KR100231124B1 - An Entraping Agent for Amines, An Entraping Apparatus for Amines and Method for Entraping and Analysing of Amines - Google Patents

Abstract

The present invention is a collection agent that can easily collect and analyze amines such as primary amines, secondary amines, ammonia, and the like contained in the atmosphere, and a collection device using the same, and further, the collected amines can be analyzed quickly and with high sensitivity. It provides a way to do it.

The amine collecting agent 2 is filled into the collecting tube 1, the air is brought into contact with the amine collecting agent 2 by sucking the air with the suction pump 4, and the amines in the air are collected, followed by fluorescence detection. For fluorescence detection, amines in the gas are collected as derivatives of the labeling agent by using a collecting agent in which solid particles are coated with an amine fluorescent labeling agent.

Description

An Entrapping Agent for Amines, An Entraping Apparatus for Amines and Method for Entraping and Analysing of Amines}

TECHNICAL FIELD The present invention relates to an analysis method for trace impurities gas contained in a gas such as air, in particular, a collecting agent for amines in the atmosphere, a collecting device for amines, and a method for collecting and analyzing the amines.

Ammonia and amines present in the atmosphere are one of the typical off-flavor substances, and the smell is known as the decaying odor of fresh fish. The odor of amines generated in fish bone treatment plants, chemical plants, etc. is a serious problem and it is desired to purify the environmental atmosphere. For this purpose, it is necessary to establish a method for collecting ammonia and amines in the atmosphere.

On the other hand, in the ultra LSI manufacturing process, it is essential to establish a management analysis technique for impurity gas in the clean room. In the analysis of inorganic ions, a method of collecting ionic components in the air in ultrapure water with an impinger or the like and detecting them by ion chromatography (IC) is used.

However, it has recently been found that contamination by extremely small amounts of organic matter in the atmosphere, which has not been considered as important until now, causes various defects in semiconductor devices and lowered yields of ultra-LSI manufacturing processes. The sensitivity of the level came to be desired. In particular, it has been found that amines such as ammonia, alkanolamines, aliphatic amines, and aromatic amines, which are organic ionic compounds, are highly reactive and cause defects such as obstacles to resist hardening in the lithography process. It is becoming particularly important.

It is thought that ammonia in the clean room is caused by external air, wafer cleaning liquid, CVD raw material gas, etc.Aminees are contained in the additives of boiler water in the clean room, and the components produced by the human body (especially exhaled breath) are trace gases. It has been found to be a factor in the yield drop of the process.

Conventionally, as a collection method of ammonia and amines, an impinger pure water collection method or a room absorption method for allowing air to pass through a sulfuric acid-coated place has been used for analysis. However, both of them have a problem in that instant sampling cannot be performed.

In addition, in the impinger method, it is difficult to concentrate because ultrapure water is used in a large amount of 100 ml or more in order to increase the collection efficiency. In addition, since the absorption method is also taken out from the filter holder after collection, the filter is placed in a beaker, soaked in a solvent, extracted, and subjected to an analysis device. Therefore, there is a problem as a high sensitivity detection method of trace impurities gas due to contamination from air or a container during operation.

Conventionally, ion chromatography method (IC method) and gas chromatography microanalysis method (GC-MS method) have been used for the analysis of amines as well as inorganic ions. However, IC method has a drawback that amines having 3 or more carbon atoms cannot be measured. . Moreover, since amine has strong adsorption characteristic to a column, it is not preferable because there exists a problem, such as tailing, by GC-MS method.

Moreover, although it is a collection method of ammonia and amines which have objectives other than an analysis, the chemical filter only for the purpose of air cleaning is known. This is to obtain clean air by collecting air of ammonia and amines by passing air through a place where phosphoric acid is coated. However, a collection method using a chemical filter has problems such as a short collection life, indeterminate replacement time, and high pump load, which consumes power.

The present invention provides a collecting agent capable of easily collecting and analyzing amines contained in a gas such as air, a collecting device using the same, and a method for quickly and sensitively analyzing the amines collected in the collecting agent by the collecting device. The purpose is to provide.

BRIEF DESCRIPTION OF THE DRAWINGS It is one specific example which showed the amine collection apparatus using the collection tube which concerns on 1st Embodiment of this invention.

Fig. 2 is a specific example showing a collecting device using thin layer chromatography according to a second embodiment of the present invention.

FIG. 3 is an explanatory view showing one specific example in the case of developing and concentrating the amine fluorescent labeling agent derivative collected from the substrate shown in FIG. 2.

4 is a schematic view of an amine collection device according to a third embodiment of the present invention.

5 is a schematic view of an amine collection device according to a fourth embodiment of the present invention.

6 is a schematic view of another amine collection device according to a fourth embodiment of the present invention.

7 is a schematic diagram of an air cleaning apparatus according to a fifth embodiment of the present invention.

8 is a chromatogram of standard amines isolated and analyzed by the method of the first embodiment of the present invention.

Fig. 9 is a chromatogram of amines in the atmosphere of a smoking room separated and analyzed by the method of the first embodiment of the present invention.

10 is a chromatogram of ammonia and amines in factory air analyzed after being collected by a collecting device according to a third embodiment of the present invention.

11 is a table showing fluorescence intensities of ammonia and amines in factory air collected by the amine collection device according to the fourth embodiment of the present invention.

<Description of the code | symbol about the principal part of drawing>

1: collection tube

2: collection agent

3: filter

4, 45: suction pump

5: collection device

6: layer without addition of labeling agent

7: concentration part

8: deployment tank

9: solvent

11: container

12: Cork

13: entrance

15: magnetic stirrer

16: stirrer

17, 27, 28, 29, 34: amine collection part

26, 46: barrel-shaped container

31: container (sample bottle)

32: atmospheric air introduction pipe to be measured

33: atmospheric exhaust pipe to be measured

35: container cover

41: rotating body

42: description

43: aqueous solution of acid (or alcohol solution of acid)

44: dryer

47: pH meter

In order to achieve the above object, the present inventors have diligently researched that the amine collecting agent coated with an amine fluorescent labeling agent on solid materials such as silica and alumina and the collecting device using the same collect amines with high efficiency. It was found that amines can be analyzed quickly by fluorescence detection of amines collected in the agent.

That is, the first feature of the present invention is obtained by coating an amine fluorescent labeling agent on at least a part of a solid material, and collecting amines selected from primary amines, secondary amines and ammonia contained in the gas as fluorescent labeling agent derivatives. An amine collecting agent and a collecting device using this collecting agent. In the present invention, primary amine, secondary amine and ammonia are collectively referred to as amines.

As a solid material used when preparing the collecting agent according to the first aspect of the present invention, inorganic and organic substances which are inert to the reaction of fluorescent labeling agents and amines may be used. As the shape, a particulate or fibrous, mesh, foam, or nonwoven solid having a large surface area is suitable. As the fibrous or nonwoven solid, one made of fiber by mixing silica gel with metal aluminum, or one made of fiber by mixing silica gel with pellet polyester can be used to increase the surface area.

In addition, the surface areas of cellulose, cellulose mixed esters, polyvinylidenediprolide (hydrophilic and hydrophobic), polytetrafluoroethylene (hydrophobic and hydrophilic), glass fibers, nickel and stainless fibers, which are used here, are expanded by etching. It may be. You may weave these fibers in mesh shape.

The method of coating the amine fluorescent labeling agent on a solid phase material is immersed in a weakly alkaline buffered solution of the labeling agent, or after the buffer solution of the labeling agent is passed through or dipped into the solid phase material, It is common to remove the solvent by drying the material.

The reason why the weak alkaline buffer is used is that there are many acidic substances such as SOx or NOx in the air.

In general, since the fluorescent labeling reaction proceeds under weak alkalinity, when the collecting agent is changed to acidic by an acidic substance in the atmosphere, the labeling reaction does not proceed and cannot be collected. In addition, as shown in FIG. 12, since the reaction rate of the labeling reaction changes with the pH at the time of the reaction, when an alkaline substance such as sodium hydroxide is used without using a buffer, quantification becomes difficult after collection. Therefore, the use of a buffer that can suppress the pH change to a minimum is desirable.

As described above, the amine collecting agent which is the first characteristic of the present invention can be produced, and the amines that can be collected by the collecting agent are primary amine, secondary amine and ammonia. Of course, amines may be a liquid or a solid at normal temperature and normal pressure, and may be a amine which has a vapor pressure in a gas, or a mist phase.

The amine collecting agent which is the 1st characteristic of this invention is filled in the inside of the collection pipe (collection part) 1 more specifically as shown in FIG. 1, and this collection pipe is filled with a suction pump, an axial flow duct fan, a sirocco fan, etc. It is preferable that the suction unit 4 is sucked by the suction means 4, and the atmosphere to be measured is passed through the collecting agent 2 in contact with the collecting agent 2 to obtain an amine collecting device.

Moreover, you may make an amine collector a thin layer form. For example, the particulate collecting agent 2 is coated on a glass substrate in a thin layer to form a collecting substrate. In addition, when using a plate for thin layer chromatography, as shown in Fig. 2, a fluorescent labeling agent solution adjusted to weak alkali by a buffer solution is added dropwise onto the plate (5), dried to remove the solvent to remove the amine collector (2). ) May be used. The shape of the thin film may be any shape other than that shown in Fig. 2 in particular.

Further, the filter paper may be immersed in the fluorescent labeling solution, then spread over a substrate, dried, and the solvent may be removed to form an amine collection device.

When such a thin layer collecting device is left in the atmosphere to be measured, the amines in the air come into contact with the collecting substrate by natural airflow, and are collected to form a derivative of the amine fluorescent labeling agent.

That is, the amine collecting agent which is the 1st characteristic of this invention, and the collection apparatus using the same can collect | recover easily the amine contained in gas, such as air | atmosphere, as a derivative of the said fluorescent labeling agent.

Ammonia, methylamine, and the like are dissolved in water, but because of their high volatility, they are not perfect even if they can be collected in ultrapure water with a conventional impinger. However, in the present invention, since these amines immediately react with the labeling agent on the collecting agent to form a derivative having a large molecular weight, the amines can be collected completely without fear of revolving. In addition, the fluorescence of amines derivatized with the labeling agent according to the present invention is very strong and is suitable for high sensitivity detection.

As an analysis method of this derivative | guide_body, fluorescence detection may be carried out by irradiating an ultraviolet-ray directly, it may extract with a solvent, and fluorescence detection may be carried out. Formation of the amine derivative causes fluorescence. Since the fluorescent labeling agent itself does not have fluorescence, the amine can be quantified by measuring the fluorescence intensity of the whole. Although molar fluorescence intensity differs with each amine, there is no big difference, For example, what is necessary is just to calculate it as "methylamine conversion value" based on the analytical curve of typical amines, such as methylamine. However, since the background fluorescence of the decomposition product derived from the reagent may be seen, it is necessary to make the same collecting device that does not reach the non-measured atmosphere, use it as a blank, subtract the value, and quantify it.

In addition, after extraction with a solvent, separation may be performed by high performance liquid chromatography (HPLC), followed by fluorescence detection for analysis. Using this method, accurate quantification of each amine can be performed.

In addition, when using the thin plate chromatography plate like FIG. 2, as shown in FIG. 3, the lower part 6 of the collection board | substrate 5 is placed in the development tank 8 in which the solvent 9 entered in the bottom. The derivative may be developed and concentrated by immersion, capillary action, and may be directly detected by fluorescence, or the concentrated part may be extracted with a solvent and subjected to fluorescence detection.

These thin-layered amine collectors are 0.01-1 mm in thickness normally. This is because if the layer is too thick, the reagent blank value becomes high by using an excess of a fluorescent labeling solution.

In these thin-layer collection agents, glass, metals, such as aluminum, plastics, such as polyethylene and a polypropylene, etc. can be used.

In addition, you may use the amine collecting agent which is a 1st characteristic of this invention for the collection part of the collection apparatus shown to FIG. 4, FIG. 5, and FIG.

After collecting the amine-containing gas through a collecting tube filled with the collecting agent described in the first aspect, the UV-excited light such as an Xe lamp or an Ar laser beam is irradiated to the gas inlet of the collecting tube. By measuring the fluorescence detection width from the amine concentration in the gas can be measured. In this case, as the material of the tube of the fluorescence detection portion, it is preferable to use a material of ultraviolet transmissionless fluorescence such as quartz glass, sapphire or quartz.

As described above, the first amine collecting agent and the amine collecting device using the same collect efficiently primary amines, secondary amines and ammonia contained in gas such as air, and are easily used as derivatives of fluorescent labeling agents. Can be captured. In addition, amines having 3 or more carbon atoms that could not be analyzed by the IC method can be analyzed with high sensitivity. The analysis method of the first aspect of the present invention is particularly effective for environmental management of indoors, outdoors, clean rooms and the like.

The second aspect of the present invention is characterized by comprising at least a container through which the atmosphere to be measured is accommodated or passed through, and an amine collection unit provided in a part of the container, and the inside of the container is treated to prevent adsorption of amines. It is a collecting device.

As this amine collecting part, you may use the amine collecting agent which coat | covered the fluorescent labeling agent which is the 1st characteristic of this invention, or the amine collecting agent which coated the acid with low volatility. Moreover, you may use reaction reagents, such as alkyl halides which react with amines and make a nonvolatile substance at normal temperature, or the indicator which reacts and colors with an amine like a pH indicator.

As the shape of the apparatus, for example, as shown in Figs. 4, 5 and 6, the containers 11, 26, 31 for accommodating or passing through the atmosphere to be measured and the amine collecting portions provided in a part of the container are shown. It is preferable to set it as the amine collection apparatus which consists of (17, 27, 28, 29, 34). In FIGS. 4 and 5, the containers 11 and 26 and the internal parts 16 and 32 are treated so that amines are not adsorbed by surface treatment such as alkali coating. In FIG. 4, after accommodating air | atmosphere to be measured, the air | atmosphere inside is stirred by the stirrer 16 etc., and amines are collected in the amine collection part 17. In FIG. In FIG. 5 and FIG. 6, the atmosphere to be measured is directly stratified to the amine collecting units 27, 28, 29, and 34 so as to be collected by the amine collecting units 27, 28, 29, and 34. FIG.

After collection, the amine collection units 1, 17, 27, 28, 29, and 34 can be removed, eluted with the addition of a solvent, and injected easily into an analytical device such as IC, HPLC, GC, or the like. In addition, the coloration of the collection parts 1, 17, 27, 26, 29, 34 may be confirmed as it is, or the light may be quantified by measuring the fluorescence or UV absorption by irradiating light such as ultraviolet rays.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described with reference to drawings. 1 shows an example of a collecting device and a collecting method of amines in a gas according to a first embodiment of the present invention. In FIG. 1, the collecting pipe 1 is filled with a collecting agent 2, and a polyethylene filter 3 having a pore diameter of 20 μm is provided at the inlet and the outlet. The collecting tube 1 has a cylindrical shape of 0.5 to 1.5 cm in diameter and 0.5 to 2 cm in length, or has a rectangular cross-sectional shape of 0.5 to 1.5 cm in one side, and has a rectangular shape of 0.5 to 2 cm in length. desirable. It is preferable that the trapping agent 2 enters about 10 to 400 mg and the exhaust conductance does not become too small. By connecting this collection pipe 1 to the suction pump 4 which is a suction means, and driving the suction pump 4, it contacts with the collection agent 2, air | atmosphere passes, and amines in a gas collect | collect in the collection pipe 1 It is collected in the second (2). As the suction means, a fan such as an axial duct fan or a sirocco fan may be used in addition to the suction pump, or a pressure difference may be provided and sucked by any method.

As a solid substance used when manufacturing the collecting agent 2 used for 1st Embodiment of this invention, the inorganic substance and organic substance which are inert to the reaction of a fluorescent labeling agent and ammonia-amines can be used. As the shape, a particulate or fibrous, mesh, foam, or nonwoven solid having a large surface area is suitable. In order to increase the surface area, the fibrous or nonwoven solid is preferably made of fiber by mixing silica gel with metallic aluminum, or made of fiber by mixing silica gel with pellet polyester. In addition, the surface area of cellulose, cellulose, mixed esters, polyvinylidenediprolide (hydrophilic and hydrophobic), polytetrafluoroethylene (hydrophobic and hydrophilic), glass fibers, activated carbon fibers or nickel or stainless fibers, which are used here, are etched. It may be widened by operation. Moreover, you may weave these fibers in mesh shape. As a foam-like solid, what mixed and foamed silica gel in nickel and titanium can be considered.

As the particulate inorganic substance used as the solid substance, for example, particles containing silica (SiO ₂ ) or alumina (Al ₂ O ₃ ) as essential components can be used. As the particulate organic substance, for example, olefin resin such as polyolefin resin such as polyethylene or polypropylene, styrene resin such as polystyrene, styrene-divinylbenzene copolymer, or fluorine resin particles such as polytetrafluoroethylene may be used as the particulate collector. It can be used as a solid phase material. As a solid containing silica or alumina as an essential component, silica, silica gel, magnesium silicate (MgO · nSiO ₂ ), alumina, silica alumina, or the like can be used. Among these, magnesium silicate is particularly preferable when used alone. These solid particles usually have a particle diameter of 1 to 500 µm, and particularly preferably inorganic solid particles having a pore diameter of 3 to 50 nm and a specific surface area of 100 to 1000 m ² / g.

In addition, it is preferable to use the thing based on a silica which the substituted silyl group couple | bonded with the surface. It is because substituted silyl group bond solid particle has the advantage of promoting reaction with amines. Substituted silyl groups include cyanopropylsilyl [-Si (CH ₃ ) (CH ₂ ) ₃ CN] (CN), octadecylsilyl [-Si (CH ₃ ) ₂ C ₁₈ H ₃₇ ] (ODS), propyloxypropanediol Silyl [-Si (CH ₂ ) ₃ OCH ₂ CH (OH) CH ₂ OH] (diol), t-octadecylsilyl [-SiC ₁₈ H ₃₇ ], octylsilyl [-Si (CH ₃ ) ₂ C ₈ H ₁₇ ] (CS), ethylsilyl [-SiC ₂ H ₅ ], phenylsilyl [-Si (CH ₃ ) ₂ C ₈ H ₅ ] (phenyl) and the like. Among these, CN, ODS, phenyl, especially CN desirable. However, since the normal phase distribution type such as diol (OH) attached to an adsorber with strong amine adsorption capacity or silica gel particles without surface treatment itself is too strong for amine adsorption, the recovery rate is low at the time of quantitative analysis extracted with a solvent, which is not preferable. .

Amine fluorescent labeling agents do not fluoresce the labeling agent itself, but react with primary or secondary amines or ammonia to give strong fluorescence, for example 4-chloro-7-nitro-2,1,3-bene Oxadiazole (NBD-Cl), 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F), 4- (N, N-dimethylaminosulfonyl) -7-fluoro Rho-2,1,3-benzoxadiazole (DBD-F), 4- (N, N-dimethylaminosulfonyl) -7-chloro-2,1,3-benzoxadiazole (DBD-Cl) , o-phthalaldehyde (OPA), 5-dimethylaminonaphthalene-1-sulfonylchloride (DNS-Cl), 4-bromo-7-nitro-2,1,3-benzoxadiazole (NBD-Br) , Ammonium-7-fluoro-2,1,3-benzoxadiazole-4-sulfonate (SBD-F), 4- (aminosulfonyl) -7-fluoro-2,1,3-benzone company Diazole (ABD-F), 4- (chlorosulfonyl) -7-fluoro-2,1,3-benzoxadiazole (CBD-F), 4- (fluorosulfonyl) -7-phenoxy -2,1,3-benzoxadiazole (PBD-SO ₂ F), 4- (fluorosulfonyl) -7-benzooxy-2,1,3-benzoxadiazole (BBD-SO ₂ F) , 2,3-naphthalenedialdehyde (NDA), 3- (2-proyl) quinoline-2-aldehyde, fluoresamine, 9-fluorenylmethylchloroformate (FMOC-Cl), 2- (1- Pyrenyl) ethylchloroformate, 3,4-dihydro-6,7-dimethoxy-4-methyl-3-oxaquinoxaline-2-carbonylchloride, 6-methoxy-2-methylsulfonylquinoline- 4-carbonyl chloride, 7-dimethylaminocoumarin-3-carbonyl chloride and the like can be used, among which NBD-F and NBD-Cl, particularly NBD-F, which have a fast reaction and have a high fluorescence intensity are preferable.

In the first embodiment of the present invention, a boric acid buffer or the like can be used as a buffer having a pH of 7.5 to 9.5 used with a fluorescent labeling agent. The boric acid buffer can be prepared by slowly adding a sodium hydroxide / methanol solution to the boric acid / methanol solution. Other buffers may include boric acid / sodium hydroxide buffers, sodium tetraborate-hydrochloric acid buffers, potassium dihydrogen phosphate-sodium hydroxide buffers, and the like. An acid such as boric acid to be used may be a reagent having a grade of "above amino acid analysis" that does not contain an amine as an impurity.

Usually, the amine fluorescent labeling agent is adjusted to a concentration of 0.5 to 2.0 (mg / ml) in a buffer solution having a concentration of 0.1 to 1.0 M. It is also effective to add a lubricant such as 0.1 to 1.0% glycerin to the solution to enhance the coating power of the fluorescent labeling agent on the solid substance.

The solid solution described above is immersed in the solution thus prepared, or the solution is dipped or dipped into the solid material, the solid material is placed in a desiccator or the like, depressurized by a vacuum pump, and the solvent is removed and dried. Amine collectors are prepared.

Solvents that may be used when the amine fluorescent labeling agent is coated on a solid material include methanol, ethanol, isopropanol, n-propanol, acetone, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, carbon tetrachloride, chloroform, dichloromethane, dichloroethane , Water and the like.

In addition, in the first embodiment of the present invention, in order to perform qualitative and quantitative analysis of amines, suction with a non-measured atmosphere is carried out using a suction pump 4 in a tube 1 filled with an amine collecting agent 2. And collecting amines, irradiating ultraviolet light directly to the collecting agent to detect fluorescence, and flowing a solvent or a supercritical fluid into the collecting agent, extracting an amine fluorescent labeling derivative, and measuring the fluorescence intensity of the solution. have.

When fluorescence is detected by directly irradiating ultraviolet rays, quartz glass, sapphire, and crystal which are optically transmissive to the excitation wavelength and the fluorescence wavelength may be used as part of the tube. That is, the collecting agent 2 gradually changes from the vicinity of the gas inlet of the collecting tube 1 toward the gas outlet toward the fluorescent labeling derivative, and the collecting agent of the changed portion is excited by Xe lamp or Ar laser light outside the collecting tube. Foot. Therefore, the amine concentration can be measured by measuring the width of fluorescence from the inlet of the collecting tube 1.

In the case of extracting with a solvent or a supercritical fluid, the fluorescence of the solution may be similarly measured. Alternatively, the fluorescence can be detected after separation using liquid chromatography or supercritical fluid chromatography. Separation allows qualitative and accurate quantitative analysis of each amine. Examples of the chromatography that can be used include column chromatography, thin layer chromatography, and the like, and high-speed liquid chromatography (HPLC) is particularly preferable because it has high resolution.

The amines that can be collected by the first embodiment of the present invention are primary amines, secondary amines and ammonia. These amines may be liquid or solid at normal temperature and pressure, and may be vaporized or gaseous amines in gas. Examples of the primary amines include alicyclic groups such as unsaturated aliphatic primary amines such as methyl amine, ethyl amine, isopropyl amine, propyl amine, butyl amine and 2-aminoethanol, and allyl amine, and aliphatic primary amines and cyclopropyl amine. Aromatic primary amines, such as a primary amine and aniline, are mentioned, As a secondary amine, Unsaturated aliphatic secondary amines, such as saturated aliphatic secondary amines, such as dimethylamine, diethylamine, and diisopropylamine, and diallylamine, are mentioned. And aromatic secondary amines such as methyl aniline and the like.

As described above, the collecting agent and the collecting device of the first embodiment of the present invention can efficiently collect the primary amine, the secondary amine and the ammonia in the gas to make derivatives of the amine fluorescent labeling agents. Can be analyzed quickly and with high sensitivity. That is, according to the first embodiment of the present invention, it is possible to detect high sensitivity of amines at the sub ppb level in the air regardless of the carbon number.

Fig. 2 shows a schematic diagram of the amine collection device according to the second embodiment of the present invention, and is an example in the case of using thin layer chromatography (TLC). In the case of using a plate for TLC, as shown in Fig. 2, a fluorescent labeling agent solution adjusted to weak alkali by a buffer solution is added dropwise onto the plate 5 and dried to remove the solvent to form an amine-type collecting agent (2). Is common. The shape of the thin layer may be any shape other than that shown in Fig. 2 in particular.

The size of the collecting substrate 5 may be, for example, 10 to 20 cm on one side. Also, reference numeral 7 denotes a portion where the derivative of the fluorescent labeling agent is concentrated. The dimension of the concentrating part 7 may be 1 cm x 1 cm, for example. Reference numeral 6 in FIG. 2 indicates a portion where the amine fluorescent labeling agent is not coated.

When using commercially available thin film chromatography, the plate may be washed well with a solvent and then immersed in a fluorescent labeling agent solution, or a fluorescent labeling agent solution may be added dropwise to coat it. Then, it puts in a desiccator, removes a solution by drying under reduced pressure with a vacuum pump, and uses it as a collection apparatus.

When thin layer chromatography is not used, the particulate matter collecting agent 2 may be coated with a thin layer on the substrate to form a collecting substrate. Further, the immersion may be immersed in the fluorescent labeling agent solution, spread on a substrate, dried, and the solution may be removed to form an amine collection device.

Such thin amine scavengers usually have a thickness of 0.01 to 1 mm. This is because when the layer is too thick, an excess of a fluorescent labeling solution is used, resulting in a high reagent blank. In these thin-layer collection agents, glass, metals, such as aluminum, plastics, such as polyethylene and a polypropylene, etc. can be used.

As a solid substance used when adjusting these trapping agents, it is preferable to use the inorganic substance and organic substance which are inert in reaction with a fluorescent labeling agent and amines similarly to a 1st actual form. As the shape, a particulate or fibrous, mesh, foam, or nonwoven solid having a large surface area is suitable. In the amine fluorescent labeling agent, as in the first embodiment of the present invention, the labeling agent itself does not have fluorescence but reacts with primary or secondary amines or ammonia to give strong fluorescence, for example, NBD-Cl, NBD-F , DBD-F, DBD-Cl. OPA, DNS-Cl, NBD-Br, SBD-F, ABD-F, CBD-F, PBD-SO ₂ F, BBD-SO ₂ F, NDA, 3- (2-proyl) quinoline-2-aldehyde, Fluoresamine, FMOC-Cl, 2- (1-pyrenyl) ethylchloroformate, 3,4-dihydro-6,7-dimethoxy-4-methyl-3-oxaquinoxaline-2-carbonylchloride , 6-methoxy-2-methylsulfonylquinoline-4-carbonyl chloride, 7-dimethylaminocoumarin-3-carbonyl chloride, and the like. Among these, NBD-F and fast reaction and very high fluorescence intensity can be used. Preference is given to NBD-Cl, in particular NBD-F. Solvents that may be used when the amine fluorescent labeling agent is coated with a solid material include methanol, ethanol, isopropanol, n-propanol, acetone, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, carbon tetrachloride, chloroform, dichloromethane, dichloroethane Etc. may be used.

When the collecting device of FIG. 2 is left in the atmosphere to be measured, the amines in the air are brought into contact with the collecting substrate by natural airflow and are collected to form a derivative of the amine fluorescent labeling agent.

As an analysis method of this derivative, fluorescence detection may be performed by directly irradiating ultraviolet rays onto the collecting agent substrate, or fluorescence detection may be performed by extraction with a solvent. When the amine derivative is formed, the fluorescence is emitted. Since the fluorescent labeling agent itself does not have fluorescence, the fluorine can be quantified by measuring the total fluorescence intensity.

In addition, when using the thin plate chromatography plate like FIG. 2, as shown in FIG. 3, the lower part 6 of the collection board | substrate 5 is placed in the development tank 8 in which the solvent 9 entered in the bottom. The derivatives may be developed and concentrated by immersion, capillary action, fluorescence extraction may be performed directly, or the concentration may be extracted with a solvent to detect fluorescence.

Moreover, after extraction with a solvent, you may isolate | separate by HPLC, and may perform fluorescence detection and analysis. This method allows accurate quantification of amines.

As a solvent used when eluting this derivative, it can select suitably from the solvent which can be used when coating said amine fluorescent labeling agent with a solid substance. The derivative may be eluted with a supercritical fluid, but carbon dioxide is suitable as the supercritical fluid, and the solvent may be added as a modifier.

According to the second embodiment of the present invention, amines contained in a gas such as air can be easily collected as a derivative of the fluorescent labeling agent. Ammonia and methylamine are soluble in water but highly volatile. In the second embodiment of the present invention, these amines immediately react with the labeling agent on the collecting agent particles to form a derivative having a large molecular weight, and thus can be completely collected without fear of revolving. In addition, according to the second embodiment of the present invention, the fluorescence of the amines labeled with the labeling agent is very strong, and is suitable for high sensitivity detection of amines having a large number of carbon atoms. The high carbon number amines include primary amines, secondary amines and ammonia. Examples of the primary amines include alicyclic groups such as unsaturated aliphatic primary amines such as methyl amine, ethyl amine, isopropyl amine, propyl amine, butyl amine and 2-aminoethanol, and allyl amine, and aliphatic primary amines and cyclopropyl amine. Aromatic primary amines, such as primary amine and aniline, are unsaturated aliphatic secondary amines, such as saturated aliphatic secondary amines, such as dimethylamine, diethylamine, and diisopropylamine, and diallylamine, and methyl Aromatic secondary amines, such as aniline, etc. are mentioned.

The amine collection apparatus which concerns on 3rd embodiment of this invention was shown in FIG. In FIG. 4, the container 11 is a spherical container with a flat bottom, an inlet 13 through which a coke 12 for connecting with a vacuum pump is connected to the top, and an amine collecting part 17 composed of an ammonia-amine collecting agent at its tip. ) Is provided. The inner wall of the container 11 is alkali-coated so as not to adsorb ammonia and amines. And the stirrer 16 which processed the alkali coating is put in the inner wall so that a wind may flow up. The air inside the coke 12 is discharged using a vacuum pump to be in a reduced pressure state and the coke 12 is blocked. Thereafter, by opening the coke 12 at the place to be sampled, the atmosphere to be measured is placed in the container 11, and the coke 12 is closed again and sealed. After that, when the stirrer 16 is rotated using the magnetic stirrer 15 from the outside, the gas inside moves violently up and down. Even if it collides with an alkali-coated container or part, since ammonia and amines are weakly alkaline, there is no fear of adsorption. All ammonia and amines in the atmosphere to be measured are collected by the ammonia and amine collecting agent inside the stopper. Then, the inlet 13 which attached the amine collection part 17 to the front end was opened, the collection body was collect | recovered, a solvent etc. were added to the ammonia amine collected by the collection agent, and eluted, ion chromatography (IC), high speed It can be easily analyzed by injecting directly into an analytical device such as liquid chromatography (HPLC) or gas chromatography (GC).

As the material of the container 11 of the third embodiment of the present invention, inorganic materials such as metals such as SUS, copper, aluminum, glass, etc. which are inert to the reaction with amines, do not pass gas and liquid, and endure pneumatics, polyethylene, poly Polyolefin resins such as propylene, styrene resins, polyacrylic acid esters, or polytetrafluoroethylene-based fluorine resins. A portion such as a chromium nickel oxide film may be formed in a portion which is in contact with the atmosphere to be measured, and an inactivation treatment may be performed. In the case of polyethylene, polypropylene, polytetrafluoroethylene, or the like having high water repellency, the portion contacting the atmosphere to be measured may be treated in the form of particles, fibrous or nonwoven fabrics, meshes, or foams having a large surface area as in the amine collecting portion. .

As a treatment for preventing ammonia and amines from adsorbing on the inner wall of the container 11, the container 11 may be heated in addition to the alkali coating. The heating is weak in the case of a strong amine adsorption force such as glass or a resin having a poor thermal conductivity, but is effective in the case of using a metal container or part such as aluminum, copper, or SUS. Since ammonia and amine can be desorbed at the same time as water, the heating temperature is preferably 100 to 200 degrees. If more than that, the amine may be decomposed.

As the alkali coating the inner wall of the container 11, strong alkalis such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, calcium carbonate and magnesium carbonate are suitable. If strong alkali is present, the ammonia and amines are weakly alkaline, so they are not adsorbed at all and there is no fear of container adsorption. Alkali coating is generally a method of passing an alkali solution on the surface of a passage part, or immersing it in a solution, dropping the solution, flushing the solution, and then drying to remove the solvent.

Examples of the solvent that can be used when the alkali is coated on the inner wall of the container 11 include methanol, ethanol, water and the like. In the case of potassium hydroxide, since boiling point is low, methanol is optimal. In the case of other alkalis, water with high solubility is suitable. In addition, the addition of a lubricant such as glycerin or a highly viscous material such as water glass can prevent the surface water repellency.

As the ammonia-amines collector used in the amine collecting unit 17 of the third embodiment of the present invention, the solid substance described in the first embodiment is coated with the amine fluorescent labeling agent to react with amine or ammonia to emit strong fluorescence. You may use the made amine collector. For example, NBD-Cl, NBD-F, DBD-F, DBD-Cl, OPA, DNS-Cl, NBD-Br, SBD-F, ABD-F, CBD-F, PBD-SO ₂ F, BBD- SO ₂ F, NDA, fluoresamine, FMOC-Cl and the like may be coated on a solid material. Among them, NBD-F having a high fluorescence intensity and fast reaction is particularly preferable. When the fluorescent labeling agent is coated, fluorescence can be readily analyzed by HPLC or the like.

Coating the NBD-F of the fluorescent labeling agent with a solid material may be carried out by passing a boric acid buffer (pH 8.5) and a methanol solution containing NBD-F through the solid material, or immersing the solid material in the solution, or Is usually added dropwise to the solid material or the solution is sprayed onto the solid material and then dried to remove the solvent. The amines that can be collected in this way are primary and secondary amines and ammonia.

As the solid substance serving as the base material of the collecting agent, as in the first embodiment, it is inert to the reaction with ammonia-amines or collecting reagents, and itself has a weak ammonia-amine adsorption force and has a large surface area, fibrous, nonwoven fabric, and mesh shape. , Inorganic and organic matters on the foam can be used.

In the third embodiment of the present invention, as the ammonia-amine collecting agent 17, an amine collecting agent coated with an acid having a low volatility may be used instead of the fluorescent labeling reagent described in the first embodiment. When this collecting agent is used, fluorescent labeling may be performed after collection, and it can also be analyzed by other methods, such as IC method and GC-MS method.

Acids coated on solid materials include phosphonic acid, phosphoric acid, diphosphoric acid, boric acid, sulfuric acid, perchloric acid, adipic acid, quinalic acid, citric acid, cinnamic acid, succinic acid, oxalic acid, tartaric acid, fumaric acid, maleic acid, malonic acid, mandelic acid, Inorganic acids, such as malic acid, and an organic acid are mentioned. Use of acetic acid, formic acid, hydrochloric acid, etc. having a low melting point is not suitable because the life time of the collecting agent is shortened and air pollution by volatilization in the air may be caused. The method of coating an acid on a solid phase material involves passing the acid solution through the solid phase material, or immersing the solid phase material in the solution, dropping the solution onto the solid phase material, or spraying the solution onto the solid phase material and then drying the solvent. How to remove is common. Solvents that can be used to coat the acid in the collecting part include water, methanol, ethanol, propanol, isopropanol, acetone, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, dichloroethane, and the like. Methanol or acetone is most suitable in that it has a low boiling point. The amines that can be collected by acid are primary to quaternary amines and ammonia.

In addition, when analyzing by GC-MS method, you may collect using benzenesulfonyl chloride (BSC), pentafluoropropionic acid (acylating agent), etc. After the reaction, the solvent can be eluted and used directly in the GC-MS method.

According to the third embodiment of the present invention, it is not necessary to bring a pump, an integrated flow meter, etc. to the sampling site, and there is an advantage that instant sampling can be performed. In addition, you may quantify by measuring the fluorescence and UV absorption by irradiating the amine collection part 17 with light, such as an ultraviolet light from the outside, without performing solvent extraction.

As shown in FIG. 5, the amine collecting device according to the fourth embodiment of the present invention has an amine collecting part 27, 28, 29 provided with a cover so that air does not pass through the end of the bent cylindrical container 26. Is installed, and the atmosphere to be measured passes from one side of the barrel. The amine collecting units 27, 28, 29 are formed by filling a predetermined container with the same ammonia-amine collecting agent as in the first embodiment or by holding a predetermined substrate in a thin layer. According to the fourth embodiment, after collection, ammonia and amine can be extracted with a small amount of solvent, and the cover and the solvent and reagent can be added directly to the collecting agent. Therefore, it is not difficult to operate and contamination can be prevented. There is an advantage.

In FIG. 5, since the linear part 26 of a cylinder is alkali-coated or heated, there is no possibility that ammonia and amines will adsorb | suck. As the suction means for passing the atmosphere to be measured into the cylinder, the pump may be sucked to a predetermined flow rate using a pump. Moreover, you may move with a pressure difference using the container whose pressure is lower than the atmosphere to be measured. The end portions 27, 28, and 29, which are bent portions of the cylinder, have a high probability of collision of gas and are likely to cause convection, and therefore, it is preferable to set an amine collection portion here. The number of the amine collecting units 27, 28, 29 may be selected depending on the flow rate and the effect of the collecting agent, but is not limited to three as shown in FIG.

As shown in Fig. 5, by providing the amine collecting portions 27, 28, and 29 at the bent portion of the pipe, it is possible to easily collect ammonia and amines in the atmosphere under measurement. For example, even if the entire ammonia-amine is not collected in the collecting part 27, it can be fully collected in the collecting part 28 or 29 next. Depending on the flow rate and the thickness of the tube, (28) and (29) do not need to be provided because they can be completely collected in (27), but they may be provided as analytical blanks. In order to allow the atmosphere to be measured to pass through the cylinder, it is a common and easy method to use the suction pump 4 as shown in FIG. 5, but in this case, it is necessary to collect it in consideration of contamination from the pump 4. It must be installed at the back of the unit. Instead of the suction pump, the vessel may be opened using a vessel decompressed with a vacuum pump or the like.

As the ammonia-amines collecting portion used for the amine collecting portions 27, 28, 29, etc. of the fourth embodiment of the present invention, a collecting agent coated with a collecting reagent on a solid substance is the same as in the third embodiment. There are two types of capture reagents. One is an acid and the other is a reaction reagent that reacts with ammonia or amine to make the ammonia or amine a nonvolatile solid. For example, phosphonic acid, phosphoric acid, diphosphoric acid, boric acid, sulfuric acid, perchloric acid, adipic acid, quinalic acid, citric acid, cinnamic acid, succinic acid, oxalic acid, tartaric acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, etc. And inorganic acids and organic acids. The method of coating the acid on the solid phase material is the same as in the third embodiment by passing the solvent solution of the acid through the solid phase material, immersing the solid phase material in the solution, dropping the solution on the solid phase material, or applying the solution to the solid phase material. It is common to flush and then dry to remove the solvent. Solvents that can be used to coat the acid on the collecting sections 27, 28, 29 include water, methanol, ethanol, propanol, isopropanol, acetone, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, dichloroethane, and the like. For example, methanol or acetone is most suitable in view of low acid solubility and boiling point. The amines that can be collected by the acid are primary to quaternary amines and ammonia.

Alkali halide etc. are mentioned as a reaction reagent, In the case of the purpose of high sensitivity detection, it is preferable to coat the UV-fluorescence labeling reagent which a substituent emits UV light or fluoresces. By coating the fluorescent labeling reagent, high sensitivity fluorescence detection can be performed using HPLC method. As the amine fluorescent labeling agent, similarly to the first to third embodiments, NBD-Cl, NBD-F, DBD-F, DBD-Cl, OPA, DNS-Cl, NBD-Br, SBD-F, ABD-F, CBD-F, PBD-SO ₂ F, BBD-SO ₂ F, NDA, fluoresamine, FMOC-Cl and the like. Among these, NBD-F having a high fluorescence intensity and fast reaction is particularly preferable.

After collecting ammonia and amines by the apparatus shown in Fig. 5, the collecting portions 27, 28 and 29 are removed, eluted by adding a solvent or the like, and directly injected into an analytical device such as HPLC, GC, MS, and IC. Can be easily analyzed. Moreover, you may quantify by measuring the fluorescence and UV absorption by just exposing light, such as an ultraviolet light, to a collection part as it is without extracting a solvent.

In the conventional filter absorbing method, after collecting the filter paper from the filter holder after collection, the filter was placed in a beaker, immersed in a solvent, extracted, and analyzed. Using the method of the fourth embodiment, it is only necessary to add a trace amount of a solvent and a reagent to the collecting portions 27, 28, and 29 as it is. For example, to perform NBD-F fluorescence labeling after acid collection, buffer and NBD-F, a standard substance are added to the cup, and the lid is heated at 70 degrees for 15 minutes, followed by high performance liquid chromatography. Fluorescence detection may be performed by direct injection into (HPLC).

It is a schematic diagram which shows the outline of another ammonia amines collection apparatus which concerns on the modification of 4th Embodiment of this invention. As shown in FIG. 6, the apparatus includes a container 31 such as a sample bottle for accommodating or passing the atmosphere under test, an amine collecting part 34 provided at the bottom of the container 31, and the amine collecting part 34. ) And a measurement atmospheric exhaust pipe (33) for evacuating the atmosphere to be measured from the container (31). The amine collection part 34 may just lay room for an acid containing, for example. Although not shown, the atmospheric air exhaust pipe 33 to be measured is connected to a suction pump, and the atmospheric air to be measured impinges through the atmospheric air exhaust pipe 33 after colliding with the amine-type collecting unit 34, whereby ammonia and amines are discharged. It is collected by the collecting part 34. Therefore, the atmospheric air introduction pipe 31 to be measured is arranged to be substantially perpendicular to the main surface of the amine-type collecting portion 34 and is fitted from the outside of the container to the vicinity of the collecting portion 34. By spreading the tip of the pipe 31 on the lever, the area where the non-measured atmosphere directly collides with the amine collection portion increases, which can increase the amine capture capacity, which is effective for long time collection. On the other hand, when the tip of the pipe 31 is closed and narrowed, the area where the non-measured atmosphere directly collides with the amine collecting portion is reduced, so that the amount of the collecting agent decreases, which is effective for short time collection.

In another example of the fourth embodiment of the present invention shown in FIG. 6, the inner wall of the non-measured atmospheric introduction pipe 32 is alkali coated. In the alkali coating, for example, 1% potassium hydroxide methanol solution (50% glycerin) is passed through the pipe 32, and then the solvent is removed using a vacuum pump. In addition, when the pipe is not alkali-coated, you may put it in the container 31, washing | cleaning the pipe 32 with a solvent etc. after collection. As the amine collecting unit 34, the ammonia-amine collecting agent described in the first to fourth embodiments described above may be used. The container 31 and the pipes 32 and 33 may be made of glass, may be metallic such as SUS, or may be a resin such as techron. When the container 31 is made into a sample bottle of IC, HPLC, GC or the like, after collection, a solvent / reagent is added to this sample bottle to elute it, and it is directly injected into an analytical device such as IC, HPLC or GC for easy analysis. can do. In addition, since the cover 35 of the container can be removed and the solvent and reagent can be added directly to the collecting portion 34, the operation is simple and the contamination can be prevented. If the bottom of the container 31 is made of a transparent material against ultraviolet rays such as glass, it is possible to quantify by measuring fluorescence or UV absorption by applying light such as ultraviolet light to the collecting portion 34 without solvent extraction.

Since the collection apparatus of 4th Embodiment of this invention can collect | acquire the ammonia and amines in air | atmosphere easily, and can be concentrated to high concentration, it can be said that it is optimal as an analysis and collection apparatus of amines. Therefore, the collection method according to the fourth embodiment of the present invention is effective for environmental management of indoors, outdoors, and clean rooms.

It is a schematic diagram which shows the outline of the air cleaning apparatus which concerns on 5th Embodiment of this invention. That is, the ammonia amine collector of this invention is set as the form of FIG. 7, and can be used as a long life chemical filter or a deodorizer. In FIG. 7, the thin layer of the base material 42 of an ammonia amine collector is coated on the surface of the cylindrical rotor 41. In FIG. As a base material of this collector, glass fiber or quartz fiber insoluble in a solvent such as water or alcohol may be used. Moreover, the surface area of nickel or stainless fiber may be expanded by the etching operation. You may weave the fibers into meshes. As the foam solid, silica gel mixed with nickel or titanium is preferably foamed. In particular, in the case of the purpose of air cleaning, it is preferable to use one having strong adsorption of ammonia and amines to the solid substance itself. For example, silica gel, activated carbon, graphite carbon, or the like is preferable. However, since these adsorption powers are too strong, since the recovery rate is low and cannot be used for analytical purposes, it is important to note that selective collection is impossible because they collect compounds other than ammonia and amines. A part of this rotating body 41 is immersed in the aqueous solution or the alcohol solution 43 of low volatility acid, etc., and a rotating body is rotated slowly. The base material 42 of the collecting agent immersed in the acid solution blows off the solvent component in the dryer 44, and only the acid is coated on the surface of the base material 42. As the acid, as in the third and fourth embodiments, phosphonic acid, phosphoric acid, diphosphoric acid, boric acid, sulfuric acid, perchloric acid, adipic acid, quinalic acid, citric acid, cinnamic acid, succinic acid, oxalic acid, tartaric acid, fumaric acid, maleic acid, mal It is preferable to use inorganic acids, organic acids and the like such as lonic acid, mandelic acid and malic acid.

The alcohol used as the acid solution is preferably methanol, ethanol, propanol, isopropanol, and in addition to alcohol, acetone, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, dichloroethane and the like may be used. However, methanol or acetone is most suitable as an acid solution for immersing a part of the rotating body 41 in that the acid solubility and boiling point are low. In addition, a liquid acid such as phosphoric acid may be used as it is. The amines that can be collected by the acid are primary to quaternary amines and ammonia.

As a dryer of 5th Embodiment of this invention shown in FIG. 7, gas purging (nitrogen, air), heating, etc. are preferable. When phosphoric acid is used as a stock solution, it is not necessary to dry it. The base material 42 whose surface is covered with acid flows the measurement air inside a cylindrical container 46 in a predetermined direction by a sirocco fan, an axial flow duct fan, a suction pump 45, or the like. When the base material 42 covered with this acid contacts, it can collect ammonia and amines in the atmosphere to be measured, and can send out clean air. In the case where it is not completely collected by one contact, the container may be zigzag structure so as to contact two to three times. After a certain time, the collecting agent on the surface of the base material 42 which collected the ammonia and the amines can be rotated and immersed again in an acid solution to dissolve the ammonia and the amines in the solution, thereby making it acidic again.

The pH of this solution can always be controlled by monitoring the pH with a pH meter 47. When the acid is weakened, by using a new acid solution, this ammonia-amine collector can be collected semi-permanently. When the method of the present invention is used, the device has a low power consumption and a low cost, because it has a long life, no filter replacement effort, and a low pump load, which is lower than that of the conventional air-pass chemical filter. There is an advantage called.

If the solution 43 is an ultraviolet ray / fluorescent labeling agent instead of an acid, quantitative analysis can also be carried out by applying ultraviolet rays to the surface of the collecting agent after the collection and measuring the amount of ultraviolet absorption or the amount of fluorescence. As the amine fluorescent labeling agent, as in the first to fourth embodiments, NBD-Cl, NBD-F, DBD-F, DBD-Cl, OPA, DNS-Cl, NBD-Br, SBD-F, ABD-F, CBD-F, PBD-SO ₂ F, BBD-SO ₂ F, NDA, fluoresamine, FMOC-Cl, and the like, with NBD-F being particularly preferred.

As described above, according to the air cleaning device according to the fifth embodiment of the present invention, ammonia and amines in the air can be easily collected with high efficiency and their maintenance is also easy.

Example

Each Example of 1st, 3rd, and 4th embodiment of this invention mentioned above is demonstrated below.

In addition, the analysis in description of the following Example was performed using the following apparatuses.

High Performance Liquid Chromatography (HPLC): Waters, HPLC610E system

Column: (Foundation) Gagakuching Kensa Kyokai (trade name: L-column ODS) (4.6 mm x 250 mm)

(Column temperature; 40 ° C., flow rate; 1.0 ml / min, mobile phase solvent; acetonitrile / water = 45/55, injection amount; 20 μl / 1 round)

Detector: Waters, 474 scanning fluorescence detector (excitation wavelength; 450 nm, fluorescence wavelength; 530 nm)

(Example of 1st Embodiment)

As the collection tube 1 of 1st Embodiment of this invention, it is 10-20 using the cartridge for solid-state extraction (made by Waters Corporation, brand name: Sep-PAK flask cartridge) of the plastics of Table 1, After flushing with ml of methanol, 1 ml or 2 ml of NBD-F-boric acid buffer solution (1.0 mg / ml) was passed. 1 mol / l boric acid buffer (pH 8.35) was used as the boric acid buffer.

This solid phase extraction cartridge (1) was placed in a desiccator and depressurized with a vacuum pump for 1 hour to remove methanol to prepare a collecting tube (1) filled with the collecting agent (2) of the present invention.

Subsequently, this collection tube 1 was connected to a tube containing impregnated wool in which 0.1 mg of quartz wool was impregnated with a standard amine methanol solution (400 ng of methylamine, 700 ng of ethylamine, 700 ng of propylamine). By flowing at a rate of 500 ml / min, the entire amount of the amine was vaporized and sent to the collecting tube.

1 ml or 1.5 ml of methanol was passed through the said collection tube (1) which carried out an amine, the methanol solution of NBD-F was collect | recovered, and methanol was added and weighed to 5 ml.

20 µl of this methanol solution was analyzed by fluorescence using an HPLC apparatus manufactured by Waters, Inc. to obtain a standard diagram shown in FIG. 8. In addition, the fluorescence intensity of methylamine at that time was measured and the results are shown in Table 1.

In addition, when using silica gel which ODS couple | bonded as a solid particle, since it is difficult to quantify because a blank peak and a peak overlap, it is not described in Table 1. In addition, the results of analysis using a solution weighed to 5 ml by adding methanol to the standard amine methanol solution as a standard solution are shown in Table 1 (indicated by reference in the table).

And body mouth sleeping Methylamine fluorescence intensity (peak intensity after 5 hours of CN is 100) Kinds Substituted silyl group Immediately after 2 hours later After 5 hours Reference - 62.4 85.2 96.3 Silica gel ¹⁾ CN 99.8 101.1 100.0 Silica gel ¹⁾ - 50.5 - 56.7 Silica gel ¹⁾ Dior 42.9 - 54.0 Magnesium silicate ²⁾ - 8.04 81.1 102.1 Alumina ³⁾ - 2.78 5.43 -

Note 1) made by Waters Corporation

2) Prolidine, product name: prolidil

3) product made by Waters Corporation, brand name: Alumina-Base

As apparent from the results of Table 1, the scavenger coated with an amine fluorescent labeling agent (NBD-F) on silica gel particles having a cyanomethylpropylsilyl group (CN) bonded to the surface has the highest amine collection rate, and room temperature. It is judged that the reaction of the formation of the fluorescently labeled derivative is terminated momentarily. In addition, magnesium silicate also requires a long time to form a fluorescently labeled derivative at room temperature, but it has been found that the same strength as that of CN can be obtained for 10 minutes by heating to 70 ° C after collection.

Furthermore, by the method of the 1st Embodiment of this invention shown in FIG. 1 using the collection tube 1 manufactured using the silica gel which CN couple | bonded as a solid particle as an analysis example of amines in air | atmosphere, The air in the smoking room was aspirated for 20 minutes at a rate of 500 ml / min, and amines contained in the cigarette smoke were analyzed by fluorescence using an HPLC apparatus. The results are shown in FIG. In FIG. 9, content of amines was 34.9 ppb of methylamine, 3.2 ppb of dimethylamine, and 6.5 ppb of ethylamine.

(Example of 3rd Embodiment)

Hereinafter, the Example of 3rd Embodiment of this invention is described in detail. In this example, an HPLC 610E system manufactured by Waters Corporation was used in the same manner as in the above-described first embodiment, and the same column and detector as in the example were used.

First, in order to form the amine collection part 17 shown in FIG. 4, the membrane filter of the hydrophobic PTFE (Teflon) type | mold (made by Toyoro Corporation, 0.5 micrometer in diameter, 25 mm in diameter, 35 micrometers in thickness) was used. . After washing the disk with methanol, it was attached to an aluminum foil sheet, and then 0.1 ml of 0.3% methanol solution of 0.3% tartaric acid was added dropwise onto the disk, placed in a desiccator, and dried under reduced pressure with a vacuum pump to collect ammonia and amines. (17) was set. At the time of release of the reduced pressure, it was substituted with nitrogen of high purity.

Next, as the container 11 of 3rd Embodiment of this invention shown in FIG. 4, the stainless steel vacuum desiccator (made of SUS304, internal volume 3L) was used. In the upper part of the container 11, the inlet 13 which has the vacuum exhaust cock 12 and amine collection part is provided.

Inside the vessel 11 was placed an agitator to create an upward flow, and the pipette was used to cover the entire inner wall with 1% potassium hydroxide methanol solution (containing 50% glycerin). And the inlet 13 which has the amine collection part 17 was woven into the container 11. Only methanol could be removed by drying under reduced pressure using a vacuum pump, and the inner wall of the container 11 was uniformly alkali-coated.

Subsequently, the container made into the pressure reduction state using the vacuum exhaust coke was put in the factory, and the coke 12 was released, and the air in the factory was sampled in the container 11. That is, after returning the container 11 to atmospheric pressure, the coke 12 was closed and sealed again.

And the whole container was heated at 100 degreeC for 1 hour, air stirring was carried out using the magnetic stirrer 15 (60 rotation / min), and the amines in the container 11 were collected by the ammonia amine collector. Then, after returning the container 11 to room temperature, unplug and immediately add 0.5 ml of boric acid buffer (pH 8.5) / methanol, 0.5 ml of 2 mg / ml NBD-F methanol solution, n-butylamine for internal standard / Methanol was added, it was made tight, and it was made to react at 70 degreeC for 15 minutes. Thereafter, the results of fluorescence detection under the above-described HPLC conditions are shown in FIG. 10.

According to the third embodiment of the present invention, as shown in FIG. 10, atmospheric ammonia and amines can be collected in a container and concentrated at a high concentration. Therefore, it can be said that this Example is suitable as a collection method for analyzing amines having many carbon atoms. Therefore, the collection apparatus which concerns on 3rd Embodiment of this invention is effective for environmental management of indoors, outdoors, a clean room, etc.

(Example of 4th Embodiment)

A glass tube having an inner diameter of 0.5 cm and a length of 50 cm was bent as shown in Fig. 5 to form a cylindrical container 26, and a hole was opened at the end thereof so as to mount the amine collecting portions 27, 28, and 29. A 1% potassium hydroxide methanol solution (containing 50% glycerin) was applied inside the tubular container 26 using a pipette. Then, it dried with the vacuum pump and alkali-coated the inner wall of the glass tube 26. The amine collection | collecting part 27, 28, 29 cuts out the filler similar to the Example of 3rd Embodiment mentioned above in the round aluminum foil cup of diameter 1.5cm, suppresses rust, and is a cylindrical container It was firmly fixed to the end of 26.

After sampling the atmosphere to be measured by aspirating the factory air into the cylindrical container 26 at 2 l / min for 10 minutes, the collection portions 27, 28, and 29 are removed, and boric acid is added to each cup constituting the collection portion. 0.5 ml of buffer (pH 8.5) / methanol was added, 0.5 ml of 1 mg / ml NBD-F methanol solution and n-butylamine / methanol for internal standard were added, tightly sealed, and reacted at 70 ° C. for 15 minutes. Thereafter, the results of fluorescence detection under the HPLC conditions are shown in FIG. 11.

Since the scavenger of the present invention efficiently collects amines and ammonia in the gas and can be used as a derivative of the amine fluorescent labeling agent, these amines can be analyzed quickly with high sensitivity.

Moreover, when collection | collection is performed using the collection apparatus of this invention, since amines in air | atmosphere can be collected easily at high concentration, it is suitable for the high sensitivity analysis of trace amount of amines in air | atmosphere.

Moreover, when air cleaning is performed using the collection apparatus of this invention, compared with the conventional chemical filter method, it consumes less power and has a long lifetime.

Therefore, the collecting agent, the collecting device, and the amine analysis method using the same of the present invention are effective for environmental management of indoors, outdoors, clean rooms and the like. In particular, since environmental management of amines in a clean room becomes favorable, the yield of semiconductor manufacturing processes, such as a resist process, can be improved and a high quality semiconductor device can be provided.

Claims (12)

An amine collecting agent comprising coating an amine fluorescent labeling agent on at least a portion of a solid material and collecting amines selected from primary amines, secondary amines and ammonia contained in a gas as fluorescent labeling agent derivatives. At least from a tubular collection tube provided with a filter on the outlet side, the amine collector filled in the collection tube, and suction means coupled to the collection tube for sucking the atmosphere to be measured through the collection tube. The amine collection apparatus using the amine collecting agent of Claim 1 characterized by the above-mentioned. The amine collecting agent according to claim 1 is coated on the surface of a predetermined substrate, characterized in that the amine collecting device using the amine collecting agent. At least a collecting portion containing a container through which the atmosphere to be measured is accommodated or passed, and an amine collecting agent according to claim 1 provided in a part of the container, and the inside of the container is treated so that amines are not adsorbed. Amine collection apparatus made into. The amine collection apparatus according to claim 4, wherein the treatment for preventing the amines from adsorbing is an alkali coating on the inner wall of the container. The amine collection device according to claim 4, wherein the treatment for preventing the amines from being adsorbed is to heat the inner wall of the vessel to 100 to 200 deg. 5. The vessel of claim 4, wherein the vessel has a coke for evacuating the interior to a vacuum, and a component for agitating the atmosphere introduced into the vessel is provided in the interior of the vessel so that the surface of the component does not adsorb amines. The amine collection apparatus characterized by the above-mentioned. The container according to claim 4, further comprising suction means for sucking the inside of the container to allow the atmosphere to be passed through, wherein the container has at least one bent portion, and the amine-like collecting portion is provided at the bent portion. Amine collection apparatus made into. The vessel according to claim 4, wherein the vessel further includes a measurement-atmosphere introduction pipe and a measurement-atmosphere exhaust pipe which are treated to prevent adsorption of amines, and the amine collection unit is provided inside the vessel, and the measurement-atmosphere An introduction pipe extends from the outside of the said container to the vicinity of the said amine collection part, The amine collection apparatus characterized by the above-mentioned. A method of capturing and analyzing amines, wherein the gas containing the amines is collected by contacting the collecting agent according to claim 1 and then collected by fluorescence detection of the amines collected in the collecting agent. After collecting a gas containing amines through a collecting tube filled with the collecting agent according to claim 1, the concentration of fluorine in the gas is measured by measuring the width of fluorescence detection from the gas inlet of the collecting tube. A collection and analysis method of amines. A method of capturing and analyzing amines, characterized by fluorescence detection of a fluorescent labeling agent derivative obtained by extracting the gas containing amines by contacting the collecting agent according to claim 1 and then collecting the collecting agent.