JPH11262659A - Collecting agent, its production, collector and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To collect basic compounds contained in gas such as the air in the form suitable for analysis, efficiently, and in high concentration. SOLUTION: A filter 1 that on a fluororesin supporting body to which hydrophilicity imparting treatment is applied an acidic layer containing 1.5-15 mg/cm<2> of acid per unit volume of the supporting body is formed is fitted in a cartridge 3. After that, by causing air to be analyzed to flow in the filter 1 in the cartridge 3 from a suction port 31 of the cartridge 3 and contacting it with the acidic layer of the filter 1, ammonia, amine or the like in the air is effectively collected in high concentration in the form of salt. The salt is solvent extracted from the filter 1 after collection, and is analyzed by a chromatographic method. In this way, the determination of a trace of basic compounds in the air can be quickly performed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a collector for a basic compound contained in a gas such as air, a method for producing the same, a collector using the collector, and a method for producing the same.

[0002]

2. Description of the Related Art The odor of basic compounds such as ammonia and amines has been known as spoilage of fish. The foul odor of amines generated from fish ilium bone processing plants and chemical plants is a serious problem, and it is desired to purify the ambient air. To that end, air ammonia and amines are collected and analyzed. Technology needs to be established.

On the other hand, in the VLSI manufacturing process, it is essential to establish a technology for managing and analyzing impurity gas in a clean room. For the analysis of inorganic ions, a technique is used in which ion components in the atmosphere are collected in ultrapure water by an impinger or the like and detected by ion chromatography (IC). However, it has become clear that contamination by ultra-trace amounts of organic matter in the atmosphere, which has been of little importance until now, also causes various defects in semiconductor devices and lowers the yield of the VLSI manufacturing process. The same level of sensitivity as inorganic substances has been required.

In particular, amines such as ammonia, alkanolamines, aliphatic amines, and aromatic amines, which are ionic organic compounds, have high reactivity and may cause problems such as hindering resist curing in a lithography process. It is becoming clear that the development of the analytical method is of particular importance.

[0005] Ammonia in the clean room is considered to be caused by outside air, wafer cleaning liquid, CVD source gas and the like. Further, it is considered that amines are derived from components contained in the additive of boiler water in the clean room and components generated from the human body. These ammonia and amines as trace gases contribute to a decrease in the yield of the semiconductor manufacturing process.

As a conventional collecting method for analyzing such ammonia and amines, an impinger pure water collecting method or a filter paper absorption method in which air is passed through a filter paper coated with sulfuric acid has been used. However, in the impinger method, 100% of ultrapure water is used in order to increase the collection efficiency.
(Ml) or more, so that it was difficult to concentrate the trapped substance because impurities were contained when the trapped substance was concentrated. Also,
In the filter paper absorption method as well, the filter paper removed from the filter paper holder after collection is placed in a beaker and a sufficient amount of solvent (diameter 5
The filter is immersed in a filter paper (10 ml to 20 ml) and extracted and then subjected to an analyzer. Therefore, there is a concern about contamination from air and containers during the analysis operation, and there is a problem as a highly sensitive detection method for trace gas.

[0007] As an apparatus capable of reducing such contamination during the operation and automating the entire operation, there is disclosed an apparatus in which a diffusion scrubber method using a gas permeable membrane and ion chromatography are integrated ( JP-A-8-
54380). By using this device, it is possible to reduce
One (ppb) level of ammonia can be automatically monitored every 20 minutes.

[0008]

As described above, ammonia and amine contained in the air react with acidic substances (for example, hydrochloric acid) in the air and are often present in the form of particles or mist. . However, the diffusion scrubber method cannot trap particles or mist due to its mechanism. For this reason, when simultaneous measurement is actually performed at the same place by the impinger method and the diffusion scrubber method, the concentration detected by the impinger collection often gives a higher result. In such a state, it is impossible to accurately measure the amounts of ammonia and amine, and consequently, it must be used in combination with an impinger. There was a problem that also came out.

Recently, in order to test the gas generated from the component material, a very small box (15c) made of the component material is used.
There is a need to produce a sample having a size of about mx 15 cm x 15 cm) and to analyze the air therein. However, there is a problem that the impinger and the diffusion scrubber are large in size and cannot be collected in such a small box.

The present invention has been made in order to solve the above-mentioned conventional problems, and an object of the present invention is to efficiently and at a high concentration a basic compound contained in a gas such as air in a form suitable for analysis. An object of the present invention is to provide a trapping agent capable of trapping, a method for producing the trapping agent, a trapping device using the trapping agent, and a method for producing the trapping agent.

[0011]

Means for Solving the Problems To achieve the above object, the present inventors have conducted intensive studies. As a result, the first aspect of the present invention is characterized in that a hydrophilized fluororesin support and this fluororesin support are provided. And an acidic layer formed at a density of 1.5 to 15 mg / cm ³ per unit volume of the fluororesin support.

According to the first aspect of the invention, a collector is prepared by adhering 1.5 to 15 mg / cm ³ of acid per unit volume of the fluororesin support to the hydrophilized fluororesin support. Then, when the collector was brought into contact with air, it was found that the basic compound contained in the air could be efficiently collected in the form of a salt at a high concentration. In addition, it was confirmed that by collecting and extracting with a small amount of water or alcohol after collection, it can be recovered in a state of high concentration and low blank suitable for analysis. In particular, a feature of the collector of the present invention is that the fluororesin support is covered with 1.5 to 15 mg of acid per cm ^{3 of} resin. When the amount of the acid is 1.5 mg or less, the amount of the acid is too small, so that it is difficult to completely collect basic compounds such as ammonia and amine in the air. Further, when the amount of the acid is 15 mg or more, the amount of the acid is too large, so that the acid may be peeled off during contact with air. As a result, there is an adverse effect that air is contaminated by the acid and the quantitativeness of the basic compound is poor. Also, if an acid is added in excess, the blank is likely to rise during analysis. Therefore, it has been found that covering with an acidic layer of 1.5 to 15 mg / cm ³ per unit volume of the fluororesin support is extremely important for exhibiting its trapping action.

A feature of the second invention is that an acid solution having a predetermined concentration is passed or dropped on the fluororesin support, or the support is immersed in the acid solution, and then the solvent is removed. 1.5 per unit volume of the fluororesin support
In depositing a acid to 15 mg / cm ^3.

According to the second aspect, the acid solution having a predetermined concentration is passed, dropped or immersed in the fluororesin support, and then the solvent is removed by decompression, heating or gas purging. At this time, as a solvent that can be used for the preparation treatment of the acidic layer, water, methanol, ethanol, propanol, isopropanol, acetone, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, dichloroethane, and the like are mentioned. Considering the lowness, methanol is optimal.

Further, a tartaric acid solution may be used as the acid solution.

According to this, an acid suitable for an acidic layer formed on a fluororesin support must be non-volatile in terms of stability at room temperature, volatility, and the like. Tartaric acid is suitable. In addition to this tartaric acid, phosphonic acid, perchloric acid, phosphoric acid, boric acid, oxalic acid, adibic acid, quinaldic acid, citric acid, cinnamic acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, It is desirable to use an acidic compound selected from the group consisting of malic acid. Acetic acid, formic acid and the like having a low melting point are not suitable because the life of the collecting agent is short and air pollution due to volatilization in the air is considered.

The third invention is characterized in that the fluororesin support subjected to the hydrophilic treatment and 1.5 to 1 per unit volume of the fluororesin support formed on the surface of the fluororesin support are provided.
An acidic layer formed at a density of 5 mg / cm ³ , a case having the fluororesin support mounted therein, and having a suction port and a discharge port through which gas or liquid flows in and out.

According to the third aspect, the fluororesin support having the acidic layer formed on the surface, that is, the collecting agent is mounted in the case, and is easily carried. The case is installed in a place where the atmosphere to be measured is located, and the case is exhausted by a pump or the like from the outlet of the case, so that the atmosphere to be measured is sucked into the case from the inlet, and the acid of the fluororesin support is By contact with the layer, a basic compound such as ammonia or amine is collected in the form of a salt by the acidic layer.
Thereafter, the fluororesin support is taken out of the case, and the trapping substance is extracted with a solvent to be used for analysis. By making the fluororesin support detachable from the case, the operability of the apparatus is improved.

A fourth aspect of the present invention is characterized in that the step of mounting the fluororesin support on the case, the step of flowing an acid solution into the case, and the step of flowing the acid solution into the case. And drying the acidic layer with a density of 1.5 to 15 mg / cm ³ per unit volume of the fluororesin support on the surface of the fluororesin support. It is in.

According to the fourth aspect of the present invention, after the fluororesin support before the formation of the acidic layer subjected to the hydrophilization treatment is mounted on the case, the acid solution is caused to flow into the case from the suction port of the case, and the fluororesin support is formed. Infiltrate the body surface with the acid solution. Thereafter, when the case is dried under reduced pressure, an acidic layer is formed on the surface of the fluororesin support and stored in a nitrogen atmosphere or the like. By controlling the concentration and the amount of the acid solution flowing into the case, the acidic layer formed at a density of 1.5 to 15 mg / cm ³ per unit volume of the fluororesin support can be obtained.

The fifth invention is characterized in that the inner tube made of a fluororesin which has been subjected to a hydrophilic treatment and the inner tube made of a fluororesin formed on the surface of the inner tube made of a fluororesin have a volume of 1.5 parts per unit volume.
An acidic layer formed at a density of １５15 mg / cm ³ , and an outer tube having the inner tube made of the fluororesin and having both ends opened.

According to the fifth aspect of the present invention, the outer pipe having the inner pipe is installed in a place where the atmosphere to be measured is located, and the outer pipe is evacuated by a pump or the like from one opening of the outer pipe.
By sucking the atmosphere to be measured into the inside from the other opening and bringing it into contact with the acidic layer of the inner tube, a basic compound such as ammonia or amine is collected in a salt form by the acidic layer. Thereafter, the fluororesin support is taken out of the case, and the trapping substance is extracted with a solvent to be used for analysis. The inner tube may be mounted in close contact with the inner wall surface of the outer tube, or may be mounted with a suitable support so that a gap is created between the inner wall surface of the outer tube and the outer peripheral surface of the inner tube.

Here, the reason why the fluororesin was selected as a constituent material of the support was that the fluororesin itself did not have any adsorptivity of a basic compound, and that nitrogen-based impurities could be contained in the synthesis step of the fluororesin. This is because the resin has a very small property and the blank of the resin itself is almost equal to zero.
As the fluororesin, polytetrafluoroethylene (P
TFE), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), tetrafluoroethylene-hexafluorofluorene copolymer (FE
P), tetrafluoroethylene-hexafluoropropylene-perfluoroalkylvinyl ether copolymer (EPE), tetrafluoroethylene-ethylene copolymer (ETFE), polychlorotrifluoroethylene (P
CTFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), polyvinylidene difluoride (PVDF), polyvinyl fluoride (PVF) and the like. Since these fluororesins have excellent chemical resistance, they are durable to acid coating or repeated extraction with an organic solvent. These generally have very high water repellency. Therefore, it is necessary that the surface of the fluororesin has a hydrophilic property so that the trapping agent can easily contact the trapping target and the eluent.

The fluororesin forming the support preferably has a porous surface, that is, a porous structure in which substantially circular holes are connected to each other. Porosity is desirable because of its large surface area. As the porous support, a filter formed by knitting a fibrous material or a tube-shaped material is easily used. Generally, a porous film filter called a membrane filter has a pore structure in which pores close to a circle are connected to each other. In the case of a membrane filter used when collecting trace components in the air,
Pore diameter is 0.025-10 μm, film thickness is 10-170 μm
m and a diameter of about 5 to 50 mm are preferable.

As a method of hydrophilizing the fluororesin material, the resin is immersed in an aqueous solution of NaAl (OH) ₄ ,
A method of irradiating an ArF laser, a method of performing low-temperature plasma treatment, a chemical activation method of dipping in a solution in which an alkali metal is dissolved in an organic solvent, a method of dipping in a wetting agent such as polyvinylpyrrolidone, and the like can be given.

Examples of the basic compound that can be collected by the above-mentioned collector of the present invention include ammonia, primary amine, secondary amine, tertiary amine, quaternary amine, sodium salt, gallium. And the like. The amines that can be collected may be liquid or solid at normal temperature and normal pressure, or may have vapor pressure in gas, or may be mist-like amines. Examples of the primary amine include saturated aliphatic primary amines such as methylamine, ethylamine, and propylamine; unsaturated aliphatic primary amines such as allylamine; and aromatic primary amines such as aniline; Examples of the amine include a saturated aliphatic secondary amine such as dimethylamine and diethylamine, an unsaturated aliphatic secondary amine such as diallylamine, and an aromatic secondary amine such as methylaniline.
Examples of the tertiary amine include trimethylamine, triethylamine and methylpiperidine, and examples of the quaternary amine include benzyltrimethylammonium chloride. When air is brought into contact with the collector, the acid on the resin surface and the basic compound in the air form a salt, and the basic compound is fixed on the resin surface.

Thereafter, for analysis, it is conceivable to extract the salt with an extraction medium. At this time, as the extraction medium, a liquid or a supercritical fluid can be considered,
Extraction with a liquid, especially water, is suitable for introduction into ion chromatography. Basically, any medium can be used as long as it is a medium from which salts can be eluted and does not contain substances that hinder measurement and analysis, and alcohols such as methanol can also be used. In the case of eluting an amine salt with water as an eluent, in the case of a hydrophilic PTFE filter having a diameter of 13 (mmφ) and a thickness of 35 (μm), 2 (ml) of water is used.
More than 9.5% of the amine salt is eluted into the eluent and recovered (see Example 2). As an analysis method, in addition to ion chromatography (IC), liquid chromatography (HP)
LC) method and the like. For example, in the case of analysis by HPLC, by performing derivatization such as fluorescent labeling,
For primary and secondary amines, it is possible to measure amines having a large number of carbon atoms which cannot be measured by IC (not applicable to tertiary and quaternary amines).

As a fluorescent labeling reagent, NBD-F (4
-Fluoro-7-nitro-2, l, 3-benzoxadiazole) will be described. After being collected by the above-mentioned collecting agent, extraction is performed with a 2 (mg / ml) NBD-F / buffer (pH 8.5) solution. Thereafter, an internal standard substance is added, the reaction is carried out at 70 ° C. for about 10 minutes, and the reaction solution is injected into HPLC (about 10 μl), separated, and subjected to fluorescence detection. With this method, highly sensitive analysis of amines is possible.

[0029]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a sectional view showing a first embodiment of a collecting device using a collecting agent of the present invention. The trapping device has a configuration in which a filter 1 made of a hydrophilic fluororesin support having an acidic layer such as tartaric acid formed on the surface thereof is mounted on a cartridge 3 made of polypropylene. However,
The acidic layer is formed at a density of 1.5 to 15 mg / cm ³ per unit volume of the fluororesin support. The filter 1 made of the acidic layer fluororesin support is fixed and supported by a filter support 2 inside the cartridge 3. The cartridge 3 further has an air or liquid inlet 31 and an air or liquid exhaust port 31 at the center of its upper and lower surfaces. It has an outlet 32. However, the inlet 31 and the outlet 3
2 has no problem even if its role is changed. After attaching the hydrophilic fluororesin support to the cartridge 3, a treatment for forming an acidic layer on the surface of the fluororesin support may be performed.

Next, a method of trapping airborne basic compounds using the trapping device of this embodiment will be described. The outlet 32 of the cartridge 3 is connected to a suction pump (not shown) to suck air. By this operation, the air or the like is sucked into the fluororesin filter 1 from the suction port 31, and the acidic layer on the filter 1 reacts with a basic compound such as ammonia or amines in the air, and is collected as a salt by the filter 1. You. As another collecting method, there is a method in which the filter 1 as a collecting agent is left in the atmosphere to be measured, and a basic compound that comes into contact with the filter 1 is naturally collected.

Next, after attaching the fluororesin support constituting the filter 1 to the cartridge 3, an acidic layer is formed on the surface of the filter 1, then the basic compound is collected, and the collected salt is transferred to the analyzer. A series of flows up to introduction will be described with reference to FIG. First, an acid solution such as tartaric acid (methanol solution or the like) is dropped from the suction port 31 of the cartridge 3, and a certain amount of the acid solution flows into the cartridge 3. Thus, the acid solution permeates and adheres to the surface of the fluororesin support constituting the filter 1 mounted in the cartridge 3.

Thereafter, the cartridge 3 is dried under reduced pressure.
By removing the internal solvent, an acidic layer is formed on the surface of the fluororesin support, and the filter 1 is formed, whereby the collecting device is completed. The completed collection device is stored in a nitrogen atmosphere or the like.

Then, the exhaust port 32 of the collection device completed as described above is connected to the pump 8 or the like, and the inside of the cartridge 3 is evacuated, whereby the atmosphere is sucked from the intake port 31. As described above, the air is sucked for a certain period of time, the air is passed through the filter 1 inside the cartridge 3, and the basic compound is collected in the form of a salt in the acidic layer of the filter 1.

Thereafter, the eluate (eg, ultrapure water) is supplied to the inlet 31.
And into the cartridge 3 to extract the collected components,
The extract is taken out from the outlet 32. The extract is injected into an analyzer such as an ion chromatograph.

When this method is used, mist-like and particulate amines which cannot be analyzed by the diffusion scrubber method can be collected. In addition, the extract requires a smaller amount than the diffusion scrubber method. It is possible to shorten the time required for concentration. In addition, since the fluororesin support is detachable from the cartridge 3, it can be regenerated by passing the acid solution again, which is economical.

FIG. 3 is a sectional view showing a second embodiment of the collecting device using the collecting agent of the present invention. It has a configuration in which a cylindrical fluororesin inner tube 6 is mounted as a filter inside a tubular cartridge (outer tube) 5 made of plastic such as polypropylene through which gas does not pass. This filter is a porous fluororesin inner tube 4
An acidic layer such as tartaric acid is formed on the outer and inner surfaces. However, the acidic layer is formed at a density of 1.5 to 15 mg / cm ³ per unit volume of the fluororesin inner tube. The porous diameter of the inner tube 6 is 0.025 to 10 μm, the film thickness is 10 to 170 μm, the diameter of the inner tube 6 is 2 to 10 mm, and the length of the inner tube 6 is 5 to 50 mm.
A size of about cm is good. If the length of the tube is long, the collection efficiency increases, but the size of the blank also increases, so that a length of about 10 cm is preferable.

The outer tube 5 which is a tubular cartridge
Is spiral or zigzag, the contact probability between the atmosphere to be measured and the surface of the inner tube type filter in the outer tube 5 which is a tubular cartridge is increased, and the collection efficiency is improved. Also in this example, the inner tube 6 made of hydrophilic fluororesin is used.
May be formed into the outer tube 5 and then the acid layer of the inner tube 6 may be formed.

As a method of trapping the airborne basic compound by such a trapping agent, one opening of the outer tube 5 is connected to a suction pump to suck air. Then, the air is sucked from the other opening of the outer tube 5, and the air comes into contact with the acidic layer of the inner tube 6, whereby the acid and the basic compound react with each other and are collected as a salt on the surface of the inner tube 6.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the analysis of the examples was performed using the following devices and the like.

(1) High Performance Liquid Chromatograph (HPL)
C): HPLC 610E system manufactured by Waters Co., Ltd. Column: Chemical Product Inspection Association (trade name: L-Column O)
DS) (4.6 mmφ × 250 mm) Column temperature: 40 ° C., flow rate: 1 (ml / min), mobile phase solvent: acetonitrile / water = 45/55 injection volume: 20 (μl / time) Detector: manufactured by Waters 474 scanning fluorescence detector (excitation wavelength 450 nm, fluorescence wavelength 530 nm) (2) Reagents: acetonitrile, water, and methanol used were solvents for high performance liquid chromatography manufactured by Wako Pure Chemical Industries, Ltd.

NBD-F was manufactured by Dojindo Chemical Co., Ltd.

All other reagents used were manufactured by Wako Pure Chemical Industries, Ltd. Standard ammonia / amine concentration is 25 ammonia
(Μg / ml), methylamine 4 (μg / ml), ethylamine 5 (μg / ml), propylamine 7 (μg / ml)
ml). The concentration of butylamine used as the internal standard is 7 (μg / ml). As the buffer solution, a borate buffer / methanol solution (pH 8.5) was used.

(3) Pump: Mini-pump (MP-603P) manufactured by Shibata Kagaku Co., Ltd. (4) Hydrophilic PTFE filter: Toyo Roshi Co., Ltd. Diameter: 13 (mmφ), pore size: 0.2 (μm), thickness 3
5 (μm), porosity: 71 (%) (5) Stainless steel syringe holder: Toyo Roshi Kaisha, Ltd.
(6) Disposable membrane filter: Toyo Roshi Kaisha, Ltd. Diameter: 13 (mmφ), hole diameter: 0.2 (μm), thickness 3
5 (μm), material: hydrophilic PTFE, housing material:
Polypropylene (7) Ion chromatograph: Apparatus: Dionex DX-100,
Guard column: CG-12 Separation column: CA-12, Concentration column: CG-12 Eluent: methanesulfonic acid (10 mM), flow rate: 1.0
(Ml / min) Detector: Conductivity detector Example 1 Filter collection and recovery test Filter 1 shown in FIG. 1 was impregnated with 1 ml of methanol and washed, and then a methanol solution of tartaric acid having various concentrations was obtained. 1
ml, picked up with tweezers and placed on aluminum foil. It was placed in a desiccator and dried under reduced pressure with a vacuum pump for 1 hour. When the vacuum was released, the atmosphere was replaced with high-purity nitrogen. The amount of tartaric acid adhering to the prepared filter was determined by immersing it in methanol again, extracting with ultrasound, removing the filter, evaporating the methanol to dryness, and measuring the remaining amount of tartaric acid. The tartaric acid-treated filter is placed in a syringe holder made of stainless steel (corresponding to the cartridge 3 in FIG. 1), and two holders are connected in series as shown in FIG. 4, and standard ammonia (10 μl) is spread on the glass wool 7 and (L / m
In) 300 (l) of nitrogen was passed through. Thereafter, 2 ml of water was flown into each holder using a syringe, and the amount of recovered ammonia was confirmed by ion chromatography.

FIG. 5 shows the result of the amount of ammonia recovered from the first holder. When tartaric acid having a concentration of 1.5 mg / cm ³ or less was coated, ammonia breakthrough was confirmed because the acid concentration was too low. Also, 1
Breakthrough was confirmed even at a concentration of 5 mg / cm ³ or more. If the concentration is too high, the hydrophilic PTFE of tartaric acid
This is probably because a weak adhesive force was formed on the filter, and part of the acid had spilled. Therefore, it was confirmed that the optimal concentration of the acid was 1.5 to 15 mg / cm ³ .

Example 2 Ammonia recovery test with water Disposable cartridge (cartridge 3 in FIG. 1)
Was washed with 5 ml of methanol and then passed through 1 ml of a methanolic tartaric acid solution to prepare a hydrophilic PTFE filter cartridge containing 2 mg / cm ³ of tartaric acid. Drying was performed for 30 minutes using a vacuum pump to remove methanol. 40 μl of standard ammonia in glass wool 7
And assembled as shown in FIG. 4, and the air was sucked in at 2 (l / min) for 150 minutes.

Thereafter, 1 ml of pure water was injected into the cartridge, and extracted three times.

As a standard, three samples were prepared by directly adding 40 μl of the above ammonia solution to 1 ml of pure water.

Table 1 shows the results of extraction from the first cartridge. In the case of recovery using water, 9
A recovery rate of 9.5 (%) or more was obtained. That is, 2 ml of eluate was sufficient for the introduction into the ion chromatograph, and the concentration could be 50 times or more as compared with the conventional impinger method.

[0049]

[Table 1] Table 1. Ammonia recovery test 1st extraction 1st extraction 2nd extraction 3rd extraction 3rd test 1 94.3% 5.3% 0.4% test 2 95.6% 3.9% 0.5% Example 3 Comparative results with impinger method Tartaric acid Hydrophilic P treated at a concentration of 2.0 mg / cm3
A TFE cartridge (corresponding to the cartridge 3 in FIG. 1) was used as a collecting agent. Using an air collecting pump, the air was collected at a flow rate of 1.1 (l / min) for 120 minutes. After sampling, 1 ml of a 2 mg / ml NBD-F / borate buffer (pH 8.52) solution was added from the collecting agent, an internal standard (5 μl of butylamine) was added, and the mixture was heated at 60 ° C. for 15 minutes. Methylpropanolamine was similarly reacted and subjected to HPLC measurement to obtain a calibration curve.

Regarding the impinger method, at the same time as the present method, 140 ml of pure water and 1 l of air were sucked into the atmosphere at a rate of 2 l / min.
Collected for 20 minutes. Thereafter, measurement was performed by ion chromatography, and the results are shown in Table 2.

[0051]

[Table 2] Table 2. Clean room sampling result ( airborne ppb) location Integrated flow rate (l) Methylpropanolamine Ammonia main method Inbinja method Main method Impinger method clean room A 203 16.7 13.0 8.0 8.1 Clean room B 114 1.0 0.87 1.3 1.4 As described above, when the actual measurement was performed in a clean room,
Compared with the result of the impinger method performed at the same time, the measured values were almost the same. When a hydrophilic PTFE cartridge is used, the blank value is sufficiently low for both ammonia and methylpropanolamine, and can be measured at the lower detection limits of 0.06 and 0.07 (airborne ppb) by using ion chromatography. Was.

The collecting agent of this example can be produced by a simple operation, and is small in size and easy to carry and handle as compared with the impinger method. In addition, since extraction can be performed with a small amount of pure water, the concentration time for IC measurement can be reduced. In this example,
Since volatile ammonia and amines are collected in a state where an acid and a salt are formed on the filter 1 or the tube surface (the inner tube 6), they are stable even during long-term storage, and can be transported over long distances without any problem. . In addition, since the collected ammonia and amines can be extracted with an organic solvent such as methanol, not only the ion chromatography method,
This is a pretreatment method capable of performing various types of analysis such as HPLC and GC.

[0053]

As described above in detail, according to the present invention, the surface of the hydrophilized fluororesin support is 1.5 to 15 mg / cm per unit volume of the fluororesin support.
By using a collecting agent formed by forming an acidic layer formed at a density of ³ , a basic compound contained in a gas such as the atmosphere can be efficiently collected in a form suitable for analysis, and It can be concentrated to a concentration and is most suitable for highly sensitive analysis of basic compounds. For this reason, it is effective in environmental management such as indoors, outdoors, and clean rooms. In particular, since the environmental management of ammonia and amines in a clean room can be improved, the yield of semiconductor manufacturing processes such as resist processing can be improved, and it can contribute to the manufacture of high-quality semiconductors. Further, since the collecting device in which the above-described collecting agent is mounted on the cartridge is small, it is possible to easily analyze ammonia and amines generated from component materials in a small box.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a first embodiment of a collecting device of the present invention.

FIG. 2 is an explanatory diagram showing an analysis procedure using the collection device shown in FIG.

FIG. 3 is a perspective view showing a collection device according to a second embodiment of the present invention.

FIG. 4 is a diagram illustrating a collection test method using the collection device shown in FIG.

FIG. 5 is a graph showing the relationship between the concentration of tartaric acid formed on the surface of the filter shown in FIG. 1 and the recovery rate of ammonia.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Filter 2 Filter support 3 Cartridge 5 Inner tube 6 Outer tube 7 Glass wool 31 Inlet 32 Outlet

Claims (5)

[Claims] 1. A fluororesin support having been subjected to a hydrophilic treatment, and an acid layer formed on the surface of the fluororesin support at a density of 1.5 to 15 mg / cm ³ per unit volume of the fluororesin support. A collector. 2. The fluororesin support unit by passing or dropping an acid solution having a predetermined concentration through the fluororesin support, or immersing the support in the acid solution, and then removing the solvent. 1.5 to 15 mg / cm ³ per volume
2. The method for producing a collector according to claim 1, wherein the acid is attached. 3. A fluororesin support subjected to a hydrophilic treatment, and an acid formed at a density of 1.5 to 15 mg / cm ³ per unit volume of the fluororesin support formed on the surface of the fluororesin support. A collecting device comprising: a layer; and a case having the fluororesin support mounted inside, and a case having a suction port and a discharge port through which gas or liquid flows in and out. 4. A step of attaching the fluororesin support to the case; a step of flowing an acid solution into the case; and drying the fluororesin support after the flow of the acid solution together with the case under reduced pressure. Then, 1.5 to 1 per unit volume of the fluororesin support on the surface of the fluororesin support.
Forming the acidic layer formed at a density of 5 mg / cm ³ . 5. An inner tube made of a fluororesin which has been subjected to a hydrophilic treatment, and a density of 1.5 to 15 mg / cm ³ per unit volume of the inner tube made of the fluororesin formed on the surface of the inner tube made of the fluororesin. A collecting device, comprising: an acidic layer formed by the method described above; and an outer tube having both ends opened with the inner tube made of the fluororesin mounted therein.