JP2003004600A - Liquid sampling apparatus for trace analysis, method of sampling liquid specimen for trace analysis and method of introducing the specimen into analytical equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus for sampling a liquid specimen for trace analysis, a method for sampling a liquid specimen for the trace analysis or the like, when the concentration of impurities contained in ultrapure water having an extremely small amount of impurity, a high-purity chemical liquid or the like is analyzed in the process inspection of the manufacturing apparatus such as ultrapure water for electronic industry, a high-purity chemical liquid, and so forth. SOLUTION: The apparatus for sampling a liquid specimen for trace analysis is constituted such that it has a water sampling chamber and air supply equipment disposed on the upper part of the chamber to which clean air is suppliable by the equipment. Inside the water sampling chamber, there are arranged a preservation container detachably disposed and an infusion solution tube arranged so as to allow itself to be guided from the inside of the container to the outside of the chamber, and an exhaust port is provided therein so that the clean air supplied to the chamber is dischargeably released to the outside of the chamber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid sampling device for microanalysis, a sampling method for a liquid sample for microanalysis, and a method for introducing the liquid sample into an analyzer. More specifically, trace analysis when analyzing the concentration of impurities contained in ultrapure water, high-purity chemicals, etc. with extremely low impurity concentration in process inspection of manufacturing equipment for ultrapure water for electronic industry, high-purity chemicals, etc. The present invention relates to a sampling device for sampling, a method for sampling a liquid sample for microanalysis using the device, and a method for introducing the liquid sample into a microanalyzer.

[0002]

2. Description of the Related Art Hydrogen peroxide solution is widely used in many fields such as bleaching of paper and pulp, chemical polishing liquid, etc., but in recent years, it has been used for electronic industry such as cleaning agent for silicon wafer and cleaning agent for semiconductor process. The use in the field is increasing, and accordingly, high-purity quality in which various impurities in hydrogen peroxide water are reduced as much as possible is required.

By the way, when producing such high-purity hydrogen peroxide water, ultrapure water or a high-purity chemical solution is used. Since such a sample has an extremely low content of impurities, an extremely clear environment free of impurities is required for analysis. Therefore, when collecting and analyzing such ultrapure water / high-purity chemical liquid from the manufacturing apparatus, it has been required to be performed in a clean room controlled cleanly.

However, since it is difficult to install a clean room in all the manufacturing processes, it is usually performed under the outside air. When analyzing and inspecting manufactured ultrapure water or high-purity chemicals, if sampling is performed in the open air, directly from the tube connected to the valve of the manufacturing tank,
It will be collected in a sample container. In this case, the dirt adhered / accumulated on the inner wall of the tube during standing may be mixed into the sample container via the tube, or the suspended matter contained in the outside air may be mixed. In particular, the impurities contained in ultrapure water and high-purity medicines are few and are on the order of several tens to several ppt. Therefore, if impurities such as these are mixed in, there is a problem that an accurate concentration cannot be analyzed. .

When analyzing such ultrapure water or high-purity chemicals, an ICP-MS or a flameless atomic absorption spectrophotometer is used. This measuring device is usually installed in a clean room, but these measuring devices are equipped with vacuum pumps, exhaust ducts, cooling devices, etc. that pollute the environment and generate dust, and the analyst himself. Although it becomes a source of pollution and is in a clean room, the vicinity of the measuring device is not necessarily a clear environment. In such an environment, even if you analyze ultrapure water or high-purity chemicals with a low content of impurities,
It was difficult to obtain an accurate analysis value because the ultrapure water and the high-purity chemical solution were contaminated.

[0006]

The present invention has been made to solve the problems associated with the prior art. The microanalysis liquid sampling apparatus according to the present invention includes a water collection chamber,
A storage container disposed above the water sampling chamber and provided with an air supply device capable of sending clear air into the water sampling chamber, and a storage container removably disposed in the water sampling chamber; An infusion tube arranged so as to extend from the inside of the container to the outside of the water sampling chamber is arranged, and the water sampling chamber has an exhaust port capable of discharging the clear air fed into the water sampling chamber to the outside of the water sampling chamber. It is characterized by being provided.

With this structure, when analyzing the impurity concentration contained in ultrapure water, high-purity chemical liquid, etc., which has an extremely low impurity concentration, the mixing of impurities can be extremely reduced. It is desirable to provide an air filter in the air supply device. With such a configuration, clear air can always be sent to the water sampling chamber.

In the present invention, it is desirable to immerse the tip of the infusion tube in ultrapure water. By doing so, dirt that has adhered to and accumulated on the inner wall of the tube during standing is mediated by the tube. Mixing in the sample container and floating substances contained in the outside air are suppressed. A sampling method of a liquid sample for microanalysis according to the present invention,
A storage container that is provided with a water sampling chamber and an air supply device that is disposed in the upper portion of the water sampling chamber and that can send clear air into the water sampling chamber, and is removably disposed in the water sampling chamber. And an infusion tube arranged so as to extend from the inside of the storage container to the outside of the water sampling chamber, and in the water sampling chamber, the clear air fed into the water sampling chamber is discharged to the outside of the water sampling chamber. Using a sampling device for microanalysis with an exhaust outlet, put the end of the infusion tube in a sampling container that is separate from the storage container, and supply clear air to the sampling chamber and continuously. In addition, while the clear air is discharged from the exhaust port, the measurement sample is collected from the infusion tube in the collection container.

The introduction method for microanalysis according to the present invention comprises a water sampling chamber and an air supply device which is disposed in the upper part of the water sampling chamber and is capable of sending clear air into the water sampling chamber. In the water sampling chamber,
A sample introduction part is arranged for the measurement sample to reach the analyzer outside the water sampling chamber, and the clear air is sent into the water sampling chamber.
While continuously discharging the clear gas from the exhaust port, open the sampling container filled with the measurement sample in the water sampling chamber, and if necessary, insert the sample introduction part into the sampling container to place the measurement sample. It is characterized by being introduced into a microanalyzer.

[0010]

The liquid sampling device for microanalysis according to the present invention will be specifically described below. In addition, in this specification,%, ppm, ppb, and ppt all show weight%, weight ppm, weight ppb, and weight ppt. Microanalysis Liquid Sampling Device A microanalysis liquid sampling device according to the present invention includes a water sampling chamber and an air supply device that is disposed in the upper part of the water sampling chamber and that can supply clear air into the water sampling chamber. In the water sampling chamber, a storage container that is removably disposed and an infusion tube that is disposed from the storage container to the outside of the water sampling chamber are disposed, and the water sampling chamber includes An exhaust port is provided to allow the clear air sent into the water sampling chamber to be discharged to the outside of the water sampling chamber.

An example of such a liquid sampling device for microanalysis according to the present invention is shown in FIG.
FIG. 1 is a schematic cross-sectional view of a liquid analyzer for microanalysis used in the present invention. In FIG. 1, suffix 1 is a liquid sampling device for microanalysis, 2 is a water collecting chamber, 3 is an air supply device,
4 is an infusion tube (or capillary tube), 5
Is an exhaust port, and 6 is a storage container.

The water collection chamber 2 is provided at the front with a door for putting the storage container 6 in and out. The structure of the door is not particularly limited as long as the storage container can be easily taken in and out, and the airtightness can be maintained.For example, a double-door double door, a sliding sliding door (single sliding door, (Drawing doors, sliding doors), outside doors, raising and lowering windows, pulling windows, protruding windows, rotating windows, etc. The material of such a water collecting chamber is preferably made of transparent acrylic having a conductive coating or vinyl chloride having a conductive coating in order to prevent corrosion of chemicals or static electricity when used. used.

The storage container is placed on the bottom of the water collection chamber 2, but the bottom of the water collection chamber 2 may have a waste liquid outlet so that the spilled sample can be discharged from the storage container. The storage container is filled with ultrapure water or a high-purity chemical liquid having the same components as the chemical liquid to be sampled, and the end of the infusion tube 4 is immersed. When storing infusion tubes for a long period of time, replace ultrapure water or high-purity chemicals every day,
It is desirable to keep the infusion tube in contact with fresh ultrapure water or high-purity drug solution at all times.

As the material of the infusion tube, known materials such as Teflon (R) resin and polyolefin resin, which do not contaminate the collected sample, are preferably used. On the side wall of the water sampling chamber, there is an opening 7 for passing a liquid collection tube 4 for sampling a product tank or a production line and a capillary tube leading to an analyzer, and the other end of the tube 4 inserted into this opening 7 is provided. It can be inserted up to the vicinity of the bottom of the storage container 6 placed on the bottom of the water sampling chamber. The inner diameter of the opening 7 is almost equal to the outer diameter of the tube 2,
Outside air hardly enters the water sampling chamber through the gap. If necessary, the opening 7 and the tube may be sealed with silicone rubber or the like. The sampling device for microanalysis according to the present invention may be provided with a plurality of tubes and openings.

At the bottom of the water sampling chamber, a discharge port 5 for discharging the clear air sent into the water sampling chamber is provided.
Further, in order to operate the storage container, the infusion tube, the sample container, etc. in the water sampling chamber, an opening is provided on the side surface of the water sampling chamber 2 (not shown), and the water sampling chamber is closed at the opening. Wearing work gloves may be worn. As the work gloves, gloves made of silicone rubber or polyethylene are preferably used.

An air supply device 3 is arranged on the upper surface of the water collection chamber 2. A blower fan 8 driven by a motor is built in the air blower so that clear air can be blown into the water sampling chamber. It is desirable that the air supply device is provided with an air filter 9 so that impurities floating in the air can be removed. HE as an air filter
Examples include PA and ULPA (ultra high performance filters for clean rooms).

A pre-filter may be provided at the air intake port on the upper part of the air supply device. The air supply amount of the air supply device is not particularly limited, but is usually 0.5 to 1.2 m / sec, preferably 0.6 to 1.0 m / s.
It is desirable to be in the range of ec. In the sampling device for microanalysis according to the present invention, it is desirable that the air supply device is constantly operating, but the air supply device may be operated at least one hour before using the device.

The size of the liquid sampling device for microanalysis according to the present invention is not particularly limited, but
It is desirable that the size is about 50 cm × 50 cm × 50 cm or less in terms of convenience and handling. With such a size, it can be carried by human power. Further, in order to make it easy to carry, the water collection chamber 2 may be provided with a handle, and the liquid sampling device for microanalysis according to the present invention may be integrated with a trolley. Further, a wheel that is pivotally movable may be attached to the outer bottom of the water sampling chamber.

Method for Sampling Liquid Sample for Microanalysis A method for sampling a liquid sample for microanalysis according to the present invention uses the above-described liquid sample sampling device for microanalysis and preserves the sample liquid while flowing it from the end of the infusion tube. Pour it into a collection container other than the container for feeding and send the clear air into the water collection chamber, and while continuously discharging the clear air from the exhaust port, collect the measurement sample from the infusion tube into the collection container. .

First, the door on the front of the water sampling chamber 2 is opened, the infusion tube 2 in the storage container is taken out, and the sample solution is allowed to flow until the inside of the tube can be replaced with the sample solution. At this time, put the sample liquid flowing out from the end of the tube in an appropriate container,
Discard. Then, the tube end is inserted into the collection container, the door is closed, and the measurement sample is poured into the collection container. The supply of the sample water may be continued even if the sample water overflows from the mouth of the sampling container, whereby the sampling container and the tube may be washed with the sample water. In addition, after discarding the sample in the collection container on the way, the sample may be supplied to the container again.

When sampling in this way, clear air is sent from the upper air supply device and continuously discharged from the exhaust port.
Remove it. After sampling the desired amount of sample,
Cap the sample container, take it out of the water collection chamber, put it in the transfer plastic storage case, and complete the collection. Then, the sampling container containing the sample water is moved to the place where the analyzer is provided and used for analysis.

In this way, since the sample in the sampling container is collected in the sampling container while the purified air is being blown into the water sampling chamber, impurities are less mixed. Therefore, it is possible to accurately analyze and measure the extremely low concentration of impurities originally contained in the sample. Method for introducing into microanalytical instrument The method for introducing into a microanalytical instrument according to the present invention is to install a sample introducing section of the microanalytical instrument into the above-mentioned microanalytical liquid sampling device and supply clear air into a water sampling chamber. At the same time, while the clear air is continuously discharged from the exhaust port, the measurement sample filled in the sampling container is introduced into the microanalyzer from the sample introduction unit.

For example, in the case of ICP-MS, the water collection chamber 2
Open the front door of the ICP and put it in the storage container
-Remove the capillary tube 4 leading to the MS, open the lid of the collection container, insert the capillary tube into the collection container, position the tip of the capillary tube at the bottom of the container, close the door, and then connect the tube to the analyzer for measurement sample. Inhale.

In the case of a flameless atomic absorption spectrophotometer, the bottom of the above-mentioned liquid sampling device for microanalysis is pulled out, attached to the upper part of the autosampler, and the measurement sample is handled under clear air. According to such an introduction method, since the collected sample is simply loaded into the microanalysis liquid sampling apparatus, it is not necessary to keep the analysis apparatus itself in a clean room as in the conventional case. In addition, if operated in a clean room, an environment with a higher level of cleanliness can be obtained.

In this way, the sample in the sampling container is sampled without being polluted by the purified air being blown into the water sampling chamber, and is introduced into the analyzer so that impurities are less mixed. . Therefore, it is possible to accurately analyze and measure the extremely low concentration of impurities originally contained in the sample.
Hereinafter, the aspects of the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

Example 1 A sampling device comprising a sampling container that is cleanly washed, and a sampling chamber, and an air supply device that is disposed in the upper part of the sampling chamber and is capable of sending clear air into the sampling chamber. Place the infusion tube in the ultrapure water from the storage container while supplying clear air to the water collection chamber, let the sample solution flow until the inside of the tube can be replaced, and then wash it together. While 31%
A sample of hydrogen peroxide solution was taken, covered and sealed.

The same ICP-
The sample was placed on a similar sampling device installed in the MS, and while blowing clear air into the water sampling chamber, the lid was opened inside the sampling device, and the hydrogen peroxide solution sample as the content was taken from the capillary tube. It was introduced into ICP-MS. In addition,
The water sampling chamber is a 30 cm square made of transparent antistatic acrylic, and the air supply device is SS-M manufactured by Japan Airtech Co., Ltd.
AC is used, the air supply rate is 0.8m / sec, ULPA
An air filter of 0.1 μm was used. As a result, the number of 0.1 μm suspended particles in the water collection chamber was 0 / CF (cubic foot).

As a result of analysis, Na was below the measurement limit (0.5 p
It was less than pt). On the other hand, in the case where the sampling device according to the present invention was not used, Na was 43 ppt.

[0029]

According to the sampling method of the present invention, a clean environment comparable to a clean room can be obtained.
Further, according to the sampling method of the present invention, it is possible to perform sample water collection in a clarification environment and maintain the cleanliness of the water collection tube. Therefore, it is possible to prevent contamination from being mixed in at the time of sampling.

Furthermore, according to the liquid feeding method of the present invention, the environment for introducing the measurement sample into the analyzer can be kept clean, so that the analysis sample is not contaminated even when the container is opened, and the analysis is performed. Since it is possible to prevent the analysis sample from being contaminated by the vacuum pump, the exhaust duct, the cooling device, etc. around the equipment and the analyst himself, it is possible to accurately analyze a very small amount of impurities contained in the sample. Further, in the present invention, the cleanliness of the sample can be maintained even if the analytical instrument is not necessarily installed in the clean room.

[Brief description of drawings]

FIG. 1 shows a schematic sectional view of a liquid sampling device for microanalysis used in the present invention.

[Explanation of symbols]

1 ... Liquid sampling device for microanalysis 2 ... Water sampling room 3 ... Air supply device 4 ... Infusion tube or capillary tube 5 ... Exhaust port 6 ... Storage container 7 ... Opening 8: Air supply fan 9 ... Air filter

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuhisa Mine             10 Otake Shinden, Imozawa, Aoba-ku, Sendai City, Miyagi Prefecture             No. 2 Santoku Chemical Industry Co., Ltd. (72) Inventor Hiroshi Wakashi             10 Otake Shinden, Imozawa, Aoba-ku, Sendai City, Miyagi Prefecture             No. 2 Santoku Chemical Industry Co., Ltd. F term (reference) 2G052 AA00 AB26 AB27 AD06 AD26                       AD46 CA04 DA01 DA03 GA13                       GA24                 3L058 BD01 BE08 BF01 BG05

Claims (5)

[Claims] 1. A water sampling chamber, and an air supply device provided above the water sampling chamber and capable of sending clear air into the water sampling chamber. The water sampling chamber is removably disposed in the water sampling chamber. The storage container and the infusion tube arranged so as to extend from the inside of the storage container to the outside of the water collection chamber are arranged, and the clear air sent into the water collection chamber is provided in the water collection chamber. A liquid sampling device for microanalysis, which is provided with an exhaust port capable of discharging to the outside of a water collection chamber. 2. The liquid sampling device for microanalysis according to claim 1, wherein an air filter is provided in the air supply device. 3. The liquid sampling apparatus for microanalysis according to claim 1, wherein the tip of the infusion tube is immersed in ultrapure water. 4. A water sampling chamber, and an air supply device disposed above the water sampling chamber and capable of sending clear air into the water sampling chamber, wherein the air sampling device is removably disposed in the water sampling chamber. And a transfusion tube arranged so as to extend from the inside of the storage container to the outside of the water collection chamber, and the clear air sent to the water collection chamber is collected in the water collection chamber. Using a sampling device for microanalysis that has an exhaust port that can discharge the water outside the chamber, put the end of the infusion tube into a sampling container that is different from the storage container, and send clear air into the sampling chamber. In addition, a liquid sampling method for a sample for microanalysis, wherein a measurement sample is collected from an infusion tube in a collection container while continuously discharging clear air from an exhaust port. 5. A water sampling chamber and an air supply device, which is disposed above the water sampling chamber and is capable of sending clear air into the water sampling chamber, wherein a sample for measurement is sampled in the water sampling chamber. A sample introduction part is installed to reach the analyzer outside the water chamber, and while clear air is sent into the water sampling chamber, while the clear gas is continuously discharged from the exhaust port, the measurement sample is collected in the water sampling chamber. A method for introducing into a microanalyzer, characterized in that a filled sampling container is opened, a sample introduction part is placed in the sampling container as necessary, and a measurement sample is introduced into an analyzer.