquid feed pipe 24 is arranged. is there. Therefore, the configurations other than the three-way valve 26 and the purification device piping 27 are the same as the configurations of the cleaning liquid contamination monitoring system 1A.

Hereinafter, each of the above components will be described in detail with reference to FIGS. 1 and 2 described above.

Examples of the cleaning liquid purification device 11 include the alcohol purification device described in JP2013-023441A. This device removes metal ions such as iron and aluminum with an ion adsorption membrane or ion exchange resin (not shown) having an H-shaped cation exchange group, and in the subsequent stage, a microfiltration membrane having a pore size of 20 nm or less. (Not shown) removes fine particles that are difficult to remove with an ion adsorption membrane or an ion exchange resin. As the ion adsorption membrane or the ion exchange resin, those having a cation exchange group, those having a cation exchange group and those having an anion exchange group may be used. Further, when the water concentration in alcohol such as IPA is as low as 200 ppm or less, some of the metal components are not ionized and exist as particles such as colloids. Therefore, microfiltration membranes are used to remove such particles. It is effective to use. Therefore, it is desirable to use the removal by a cation exchange group and the microfiltration membrane together. As the microfiltration membrane, either one having a modified ion exchange group or one having no modified ion exchange group may be used. When the cleaning liquid is purified by the cleaning liquid purification apparatus 11 by the above method, the ion adsorption membrane and the ion exchange resin are exchanged before all the ion exchange groups of the ion adsorption membrane and the ion exchange resin are consumed, and the microfiltration membrane is also used. It is desirable to replace and operate before causing clogging.

As a specific example of the cleaning liquid purification apparatus 11, if the metal ions in the cleaning liquid to be treated are about a single digit ppb, an ion adsorption membrane or ion exchange resin (not shown) and a microfiltration membrane (not shown) are used in the subsequent stages. Use the cleaning liquid purification equipment that you have. As a result, a purified cleaning liquid having a metal ion at a level of 1 to 2 digits ppt is obtained. It is desirable to use a pump whose cleanliness is maintained without mixing metal ions or the like, or to pump the liquid of the cleaning liquid purification apparatus 11 using clean nitrogen. Examples of the pump whose cleanliness is maintained include a PFA bellows pump manufactured by Teflon (registered trademark). Examples of clean nitrogen include nitrogen gas having a cleanliness of 99.999% or more. The cleaning liquid used for cleaning is either stored in a waste liquid tank and discarded, or mixed with the original cleaning liquid to be treated, and the cleaning liquid is circulated for treatment. Further, the cleaning liquid purification device 11 receives the analysis value from the analyzer 40, and displays an alarm as necessary.

The cleaning liquid tank 13 is a container in which the upper part is opened so that the collecting tool 23 can be immersed and the cleaning liquid 70 is filled. For example, the cleaning container described in Japanese Patent Application Laid-Open No. 2015-144992 can be used.
The cleaning liquid tank 13 is usually filled with the cleaning liquid 70 at the time of cleaning the sampling tool 23. The cleaning liquid tank 13 constitutes a circulation system of the cleaning liquid 70 by the cleaning liquid feed pipe 12 and the cleaning liquid return pipe 14 connected to the cleaning liquid purification device 11. On the cleaning liquid tank 13 side of the cleaning liquid feed pipe 12, a sluice valve (not shown) is arranged on the liquid feed side of the purified cleaning liquid so that the cleaning liquid used for cleaning does not flow back. This sluice valve is opened when the purified cleaning liquid is sent to the cleaning liquid tank 13, and is closed when cleaning and when the cleaning liquid is returned to the cleaning liquid purification apparatus. Further, a sluice valve (not shown) is arranged on the cleaning liquid tank 13 side of the cleaning liquid return pipe 14 so that the cleaning liquid 70 in the cleaning liquid tank 13 does not flow out. This sluice valve is closed when the purified cleaning liquid is sent to the cleaning liquid tank 13 or during cleaning, and is opened when the cleaning liquid 70 is discharged from the cleaning liquid tank 13. By performing such an operation by the sluice valve, the cleaning liquid 70 in the cleaning liquid tank 13 can be replaced with the purified cleaning liquid. It is also possible to open both sluice valves to send the purified cleaning liquid to the cleaning liquid tank 13 and return the cleaning liquid in the cleaning liquid tank 13 to the cleaning liquid purification device.
It is preferable that each of the above sluice valves is an automatically controlled valve.

As described above, the cleaning liquid feeding pipe 12 is a pipe for feeding the cleaning liquid purified from the cleaning liquid purification device 11 to the cleaning liquid tank 13. The cleaning liquid return pipe 14 is a pipe for returning the cleaning liquid used for cleaning in the cleaning liquid tank 13 to the cleaning liquid purification device 11.

The sample introduction device 21 supports the sampling tool 23 that sucks the sample in the sample container 31, the collecting tool 23, and the arm 22 that moves the sampling tool 23 while supporting the sampling tool 23. It has a drive device 25 that moves freely in a direction.

The sampling tool 23 has a structure in which holes (not shown) for sucking the cleaning liquid 70 and the sample 32 are opened, and even if the tip of the liquid feeding pipe 24 is cut, the liquid feeding pipe 24 is It may be a tubular one to be attached separately. The sampling tool 23 is composed of, for example, a suction nozzle, and is connected to a liquid feeding pipe 24 connected to the analyzer 40. Therefore, the sample 32 sucked by the sampling tool 23 is sent to the analyzer 40 through the liquid feeding pipe 24.

The arm 22 that supports and moves the sampling tool 23 is arranged by the driving device 25 so as to be freely movable, for example, in the front-back, left-right, up-down directions. Therefore, by driving the arm 22 by the driving device 25, the sampling tool 23 can be lowered and inserted into the sample 32 in each sample container 31, and the sampling tool 23 is raised and pulled out from the sample container 31. You can also. Further, the sampling tool 23 can be moved above each sample container 31 and the cleaning liquid tank 13. In this way, the drive device 25 drives the arm 22 to move the sampling tool 23 horizontally above the cleaning liquid tank 13 and the sample container 31, or to immerse the sampling tool 23 in the cleaning liquid 70 or the sample 32 in the vertical direction. Operates to move. When the sampling tool 23 is immersed in the cleaning liquid 70 or the sample 32, the cleaning liquid 70 or the sample 32 is sucked and sent to the liquid feeding pipe 24.

The liquid feeding pipe 24 is a pipe for guiding the sample 32 or the cleaning liquid 70 sucked by the sampling tool 23 to the nebulizer 41 of the analyzer 40, and is preferably flexible. For example, such a pipe has an inner diameter of about 0.5 mm to 1.5 mm, and examples thereof include a pipe made of a fluorine-based resin such as polytetrafluoroethylene (PTFE). It is preferable that a three-way valve 26, which will be described later, is arranged in the middle of the liquid feeding pipe 24. The liquid feeding pipe 24 is washed with the cleaning liquid 70 sent to the cleaning liquid tank 13 before sucking the sample 32.

The purification device pipe 27 is a pipe that connects the cleaning liquid purification device 11 and the three-way valve 26 arranged in the liquid feeding pipe 24, and the cleaning liquid (not shown) in the cleaning liquid purification device 11 is placed in the middle of the liquid feeding pipe 24. This is a pipe that guides the liquid to the liquid feeding pipe 24 via the arranged three-way valve 26.
For the purification device piping 27, a piping having the same inner diameter and material as the liquid feeding piping 24 can be used. Since the purification device pipe 27 has the same inner diameter and material as the liquid feed pipe 24, when the cleaning liquid merges with the liquid feed pipe 24 via the three-way valve 26, the flow of the cleaning liquid is not disturbed. The cleaning liquid flows in the direction of the analyzer 40 or the sampling tool 23.
In order to check the purification state of the cleaning liquid in the cleaning liquid purification device 11, the cleaning liquid in the cleaning liquid purification device 11 can be sent to the analyzer 40 through the three-way valve 26 and the liquid feeding pipe 24 by the purification device piping 27.

As a result of the cleaning liquid purification device 11 and the analyzer 40 being connected by pipes in this way, the cleaning liquid purification device 11 changes the detection signal S of either one or both of the metal and the fine particles detected by the analyzer 40. It can be received in real time. By monitoring the cleaning liquid of the cleaning liquid purification device 11 based on the change of the detection signal S, the cleaning liquid purified to a required level is surely collected by the sampling tool 23 and each of the sampling tools 23 for sucking the sample to be analyzed by the analyzer 40. It will be used as a cleaning solution for pipes.

The three-way valve 26 makes it possible to select a path communicating the upstream side (collecting tool 23 side) and the downstream side (analyzer 40 side) of the liquid feeding pipe 24. Further, it is possible to select a route that communicates between the upstream side of the purification apparatus pipe 27 (cleaning liquid purification apparatus 11 side) and the downstream side of the liquid feed pipe 24 (analyzer 40 side). Further, it is possible to select a route for communicating the upstream side of the purification device pipe 27 (cleaning liquid purification device 11 side) and the upstream side of the liquid feeding pipe 24 (collecting tool 23 side).
The three-way valve 26 can close the purification device piping 27 side and open the path for sending the sample 32 or the cleaning liquid 70 from the sampling tool 23 to the analyzer 40. Further, the liquid feeding pipe 24 side from the sampling tool 23 can be closed, and the path for feeding the cleaning liquid from the cleaning liquid purification device 11 to the analyzer 40 can be opened. Further, the liquid phase pipe 24 side toward the analyzer 40 can be closed, and the path from the cleaning liquid purification device 11 to the sampling tool 23 can be opened.
In the present specification, the terms "upstream" and "downstream" are used with respect to the flow direction of the fluid. That is, the "upstream side" with respect to a certain part in the flow path means the side where the fluid flows toward the part, and the "downstream side" means the side where the fluid flows out from the part. Means.

The sample container 31 holds the sample 32, and is shaped like a test tube having an open upper part, for example. The opening diameter of the sample container 31 has a size that allows the sampling tool 23 to be taken in and out. The sample table 33 can support a plurality of sample containers 31 in an upright state, and has a plurality of holes 34 having a size that allows the sample container 31 to be taken in and out. The sample table 33 is not limited to the above configuration as long as it can support a plurality of sample containers 31 in an upright state. For example, it may have a shape like the holder described in Japanese Patent Application Laid-Open No. 2015-144992.

The analyzer 40 analyzes the sample 32, the cleaning liquid 70, and the like, and for example, analyzes the components and mass. As such an analyzer 40, it is preferable to use an inductively coupled plasma mass spectrometer (hereinafter, also referred to as ICP-MS).

The inductively coupled plasma mass spectrometer excites a sample using inductively coupled plasma and mass spectrometrically analyzes the excited ions. That is, the amount of ions is electrically detected, the amount of ions is precisely measured, and the element to be measured in the sample is analyzed with high accuracy. The electrically detected signal has a mass-to-charge ratio (m / Q) [m is mass and Q is charge. ], It is expressed as the signal strength (see FIG. 1). When analyzing the concentration of a specific substance, the signal intensity of the mass-to-charge ratio of that substance is calculated based on a calibration curve prepared from a standard solution having a known concentration.

The inductively coupled plasma mass spectrometer is generally composed of a nebulizer 41, a spray chamber 42, a plasma torch 43, a work coil 44, a high frequency power supply 45, an analyzer tube 46, and a detection unit 47.

The nebulizer 41 is connected to a liquid feeding pipe 24, and a sample or a cleaning liquid sent by the liquid feeding pipe 24 is introduced together with argon gas and sprayed in a mist form. The spray chamber 42 classifies the particle size of the sample 32 or the cleaning liquid 70 atomized by the nebulizer 41.
In recent ICP-MS devices, there is also a device in which the spray chamber 42 is omitted and the sample or cleaning liquid atomized by the nebulizer 41 is directly guided to the plasma torch 43.

The plasma torch 43 is arranged so that the work coil 44 is wound around the tip portion 43A of the plasma torch 43, and high frequency power from the high frequency power supply 45 is applied to the work coil 44. Inside, plasma of the atomized sample or cleaning liquid is generated. That is, the atomized sample or cleaning liquid is introduced into the plasma torch 43 together with the argon gas. Then, for example, by applying a high frequency power of 27 MHz or 40 MHz to the work coil 44, a mist of a sample or a cleaning liquid and a plasma of argon gas introduced at the same time are generated in the plasma torch 43. That is, argon gas is introduced into the plasma torch 43 to form inductively coupled plasma (ICP). The plasma torch 43 is located at the center of the work coil 44 to which high frequency (RF) energy is applied, so that a strong high frequency causes collisions between argon atoms to generate high energy argon plasma. The atomized sample or cleaning solution is instantly decomposed in plasma (temperature: 6000 to 10000K), and the element to be measured is atomized and ionized. Then, the ion to be measured is guided to the analyzer tube 46. The gas that generates ICP is not limited to argon, and other rare gases can be used, but argon is preferable for mass spectrometry from the viewpoint of stability, plasma temperature, and the like.

The analyzer 46 analyzes the ions and light of the impurity elements in the sample in the plasma and the cleaning liquid generated in the plasma torch 43, identifies the impurity elements from the mass of the ions, and strengths (ion count rate and count). Quantify from the number). Specifically, the analyzer 46 has an ORS (Octopole Reaction System) collision cell and a quadrupole mass analyzer (not shown). The ORS collision cell eliminates the interference caused by the plasma and the sample matrix. In the quadrupole mass analyzer, the mass analyzer is basically composed of four parallel rods, and RF voltage and DC voltage are applied to the rods in combination. In the analyzer 46, the measurement element ions are converged on the quadrupole mass analyzer by the ion lens system and separated based on the mass-to-charge ratio. The combination of RF voltage and DC voltage allows the quadrupole mass analyzer to transmit only ions with a particular mass-to-charge ratio.

In addition to the inductively coupled plasma mass spectrometer 40, the analyzer 40 includes an atomic absorption spectrophotometer (AA), an inductively coupled plasma spectroscopic analysis (ICP-OES) apparatus, a liquid chromatograph mass spectrometer (LC-MS), and the like. Can also be applied.

The detection unit 47 has a secondary electron multiplier tube (not shown), and the ions that have passed through the analyzer tube 46 are measured by the secondary electron multiplier tube to obtain a signal for each mass number. The resulting mass spectrum is quite simple. An isotope signal for each element appears at each mass number. The signal strength is proportional to the concentration of the isotope in the measured sample or cleaning solution. A large number of elements from low mass number lithium (Li) to high mass number uranium (U) can be analyzed at the same time, and the required time is usually about 1 to 3 minutes. Using the ICP-MS apparatus in this way, various elements with concentrations ranging from ppt order to ppm order can be measured at once.

The determination unit 51 may be incorporated in the cleaning liquid purification device 11 or may be independent of the cleaning liquid purification device 11. Although not shown, the determination unit 51 compares the input unit for inputting the value of the detection result, the input value of the detection result, and the value of the allowable range of the detection result set in advance, and the detection result. It has a judgment judgment unit for judging whether or not is within the permissible range and judging suitability. Further, it has an output unit that outputs a judgment and a judgment result. As shown in FIG. 3, the value of the detection result is obtained by a spike-shaped signal (mass spectrum) for each mass number, in which the ions that have passed through the analyzer 46 are measured by the secondary electron multiplier tube. The obtained mass spectrum appears at each mass number as a signal of isotopes of each element. The signal strength is proportional to the concentration of the isotope in the measured sample or cleaning solution.
Regarding the suitability of the purified cleaning liquid of the cleaning liquid purification device 11 in the determination unit 51, the judgment criteria of "suitable" when it is suitable as a cleaning liquid and "no" when it is not suitable as a cleaning liquid are, for example, the concentration of pollutants in the cleaning liquid. Judgment based on. The pollutants in the cleaning solution differ depending on what the cleaning solution is to be cleaned. As an example, in the case of a cleaning solution for cleaning isopropyl alcohol (IPA) used in a wafer rinsing solution, Na, Mg, Al, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Cd, Pb, etc. Can be a pollutant. The permissible pollutant concentration in this case is, for example, 5 ppt or less for each element. Further, in the case of a cleaning solution for cleaning propylene glycol monomethyl ether acetate (PGMEA) having a low degree of purification, Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb and the like are used. It can be a pollutant. The permissible contaminant concentration in this case is, for example, 50 ppt or less.

<Method of monitoring contamination of cleaning liquid>
Next, a contamination monitoring method using the cleaning liquid contamination monitoring system 1 will be described.
Since the cleaning liquid 70 in the cleaning liquid tank 13 cleans the sampling tool 23, the cleaning liquid 70 is contaminated with the residue of the sample adhering to the sampling tool 23, even if it is very small. In this way, the cleaning liquid 70 containing a small amount of the sample 32 is sent to the analyzer 40 by the liquid feeding pipe 24. The delivered cleaning liquid 70 is analyzed by the analyzer 40. Then, based on the detection result obtained by the detection unit 47 of the analyzer 40, the cleaning liquid 70 in the cleaning liquid tank 13 is replaced, and the cleaning liquid in the cleaning liquid purification device 11 is further purified. In this way, the degree of purification of the cleaning liquid 70 in the cleaning liquid tank 13 and the cleaning liquid in the cleaning liquid purification device 11 is maintained so that cleaning can be performed with a clean cleaning liquid.

In short, the cleaning liquid 70 for cleaning the sampling tool 23 that sucks the sample 32 is analyzed by the analyzer 40 that analyzes the sample 32. Then, the cleaning liquid 70 is monitored based on the detection signal S of the pollutant obtained by the analysis. It is preferable to use an inductively coupled plasma mass spectrometer 40 as the analyzer 40 from the viewpoint that a plurality of metal elements can be simultaneously measured up to a low concentration of ng / L level.

The monitoring of the cleaning liquid 70 determines whether or not the detection signal S is within the allowable range of the contamination standard of the cleaning liquid set in advance, and determines the suitability of the cleaning liquid 70. The suitability of the cleaning liquid 70 means whether or not the cleaning liquid 70 can be used for cleaning the sampling tool 23, the liquid feeding pipe 24, and the like.

When the detection signal S becomes a detection signal corresponding to the allowable range of the contamination standard of the cleaning liquid set in advance in a state where the cleaning liquid 70 is continuously sent from the cleaning liquid tank 13 to the analyzer 40 through the liquid feeding pipe 24. Stop sending the cleaning liquid 70 to the analyzer 40. The same applies to a state in which the cleaning liquid 70 is continuously sent from the cleaning liquid purification device 11 to the analyzer 40 through the purification device pipe 27, the three-way valve 26, and the liquid feeding pipe 24. That is, when the detection signal S as a result of analyzing the cleaning liquid becomes a detection signal corresponding to the allowable range of the contamination standard of the cleaning liquid set in advance, the feeding of the cleaning liquid 70 to the analyzer 40 is stopped.

Further, when the suitability of the cleaning liquid in the cleaning liquid tank 13 in which the cleaning liquid 70 is stored is unacceptable, it is preferable to replace the cleaning liquid 70 in the cleaning liquid tank 13. To replace the cleaning liquid 70, either discard the cleaning liquid 70 in the cleaning liquid tank 13 or return the cleaning liquid 70 to the cleaning liquid purification device 11. Then, by putting the cleaning liquid purified by the cleaning liquid purification device 11 into the empty cleaning liquid tank 13, the cleaning liquid 70 in the cleaning liquid tank 13 is replaced with the purified cleaning liquid. Alternatively, the cleaning liquid 70 in the cleaning liquid tank 13 is discharged and the purified cleaning liquid is put in the cleaning liquid tank 13 to replace the cleaning liquid 70 in the cleaning liquid tank 13 with the purified cleaning liquid. Specifically, for such replacement of the cleaning liquid 70, for example, the cleaning liquid 70 in the cleaning liquid tank 13 is returned to the cleaning liquid purification device 11 for purification, and the cleaning liquid purified from the cleaning liquid purification device 11 is sent to the cleaning liquid tank 13. It is done by liquid. As a result, the cleaning liquid 70 in the cleaning liquid tank 13 is replaced with the purified cleaning liquid.

When the suitability of the cleaning liquid (not shown) in the cleaning liquid purification apparatus 11 for purifying the cleaning liquid is unsuitable, it is preferable to further purify the cleaning liquid in the cleaning liquid purification apparatus 11. In this case, although not shown, it is preferable that the cleaning liquid purification apparatus 11 has a flow path for returning the purified cleaning liquid to the piping of the cleaning liquid before purification. For example, it is configured by arranging a direct connection pipe (not shown) directly connected from the cleaning liquid feed pipe 12 to the cleaning liquid return pipe 14, and arranging a sluice valve (not shown) in the directly connected pipe. As a result of analyzing the purified cleaning liquid of the cleaning liquid purification apparatus 11, if the suitability as the cleaning liquid is unacceptable, the sluice valves (not shown) of the cleaning liquid feed pipe 12 and the cleaning liquid return pipe 14 are closed, and the sluice valve of the directly connected pipe is closed. It is opened and the cleaning liquid feed pipe 12 is directly connected to the cleaning liquid return pipe 14. Then, it is preferable that the cleaning liquid sent from the cleaning liquid feed pipe 12 is returned from the directly connected pipe to the cleaning liquid return pipe 14 to purify the cleaning liquid again.

In addition, the guideline for replacing the cleaning liquid 70 in the cleaning liquid tank 13 may be as follows. For example, before or after introducing the sample 32 into the analyzer 40, the detection signal S obtained by analyzing the cleaning liquid is detected at a set time. Then, when the value obtained from the detection signal S indicates a value deviating from the preset reference value range for a specified time or more, the cleaning liquid 70 in the cleaning liquid tank 13 in which the cleaning liquid 70 is stored is purified. Replace with the cleaning solution. Specifically, it is carried out by the cleaning liquid replacement method as described above. The detection set time of the detection signal S is preferably from several tens of seconds to about ten and several minutes. Further, if the cleaning liquid is retained before the start of detection of the detection signal S, it may be affected by elution from the liquid feeding pipe 24, etc., so that the purified cleaning liquid and the cleaning liquid in the liquid feeding pipe 24 are affected. It is preferable that the time for replacement is set as the detection set time. When the cleaning liquid circulates in the liquid feeding pipe 24 before the detection signal S of the cleaning liquid is obtained, or when the elution from the liquid feeding pipe 24 is low, the detection set time is not necessarily the sampling tool 23 that sucks the sample 32. It is not necessary to take a time to replace all the liquid in the liquid feeding pipe 24. Further, the time for monitoring whether the detection signal S does not deviate from the preset reference value range is preferably from several tens of seconds to about ten and several minutes for the same setting reason as the above-mentioned detection set time, and the purified cleaning liquid. It is preferable that the time is such that the cleaning liquid in the liquid feeding pipe is replaced.

Pure water, alcohol, or the like can be used as the cleaning liquid. When the analysis sample is an organic solvent, alcohol is preferably used as the cleaning liquid, and for example, isopropyl alcohol (IPA) is preferably used. The use of IPA has an advantage that it is easily mixed in the flow path because the polarity is close to that of the organic solvent used as the analysis sample as compared with pure water.

Next, before starting the analysis of the sample in the cleaning liquid contamination monitoring method, a specific description will be given below with reference to the flowchart shown in FIG. The contamination monitoring method shown in this flowchart is a contamination monitoring method for the cleaning liquid performed before starting the analysis of the sample.

As shown in FIG. 4, it is a method of monitoring contamination of a cleaning liquid by an analyzer (ICP-MS apparatus) 40, a sample introduction apparatus 21 (autosampler), and a cleaning liquid purification apparatus 11. The reference numerals attached to the constituent devices, components, and the like are the reference numerals shown in FIGS. 1 and 2.
First, on the "analyzer and sample introduction device" side, the IPC-MS device and sample introduction device 21 of the analyzer 40 are started up by "accepting the device start-up signal" S1. Next, the start signal is transmitted to the cleaning liquid purification apparatus 11 by "transmitting the start signal" S2.

The cleaning liquid purification device 11 receives the start signal by "receive the start signal" S11. Next, the purified cleaning liquid is sent from the cleaning liquid purification device 11 to the cleaning liquid tank 13 by "starting sending the cleaning liquid to the cleaning liquid tank" S12. Subsequently, the liquid feed signal is transmitted from the cleaning liquid purification device 11 to the analyzer 40 and the sample introduction device 21 by "transmitting the liquid feed signal" S13. At this time, the three-way valve 26 is used as a path for communicating the upstream side (collecting tool 23 side) and the downstream side (analyzer 40 side) of the liquid feeding pipe 24.

On the side of the analyzer 40 and the sample introduction device 21, "receive the liquid feed signal" S3 for receiving the liquid feed signal is performed. Next, the sampling tool 23 is moved to a position where it is immersed in the cleaning liquid 70 in the cleaning liquid tank 13 by "moving the sampling tool to the cleaning liquid tank by the sample introduction device" S4. Subsequently, the sampling tool 23 is immersed in the cleaning liquid 70 in the cleaning liquid tank 13, the cleaning liquid 70 is sucked, and the liquid is sent to the analyzer 40. Then, "analyze the cleaning liquid with an analyzer" S5 is performed. That is, the cleaning liquid 70 of the cleaning liquid tank 13 sent to the analyzer 40 is analyzed by the analyzer 40. After that, the analysis result is sent to the cleaning liquid purification apparatus 11 by "Transmission of analysis result" S6.

Performs S14 and "analysis receive and record" in the washing solution purification device 11 receives the analysis result, and records the analysis result in the storage unit in the cleaning liquid purification apparatus 11 (not shown). Then, "determination of suitability of analysis result" S15 is performed. When the analysis result is "No", the "Warning" S16 informs that the analysis result is No, that is, not suitable. Examples of the warning means include a warning by displaying a screen, a warning by voice, a warning by lighting or blinking a lamp, and the like. On the other hand, when the analysis result is "appropriate", a signal permitting the start of analysis of the sample 32 in the sample container 31 is transmitted from the cleaning liquid purification device 11 to the sample introduction device 21 by the "transmission of permission signal" S17.

The sample introduction device 21 receives the permission signal by "receive the permission signal" S7, and starts the analysis of the sample 32 by "start analysis of the sample" S8.

When a "warning" is given in the above-mentioned cleaning liquid contamination monitoring method, the cleaning liquid 70 in the cleaning liquid tank 13 is replaced, although not shown. To replace the cleaning liquid 70, the cleaning liquid 70 in the cleaning liquid tank 13 is returned to the cleaning liquid purification device 11 by the cleaning liquid return pipe 14 (see FIG. 1). Then, the cleaning liquid purified from the cleaning liquid purification device 11 through the cleaning liquid feed pipe 12 is sent into the cleaning liquid tank 13, and the inside of the cleaning liquid tank 13 is filled with the purified cleaning liquid. That is, it is a method of replacing the cleaning liquid 70 in the cleaning liquid tank 13. Alternatively, when the contamination in the cleaning liquid tank 13 is very small, the cleaning liquid 70 in the cleaning liquid tank 13 is returned to the cleaning liquid purification device 11 through the cleaning liquid return pipe 14. At the same time, the purified cleaning liquid in the cleaning liquid purification apparatus 11 is sent into the cleaning liquid tank 13 by the cleaning liquid feeding pipe 12, so that the cleaning liquid in the cleaning liquid tank 13 is replaced with the purified cleaning liquid. The replacement means replacing the old cleaning liquid with a new cleaning liquid while discharging the old cleaning liquid in the cleaning liquid tank 13 and putting a new cleaning liquid in the cleaning liquid tank 13. Further, the term "very slight contamination of the cleaning liquid" means, for example, 5 ppt or less if the concentration of the pollutant in the cleaning liquid 70, for example, the Na ion concentration. Further, when the concentration of the pollutant in the cleaning liquid 70 exceeds 5 ppt, it is preferable to replace the cleaning liquid. The replacement of the cleaning liquid means that the old cleaning liquid is replaced with a new cleaning liquid by completely discharging the old cleaning liquid in the cleaning liquid tank 13 and then putting a new cleaning liquid in the cleaning liquid tank 13 in which the cleaning liquid is discharged. The concentration of the pollutant is appropriately changed depending on the sample. Then, after exchanging the cleaning liquid 70 in the cleaning liquid tank 13, it is preferable to analyze the cleaning liquid 70 again according to the above flowchart.

Even when the analysis of one sample 32 is completed and the analysis of the next sample is performed, it is preferable to analyze the degree of contamination of the cleaning liquid by the procedure shown in the above flowchart. In this case, since each device is up, it starts from "transmission of start signal" S2.

When examining the cleaning liquid (not shown) of the cleaning liquid purification device 11, the flow path by the three-way valve 26 is the upstream side of the purification device pipe 27 (cleaning liquid purification device 11 side) and the downstream side of the liquid feeding pipe 24 (analyzer). The route communicates with (40 side). Next, the cleaning liquid purification device 11 “receives the start signal” S11, and instead of sending the cleaning liquid to the cleaning liquid tank 13, purification is performed from the cleaning liquid purification device 11 through the three-way valve 26 and the liquid feed pipe 24 from the purification device pipe 27. The cleaning liquid is sent to the analyzer 40. Subsequently, the liquid feed signal is transmitted from the cleaning liquid purification device 11 to the analyzer 40 by the “transmission of liquid feed signal” S13.

The analyzer 40 receives the liquid feed signal from "Receive liquid feed signal" S3. Next, "analyze the cleaning liquid with an analyzer" S5 is performed. That is, the purified cleaning liquid of the cleaning liquid purification device 11 sent to the analyzer 40 is analyzed by the analyzer 40. After that, "transmission of analysis result" S6 and subsequent steps shown in the above flowchart may be performed.

The detection signal S of both or one of the metal and / or fine particles of the cleaning liquid purified as described above is directly transmitted from the detection unit 47 of the analyzer 40 to the cleaning liquid purification device 11. The detected signal is recorded by the cleaning liquid purification device 11 for a period specified, for example, a change in the detection signal S from the start of use to the start-up of the device. Then, from the recording result, it is confirmed whether or not there is a performance change in the cleaning liquid purification device 11. It is desirable that the cleaning liquid purification device 11 automatically performs the above inspection as a daily inspection. If the detected signal deviates from a certain value and performance deterioration is confirmed, the operation to increase the purification degree of the cleaning liquid purification device 11 is performed, and the display device attached to the main body indicates that the performance has deteriorated. It is desirable that operations such as displaying on the screen and contacting the manufacturer of the cleaning liquid purification device are performed.

The analysis of the purified cleaning liquid of the cleaning liquid purification device is performed from immediately after the cleaning liquid purification device 11 is started up to the time when the cleaning liquid for internal cleaning of the sampling tool 23 and the liquid feeding pipe 24 is sucked from the cleaning liquid tank 13. It can be carried out. By this analysis, the stability of the detection signal S of both or one of the metal and the fine particles in the cleaning liquid purified by the cleaning liquid purification apparatus 11 can be confirmed. After the stability is confirmed, the purified cleaning liquid is used as the cleaning liquid of the sampling tool 23 or the internal cleaning liquid of the liquid feeding pipe 24. When there is no residual sample in the liquid feeding pipe 24 from the sampling tool 23 to the analyzer 40, or when the residual sample can be easily washed with the purified cleaning liquid, it is purified directly from the cleaning liquid tank 13 as described above. Clean by sucking the cleaning solution.

Further, it is preferable to perform both the analysis of the cleaning liquid 70 of the cleaning liquid tank 13 in which the above-mentioned collection tool 23 has been washed and the analysis of the cleaning liquid produced by the cleaning liquid purification apparatus. In that case, it is preferable that the analysis of the purified cleaning liquid of the cleaning liquid purification apparatus is performed before the analysis of the cleaning liquid 70 of the cleaning liquid tank 13. That is, as a result of analyzing the purified cleaning liquid of the cleaning liquid purification device 11, if the cleaning liquid is suitable as the cleaning liquid, the purified cleaning liquid of the cleaning liquid purification device 11 can be sent to the cleaning liquid tank 13. If the purified cleaning liquid of the cleaning liquid purification apparatus 11 is not analyzed and the cleaning liquid of unknown suitability is sent to the cleaning liquid tank 13, the cleaning liquid 70 in the cleaning liquid tank 13 may not be a suitable cleaning liquid. Therefore, it is preferable to first analyze the purified cleaning liquid of the cleaning liquid purification apparatus 11 to confirm that the cleaning liquid is compatible.

Further, the purified cleaning liquid of the cleaning liquid purification apparatus 11 can be used for cleaning the collecting tool 23. For that purpose, the three-way valve 26 is used as a path for communicating the upstream side of the purification device piping 27 (cleaning liquid purification device 11 side) and the upstream side of the liquid feeding pipe 24 (collecting tool 23 side). Then, the purified cleaning liquid of the cleaning liquid purification device 11 may be sent to the sampling tool 23 through the purification device pipe 27, the three-way valve 26, and the liquid feeding pipe 24. In this case, the cleaning liquid obtained by cleaning the sampling tool 23 can be stored in the cleaning liquid tank 13, and the stored cleaning liquid can be returned to the cleaning liquid purification device 11 through the cleaning liquid return pipe 14.

In the cleaning liquid contamination monitoring method, since the contamination state of the cleaning liquid is analyzed by the analyzer 40 that analyzes the sample 32, a new analyzer for analyzing the cleaning liquid is not required. In addition, before the analysis of the analysis sample, the sampling tool can be cleaned and cleaned, and the degree of purification of the cleaning solution can be easily confirmed. Therefore, the cleaning solution in a clean state is always washed. Can be used for. Further, since the contaminated state of the cleaning liquid can be acquired in real time, it is possible to constantly grasp the presence or absence of contamination of the cleaning liquid and the degree of contamination. Therefore, it is sufficient to replace the cleaning liquid when contamination that cannot be used as the cleaning liquid is found, so that it is not necessary to replace the cleaning liquid frequently. Furthermore, by being able to monitor the degree of purification of the cleaning liquid on a daily basis, it is possible to prevent accidentally using a cleaning liquid having a low degree of purification.

In the above-mentioned cleaning liquid contamination monitoring method, a cleaning liquid such as IPA can be continuously poured into the cleaning liquid tank 13 for use. That is, the cleaning liquid 70 can be pumped into the cleaning liquid tank 13 and used while being appropriately replaced. This has the advantage of being easier to operate. In addition, the amount of the cleaning liquid used is not limited as in the case of purification without circulation. Further, a large container for storing the cleaning liquid 70 discharged from the cleaning liquid tank 12 is not required.

In the above-mentioned cleaning liquid contamination monitoring method, the cleaning liquid can be purified to a level that does not affect the sample analysis. As the operation of the cleaning liquid purification apparatus 11, it is premised that the metal removal performance is not suddenly deteriorated, and the membrane or resin that removes metal with a margin is regularly replaced so that stable performance can be obtained. is there. Even if the operation is performed so that stable performance can be obtained, the cleaning liquid for cleaning the sampling tool 23 of the analyzer 40 used for microanalysis is appropriately managed by the performance change from the start of use and the analysis data from daily inspection. It is preferable to be done.

According to the method for monitoring contamination of the cleaning liquid, the trace metal in the cleaning liquid is analyzed by the analyzer 40 that analyzes the sample, so that the trace metal at the ng / L level in the cleaning liquid can be analyzed. Therefore, the degree of purification of the cleaning liquid can be easily confirmed.
Further, by using the analyzer as an analyzer for monitoring the performance of the cleaning solution purification device together with the sample analysis, it is possible to perform the sample analysis operation after performing cleaning with the cleaning solution that has been reliably purified. Further, even when the cleaning liquid is not sufficiently purified by the cleaning liquid purification device due to an unexpected situation, it is possible to confirm the abnormality of the cleaning liquid purification device before analyzing the sample.

Further, in the method for monitoring contamination of the cleaning liquid, an operation method can be performed in which the cleaning liquid 70 in the cleaning liquid tank 13 is replaced with a newly purified cleaning liquid until the detection signal S becomes stable. As a result, it is not necessary for the analyst to manually replace the cleaning liquid, so that it is possible to prevent impurities from being mixed into the cleaning liquid by the manual replacement operation.

The effect obtained by the cleaning liquid contamination monitoring method is, of course, also the effect produced by the cleaning liquid contamination monitoring system of the present invention.

Further, according to the cleaning liquid purification device 11 of the present invention, as described above, it has a route for guiding the cleaning liquid purified by the cleaning liquid purification device 11 to the analyzer 40 in which the sample 32 is analyzed. Through this route, the cleaning liquid purified by the cleaning liquid purification device 11 can be sent to the cleaning liquid tank 13 by the cleaning liquid feed pipe 12, and the cleaning liquid 70 in the cleaning liquid tank 13 can be sent to the analyzer 40 via the liquid feed pipe 24. Further, the cleaning liquid purified by the cleaning liquid purification device 11 can be guided to the analyzer 40 via the purification device pipe 27, the three-way valve 26, and the liquid feeding pipe 24 in this order. This makes it possible to easily analyze the cleaning liquid without any trouble. Further, it has a signal path for transmitting a detection signal S indicating the analysis result of the cleaning liquid by the analyzer 40 to the cleaning liquid purification device 11. Then, the determination unit 51 can determine the suitability as the cleaning liquid from the detection signal S as described above. Further, based on the judgment, when the cleaning liquid is contaminated, the cleaning liquid described above can be replaced.

1, 1A, 1B Cleaning liquid contamination monitoring system 11 Cleaning liquid purification device 12 Cleaning liquid feed piping 13 Cleaning liquid tank 14 Cleaning liquid return piping 21 Sample introduction device 22 Arm 23 Sampling tool 24 Liquid transfer piping 25 Drive device 26 Three-way valve 27 Purification device piping 31 Sample Container 32 sample (analytical sample)
33 Sample stand 34 Hole 40 Analyzer 41 Nebulizer 42 Spray chamber 43 Plasma torch 43A Tip 44 Work coil 45 High frequency power supply 46 Analytical tube 47 Detector 51 Judgment unit 70 Cleaning liquid S Detection signal

Claims (11)

A cleaning liquid contamination monitoring method that analyzes the cleaning liquid that cleans the sampling tool that sucks the analytical sample with an analyzer that analyzes the analytical sample, and monitors the cleaning liquid based on the detection signal of the contaminants obtained by the analysis. There,
The detection signal is detected for a set time, and it is determined whether or not the value obtained from the detection signal deviates from the preset reference value range by a specified time or more to determine the suitability of the cleaning solution. How to monitor the contamination of the cleaning liquid . The method for monitoring contamination of a cleaning liquid according to claim 1, wherein the range of the preset reference value is an allowable range of the contamination standard of the cleaning liquid set in advance. When the detection signal becomes a detection signal corresponding to the allowable range of the contamination standard of the cleaning liquid set in advance in a state where the cleaning liquid is continuously sent to the analyzer, the cleaning liquid is sent to the analyzer. The method for monitoring contamination of a cleaning liquid according to claim 2, wherein the liquid feeding is stopped. The method for monitoring contamination of a cleaning liquid according to claim 2 or 3, wherein when the cleaning liquid in the cleaning liquid tank in which the cleaning liquid is stored is unsuitable, the cleaning liquid in the cleaning liquid tank is replaced. The replacement of the cleaning liquid, together with the purified return the washing liquid of the washing liquid tank to the wash solution purification device, the cleaning solution according to claim 4 for feeding a cleaning solution purified from the washing liquid purification apparatus to the washing liquid tank Pollution monitoring method. The case propriety of cleaning liquid in the cleaning liquid purifier is negative, pollution monitoring method of the cleaning solution according to claim 5 further purification cleaning liquid in the cleaning liquid purifying device for purifying the cleaning liquid. Either or both before and after introduction introducing the analytical sample into the analyzer, the value obtained from the previous SL detection signal, deviates specified time or more from a range of pre-set reference value of the The method for monitoring contamination of a cleaning liquid according to any one of claims 1 to 6, wherein when a value is shown, the cleaning liquid in the cleaning liquid tank in which the cleaning liquid is stored is replaced with a purified cleaning liquid. The method for monitoring contamination of a cleaning solution according to any one of claims 1 to 7, wherein the cleaning solution is isopropyl alcohol. A cleaning liquid purification device that purifies the cleaning liquid,
A cleaning liquid tank to which the cleaning liquid purified from the cleaning liquid purification device is sent, and
A sampling tool that sucks the cleaning liquid stored in the cleaning liquid tank, and
A liquid feeding pipe that sends the cleaning liquid taken into the sampling tool to the analyzer that analyzes the analytical sample, and
It has a determination unit for determining the suitability of the cleaning liquid based on the detection signal of the cleaning liquid obtained by the analysis by the analyzer.
The determination unit detects the detection signal of the cleaning liquid for a set time, and determines whether or not the value obtained from the detection signal deviates from the preset reference value range by a specified time or more. to, is intended to determine the appropriateness of the washing solution, when propriety of the washing liquid of the washing liquid tub is negative, indicates the replacement of the cleaning solution of the cleaning solution tank, and / or further purification of the cleaning solution before Symbol cleaning liquid purifying device A cleaning liquid contamination monitoring system that directs. A cleaning liquid purification device that purifies the cleaning liquid,
A cleaning liquid tank to which the cleaning liquid purified from the cleaning liquid purification device is sent, and
A sampling tool from which the analysis sample is sucked and
A liquid feeding pipe that sends the analytical sample sucked into the sampling tool to the analyzer,
A purification device pipe that is connected to a three-way valve arranged in the liquid delivery pipe and sends the cleaning liquid in the cleaning liquid purification device to the analyzer via the three-way valve and the liquid supply pipe.
It has a determination unit for determining the suitability of the cleaning liquid based on the detection signal of the cleaning liquid obtained by the analysis by the analyzer.
The determination unit is a cleaning liquid contamination monitoring system that instructs the cleaning liquid purification device to further purify the cleaning liquid when the suitability of the cleaning liquid of the cleaning liquid purification device is unacceptable. A cleaning liquid purification device that purifies the cleaning liquid that cleans the sampling tool that sucks the analytical sample.
A route that guides the cleaning liquid purified by the cleaning liquid purification device to the analyzer in which the analysis sample is analyzed , and
A signal path for transmitting a detection signal indicating the analysis result of the cleaning liquid by the analyzer to the cleaning liquid purification device, and
The detection signal is detected for a set time, and it is determined whether or not the value obtained from the detection signal deviates from the preset reference value range by a specified time or more to determine the suitability of the cleaning solution. cleaning liquid purifying device for chromatic and a determination unit for.

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