JP3479412B2 - Amine collector, amine collector, and method for collecting and analyzing amines - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for analyzing a trace amount of impurity gas contained in a gas such as the atmosphere, and in particular, a collector for amines in the atmosphere, a collector for amines and a collector for the amines. -Regarding the analysis method.

[0002]

2. Description of the Related Art Ammonia and amines present in the atmosphere are one of typical off-flavor substances, and the odor is known as the rotten odor of fresh fish. The bad odor of amines generated from fish iliac processing plants and chemical plants is a serious problem,
Although it is desired to clean the ambient air, it is necessary to establish a method for collecting ammonia and amines in the atmosphere.

On the other hand, in the VLSI manufacturing process, it is indispensable to establish the management analysis technique of the impurity gas in the clean room. For the analysis of inorganic ions, there is used a method 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 recently become clear that contamination by an extremely small amount of organic substances in the air, which has been of little importance until now, causes various defects in semiconductor devices and a reduction in the yield of VLSI manufacturing processes. As for the detection of organic substances, the same level of sensitivity as inorganic substances has come to be required. In particular, it is clear that amines such as ammonia, alkanolamines, aliphatic amines, and aromatic amines, which are organic ionic compounds, are highly reactive and cause troubles such as resist curing in the lithography process. The development of such analytical methods has become particularly important.

Ammonia in the clean room is considered to originate from the outside air, the wafer cleaning liquid, the CVD source gas, and the like. Further, amines are considered to be components contained in the additive for boiler water in clean rooms and components generated by the human body. It is becoming clear that these ammonia and amines, as trace gases, contribute to the reduction in yield of semiconductor manufacturing processes.

[0006]

Conventionally, as a method for collecting ammonia / amines, the one whose purpose is to analyze is an impinger pure water collecting method or a filter paper absorbing method in which air is passed through a filter paper coated with sulfuric acid. Has been used.
However, both have a problem that instantaneous sampling cannot be performed.

Further, in the Impinger method, ultrapure water is used in a large amount of 100 ml or more in order to improve the collection efficiency, so that concentration is difficult. In addition, in the filter paper absorption method, the filter paper is removed from the filter paper holder after collection, placed in a beaker, immersed in a solvent for extraction and applied to an analyzer. There was a problem as a sensitivity detection method.

Conventionally, the amine chromatograph method (IC method) and the gas chromatograph-mass spectrometric method (GC-MS method) have been used for the analysis of amines like the inorganic ions. There is a drawback that amines of 3 or more cannot be measured. Further, since amine has a strong adsorption property to the column, there is a problem such as tailing in the GC-MS method, which is not desirable.

Although a method for collecting ammonia / amines for purposes other than analysis, a chemical filter for the purpose of air cleaning only is known. This is to pass clean air through a filter paper coated with phosphoric acid to collect ammonia and amines. However, the collection method using a chemical filter has problems that the collection life is short, the breakthrough time is indefinite, and the pump load is large, resulting in power consumption.

The present invention provides a scavenger capable of easily collecting and analyzing amines contained in a gas such as the atmosphere, a scavenger using the scavenger, and a scavenger using the scavenger. It is an object of the present invention to provide a method for analyzing collected amines quickly and with high sensitivity.

[0011]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the inventors of the present invention have conducted extensive research and as a result, as a result, an amine scavenger obtained by coating a solid substance such as silica or alumina with an amine fluorescent labeling agent. It was also found that a collector using the same can collect amines with high efficiency, and that amines collected by the collector can be rapidly analyzed by fluorescence detection.

That is, the first feature of the present invention is that at least a part of a solid substance is coated with an amine fluorescent labeling agent, and a primary amine, a secondary amine and ammonia contained in a gas are used. It is an amine-scavenger that collects amines selected from the following as a fluorescent labeling agent derivative, and a collector using this collector. In addition,
In the present invention, primary amines, secondary amines and ammonia are collectively referred to as amines.

As the solid substance used for preparing the scavenger according to the first aspect of the present invention, an inorganic substance or an organic substance which is inert to the reaction with the fluorescent labeling agent and amines can be used. As the shape, a solid having a large surface area such as particles, fibers, meshes, foams, or non-woven fabrics is suitable. As the fibrous or non-woven solid, there may be considered one in which silica gel is mixed with metallic aluminum to form a fiber, and one in which silica gel is mixed into pellet polyester to form a fiber in order to increase the surface area. In addition, cellulose used for paper, cellulose mixed ester,
The surface area of polyvinylidene difluoride (hydrophilic / hydrophobic), polytetrafluoroethylene (hydrophobic / hydrophilic), glass fiber, nickel or stainless fiber may be expanded by an etching operation. These fibers may be knitted in a mesh shape.

The solid fluorescent substance is coated with the amine fluorescent labeling agent by immersing the solid substance in a weak alkaline buffer solution of the labeling agent or by buffering the solid substance with a buffer solution of the labeling agent. After passing through the solution or dropping, the solid material is generally dried to remove the solvent. The reason why the weakly alkaline buffer is used here is that many acidic substances such as SO _x and NO _x are present in the atmosphere at present. In general, the fluorescent labeling reaction proceeds under weak alkalinity, so that if the scavenger changes to acidity due to an acidic substance in the atmosphere, the labeling reaction will not proceed and the collection cannot be performed. In addition, FIG.
This is because the reaction rate of the labeling reaction varies depending on the pH during the reaction, as shown in Fig. 6, and it is difficult to quantify after collection if an alkaline substance such as sodium hydroxide is used without using a buffer. . Therefore, it is desirable to use a buffer that can minimize pH changes.

The amine-scavenger of the first feature of the present invention can be prepared as described above. The amines that can be collected by the scavenger are primary amine, secondary amine Primary amines and ammonia. Needless to say, the amines may be liquid or solid at room temperature and atmospheric pressure, or may have a vapor pressure in a gas, or may be a mist-like amine.

The amine scavenger of the first feature of the present invention is
More specifically, as shown in FIG. 1, the inside of a collecting pipe (collecting portion) 1 is filled, and this collecting pipe is sucked by a suction means 4 such as a suction pump, an axial duct fan or a sirocco fan. It is preferable to use an amine-scavenging device which is configured so as to come into contact with the air to be measured and pass through the scavenger 2.

Alternatively, the amine-scavenger may be formed in a thin layer. For example, the particulate collecting agent 2 may be coated on a glass substrate in a thin layer to form a collecting substrate. Alternatively,
When using a thin-layer chromatography plate,
As shown in FIG. 2, a fluorescent labeling agent solution adjusted to be weakly alkaline with a buffer is dropped on the plate 5,
The solvent may be removed by drying to obtain the amine scavenger 2. The shape of this thin layer may be any shape other than that shown in FIG.

Alternatively, the filter paper may be dipped in the above fluorescent labeling agent solution, spread on a substrate, and dried to remove the solvent to form an amines-collecting device.

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

That is, the amine-scavenger of the first feature of the present invention and the apparatus using the same can easily collect amines in the atmosphere as a derivative of the fluorescent labeling agent.

Ammonia, methylamine, and the like dissolve in water, but have high volatility, so even if they can be collected in ultrapure water by a conventional impinger, they are not perfect. But,
In the present invention, these amines react with the labeling agent immediately on the scavenger and become a derivative having a large molecular weight, so that they can be completely trapped without fear of re-volatilization. Further, the fluorescence of amines derivatized with the labeling agent according to the present invention is very strong, and is suitable for highly sensitive detection.

As a method of analyzing this derivative, fluorescence may be detected by directly irradiating it with ultraviolet rays, or fluorescence may be detected by extracting with a solvent. When an amine derivative is formed, fluorescence is emitted, but since the fluorescent labeling agent itself has no fluorescence, it is possible to quantify the entire amines by measuring the fluorescence intensity of the whole. The molar fluorescence intensity differs depending on each amine, but since there is no great difference, it may be calculated as a “methylamine conversion value” based on a calibration curve of a typical amine such as methylamine.
However, since background fluorescence consisting of decomposition products derived from reagents may be observed, it is necessary to make the same collection device that does not expose it to the non-measurement atmosphere, use it as a blank, and subtract the value for quantification.

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

Alternatively, when a thin layer chromatography plate as shown in FIG. 2 is used, as shown in FIG. 3, the lower portion 6 of the collection substrate 5 is immersed in a developing tank 8 containing a solvent 9 at the bottom thereof. Alternatively, the derivative may be developed and concentrated by capillarity and directly detected by fluorescence, or fluorescence may be detected by extracting the concentrated portion with a solvent.

These thin layer amine scavengers usually have a thickness of 0.01 mm to 1 mm. This means using too much fluorescent labeling agent solution if the layer is too thick,
This is because the reagent blank value becomes high.

Substrates that can be used as the substrate in these thin layer collectors include glass, metals such as aluminum,
Examples include plastics such as polyethylene and polypropylene.

The amine-scavenger according to the first feature of the present invention may be used in the trap portion of the trap shown in FIGS. 4, 5 and 6.

Further , after a gas containing the amines is passed through a collection tube filled with the scavenger described in the first feature to collect the ultraviolet rays, an ultraviolet excitation light such as a Xe lamp or an Ar laser light is emitted. The concentration of amines in the gas can also be measured by irradiating and measuring the fluorescence detection width from the gas inlet of the collection tube. In this case, as the material of the tube of the fluorescence detecting portion, it is desirable to use an ultraviolet-transparent non-fluorescent material such as quartz glass, sapphire or crystal.

As described above, the amine-scavenger of the first feature of the present invention and the amine-scavenger using the same collect the primary amine, secondary amine and ammonia in the gas such as air. It can be efficiently collected and easily collected as a fluorescent labeling agent derivative. Further, amines having 3 or more carbon atoms, which could not be analyzed by the IC method, can be analyzed with high sensitivity.
The analysis method of the first feature of the present invention is particularly effective for environmental management such as indoors, outdoors, and cream rooms.

A second feature of the present invention is at least a container for accommodating or passing an atmosphere to be measured, and an amines trap provided in a part of the container, wherein the inside of the container is amine. It is a device for collecting amines, which is characterized in that it is treated so as not to adsorb compounds.

As the amine trap, an amine trap coated with the fluorescent labeling agent, which is the first feature of the present invention, may be used, or an amine coated with a low-volatile acid may be used. You may use a class collector. Alternatively, a reaction reagent such as a halogenated alkyne that reacts with amines to become a non-volatile substance at room temperature, or p
You may use the indicator etc. which react with amine and show a color like H indicator. As for the shape of the device, for example, as shown in FIGS. 4, 5, and 6, containers 11, 26, 31 that contain or pass the atmosphere to be measured, and an amine-collecting portion provided in a part of this container It is preferable that the amines-collecting device is composed of 17, 27, 28, 29 and 34. 4 and 5, the containers 11 and 26 and the internal parts 16 and 32 are shown.
Is treated by surface treatment such as alkali coating so that amines are not adsorbed. In FIG. 4, after the measured air is stored, the internal air is stirred by the stirrer 16 or the like, and the amines are collected in the amine collecting unit 17. In FIG. 5 and FIG. 6, the atmospheric air to be measured directly collides with the amines-collecting portions 27, 28, 29, 34 and is collected by the amines-collecting portions 27, 28, 29, 34. It is a thing.

After the collection, the amine collection parts 1, 17, 27,
By taking out 28, 29 and 34, eluting by adding a solvent or the like, and directly injecting into an analyzer such as IC, HPLC, GC, etc., analysis can be easily carried out. In addition, the solvent is not eluted and the collecting portions 17, 27, 28, 29, and
Quantification may be performed by confirming the coloration of 34 or by irradiating light such as ultraviolet rays and measuring fluorescence or UV absorption.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows an example of a device and a method for collecting amines in a gas according to a first embodiment of the present invention. In FIG. 1, a collecting tube 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 collection tube 1 has a cylindrical shape with a diameter of 0.5 to 1.5 cm and a length of 0.5 to 2 cm, or a quadrangular cross section with a side of 0.5 to 1.5 cm, and a length of 0.5. A rectangular parallelepiped shape of ˜2 cm is preferable. It is preferable that about 10 to 400 mg of the scavenger 2 is contained and the exhaust conductance does not become too small. By connecting this collection tube 1 to a suction pump 4 as a suction means and driving the suction pump 4, the atmosphere passes by coming into contact with the scavenger 2 and amines in the gas are collected in the collection tube 1. It is collected by the collecting agent 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, and the suction may be performed by providing a pressure difference by some method.

As the solid substance used when preparing the scavenger 2 used in the first embodiment of the present invention, there are used inorganic substances and organic substances which are inert to the reaction with the fluorescent labeling agent and ammonia / amines. Can be used. As the shape, a solid having a large surface area such as particles, fibers, meshes, foams, or non-woven fabrics is suitable. As the fibrous or non-woven solid, it is preferable to mix metal aluminum with silica gel to form a fiber, or pellet polyester to mix silica gel to form a fiber in order to increase the surface area. In addition, cellulose, cellulose mixed ester, polyvinylidene difluoride (hydrophilic / hydrophobic), polytetrafluoroethylene (hydrophobic / hydrophilic), glass fiber, activated carbon fiber or nickel or stainless fiber used for paper The surface area may be expanded by an etching operation. Further, these fibers may be knitted in a mesh shape. As the foam-like solid, it is considered that nickel or titanium is mixed with silica gel and foamed.

As the particulate inorganic substance used for the solid substance, for example, silica (SiO ₂ ) or alumina (Al ₂
Particles containing O ₃ ) as an essential component can be used. Examples of the particulate organic substance include particles of a polyolefin resin such as polyethylene and polypropylene, polystyrene, a styrene resin such as styrene-divinylbenzene copolymer, or a fluorine resin such as polytetrafluoroethylene. It can be used as a solid substance. As a solid containing silica or alumina as an essential component,
Silica, silica gel, magnesium silicate (MgO · n
SiO ₂ ), alumina, silica-alumina, etc. can be used. Of these, magnesium silicate is particularly desirable when used alone. These solid particles usually have a particle size of 1 to 500 μm, and particularly inorganic solid particles have a pore size of 3 to 50 nm and a specific surface area of 100 to 100.
A porous material having a pore size of 0 m ² / g is preferable.

Further, it is preferable to use a silica-based material having a substituted silyl group bonded to the surface thereof. This is because the substituted silyl group-bonded solid particles have the feature of promoting the reaction with amines. The substituted silyl group, cyanopropyl silyl [-Si (CH ₃₎ (C
_{H 2) 3 CN] (CN} ), octadecylsilyl [-Si
_{(CH 3) 2 C 18 H} 37] (ODS), propyloxy propanediol silyl _{[-Si (CH 2) 3 OCH} 2 C
_{H (OH) CH 2 OH]} ( diol), t-octadecylsilyl [-SiC ₁₈ H _37], octylsilyl [-Si
_{(CH 3) 2 C 8 H} 17] (C8), ethylsilyl [-S
iC ₂ H _5], phenyl silyl [-Si (CH _{3) 2} C
₆ H ₅ ] (phenyl) and the like can be mentioned, and among these, CN, ODS and phenyl are preferable, and CN is particularly preferable.
However, normal-phase partitioning types such as diol (OH) and silica gel particles that are not surface-treated with a substituent having strong amine adsorption force have too strong amine adsorption force, so when extracting with a solvent and performing quantitative analysis. The recovery rate becomes low, which is not preferable.

The amine fluorescent labeling agent does not have fluorescence itself, but emits strong fluorescence by reacting with a primary or secondary amine or ammonia, for example, 4-chloro-7-nitro. -2,1,3-benzoxadiazole (NBD-Cl), 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-)
F), 4- (N, N-dimethylaminosulfonyl) -7
-Fluoro-2,1,3-benzoxadiazole (DB
DF), 4- (N, N-dimethylaminosulfonyl)
-7-Chloro-2,1,3-benzoxadiazole (D
BD-Cl), o-phthalaldehyde (OPA), 5-
Dimethylaminonaphthalene-1-sulfonyl chloride (DNS-C1), 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-Benzoxadiazole (ABD-F), 4- (chlorosulfonyl)-
7-Fluoro-2,1,3-benzoxadiazole (C
BD-F), 4- (fluorosulfonyl) -7-phenoxy-2,1,3-benzoxadiazole (PBD-S
O ₂ F), 4- (fluorosulfonyl) -7-benzorosioxy-2,1,3-benzoxadiazole (BBD
-SO ₂ F), 2,3-naphthalenedialdehyde (ND
A), 3- (2-furoyl) quinoline-2-aldehyde, fluoresthamine, 9-fluorenylmethyl chloroformate (FMOC-C1), 2- (1-pyrenyl).
Ethyl chloroformate, 3,4-dihydro-6,7-
Dimethoxy-4-methyl-3-oxaquinoxaline-2
-Carbonyl chloride, 6-methoxy-2-methylsulfonylquinoline-4-carbonyl chloride, 7-dimethylaminocoumarin-3-carbonyl chloride and the like can be used, but among them, N has a fast reaction and very high fluorescence intensity.
BD-F and NBD-Cl, especially NBD-F, are preferred.

In the first embodiment of the present invention, a borate buffer or the like may be used as the buffer having a pH of 7.5 to 9.5 together with the fluorescent labeling agent. The borate buffer solution can be prepared by gradually adding a potassium hydroxide / methanol solution to a boric acid / methanol solution. Other buffer solutions include boric acid-sodium hydroxide buffer solution, sodium tetraborate-hydrochloric acid buffer solution, potassium dihydrogen phosphate-sodium hydroxide buffer solution and the like. As the acid such as boric acid used at this time, it is preferable to use a reagent of “for amino acid analysis” or higher grade which does not contain 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 M to 1.0 M. Also, in the solution,
Add a lubricant such as 0.1-1.0% glycerin,
It is also effective to enhance the coating power of the fluorescent labeling agent on the solid substance.

The above-prepared solution is immersed in the solid substance described above, or the solution is passed through or dropped into the solid substance, the solid substance is put in a desiccator or the like, and the pressure is reduced by a vacuum pump. Take the method of removing the solvent and drying,
Create an amine scavenger.

Solvents that can be used when coating the above-mentioned amine fluorescent labeling agent on a solid substance include methanol, ethanol, isopropanol, n-propanol, acetone, acetonitrile, tetrahydrofuran,
Dimethyl sulfoxide, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, water and the like can be mentioned.

In the first embodiment of the present invention,
To perform qualitative and quantitative analysis of amines, a suction pump 4 is used to suction into the atmosphere to be measured in a tube 1 filled with an amine-scavenger 2 and the amines are collected. And a method of detecting fluorescence by irradiating with a solvent, a solvent or a supercritical fluid, etc., is passed through the scavenger to extract an amine fluorescent labeled derivative,
It can be performed by measuring the fluorescence intensity of the solution.

When the fluorescence is detected by directly irradiating it with ultraviolet rays, it is advisable to use quartz glass, sapphire, or quartz, which is optically transparent to the excitation wavelength and the fluorescence wavelength, as a part of the tube. That is, the scavenger 2 gradually changes from the vicinity of the gas inlet of the collecting tube 1 toward the gas outlet, and the scavenger in the changed portion is collected from outside the collecting tube by Xe. When excited by a lamp or Ar laser light, it emits fluorescence. Therefore, the concentration of amines can be measured by measuring the width of fluorescence from the inlet of the collection tube 1.

Further, when extracting with a solvent or a supercritical fluid, the fluorescence of the solution may be measured in the same manner, but as another method, the fluorescence may be detected after separation using fluid chromatography or supercritical fluid chromatography. You can also do it. Once separated, a qualitative and accurate quantitative analysis of each amine can be performed. Examples of liquid chromatography that can be used include column chromatography and thin layer chromatography, and particularly high performance liquid chromatography (HP
LC) has high resolution and is desirable.

The amines that can be collected by the first embodiment of the present invention are primary amines, secondary amines and ammonia. The amines may be liquid or solid at room temperature and atmospheric pressure, or may have vapor pressure in a gas or mist-like amines. Examples of primary amines include saturated aliphatic primary amines such as methylamine, ethylamine, isopropylamine, propylamine, butylamine, and 2-aminoethanol, unsaturated aliphatic primary amines such as allylamine, and cyclopropylamine. Alicyclic primary amines, aromatic primary amines such as aniline, secondary amines include saturated aliphatic secondary amines such as dimethylamine, diethylamine, diisopropylamine, unsaturated fatty acids such as diallylamine. Group secondary amines, aromatic secondary amines such as methylaniline, and the like can be mentioned, respectively.

As described above, the scavenger and the scavenger according to the first embodiment of the present invention efficiently collect the primary amine, the secondary amine and the ammonia in the gas to obtain the amine fluorescence. It can be a derivative of a labeling agent, and these amines can be analyzed rapidly and with high sensitivity. That is, according to the first embodiment of the present invention, it is possible to detect amines at sub-ppb level in the atmosphere with high sensitivity regardless of the number of carbon atoms.

FIG. 2 is a schematic view of an amines-collecting device according to the second embodiment of the present invention, which is an example of the case where thin layer chromatography (TLC) is used. When using a TLC plate, as shown in FIG. 2, a fluorescent labeling agent solution adjusted to be weakly alkaline with a buffer is dropped on the plate 5 and dried to remove the solvent to remove the amine-scavenger. It is generally set to 2. The shape of this thin layer may be any shape other than that shown in FIG.

The size of the collection substrate 5 is, for example, 10 per side.
It may be about 20 cm. Reference numeral 7 represents a portion where the derivative of the fluorescent labeling agent is concentrated. The dimensions of the concentration section 7 may be, for example, 1 cm × 1 cm. Reference numeral 6 in FIG.
The part which is not coated with the amine fluorescent labeling agent is shown.

When using a commercially available thin layer chromatography, the plate may be thoroughly washed with a solvent and then dipped in the fluorescent labeling agent solution, or the fluorescent labeling agent solution may be dropped to perform coating. . Then, it is put in a desiccator and dried under reduced pressure with a vacuum pump to remove the solvent and used as a collector.

When thin-layer chromatography is not used, the particulate collecting agent 2 may be coated on the substrate in a thin layer to form a collecting substrate. Alternatively, the filter paper may be dipped in the fluorescent labeling agent solution, spread on a substrate, and dried to remove the solvent to form an amines-collecting device.

These thin layer amine-scavengers usually have a thickness of 0.01 mm to 1 mm. This means using too much fluorescent labeling agent solution if the layer is too thick,
This is because the reagent blank value becomes high. Substrates that can be used as the substrate in these thin-layer collectors are glass, metals such as aluminum, plastics such as polyethylene and polypropylene, and the like.

As the solid substance used for adjusting these scavengers, an inorganic substance or an organic substance inert to the reaction with the fluorescent labeling agent and amines is used as in the first embodiment. Is preferred. As the shape, a solid having a large surface area such as particles, fibers, meshes, foams, or non-woven fabrics is suitable. The amine fluorescent labeling agent has no fluorescence as in the first embodiment of the present invention, but emits strong fluorescence by reacting with a primary or secondary amine or ammonia. For example, NBD
-Cl, NBD-F, DBD-F, DBD-Cl, OP
A, DNS-C1, NBD-Br, SBD-F, ABD
-F, CBD-F, PBD- SO 2 F, BBD-SO 2
F, NDA, 3- (2-furoyl) quinoline-2-aldehyde, fluoresamine, FMOC-C1, 2- (1
-Pyrenyl) ethyl chloroformate, 3,4-dihydro-6,7-dimethoxy-4-methyl-3-oxaquinoxaline-2-carbonyl chloride, 6-methoxy-2
-Methylsulfonylquinoline-4-carbonyl chloride, 7-dimethylaminocoumarin-3-carbonyl chloride and the like can be used, but among them, NBD-F and NBD-Cl, especially NBD-F, which has a fast reaction and extremely high fluorescence intensity, are particularly usable.
-F is desirable. Solvents that can be used when coating the above-mentioned amine fluorescent labeling agent on a solid substance include methanol, ethanol, isopropanol, n-propanol, acetone, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, carbon tetrachloride, chloroform, dichloromethane, dichloroethane and the like. Can be used.

When the collector shown in FIG. 2 is left to stand in the atmosphere to be measured, the amines in the atmosphere come into contact with the collecting substrate by a natural air flow and are collected to become a derivative of the amine fluorescent labeling agent. .

As a method of analyzing this derivative, fluorescence may be detected by directly irradiating the collecting substrate with ultraviolet rays, or fluorescence may be detected by extracting with a solvent. When an amine derivative is formed, it emits fluorescence, but since the fluorescent labeling agent itself does not have fluorescence, it is possible to quantify the entire amines by measuring the fluorescence intensity of the whole.

When the thin-layer chromatography plate as shown in FIG. 2 is used, as shown in FIG. 3, the lower portion 6 of the collection substrate 5 is placed in the developing tank 8 containing the solvent 9 at the bottom thereof.
Alternatively, the derivative may be developed by capillary action and concentrated to directly detect fluorescence, or the concentrated portion may be extracted with a solvent to detect fluorescence.

Alternatively, after extraction with a solvent, separation may be performed by HPLC and fluorescence detection may be performed for analysis. This method allows accurate quantification of amines.

The solvent used for eluting the derivative can be appropriately selected from the solvents that can be used for coating the above-mentioned amine fluorescent labeling agent on a solid substance. Further, the derivative may be eluted with a supercritical fluid, carbon dioxide is suitable as a supercritical fluid, and the above solvent may be added as a modifier.

According to the second embodiment of the present invention, amines in a gas such as air can be easily collected as a derivative of the fluorescent labeling agent. Ammonia, methylamine, and the like are soluble in water but have high volatility, but in the second embodiment of the present invention, these amines immediately react with the labeling agent on the scavenger particles and have a molecular weight of Since it becomes a large derivative of, it can be collected completely without the risk of re-volatilization. Further, according to the second embodiment of the present invention, the fluorescence of the amines labeled with the labeling agent is very strong, which is suitable for highly sensitive detection of amines having a large number of carbon atoms. The amines having a large number of carbon atoms are primary amines, secondary amines and ammonia. Examples of primary amines include saturated aliphatic primary amines such as methylamine, ethylamine, isopropylamine, propylamine, butylamine, and 2-aminoethanol, unsaturated aliphatic primary amines such as allylamine, and cyclopropylamine. Alicyclic primary amines, aromatic primary amines such as aniline, secondary amines include saturated aliphatic secondary amines such as dimethylamine, diethylamine, diisopropylamine, unsaturated fatty acids such as diallylamine. Group secondary amines, aromatic secondary amines such as methylaniline, and the like can be mentioned, respectively.

FIG. 4 shows an amines-collecting device according to the third embodiment of the present invention. In FIG. 4, the container 11 is a spherical container having a flat lower portion, and has a cock 12 for connecting to a vacuum pump at the upper portion and a port 13 at the tip of which an amine-scavenging portion 17 made of an ammonia / amine scavenger is attached. It is provided. The inner wall of the container 11 is alkali-coated to prevent adsorption of ammonia and amines. Then, an agitator 16 coated with an alkali is placed inside so that the air flows upward. The inside air is discharged from the upper cock 12 by using a vacuum pump to reduce the pressure,
Close the cock 12. After that, by opening the cock 12 at the place where sampling is desired, the atmosphere to be measured is put into the container 11, and the cock 12 is closed and sealed again. Then, when the stirrer 16 is rotated from the outside using the magnetic stirrer 15, the gas inside moves violently up and down. Even if it collides with an alkali-coated container or part, ammonia and amines are weakly alkaline, so there is no risk of adsorption. The ammonia / amine scavenger inside the lid collects all the ammonia / amine in the measured atmosphere. After that, the mouth 13 having the amines collecting portion 17 at the tip is opened, the scavenger is collected, and the ammonia / amine collected by the scavenger is eluted by adding a solvent or the like, and ion chromatography (IC) is performed. , High performance liquid chromatography (HPLC), gas chromatography (G
It can be directly injected into an analyzer such as C) and analyzed easily.

As the material of the container 11 of the third embodiment of the present invention, SUS, copper, aluminum, etc., which are inert to the reaction with amines, do not pass gas / liquid, and do not lose air pressure, etc. Metals, inorganic materials such as glass, polyolefin resins such as polyethylene and polypropylene, styrene resins,
A polyacrylic acid ester or polytetrafluoroethylene fluorine resin can be used. The passivation treatment may be performed by performing a treatment such as forming a chromium-nickel oxide film on a portion in contact with the measured atmosphere. In the case of polyethylene, polypropylene, polytetrafluoroethylene, etc., which have high water repellency, the part that comes into contact with the air to be measured has a large surface area like the amine trap, such as particulate, fibrous, or non-woven, reticulated, foamed. You may process in a physical form.

As a treatment for preventing the adsorption of ammonia / amines on the inner wall of the container 11, heating of the container 11 may be performed in addition to the alkali coating. Heating is less effective for materials with strong amine adsorption such as glass and resins with poor thermal conductivity, but aluminum,
It is effective when a metal container / part such as copper or SUS is used. Since the ammonia and amine can be desorbed together with water, the heating temperature is preferably 100 to 200 degrees. If it is more than this, there is a risk of amine decomposition.

As an alkali for coating the inner wall of the container 11, a strong alkali such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, calcium carbonate or magnesium carbon is suitable. In the presence of a strong alkali, ammonia and amines are weakly alkaline, so that they are not adsorbed at all, and there is no fear of adsorption in a container. The alkali coating method is generally a method in which an alkali solution is passed over the surface of the passage portion, immersed in the solution, dropped into the solution, or sprayed with the solution, and then dried to remove the solvent.

Examples of the solvent that can be used for coating the inner wall of the container 11 with the above-mentioned alkali include methanol, ethanol and water. In the case of potassium hydroxide,
Methanol is optimal because of its low boiling point. For other alkalis, highly soluble water is suitable. Further, when a lubricant such as glycerin or a highly viscous substance such as water glass is added to this solution, water repellency of the surface can be prevented.

As the ammonia / amines-collecting agent used in the amines-collecting section 17 of the third embodiment of the present invention, an amine fluorescent labeling agent is added to the solid substance as described in the first embodiment. Alternatively, an amine-scavenger coated with a substance that emits strong fluorescence by reacting with an amine or ammonia may be used. For example, NBD-Cl, NBD-
F, DBD-F, DBD-Cl, OPA, DNS-C
1, NBD-Br, SBD-F, ABD-F, CBD-
The solid substance may be coated with F, PBD-SO ₂ F, BBD-SO ₂ F, NDA, fluoresamine, FMOC-Cl or the like. Of these, NBD-F, which has a strong fluorescence intensity and a fast reaction, is particularly desirable. If a fluorescent labeling agent is coated, then it becomes possible to easily perform fluorescence analysis by HPLC or the like.

As a method for coating the solid substance with the fluorescent labeling agent NBD-F, a methanol solution containing a borate buffer (pH 8.5) and NBD-F is passed through the solid substance or the solid substance is added to the solution. A general method is to remove the solvent by immersing the substance, dropping the solution onto the solid substance, or spraying the solution onto the solid substance and then drying. The amines that can be collected by these are
They are primary and secondary amines and ammonia.

The solid substance which is the base material of the scavenger is
It is inert to the reaction with ammonia / amines or scavenging reagents, itself has a weak adsorption power for ammonia / amine, and has a large surface area in the form of particles, fibers, non-woven fabrics, meshes, foam-like inorganic substances, organic substances. Can be used as in the first embodiment.

In the third embodiment of the present invention, the ammonia / amine-scavenger 17 is coated with an acid having low volatility instead of the fluorescent labeling reagent described in the first embodiment. An amine scavenger may be used. When this scavenger is used, fluorescent labeling may be carried out after the scavenging, or it can be analyzed by other methods such as the IC method and the GC-MS method.

Examples of acids for coating solid substances include phosphonic acid, phosphoric acid, diphosphoric acid, boric acid, sulfuric acid, perchloric acid, adipic acid, quinaldic acid, citric acid, cinnamic acid, succinic acid, and oxalic acid. Inorganic and organic acids such as tartaric acid, fumaric acid, maleic acid, malonic acid, mandelic acid and malic acid are considered. Acetic acid, formic acid, hydrochloric acid, etc., which have a low melting point, are not suitable because the service life of the scavenger is shortened and air pollution due to volatilization into the air is considered. The method for coating an acid on a solid substance is such that an acid solution is passed through the solid substance, or the solid substance is immersed in the solution, or the solution is dropped onto the solid substance, or the solution is sprayed on the solid substance, and then dried. Then, the method of removing the solvent is common. Examples of the solvent that can be used when the acid is coated on the trapping portion include water, methanol, ethanol, propanol, isopropanol, acetone, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, dichloroethane, etc., but the solubility and boiling point of the acid Methanol or acetone is most suitable because of its low temperature. Amines that can be collected by acid are
They are primary to quaternary amines and ammonia.

When analysis is carried out by the GC-MS method, benzenesulfonyl chloride (BSC), pentafluoropropionic anhydride (acylating agent) or the like may be used for collection. After the reaction, elution with a solvent allows direct GC-M
It can be used for the S method.

According to the third embodiment of the present invention, there is an advantage that instantaneous sampling can be performed without the need to carry a pump, an integrating flowmeter, etc. to the sampling site. Alternatively, the solvent may not be extracted, and the amines may be quantified by directly irradiating the amine-collecting portion 17 with light such as ultraviolet light from the outside and measuring fluorescence or UV absorption.

The amines-collecting device according to the fourth embodiment of the present invention is such that the amines-collecting device has a cover at the end of a bent cylindrical container 26 as shown in FIG. It is a structure in which the parts 27, 28 and 29 are installed and the measured air is passed from one of the cylinders. Amine collection unit 27,2
Reference numerals 8 and 29 are formed by filling a predetermined container with the same ammonia / amine scavenger as in the first embodiment or holding it in a thin layer on a predetermined substrate. According to the fourth embodiment, ammonia / amine can be extracted with a small amount of solvent after the collection, and the solvent and the reagent can be directly added to the collecting agent by removing the cover, so that the operation is troublesome. Therefore, there is an advantage that contamination can be prevented.

In FIG. 5, since the straight portion 26 of the cylinder is alkali-coated or heated, there is no possibility that ammonia / amines will be adsorbed. A pump may be used as the suction means for passing the atmosphere to be measured into the cylinder so that a predetermined flow velocity is obtained. Alternatively, a container having a pressure lower than that of the atmosphere to be measured may be attached and the container may be moved by the pressure difference. Ends 27 and 2 where the cylinder is bent
Nos. 8 and 29 have a high gas collision probability and are liable to cause convection. The number of the amine traps 27, 28, 29 may be selected depending on the flow rate and the effect of the trapping agent, and is not limited to three as shown in FIG.

As shown in FIG. 5, by installing the amines-collecting parts 27, 28, and 29 at the bent parts of the pipe, ammonia / amines in the measured atmosphere can be easily collected. Even if all the ammonia and amines are not collected in the collection unit 27, next, the collection unit 28 or 29 is collected.
Can be completely collected with. 27 depending on the flow velocity and the thickness of the pipe
It is not necessary to install 28 and 29 because they can be completely collected with, but they may be installed as a blank for analysis. In order to pass the measured air into the cylinder, it is a general and easy method to use the suction pump 4 as shown in FIG. 5, but considering the contamination from the pump 4, in this case, Must be installed behind the collection area. Instead of the suction pump, a container whose pressure has been reduced by a vacuum pump or the like may be attached and opened.

As the ammonia / amines-collecting section used in the amines-collecting sections 27, 28, 29, ... Of the fourth embodiment of the present invention, a solid substance is used as in the third embodiment. A collection agent coated with a collection reagent is preferable. There are roughly two types of collection reagents. One is an acid and the other is a reaction reagent that reacts with ammonia or amine to make ammonia or amine into a non-volatile solid. For example, as the acid, phosphonic acid, phosphoric acid, diphosphoric acid, boric acid,
Inorganic / organic acids such as sulfuric acid, perchloric acid, adipic acid, quinaldic acid, citric acid, cinnamic acid, succinic acid, oxalic acid, tartaric acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid are considered. To be The method of coating an acid on a solid substance is the same as in the third embodiment, in which a solvent solution of an acid is passed through the solid substance, or the solid substance is dipped in the solution, or the solution is dropped onto the solid substance, or It is common practice to spray the solution onto a solid substance and then dry it to remove the solvent. Collection unit 27, 28, 2 for the above acid
As a solvent that can be used for coating No. 9, water,
Methanol, ethanol, propanol, isopropanol, acetone, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, dichloroethane and the like can be mentioned, but methanol or acetone is most suitable from the viewpoint of solubility of acid and low boiling point. Amines that can be collected by an acid are primary to quaternary amines and ammonia.

Although an alkyl halide or the like can be considered as a reaction reagent, it is preferable to coat a UV / fluorescence labeling reagent whose substituent emits UV absorption or fluorescence for the purpose of highly sensitive detection. Coating with the fluorescent labeling reagent enables highly sensitive fluorescence detection using the HPLC method. The amine fluorescent labeling agent includes NBD-Cl, NBD-F, and DB, as in the first to third embodiments.
DF, DBD-Cl, OPA, DNS-Cl, NBD
-Br, SBD-F, ABD-F, CBD-F, PBD
-SO ₂ F, BBD-SO ₂ F, NDA, fluoresmin, FMOC-Cl and the like are considered, but NBD-F having a strong fluorescence intensity and a fast reaction is particularly preferable.

After the ammonia / amines are collected by the apparatus shown in FIG. 5, the collecting portions 27, 28 and 29 are removed, and the mixture is eluted by adding a solvent or the like. HPLC, GC-MS, IC
It can be easily analyzed by directly injecting it into an analyzer such as. Alternatively, the amount may be determined by directly irradiating the collecting portion with light such as ultraviolet light and measuring fluorescence or UV absorption without performing solvent extraction.

In the conventional filter paper absorption method, it was necessary to remove the filter paper from the filter paper holder after collection, put it in a beaker, soak it in a solvent and extract it for analysis. However, when the method of the fourth embodiment of the present invention is used, it is only necessary to add a trace amount of the solvent and the reagent to the collection units 27, 28 and 29 as they are. . For example, to perform NBD-F fluorescence labeling after acid collection, add buffer and NBD-F to the cup and a standard substance inside,
It may be covered and heated at 70 degrees for 15 minutes, and then directly injected into high performance liquid chromatography (HPLC) for fluorescence detection.

FIG. 6 is a schematic view showing the outline of another ammonia-amines trapping apparatus according to a modification of the fourth embodiment of the present invention. As shown in FIG. 6, this device includes a container 31, such as a sample bottle, for accommodating and passing an atmosphere to be measured, an amine-collecting section 34 provided at the bottom of the container 31, and an amine-collecting section. The measured air introduction pipe 32 for introducing the measured air into the measuring atmosphere 34 and the measured air exhaust pipe 33 for exhausting the measured atmosphere from the container 31. The amines-collecting section 34 may be laid with, for example, a filter paper containing an acid. Although not shown, the measured air exhaust pipe 33 is connected to a suction pump, and the measured air collides with the amines collecting section 34 and is exhausted through the measured air exhaust pipe 33 to ammonia / amine. The kind is collected in the collection unit 34. Therefore, the measured air introduction pipe 31 is arranged so as to be substantially perpendicular to the main surface of the amine trap 34, and is inserted into the vicinity of the trap 34 from the outside of the container.

When the tip of the pipe 32 is spread over the trumpet, the area where the air to be measured directly collides with the amine trap increases and the amine trapping capacity can be increased, which is effective for long time trapping. is there. On the other hand, if the end of the pipe 32 is narrowed and narrowed, the area in which the non-measured atmosphere directly collides with the amine trap becomes small, so the amount of the trapping agent can be reduced, and it is effective for short-time trapping. .

In another example of the fourth embodiment of the present invention shown in FIG. 6, the inner wall of the measured air introduction pipe 32 is alkali-coated. For alkali coating, for example, a 1% potassium hydroxide methanol (glycerin 50%) solution may be passed through the pipe 32, and then the solvent may be removed using a vacuum pump. If the pipe is not coated with alkali, the pipe 32
It is advisable to wash into the container 31 while washing away with a solvent or the like. For the amines-collecting section 34, the ammonia / amines-collecting agent described in the first to fourth embodiments may be used. Even if the container 31 and the pipes 32 and 33 are made of glass, SU
It may be metallic such as S or resin such as Teflon. If the container 31 is used as a sample bottle for IC, HPLC, GC, etc., after collection, it is eluted by adding a solvent, reagent, etc. to this sample bottle and directly injected into an analyzer such as IC, HPLC, GC, etc. Can be analyzed. In addition, since the solvent and the reagent can be directly added to the collection unit 34 by removing the cover 35 of the container, there is an advantage that the operation is not troublesome and contamination can be prevented. Further, if the container 31 is made of a material transparent to ultraviolet rays such as glass, solvent extraction is not performed, and the collection portion 34 is directly irradiated with light such as ultraviolet light to measure fluorescence and UV absorption for quantitative determination. You can go.

The collecting device according to the fourth embodiment of the present invention is
Since it can easily collect ammonia and amines in the atmosphere and concentrate them to a high concentration, it can be said that this is the most suitable amine analysis and collection device. Therefore, the collection method according to the fourth embodiment of the present invention is effective for environmental management such as indoors, outdoors, and clean rooms.

FIG. 7 is a schematic view showing the outline of an air cleaning apparatus according to the fifth embodiment of the present invention. That is, the ammonia / amine scavenger of the present invention can be used as a long-life chemical filter or a deodorizing device by forming it into a shape as shown in FIG. In FIG. 7, the cylindrical rotating body 4
The surface of No. 1 is coated with a thin layer of the base material 42 of the ammonia / amine scavenger. The base material for this collector is
For example, glass fiber, quartz fiber, or the like, which is insoluble in a solvent such as water or alcohol, may be used. Alternatively, the surface area of nickel or stainless fiber may be expanded by an etching operation. The fibers may be knitted in a mesh. As a foam solid, mix silica gel with nickel or titanium,
Foamed ones are preferred. Particularly for the purpose of air cleaning, it is preferable to use a solid substance which has a strong adsorption of ammonia / amines. For example,
Silica gel, activated carbon, graphite carbon, etc. are preferable.
However, these have too strong adsorptive power and their subsequent recovery rate is low and cannot be used for analytical purposes.Because they also collect compounds other than ammonia and amines, they cannot be selectively collected. There are some points to note. A part of the rotating body 41 is dipped in an aqueous solution of an acid or alcohol solution 43 having low volatility, and the rotating body is slowly rotated.
The base material 42 of the scavenger dipped in the acid solution has the solvent removed by the dryer 44, so that only the acid is coated on the surface of the base material 42. Examples of the acid include phosphonic acid, phosphoric acid, diphosphoric acid, boric acid, sulfuric acid, perchloric acid, adipic acid, quinaldic acid, citric acid, cinnamic acid, and succinic acid as in the third and fourth embodiments. Inorganic and organic acids such as oxalic acid, tartaric acid, fumaric acid, maleic acid, malonic acid, mandelic acid and malic acid are preferably used.

The alcohol used as the acid solution is preferably methanol, ethanol, propanol or isopropanol, and acetone, acetonitrile, tetrahydrofuran, chloroform, dichloromethane or dichloroethane other than alcohol may be used. However, methanol or acetone is most suitable as the acid solution for immersing a part of the rotating body 41 in view of the acid solubility and the low boiling point. 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 the dryer of the fifth embodiment of the present 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 an acid causes the air to be measured to flow in a fixed direction inside the cylindrical container 46 by a sirocco fan, an axial duct fan, a suction pump 45, or the like. By contacting the base material 42 covered with, the ammonia and amines in the measured atmosphere can be collected and clean air can be sent out. If the contact cannot be completely collected with one contact, the cylindrical container may have a zigzag structure so as to contact it two or three times. After a certain time,
The scavenger on the surface of the base material 42 that has collected the ammonia / amines is rotated and is immersed again in the acid solution, so that the ammonia / amines are dissolved in the solution and can be returned to acidic again.

By constantly monitoring the pH of this solution with the pH meter 47, the life can be examined.
When the acidity is weakened, a new acid solution is used so that this ammonia-amine scavenger can semi-permanently collect. Using this method, compared with the conventional air-passing type chemical filter, it has a longer life, does not require the trouble of filter replacement, and because the pump load is smaller than the passing type, it has low power consumption, It has the advantage of being an inexpensive device.

If the solution 43 is used as a fluorescent labeling agent instead of an acid, it is possible to perform quantitative analysis by irradiating the surface of the collecting agent with ultraviolet rays and measuring the fluorescence amount after the collection. . The amine fluorescent labeling agent includes NBD-Cl, NBD-F, and DBD, as in the first to fourth embodiments.
-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 are particularly preferable NBD-F.

As described above, according to the air cleaning apparatus of the fifth embodiment of the present invention, ammonia and amines in the atmosphere can be collected efficiently and easily, and the maintenance thereof is easy. Is.

[0088]

EXAMPLES Examples of each of the above-described first, third and fourth embodiments of the present invention will be described below.

The analysis in the following description of the examples was carried out using the following equipment.

High Performance Liquid Chromatography (HPL
C): manufactured by Waters, HPLC6
10E system column: manufactured by Japan Chemicals Inspection Association (brand name L-column O
DS) (4.6 mmφ × 250 mm) (column temperature; 40 ° C., flow rate; 1.0 ml / min, mobile phase solvent; acetonitrile / water = 45/55, injection amount; 20
μl / once) Detector: Waters 474 scanning fluorescence detector (excitation wavelength; 450 nm, fluorescence wavelength; 530 nm) (Example of the first embodiment) Capture of the first embodiment of the present invention As the collecting tube 1, a plastic solid-phase extraction cartridge (manufactured by Waters, trade name Sep-PAK plus cartridge) shown in Table 1 was prepared.
After washing by flowing 10 to 20 ml of methanol, NB
1 ml or 2 ml of a DF-borate buffer (1.0 mg / ml) solution was passed through. 1mo for borate buffer
A 1 / l borate buffer (PH 8.35) was used.

The solid phase extraction cartridge 1 was placed in a desiccator, depressurized by a vacuum pump for 1 hour, and methanol was removed to prepare a collection tube 1 filled with the collection agent 2 of the present invention.

Next, 0.1 W of quartz wool was placed in the collection tube 1.
mg to standard amine-methanol solution (methylamine 40
0 ng, ethylamine 700 ng, propylamine 70
Connect a tube containing quartz wool impregnated with
Nitrogen gas was caused to flow at a rate of 500 ml / min to vaporize the entire amount of the amine and send it to the collection tube.

Methanol (1 ml or 1.5 ml) was passed through the collection tube 1 into which the amine was fed, and NBD-F was used.
Of the methanol solution, and add more methanol to add 5
Weighed to ml.

20 μl of this methanol solution was subjected to fluorescence analysis using the HPLC apparatus manufactured by Waters Co. to obtain a standard chart shown in FIG. Further, the fluorescence intensity of methylamine at that time was measured, and the results are shown in Table 1.

When silica gel to which ODS was bound was used as solid particles, blank peaks overlapped with peaks, and it was difficult to quantify them, so that they are not listed in Table 1. Table 1 shows the results of analysis using a solution in which methanol was added to the above standard amine-methanol solution and weighed to 5 ml as a standard solution (referred to in the table).

As is clear from the results shown in Table 1, the scavenger obtained by coating the silica gel particles having the cyanomethylpropylsilyl group (CN) bonded to the surface thereof with the amine fluorescent labeling agent (NBD-F) was used. It can be seen that the reaction with which the fluorescently labeled derivative is formed is instantly completed at room temperature with the highest concentration. Also, magnesium silicate takes a long time to form a fluorescent labeled derivative at room temperature, but 70% after collection.
It was found that by heating to 0 ° C, a strength comparable to that of CN was obtained in 10 minutes.

[0097]

[Table 1] Further, as an analysis example of amines in the air, by using the collection tube 1 produced by using silica gel bonded with CN as solid particles, by the method of the first embodiment of the present invention shown in FIG. , Air in the smoking room at a rate of 500 ml / min for 20
Suction for a minute, and analyze amines contained in cigarette smoke by HPLC
Fluorescence analysis was performed using the instrument. The result is shown in FIG. In FIG. 9, the content of amines is methylamine 34.
It was 9 ppb, dimethylamine 3.2 ppb, and ethylamine 6.5 ppb.

(Example of Third Embodiment) Hereinafter, an example of the third embodiment of the present invention will be described in detail. In this example, the HPLC610E system manufactured by Waters Co., which is the same as the example of the first embodiment described above, was used, and the same column and detector were used.

First, a hydrophilic PTFE (Teflon) type membrane filter (Toyo Roshi Kaisha, Ltd., pore diameter 0.2 μm, diameter 25 mm, thickness 35 μm) was prepared in order to construct the amine-collecting portion 17 shown in FIG. . After washing this disk with methanol, it was attached to an aluminum foil sheet, and then 0.1% of a 0.3% methanol solution of tartaric acid was added.
1 was evenly dropped onto the disk, placed in a desiccator, and dried under reduced pressure with a vacuum pump to obtain an ammonia / amines collecting section 17. When the reduced pressure was released, it was replaced with high-purity nitrogen.

Next, as a container 11 according to a third embodiment of the present invention shown in FIG. 4, a stainless steel vacuum desiccator (SUS) is used.
304, internal volume 3 L) was prepared. An upper portion of the container 11 is provided with a vacuum exhaust cock 12 and a port 13 for attaching an amines collecting section. A stirrer that creates an upward flow is placed inside the container 11, and a 1% potassium hydroxide methanol solution (containing 50% glycerin) is used with a pipette.
Apply to cover the entire inner wall with. And amine collection part 1
The mouth 13 to which 7 was attached was incorporated into the container 11. Only the methanol can be removed by drying under reduced pressure using a vacuum pump, and the inner wall of the container 11 was uniformly alkali-coated.

Next, in the factory, the cock 12 was released from the container that had been decompressed using the vacuum exhaust cock, and the air in the factory was sampled in the container 11. That is, after returning the container 11 to the atmospheric pressure, the cock 12 was closed and sealed again.

Then, while heating the entire container at 100 ° C. for 1 hour, air stirring was performed using a magnetic stirrer 15 (60 rpm) to collect the amines in the container 11 with an ammonia / amines collecting agent. did. Then, after returning the container 11 to room temperature, remove the lid and immediately add 0.5 ml of borate buffer (pH 8.5) / methanol to 2 m.
0.5 ml of g / ml NBD-F methanol solution and n-butylamine / methanol for internal standard were added, and the bottle was tightly capped.
The reaction was carried out at 0 ° C for 15 minutes. Then, the above-mentioned HPLC
The results of fluorescence detection under the conditions are shown in FIG.

According to the third embodiment of the present invention, FIG.
As shown in 0, the ammonia and amines in the atmosphere can be collected in a container and concentrated to a high concentration. Therefore, it can be said that this example is the most suitable as a collection method for analysis of amines having a large number of carbon atoms. Therefore, the trapping device according to the third embodiment of the present invention is effective for environmental management such as indoor, outdoor, and clean room.

Example of Fourth Embodiment Inner Diameter 0.5
A glass tube having a length of 50 cm and a length of 50 cm was bent to form a cylindrical container 26 as shown in FIG. 5, and a hole was formed in the end portion of the container 26 so that the amine collecting portions 27, 28 and 29 were attached. A 1% potassium hydroxide methanol solution (containing 50% glycerin) is applied to the inside of the cylindrical container 26 using a pipette. Then, it was dried by a vacuum pump and the inner wall of the glass tube 26 was alkali-coated. Amine collection unit 27,2
8, 29, the same filler as in the example of the third embodiment is cut out and put in a circular aluminum foil cup having a diameter of 1.5 cm, the edges are pressed, and the end portion of the cylindrical container 26 is firmly held. Fixed

Cylindrical container 2 with factory air for 10 minutes at 2 L / min
After sucking into 6 and sampling the air to be measured, the collection parts 27, 28 and 29 are removed, and 0.5 ml of borate buffer (pH 8.5) / methanol is added to each cup constituting the collection part. 0.5 mg of 1 mg / ml NBD-F methanol solution and n-butylamine / methanol for internal standard were added, and the bottle was tightly capped and reacted at 70 ° C. for 15 minutes. Then, the results of fluorescence detection under the above HPLC conditions are shown in FIG.
Shown in 1.

[0106]

The scavenger of the present invention is a derivative of an amine fluorescent labeling agent, which efficiently traps amines having a large number of carbon atoms such as primary amines and secondary amines in gas and ammonia, and is an amine fluorescent labeling agent. Therefore, the amines can be analyzed rapidly and with high sensitivity.

Further, when the collection device of the present invention is used to collect, amino acids in the air can be easily collected at a high concentration, which is suitable for highly sensitive analysis of trace amines in the air. There is.

Further, when air is cleaned using the trap of the present invention, the power consumption is low and the life is long as compared with the conventional chemical filter method.

Therefore, the scavenger of the present invention, the scavenger, and the amine analysis method using the scavenger are effective for environmental management such as indoor, outdoor, and clean room. In particular, the environmental management of amines in a clean room is improved, so that the yield of semiconductor manufacturing processes such as resist processing is improved, and a high-quality semiconductor device can be provided.

[Brief description of drawings]

FIG. 1 is a specific example showing a device for collecting amines using a collecting tube according to a first embodiment of the present invention.

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

FIG. 3 is an explanatory diagram showing a specific example of the case where the collected amine fluorescent labeling agent derivative is developed and concentrated from the substrate shown in FIG.

FIG. 4 is a schematic diagram of an amines-collecting device according to a third embodiment of the present invention.

FIG. 5 is a schematic view of an amines-collecting device according to a fourth embodiment of the present invention.

FIG. 6 is a schematic view of another amines-collecting device according to a modification of the fourth embodiment of the invention.

FIG. 7 is a schematic view of an air cleaning device according to a fifth embodiment of the present invention.

FIG. 8 is a chromatogram of standard amines separated and analyzed by the method according to the first embodiment of the present invention.

FIG. 9 is a chromatogram of amines in the air of a smoking room separated and analyzed by the method according to the first embodiment of the present invention.

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

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

FIG. 12 is a diagram showing the relationship between pH and fluorescence intensity.

[Explanation of symbols] 1 collection tube 2 Collection agent 3 filters 4,45 suction pump 5 Collection board 6 Labeling agent-free layer 7 Concentration part 8 development tanks 9 solvent 11 containers 12 cooks 13 mouths 15 Magnetic Tech Stirrer 16 Stirrer 17, 27, 28, 29, 34 Amine collection part 26,46 Cylindrical container 31 containers (sample bottles) 32 Measured air introduction pipe 33 Measured air exhaust pipe 35 Container cover 41 rotating body 42 Base material 43 Acid aqueous solution (or acid alcohol solution) 44 dryer 47 PH meter

Front Page Continuation (72) Hideyuki Sasaki Inventor Hideyuki Sasaki 1 Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa Within Toshiba Research and Development Center Co., Ltd. (56) Reference JP-A-7-149760 (JP, A) JP-A-5- 142152 (JP, A) JP-A-2-167448 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G01N 21/75-21/84 G01N 31/00-31/22 JISST File (JOIS) CAPLUS (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A fluorescent label for amines selected from primary amines, secondary amines and ammonia contained in a gas, which is obtained by coating at least a part of a solid substance with an amine fluorescent labeling agent. An amine-scavenger characterized by collecting as an agent derivative. 2. A cylindrical collection tube having a filter installed on the outlet side, the amine-scavenger filled in the collection tube, and the atmosphere to be measured are sucked through the collection tube. 2. An amines-collecting device using an amines- collecting agent according to claim 1, further comprising: a suction means connected to the collecting pipe for carrying out. 3. The amine trap using the amine trap according to claim 1, wherein the surface of a predetermined substrate is coated with the amine trap. 4. A gas containing the amines is brought into contact with the scavenger according to claim 1, and the amines collected by the scavenger are detected by fluorescence. A method for collecting and analyzing amines.