Adsorption tubular column for capturing acid component or alkali component in gas, and application thereof

Abstract

Provided is an adsorption column for trapping which can be quantitatively used for trapping an acid component or an alkali component in a gas in a short time and with high sensitivity. As a result, a collection adsorption tubular column for collecting an acid component or an alkali component in a gas is used, the collection adsorption tubular column being filled with a non-porous base material that holds an acid adsorbent for adsorbing an acid component or an acid adsorbent for adsorbing an alkali component, and having a pressure loss of 10 kPa or less when the gas inside is sucked at a suction rate of 2.0 L / min.

Description

TECHNICAL FIELD

[0001] The present application relates to a trapping adsorption column for trapping an acid component or a base component in a gas and an application thereof. The application specifically includes a method for trapping an acid component or a base component in a gas, a method for quantifying a concentration of an acid component or a base component in a gas using the trapping method, and a method for managing cleanliness of a clean room using the quantifying method. BACKGROUND

[0002] In an environment in which a semiconductor wafer, a liquid crystal substrate, a magnetic disk, or the like (hereinafter referred to as a substrate) is manufactured, sometimes, a yield of a product or a quality thereof is reduced due to, for example, adsorption of a contaminant such as an acid substance (acid component) or a base substance (base component) in a manufacturing space of the substrate. In this regard, in order to prevent the reduction of the yield and the quality, a process of manufacturing the substrate is performed in a clean room. Further, it is necessary to evaluate a contamination condition, that is, cleanliness, of the clean room by the acid substance, the base substance, or the like in each manufacturing process, and to eliminate a cause of contamination or the like in a case where the cleanliness is deteriorated, thereby managing the cleanliness of the clean room. In addition, in recent years, along with a request for ensuring a highly clean space in the clean room, a method for evaluating the contamination condition, that is, the cleanliness, of the clean room by the acid component or the base component with higher sensitivity in a shorter time is now demanded. Furthermore, in recent years, in order to make the management of the cleanliness of the clean room easy, it is also requested to shorten a required time for the evaluation.

[0003] As the method for evaluating the cleanliness with high sensitivity and in a short time, for example, a method for quantifying a contaminant using a gas adsorption column as described in Patent Documents 1 and 2, or a method for quantifying a contaminant using a liquid-free trap as described in Patent Document 3 can be cited. Here, the contaminant refers to an acid component and / or a base component in air. The method for quantifying the contaminant specifically, for example, is a method in which air in a clean room is caused to flow through the gas adsorption column or the liquid-free trap to adsorb the contaminant in the air, and then an amount of the adsorbed contaminant is quantified. (Prior Art Documents)

[0004] Patent Document 1: Japanese Patent Application Publication No. 2009-14522 Patent Document 2: International Publication No. 2010 / 067464 Patent Document 3: Japanese Patent No. 6563396 SUMMARY (PROBLEMS TO BE SOLVED BY THE INVENTION)

[0005] However, the evaluation method using a gas adsorption column described in Patent Literatures 1 and 2 has room for improvement in the evaluation time. In addition, the evaluation method using a liquid-free trap described in Patent Literature 3 has room for improvement in the sensitivity.

[0006] The present application has been achieved in view of the above problems, and an object of the present application is to provide a trap adsorption column capable of quantifying an acid component or a base component in a gas with a short time and a high sensitivity, and a trapping method and a quantification method for the acid component or the base component. In addition, another object of the present application is to provide a space cleanliness management method capable of easily ensuring a highly clean space. (Technical means for solving the problems)

[0007] To achieve the object, a trap adsorption column according to an embodiment of the present application is used to trap an acid component or a base component in a gas, and the trap adsorption column is filled with a non-porous base material that holds a basic adsorbent for adsorbing an acid component or an acid adsorbent for adsorbing a base component, and has a pressure loss of 10 kPa or less when a gas in the trap adsorption column is sucked at a suction rate of 2.0 L / min.

[0008] In addition, to achieve the object, a trapping method according to an embodiment of the present application is used to trap an acid component or a base component in a gas, and the acid component or the base component in the gas is trapped by causing the gas to flow through a trap adsorption column according to an embodiment of the present application.

[0009] Further, to achieve the object, a quantification method according to an embodiment of the present application is used to quantify a concentration of an acid component or a base component in a gas, and includes: a trapping step of trapping the acid component or the base component in the gas using the trapping method according to an embodiment of the present application; an elution step of causing a solvent to flow through the trap adsorption column in which the acid component or the base component is trapped, thereby eluting the trapped acid component or base component into the solvent to obtain an eluate; and a measurement step of measuring a concentration of the acid component or the base component in the eluate.

[0010] Further, to achieve the other object, a management method according to an embodiment of the present application is used to manage cleanliness of a space, and includes: a quantification step of quantifying a concentration of an acid component or a base component in a gas in a space using the quantification method according to an embodiment of the present application; and an exclusion step of determining and excluding a source of the acid component or the base component in the gas inside the space when the concentration of the acid component or the base component quantified in the quantification step exceeds a threshold value. (Effects of the Invention)

[0011] According to the trapping adsorption column according to one embodiment of the present application, the trapping method according to one embodiment of the present application, and the quantitative method according to one embodiment of the present application, it is possible to quantify an acid component or a base component in a gas with high sensitivity in a short time. In addition, according to the space cleanliness management method according to one embodiment of the present application, it is possible to easily ensure a highly clean space. BRIEF DESCRIPTION OF DRAWINGS

[0012] Figure 1 FIG. 1 is a schematic configuration view of a quantitative device used in Examples 4 and 5. <LEGEND> 1 Acid component adsorption column 2 Base component adsorption column 3 Suction pump 4 Connection tube DETAILED DESCRIPTION

[0013] One embodiment of the present application will be described below, but the present application is not limited to the following described embodiments. The present application can be variously changed within the technical concept described in the specification, and embodiments obtained by appropriately combining the technical means disclosed in each of the embodiments are also included in the technical scope of the present application.

[0014] [Embodiment 1: Trapping adsorption column] One embodiment of the present application relates to a trapping adsorption column (hereinafter also referred to as "the present trapping adsorption column") for trapping an acid component or a base component in a gas. A non-porous base material is filled therein. The non-porous base material holds a basic adsorbent for adsorbing an acid component or an acid adsorbent for adsorbing a base component. The pressure loss of the present trapping adsorption column is 10 kPa or less when a gas in the present trapping adsorption column is sucked at a suction speed of 2.0 L / min.

[0015] The present trapping adsorption column filled with a non-porous base material holding a basic adsorbent is a column for trapping an acid component in a gas, and is hereinafter also referred to as "an acid component adsorption column". In addition, the present trapping adsorption column filled with a non-porous base material holding an acid adsorbent is a column for trapping a base component in a gas, and is hereinafter also referred to as "a base component adsorption column". The present trapping adsorption column is either an acid component adsorption column or a base component adsorption column.

[0016] (non-porous base material) A non-porous base material holding a basic adsorbent for adsorbing an acid component or an acid adsorbent for adsorbing a base component is filled in the present trapping adsorption column.

[0017] Here, as a material constituting an adsorption component filled in the trapping adsorption column, a porous material having a large surface area and a property of easily adsorbing an object substance into the inside has been used in the past from the viewpoint of ensuring the adsorption force to the object substance. However, if the substance adsorbed by the trapping adsorption column is quantified, the adsorbed substance needs to be desorbed and eluted into a solvent to prepare an eluate, and then the eluate is subjected to quantification. Since the adsorption component constituted by the porous material has a strong adsorption force to the object substance, it is difficult to desorb the substance into the solvent in the case of adsorbing a very small amount of the substance. Therefore, the method of quantification using the trapping adsorption column filled with the adsorption component constituted by the porous material is difficult to quantify a very small amount of the substance.

[0018] In addition, the adsorption component constituted by the porous material can adsorb a substance other than the object substance into the inside. Therefore, the method of quantification using the trapping adsorption column filled with the adsorption component constituted by the porous material can trap a substance other than the object substance, that is, a substance other than the object substance of quantification, into the inside of the adsorption column. As a result, the presence of the other substance can become noise to make it difficult to quantify a very small amount of the substance.

[0019] On the other hand, the non-porous base material has a weaker adsorption force to the object substance than the porous material, and even if a very small amount of the substance is adsorbed, the adsorbed substance can be easily desorbed into the solvent. Therefore, by the quantification method using the present trapping adsorption column, a very small amount of the substance can be quantified.

[0020] In addition, the present trapping adsorption column is filled with the non-porous base material, and therefore the other substance is not adsorbed by the non-porous base material. Therefore, it is possible to prevent the case where a very small amount of the substance cannot be quantified due to the presence of the other substance. Here, in one embodiment of the present application, the substance of quantification is an acid component or a base component in a gas.

[0021] As described above, according to the present trapping adsorption column, it is possible to trap and quantify an acid component or a base component in a gas with high sensitivity. In addition, in the present specification, trapping and quantification with high sensitivity means, for example, trapping and quantifying the concentration of the acid component or the base component in the gas in the order of about 10 -2 μg / m 3

[0022] ​The non-porous base material is not particularly limited as long as it is not porous, and the material is not particularly limited. Examples of the material of the non-porous base material include quartz, glass, polycarbonate resin, polystyrene resin, polyamide resin, silicon carbide (SiC), aluminum oxide (AI2O3), silicon nitride (SiN), and the like. From the viewpoint of more effectively preventing the non-porous base material from being contaminated during use of the present trapping adsorption column, the material of the non-porous base material is preferably quartz or glass, and particularly preferably quartz.

[0023] The shape of the non-porous base material is not particularly limited, and a shape having a large surface area is preferable from the viewpoint of more effectively trapping the acid component or the base component in the present trapping adsorption column. Examples of the shape having a large surface area include a granular shape, a fibrous shape, and the like. The shape of the non-porous base material is more preferably a granular shape.

[0024] From the viewpoint of improving the efficiency of gas passage into the present trapping adsorption column, the lower limit of the average particle diameter or the cross-sectional average diameter of the non-porous base material is preferably 300 μm, more preferably 400 μm, further preferably 450 μm, still further preferably 500 μm, and particularly preferably 600 μm. From the viewpoint of improving the efficiency of trapping the acid component or the base component in the present trapping adsorption column, the upper limit of the average particle diameter or the cross-sectional average diameter of the non-porous base material is preferably 1200 μm, more preferably 1100 μm, further preferably 1050 μm, still further preferably 1000 μm, and particularly preferably 850 μm. Note that the average particle diameter and the cross-sectional average diameter are measured according to JIS K0069 "Chemical Products - Sieving Test Method".

[0025] The basic adsorbent is an adsorbent for adsorbing an acid component, and specifically can be an adsorbent composed of a basic substance or an adsorbent containing a basic substance. In addition, the acidic adsorbent is an adsorbent for adsorbing a base component, and specifically can be an adsorbent composed of an acidic substance or an adsorbent containing an acidic substance.

[0026] In one embodiment of the present application, the acid component is not particularly limited. Examples of the acid component include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, formic acid, acetic acid, bromic acid, iodine, lactic acid, propionic acid, butyric acid, valeric acid, and the like, and also include ammonium fluoride, ammonium formate, ammonium acetate, and the like. In addition, in one embodiment of the present application, the base component is not particularly limited. Examples of the base component include ammonia, trimethylamine, triethylamine, alkanolamine, dimethylamine, diethylamine, and the like, and also include ammonium fluoride, ammonium formate, ammonium acetate, and the like.

[0027] The amount of the basic adsorbent or the acidic adsorbent in the trapping adsorption column is preferably 0.4 μeq or more, more preferably 0.7 μeq or more, and further preferably 0.8 μeq or more. The amount of the basic adsorbent or the acidic adsorbent is preferably adjusted to 0.4 μeq or more from the viewpoint of exerting the effect of preventing column breakthrough when trapping a gas at a high concentration. On the other hand, the amount of the basic adsorbent or the acidic adsorbent is preferably 50 μeq or less, more preferably 30 μeq or less, and further preferably 20 μeq or less. The amount of the basic adsorbent or the acidic adsorbent is preferably adjusted to 50 μeq or less from the viewpoint of exerting the effect of preventing an excess of the adsorbent component from interfering with the measurement. The amount of the basic adsorbent or the acidic adsorbent is a value expressed in equivalents and can be measured by the method described in the Examples.

[0028] As the basic adsorbent, inorganic bases and organic bases can be given. As the inorganic bases, carbonates of alkali metals, hydroxides of alkali metals, and the like can be given. As the organic bases, amines, ammonium compounds, and the like can be given.

[0029] The basic adsorbent is preferably at least one compound selected from among the above-listed compounds, among which are alkali metal carbonates, alkali metal hydroxides, amines, and ammonium compounds.

[0030] As the alkali metal carbonates, sodium carbonate, potassium carbonate, potassium bicarbonate, and the like can be given. As the alkali metal hydroxides, strontium hydroxide, potassium hydroxide, sodium hydroxide, and the like can be given. As the amines, triethanolamine, and the like can be given. As the ammonium compounds, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and the like can be given.

[0031] The basic adsorbent is more preferably at least one compound selected from among sodium carbonate, sodium hydroxide, and triethanolamine.

[0032] As the acidic adsorbent, inorganic acids and organic acids can be given.

[0033] As the inorganic acids, sulfuric acid, phosphoric acid, and the like can be given. As the organic acids, methanesulfonic acid, maleic acid, malonic acid, and the like can be given.

[0034] The acidic adsorbent is preferably at least one compound selected from among the above-listed compounds, among which are sulfuric acid, phosphoric acid, and methanesulfonic acid.

[0035] In one embodiment of the present application, the form of the non-porous base material holding the basic adsorbent or the acidic adsorbent is not particularly limited. The form can be, for example, a form in which the non-porous base material is coated with a liquid phase containing the basic adsorbent or the acidic adsorbent, or a form in which the non-porous base material is attached with the basic adsorbent or the acidic adsorbent in a solid state on the surface of the non-porous base material.

[0036] The liquid phase is a liquid containing the basic adsorbent or the acidic adsorbent, and contains a solvent as necessary. In other words, in the case where the basic adsorbent or the acidic adsorbent is a solid, the liquid phase can be prepared by dissolving the basic adsorbent or the acidic adsorbent in a solvent. As the solvent, a solvent capable of dissolving the basic adsorbent or the acidic adsorbent without causing adverse effects on the non-porous base material can be used, and is not particularly limited. As specific examples of the solvent, water, hydrogen peroxide, ethanol, acetonitrile, or a mixture liquid thereof, and the like can be given. The solvent is preferably a solvent containing water, for example, a mixture of water and a solvent other than water among the specific examples of the solvent given above, and more preferably a solvent consisting only of water. On the other hand, in the case where the basic adsorbent or the acidic adsorbent is a liquid, the basic adsorbent or the acidic adsorbent can be used directly as the liquid phase.

[0037] In one embodiment of the present application, the method of coating the non-porous base material with the liquid phase is not particularly limited. As the method, a method of applying the liquid phase to the non-porous base material, and a method of immersing the non-porous base material in the liquid phase, then taking up the non-porous base material and drying the same, and the like can be given. As a specific example of the method of applying the liquid phase to the non-porous base material, a method of applying the liquid phase by flowing the liquid phase through a container filled with the porous base material, for example, a column, can be given. Here, the "flowing through" means flowing the liquid phase through a container filled with the porous base material, for example, a column. Note that in the case where the drying conditions are set to high temperature and long time, sometimes the solvent in the liquid phase evaporates to cause the solid of the basic adsorbent or the acidic adsorbent to be deposited on the surface of the non-porous base material. At this time, the non-porous base material in which the basic adsorbent or the acidic adsorbent in a solid state is attached on the surface of the non-porous base material can be obtained.

[0038] In one embodiment of the present application, the non-porous substrate can further hold a humectant. Note that in the case where the non-porous substrate further holds a humectant and the basic adsorbent or the acidic adsorbent is held in the form of the liquid phase, the liquid phase can further contain the humectant. As the humectant, a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerol, or the like; a polyalkylene glycol such as polyethylene glycol, polypropylene glycol, or the like can be exemplified. In addition, the content of the humectant can be 0.01% by weight or more and 1.0% by weight or less, preferably 0.1% by weight or more and 0.5% by weight or less, with respect to the total weight of the non-porous substrate coated with the liquid phase. (Structure of the adsorption column for trapping)

[0039] The adsorption column for trapping of the present application can be composed of a housing (i.e., a jacket portion) and a filter (i.e., a grid) for preventing the non-porous substrate disposed inside the housing from flowing out. As for the material of the housing and the grid, there is no particular limitation as long as it is a material that does not affect the acid component or the base component as a trapping target and is not adversely affected by corrosion of the basic adsorbent or the acidic adsorbent. As for the material of the housing, for example, polypropylene, glass, polyethylene (PE), polyether ether ketone (PEEK), polyvinyl chloride (PVC), polystyrene (PS), ABS resin (ABS), methacrylic resin, acrylic resin (PMMA), polyamide (PA), polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (mPPE), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polysulfone (PSU), polyarylate (PAR), fluororesin (PFA), and a mixture thereof can be exemplified. In addition, as for the material of the grid, for example, polyethylene, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethersulfone (PES), cellulose, glass fiber, carbon fiber, diatomite, cellulose, polyethylene terephthalate (PET), nylon, and a mixture thereof, or the like can be exemplified. The material of the housing and the grid can be the same or different.

[0040] The shape of the adsorption column for trapping of the present application is not particularly limited, and a cylindrical shape can be generally employed. As the adsorption column for trapping, a column composed of a column main body, a grid, a sleeve, and a terminal fitting, for example, the column described in Japanese Patent Application Publication No. 2001-249120 can be exemplified.

[0041] The inner volume of the adsorption column for trapping (the inner volume of the housing) can be appropriately sized in accordance with the amount of analysis processing. The volume is, for example, 0.6 ml to 5 ml, 0.6 ml to 3 ml, or 0.7 ml to 2 ml.

[0042] The void volume of the trapping adsorption column refers to the volume of the voids in the trapping adsorption column that are not occupied by the non-porous substrate coated with the liquid phase. The void volume can be measured, for example, by the method described in the examples. When trapping the acid component or the base component in a gas, the larger the void volume, the greater the amount of the gas flowing through the trapping adsorption column per unit time, i.e., the gas flow rate. Here, if the trapping adsorption column is used for quantification, a predetermined amount of the gas can be collected in the trapping adsorption column and caused to flow therethrough, thereby trapping the acid component or the base component contained in the predetermined amount of the gas. Therefore, the larger the void volume, the shorter the time required for collecting the predetermined amount of the gas by causing the gas to flow through the trapping adsorption column. Thus, in the trapping adsorption column, the larger the void volume, the more rapidly the acid component or the base component in the gas can be trapped and quantified.

[0043] From the viewpoint of quantifying the acid component or the base component in a gas in a shorter time using the trapping adsorption column, the void volume is preferably 200 μL or more, more preferably 300 μL or more, and further preferably 400 μL or more.

[0044] On the other hand, when the void volume is equal to or less than a predetermined value, the amount of the non-porous substrate holding the basic adsorbent or the acidic adsorbent in the trapping adsorption column is sufficiently large, and the ability to trap the acid component or the base component in the gas can be sufficiently ensured. Thus, according to the trapping adsorption column, the acid component or the base component in the gas can be trapped and quantified with higher sensitivity. From the viewpoint of being able to trap and quantify the acid component or the base component in the gas with higher sensitivity, the void volume is preferably 5,000 μL or less, more preferably 3,000 μL or less, further preferably 600 μL or less, and particularly preferably 500 μL or less.

[0045] The void ratio of the trapping adsorption column can be defined by "void ratio (%) = void volume ÷ internal volume of the trapping adsorption column x 100". In this case, the lower limit of the void ratio of the trapping adsorption column is not limited, but can be, for example, 10%, 20%, 30%, 40%, 50%, 60%, or 70%. On the other hand, the upper limit of the void ratio of the trapping adsorption column is also not limited, but can be, for example, 90%, 80%, or 70%. This embodiment is preferable because it can sufficiently exhibit the effect of preventing the decrease in the suction rate at the time of gas collection caused by a low void ratio and the decrease in the adsorption amount of the acid component or the base component to the adsorbent.

[0046] The upper limit value of the pressure loss when the gas in the present trapping adsorption column is drawn at a drawing speed of 2.0 L / min is 10 kPa or less. Hereinafter, the pressure loss when drawn at a drawing speed of 2.0 L / min is referred to as "pressure loss A". Here, as described above, in the case where the present trapping adsorption column is used to perform the quantification, it is necessary to cause a prescribed amount of gas to be drawn through the present trapping adsorption column to trap the acid component or the base component contained in the prescribed amount of gas. By causing the pressure loss A to be 10 kPa or less, when the gas to be measured is collected in the present trapping adsorption column and is caused to flow through the present trapping adsorption column in order to perform the quantification, the gas can be drawn at high speed without imposing a load on the drawing pump used for the gas collection. Therefore, the prescribed amount of gas can be collected and caused to flow through the present trapping adsorption column in a short time. Therefore, according to the present trapping adsorption column, the acid component or the base component in the gas can be trapped and quantified in a short time.

[0047] From the viewpoint of quantifying the acid component or the base component in the gas in a short time using the present trapping adsorption column, the upper limit value of the pressure loss A is preferably 7 kPa, and more preferably 5 kPa.

[0048] [Embodiment 2] The trapping method (hereinafter, also referred to as "the present trapping method") of one embodiment of the present application is a trapping method of an acid component or a base component in a gas, in which the gas is caused to flow through the present trapping adsorption column to trap the acid component or the base component in the gas.

[0049] The present trapping method traps the acid component or the base component in the gas using the present trapping adsorption column. Here, as described above, according to the present trapping adsorption column, the trace amount of the acid component or the trace amount of the base component in the gas can be trapped in a short time. Therefore, by the present trapping method, a quantification method which can trap and quantify the acid component or the base component in the gas in a short time and with high sensitivity can be performed.

[0050] Hereinafter, the present trapping method in the case where the acid component in the gas is trapped using the acid component adsorption column is also referred to as "the acid component trapping method". In addition, the present trapping method in the case where the base component in the gas is trapped using the base component adsorption column is also referred to as "the base component trapping method". The present trapping method is the acid component trapping method or the base component trapping method.

[0051] The configuration and the like of the present trapping adsorption column used in the present trapping method are cited from the configuration and the like described in "[Embodiment 1: Trapping Adsorption Column]". In addition, the acid component and the base component which are the objects of the quantification of the present trapping method are not particularly limited, and can be the acid component and the base component exemplified in the column of "[Embodiment 1: Trapping Adsorption Column]" described above.

[0052] In this case, the acid component trapping method and the base component trapping method can be simultaneously performed on the same gas, thereby trapping both the acid component and the base component in the gas.

[0053] In the present trapping method, by flowing the gas to be trapped through the present trapping adsorption column, the acid component or the base component in the gas is trapped by being adsorbed to the non-porous base material of the acid component adsorbent or the base component adsorbent material. The flowing can be performed using a suction pump, for example.

[0054] In the present trapping method, by flowing the gas at a higher ventilation flow rate through the trapping adsorption column for trapping the acid component or the base component in the gas, the time required for the trapping step to trap the acid component or the base component can be shortened. As a result, by the present trapping method, the acid component or the base component in the gas can be trapped and quantified in a short time. From the viewpoint of trapping and quantifying the acid component or the base component in the gas in a short time, the ventilation flow rate is preferably 2.0 L / min or more, more preferably 3.0 L / min or more. On the other hand, if the ventilation flow rate is too high, the pressure applied to the present trapping adsorption column when the gas flows through the column can increase, and the present trapping adsorption column can be damaged. From the viewpoint of preventing the present trapping adsorption column from being damaged, the ventilation flow rate is preferably 10 L / min or less, more preferably 7 L / min or less. From the viewpoint of excellent time required for the quantification and excellent prevention of the damage, the ventilation flow rate is particularly preferably 5 L / min.

[0055] The flowing in the present trapping adsorption column is generally performed in an evaluation target space such as a dust-free room or a clean room. The present trapping adsorption column can be transported by sealing the port of the column with a plug that is not contaminated with the analysis target substance, and / or by housing the column in a closed container that is not contaminated with the analysis target substance.

[0056] If the acid component trapping method and the base component trapping method are performed together, a device having a structure in which an acid component adsorption column and a base component adsorption column are connected in series can be used to continuously perform the acid component trapping method and the base component trapping method separately. That is, the device can be caused to suck the air so that the air flows through both the acid component adsorption column and the base component adsorption column formed in the device continuously. More specifically, the air after flowing through the acid component adsorption column can be caused to flow through the base component adsorption column (i), or the air after flowing through the base component adsorption column can be caused to flow through the acid component adsorption column (ii). In these cases, the acid component adsorption column and the base component adsorption column can be directly connected or connected via a connecting pipe. [Embodiment 3: Quantification method] The quantitative method of one embodiment of the present application (hereinafter, also referred to as "the present quantitative method") is a method for quantifying the concentration of an acid component or a base component in a gas, and includes: a trapping step of trapping the acid component or the base component in the gas by the present trapping method; an elution step of flowing a solvent through the trapping adsorption column in which the acid component or the base component is trapped, so that the trapped acid component or base component is eluted into the solvent to obtain an eluate; and a measurement step of measuring the concentration of the acid component or the base component in the eluate.

[0057] The present quantitative method quantifies the acid component or the base component in a gas by the present trapping method using the present trapping adsorption column. Here, as described above, according to the present trapping adsorption column and the present trapping method, the acid component or the base component in a gas can be trapped and quantified in a short time and with high sensitivity. Thus, the present quantitative method can also trap and quantify the acid component or the base component in a gas in a short time and with high sensitivity.

[0058] Hereinafter, the present quantitative method in which the concentration of an acid component in a gas is quantified using an acid component adsorption column will also be referred to as an "acid component quantitative method". In addition, the present quantitative method in which the concentration of a base component in a gas is quantified using a base component adsorption column will also be referred to as a "base component quantitative method". The present quantitative method is either an acid component quantitative method or a base component quantitative method.

[0059] The configuration and the like of the present trapping adsorption column used in the present quantitative method are as described in "[Embodiment 1: Trapping Adsorption Column]". In addition, the acid component and the base component that are the objects of quantification of the present quantitative method are not particularly limited, and can be the acid component and the base component exemplified in the column of "[Embodiment 1: Trapping Adsorption Column]" described above.

[0060] Here, it is also possible to perform both the acid component quantitative method and the base component quantitative method on the same gas to quantify the acid component and the base component in the gas together. In addition, the present quantitative method can perform the trapping step and the elution step described below in a state in which the present trapping adsorption column is not connected to a measurement device that measures the concentration of an acid component or a base component in an eluate, that is, so-called off-line.

[0061] (trapping step) The present quantitative method includes a trapping step of trapping the acid component or the base component in the gas by the present trapping method. In addition, the configuration and the like of the present trapping method used in the trapping step are as described in "[Embodiment 2: Trapping Method]".

[0062] If the acid component quantitative method and the base component quantitative method are implemented together, the acid component quantitative method and the base component quantitative method can be implemented simultaneously by the same method as in the case where the acid component trapping method and the base component trapping method are implemented together. That is, the device having a structure in which the acid component adsorption column and the base component adsorption column are connected in series can be used to draw the air, and the air can be caused to flow through both the acid component adsorption column and the base component adsorption column formed in the device simultaneously. Then, the acid component adsorption column and the base component adsorption column are separated from the device, and the elution step and the measurement step described later are implemented for each of them.

[0063] (elution step) The present quantitative method includes an elution step of causing a solvent to flow through the trapping adsorption column in which the acid component or the base component is trapped, thereby eluting the trapped acid component or base component into the solvent to obtain an eluate.

[0064] By the elution step, the acid component or the base component trapped by the trapping adsorption column is eluted into the solvent, and as a result, an eluate containing the acid component or the base component can be obtained. The solvent is not particularly limited as long as it is a solvent capable of eluting the acid component or the base component. From the viewpoint of the sensitivity of the present quantitative method, it is preferable to use a solvent that does not contain an impurity that can cause a decrease in the sensitivity or a solvent in which the content of the impurity is extremely small. From this viewpoint, pure water is particularly preferable as the solvent. Here, pure water refers to water having a specific resistance in the range of 0.1 MΩ-cm or more and 18 MΩ-cm or less.

[0065] (measurement step) The present quantitative method includes a measurement step of measuring the concentration of the acid component or the base component in the eluate.

[0066] The acid component or the base component in the eluate is the acid component or the base component in the gas trapped by the trapping step. Therefore, the concentration of the acid component or the base component in the eluate measured by the measurement step substantially corresponds to the concentration of the acid component or the base component in the gas. Thus, the concentration of the acid component or the base component in the gas can be quantified by the measurement step.

[0067] As a method of measuring the concentration of the acid component or the base component in the eluate (hereinafter also referred to as "the present measurement method"), a publicly known method can be used without particular limitation. The present measurement method can be, for example, liquid chromatography. As the liquid chromatography, for example, anion exchange and cation exchange using an ion exchange column, and suppressor ion chromatography using a suppressor can be given.

[0068] In addition, the acid component exists in the eluate in an anion form, and the base component exists in the eluate in a cation form. Therefore, the total concentration of anions in the eluate is measured by the above-described method, and the obtained concentration measurement value is used as the concentration of the acid component. Similarly, the total concentration of cations in the eluate is measured by the above-described method, and the obtained concentration measurement value is used as the concentration of the base component.

[0069] [Embodiment 4: Management method of spatial cleanliness] The management method of spatial cleanliness according to one embodiment of the present application (hereinafter, also referred to as "the present management method") is a management method including: a quantification step of quantifying the concentration of an acid component or a base component in a gas in a space, using the present quantification method; and an exclusion step of determining and excluding a source of generation of the acid component or the base component in the gas in the interior of the space, in a case where the concentration of the acid component or the base component quantified in the quantification step exceeds a threshold value.

[0070] According to the present management method, the quantification step quantifies the concentration of a contaminant, i.e., the acid component or the base component, in the space with high sensitivity in a short time. On this basis, when the quantified concentration of the acid component or the base component exceeds a prescribed threshold value, the exclusion step of determining and excluding a source of generation of the acid component or the base component in the gas in the interior of the space is entered.

[0071] Since the quantification can be performed with high sensitivity, the prescribed threshold value can be set to a low value for the present management method. Therefore, according to the present management method, by setting the prescribed threshold value to a low value, a source of contamination, i.e., the acid component or the base component, can be determined and excluded at a stage where the amount of the contaminant is still small, and as a result, a highly clean space can be ensured. In addition, since the quantification can be performed in a short time, the time from the start of the quantification to the end of the determination and exclusion of the source of contamination can be shortened, and as a result, a highly clean space can be ensured easily. Therefore, by the present management method, a highly clean space can be ensured easily. Here, in the present specification, the "source of contamination" refers to the "source of generation of the acid component or the base component in the gas in the interior of the space".

[0072] (Quantification step) The present management method includes a quantification step of quantifying the concentration of an acid component and a base component in a gas in a space, using the present quantification method. By performing the quantification step, the concentration of a contaminant, i.e., the acid component and the base component, in the gas in the space can be quantified easily.

[0073] The space described in the present specification is an object space of the evaluation performed by the present trapping adsorption column, an object space of the quantification, etc., and can be, for example, a space in which the concentration of the contaminant, i.e., the acid component and the base component, is required to be below a certain threshold value in order to perform an operation in electronic substrate manufacturing, etc. In addition, the space described in the present management method can generally be a space having a prescribed volume formed by walls, floors, etc. The space is not particularly limited and can be, for example, a clean room, a clean booth, or a space inside a manufacturing device.

[0074] As for the constitution, etc. of the quantification method employed in the quantification step, the constitution, etc. described in the aforementioned "[Embodiment 3: Quantification method]" can be cited.

[0075] In the present management method, in order to secure a highly clean space, the amount (concentration) of the contaminant, i.e., the acid component and / or the base component, in the gas in the space is quantified. On this basis, a contamination source is also determined and excluded according to the quantified concentration. Therefore, in the quantification step, either the acid component quantification method or the base component quantification method can be implemented, or both the acid component quantification method and the base component quantification method can be implemented, and it is preferable that both the acid component quantification method and the base component quantification method be implemented. In order to implement both the quantification methods, it is preferable to use a device having a structure in which an acid component adsorption column and a base component adsorption column are arranged in series. In the case of using this device, by performing a single suction of the device, both the acid component adsorption column and the base component adsorption column constituting the device can be aerated, and thus the quantification step and the present management method can be implemented easily.

[0076] (Determining and excluding a contamination source) The present management method includes a step of determining and excluding a contamination source in the case where the concentration of the acid component or the base component quantified in the quantification step exceeds a threshold value. By implementing this step, it is possible to control the concentration of the contaminant, i.e., the acid component or the base component, inside the space to be below the threshold value, and thus to secure a highly clean space.

[0077] The threshold value involved in the step can be appropriately decided according to the kind of operation performed in the space and the required quality of the product manufactured by the operation, etc., and is not particularly limited. For example, if a high-quality electronic substrate is manufactured in the space, the threshold value can be 1.0 μg / m 3 , 0.1 μg / m 3 , or 0.01 μg / m 3 , etc.

[0078] The determination and exclusion of the contamination source means an operation of grasping the concentration of the contaminant, i.e., the acid component and the base component, inside the space and taking appropriate measures, and the specific method is not particularly limited and can be a publicly known method.

[0079] One embodiment of the present application can be the inventions described in [1] to [7] below. [1] A trapping adsorption column for trapping an acid component or a base component in a gas, wherein The trapping adsorption column is filled with a non-porous base material, The non-porous base material holds a basic adsorbent for adsorbing an acid component or an acid adsorbent for adsorbing a base component, The pressure loss of the trapping adsorption column is 10 kPa or less when a gas inside the trapping adsorption column is sucked at a suction rate of 2.0 L / min. [2] The trapping adsorption column according to [1], wherein the void volume of the trapping adsorption column is 200 μL or more and 3000 μL or less. [3] The trapping adsorption column according to [1] or [2], wherein the amount of the basic adsorbent or the acid adsorbent is 0.4 μeq or more and 50 μeq or less. [4] A trapping method for trapping an acid component or a base component in a gas, which causes a gas to flow through the trapping adsorption column according to any one of [1] to [3] to trap the acid component or the base component in the gas. [5] The trapping method according to [4], wherein the gas is caused to flow through the trapping adsorption column at a ventilation flow rate of 2.0 L / min or more. [6] A quantification method for quantifying the concentration of an acid component or a base component in a gas, comprising: a trapping step of trapping the acid component or the base component in the gas by the trapping method according to [4] or [5]; an elution step of causing a solvent to flow through the trapping adsorption column in which the acid component or the base component is trapped, thereby eluting the trapped acid component or base component into the solvent to obtain an eluate; and a measurement step of measuring the concentration of the acid component or the base component in the eluate. [7] A management method for managing the cleanliness of a space, comprising: a quantification step of quantifying the concentration of an acid component or a base component in a gas inside a space by the quantification method according to [6]; and In the case where the concentration of the acid component or the base component quantified in the quantifying step exceeds a threshold value, a source of the acid component or the base component in the gas inside the space is determined and excluded. <Embodiment>

[0080] The present application will be described in more detail by way of examples, but the present application is not limited to these examples.

[0081] [Measurement method] The method for measuring the physical properties of the trapping adsorption column described in the examples is as follows.

[0082] (weight) In the present embodiment, the weight measurement of the trapping adsorption column was performed using a weight meter (manufacturing company: Metratred Corporation; product name: electronic non-automatic scale PB3003-L).

[0083] (void volume) The trapping adsorption column described in the examples was dried by a method in which compressed air was passed at a flow rate of 2 L / min for 17 hours. The weight of the trapping adsorption column after drying was measured. The measured value was set as W0 (g). Next, pure water at room temperature was introduced into the inside of the trapping adsorption column after drying, and the inside of the trapping adsorption column was filled with the pure water. The weight of the trapping adsorption column filled with the pure water was measured. The measured value was set as W1 (g). Here, the density of the pure water was regarded as 1 g / cm 3 , and the void volume of the trapping adsorption column was calculated. Specifically, the value of the void volume was equal to the value of the weight W2 (g) of the pure water filled in the trapping adsorption column, and therefore the void volume was calculated based on the following equation (1). Void volume (cm 3 ) of trapping adsorption column = W 2( g) = W1 (g) - W0 (g) (1)

[0084] (equivalents of basic adsorbent contained in acid component adsorption column and acid adsorbent contained in base component adsorption column) The basic adsorbent in the acid component adsorption column was eluted by passing 10 mL of pure water through the acid component adsorption column described in the example, to obtain a first eluate. Next, the basic adsorbent in the acid component adsorption column was further eluted by passing 40 mL of pure water through the acid component adsorption column after the passage of the 10 mL of pure water, to obtain a second eluate. The first eluate and the second eluate were supplied to an ion chromatograph, and the equivalents of the basic adsorbent contained in each eluate were measured. The sum of the equivalents of the basic adsorbent contained in each eluate as measured was taken as the equivalent of the basic adsorbent contained in the acid component adsorption column.

[0085] Likewise, the acid adsorbent in the base component adsorption column was eluted by passing 10 mL of pure water through the base component adsorption column described in the example, to obtain a first eluate. Next, the acid adsorbent in the base component adsorption column was further eluted by passing 40 mL of pure water through the base component adsorption column after the passage of the 10 mL of pure water, to obtain a second eluate. The first eluate and the second eluate were supplied to an ion chromatograph, and the equivalents of the acid adsorbent contained in each eluate were measured. The sum of the equivalents of the acid adsorbent contained in each eluate as measured was taken as the equivalent of the acid adsorbent contained in the base component adsorption column.

[0086] (Pressure loss) The trapping adsorption column described in the example was connected to a gas suction pump, and suction was performed at a suction rate of 2.0 L / min, and the pressure loss at this time was measured with a differential pressure gauge. Here, in the present example, and in the measurement of the pressure loss and the following Examples 3 to 5, a gas suction pump manufactured by Shibata Science Co., Ltd., product name: Mini Pump-MP MP-Σ300, was used as the gas suction pump.

[0087] (Ion chromatography) The measurement method using an ion chromatograph used in the measurement of the equivalents of the aforementioned basic adsorbent and acid adsorbent, and the measurement of the amounts of attachment of anions and cations described in the following Examples 3 to 5, is described below.

[0088] An eluate was analyzed using an ion chromatography system having an electrolysis suppression function and a conductivity detection function. A potassium hydroxide (KOH) gradient eluent and an inorganic anion and organic acid anion analysis column were used for the anion channel of the ion chromatography system. A methanesulfonic acid gradient eluent and a cation analysis column were used for the cation channel of the ion chromatography system.

[0089] [Example 1: Manufacture of acid component adsorption column] Quartz particles of 0.5 mm to 1.0 mm in particle size, 0.9 g, were packed into a cylindrical column case of polypropylene having an inner volume of 0.92 mL. After passing methanol, purified water (resistivity 18 MΩ-cm) was passed through the inside of the column to perform washing.

[0090] A mixed aqueous solution of sodium carbonate and glycerin was passed through the washed column, and then clean air was passed to dry, thereby producing an acid component adsorption column.

[0091] The physical properties of the acid component adsorption column produced were measured by the aforementioned method. As a result, the void volume of the acid component adsorption column was 0.44 cm 3 , the equivalent of the adsorbent contained was 1.80 μeq, and the pressure loss when suction was performed at a suction rate of 2.0 L / min was 2.73 kPa.

[0092] [Example 2: Production of a basic component adsorption column] Quartz particles of 0.5 mm to 1.0 mm in particle size, 0.9 g, were packed into a cylindrical column case of polypropylene having an inner volume of 0.92 mL. After passing methanol, purified water (resistivity 18 MΩ-cm) was passed through the inside of the column to perform washing.

[0093] A mixed aqueous solution of sulfuric acid and glycerin was passed through the washed column, and then clean air was passed to dry, thereby producing a basic component adsorption column.

[0094] The physical properties of the basic component adsorption column produced were measured by the aforementioned method. As a result, the void volume of the basic component adsorption column was 0.44 cm 3 , the equivalent of the adsorbent contained was 1.01 μeq, and the pressure loss when suction was performed at a suction rate of 2.0 L / min was 2.70 kPa.

[0095] [Example 3: Elution of a trapping adsorption column after clean room air is trapped] The acid component adsorption column produced in Example 1 and the basic component adsorption column produced in Example 2 were each connected to a gas suction pump, and air in a clean room in a laboratory was passed through each column at a suction rate of 2.0 L / min for 5 hours.

[0096] After the air flow, ultrapure water was passed through the acid adsorption column and the alkali adsorption column at a flow rate of 2 mL / min for 5 minutes, respectively, to obtain eluents from the anions and cations (i.e., acid and alkali components) in the columns. The eluents were then subjected to ion chromatography, and the concentrations (in ng / mL) of the anions and cations (i.e., acid and alkali components) in the eluents were determined. The same procedure was performed again, except that the air flow was not performed, and the lower limit of quantitation (LOQ) was determined based on the results. The measured LQ and the concentrations of acid and alkali components in the eluents are recorded in Table 1. In Table 1, the acid adsorption column is referred to as "Column A," and the alkali adsorption column is referred to as "Column B." The concentrations of acid and alkali components in the eluents are abbreviated as "concentration in eluent." [Table 1] Table 1: Measurement results of Example 3 (concentrations of acid and alkali components in the eluent) [Example 4: Analysis Results of Clean Indoor Air] Making with Figure 1 The quantitative device shown is a device made by connecting the acid adsorption column 1 manufactured in Example 1 and the alkali adsorption column 2 manufactured in Example 2 via a connecting pipe 4, and connecting the suction pump 3 to the opposite side of the alkali adsorption column 2 connected to the acid adsorption column 1, thereby creating a quantitative device.

[0097] A chemically filtered cleanroom was connected to the opposite side of the acid adsorption column 1 and the alkali adsorption column 2 in the quantitative device. Then, using a suction pump 3, air was drawn through both the acid adsorption column 1 and the alkali adsorption column 2 at a flow rate of 2 L / min for 5 hours. After the air flow, 10 mL of pure water was passed through each column to obtain eluent (4a) and eluent (4b). Eluent (4a) and eluent (4b) were respectively fed to an ion chromatograph, and the concentrations of the anions (acid component) in eluent (4a) and the cations (alkali component) in eluent (4b) were quantified. The quantified concentrations of eluent (4a) and eluent (4b) were multiplied by the eluent volume and divided by the air extraction volume to calculate the concentrations of the acid and alkali components in the cleanroom air. In addition, the same procedures as described above were performed, except that airflow was not implemented, and the lower limit of quantitation was calculated based on the results. Here, the calculation of each concentration and the calculation of the lower limit of quantitation were both repeated twice, and the average of the two calculated values ​​was used as the concentration and the lower limit of quantitation.

[0098] The calculated quantitative lower limit value, and the respective concentrations of the acid component and the base component in the clean room are shown in Table 2 below. As in Table 1, in Table 2, the acid component adsorption column is referred to as "column A", and the base component adsorption column is referred to as "column B". In addition, in Table 2, the respective concentrations of the acid component and the base component in the clean room are simply referred to as "concentrations in the clean room". [Table 2] Table 2: Measurement results of Example 4 (concentrations of acid component and base component in clean room)

[0099] [Results of periodic analysis of air in clean room] The clean room at each stage of immediately after starting work, and after 1 month, 2 months, and 3 months from the start of work was taken as the subject, and the respective concentrations of the acid component and the base component in the air in the clean room at each stage, and the quantitative lower limit value were calculated in the same manner as in Example 4.

[0100] The calculated quantitative lower limit value, and the respective concentrations of the acid component and the base component in the clean room are shown in Table 3 below. As in Table 2, in Table 3, the acid component adsorption column is referred to as "column A", and the base component adsorption column is referred to as "column B", and the respective concentrations of the acid component and the base component in the clean room are simply referred to as "concentrations in the clean room". [Table 3] Table 3: Measurement results of Example 5 (concentrations of acid component and base component in clean room after a prescribed period from the start) [Results] As shown in Examples 1 and 2, the trapping adsorption column manufactured in Examples 1 and 2 satisfies the following elements (i) to (iii), and thus corresponds to the present trapping adsorption column. (i) is filled with a non-porous base material. (ii) the non-porous base material retains a basic adsorbent for adsorbing an acid component or an acid adsorbent for adsorbing a base component. (iii) the pressure loss of the trapping adsorption column is 10 kPa or less when a gas in the trapping adsorption column is sucked at a suction speed of 2.0 L / min.

[0101] In addition, according to the description of Examples 4 and 5, the method of Examples 4 and 5 for trapping an acid component and a base component is a method of causing a gas to flow through the present trapping adsorption column to trap an acid component or a base component in the gas, and thus corresponds to the present trapping method.

[0102] Further, according to the descriptions of Examples 4 and 5, the method for quantifying the acid component and the base component in Examples 4 and 5 is a method for quantifying the concentration of the acid component or the base component in a gas, which includes steps (iv) to (vi) below, and thus corresponds to the present quantification method. (iv) a trapping step of trapping the acid component or the base component in the gas by using the present trapping method. (v) an elution step of flowing a solvent through the trapping adsorption column in which the acid component or the base component is trapped, thereby eluting the trapped acid component or base component into the solvent to obtain an eluate. (vi) a measurement step of measuring the concentration of the acid component or the base component in the eluate.

[0103] In addition, as is clear from the descriptions of Examples 3 to 5 and Tables 1 to 3, by using the trapping method and the quantification method using the trapping adsorption column manufactured in Examples 1 and 2, even if the ventilation time is as short as 5 hours, the acid component and the base component can be trapped and quantified with high sensitivity. Similarly, as is clear from the descriptions of Examples 4 and 5 and Tables 2 and 3, by using the trapping method and the quantification method of Examples 4 and 5, even if the ventilation time is as short as 5 hours, the acid component and the base component can be trapped and quantified with high sensitivity.

[0104] Thus, according to the present trapping adsorption column, the present trapping method, and the present quantification method, the acid component or the base component in a gas can be trapped and quantified with high sensitivity in a short time. Therefore, according to the present management method using the present trapping adsorption column, the present trapping method, and the present quantification method, the source of pollution can be determined and removed in a short time from a stage at which the concentration of the contaminant is still low, and as a result, a highly clean space can be easily ensured. Thus, the present trapping adsorption column, the present trapping method, the present quantification method, and the present management method can be used for managing a working space in which a highly clean area is required, such as electronic substrate manufacturing. (Industrial applicability)

[0105] Thus, according to the present trapping adsorption column, the present trapping method, and the present quantification method, the acid component or the base component in a gas can be trapped and quantified with high sensitivity in a short time. Therefore, according to the present management method using the present trapping adsorption column, the present trapping method, and the present quantification method, the source of pollution can be determined and removed in a short time from a stage at which the concentration of the contaminant is still low, and as a result, a highly clean space can be easily ensured. Thus, the present trapping adsorption column, the present trapping method, the present quantification method, and the present management method can be used for managing a working space in which a highly clean area is required, such as electronic substrate manufacturing.

Claims

1. An adsorption column for capturing acidic or alkaline components in a gas, characterized in that, The adsorption column used for trapping is filled with a non-porous substrate. The non-porous substrate contains an alkaline adsorbent for adsorbing acidic components or an acidic adsorbent for adsorbing alkaline components. When the gas in the adsorption column is attracted at an attraction rate of 2.0 L / min, the pressure loss of the adsorption column is less than 10 kPa.

2. The adsorption column for collection according to claim 1, wherein, The pore volume of the adsorption column used for trapping is more than 200 μL and less than 3000 μL.

3. The adsorption column for collection according to claim 1, wherein, The amount of the alkaline adsorbent or the acidic adsorbent is 0.4 μeq or more and 50 μeq or less.

4. A method for capturing acidic or alkaline components in a gas, characterized in that, The gas is passed through the adsorption column for trapping according to any one of claims 1 to 3 to trap the acid or alkali components in the gas.

5. The capture method according to claim 4, wherein, The gas is passed through the adsorption column for collection at a flow rate of 2.0 L / min or higher.

6. A quantitative method for quantifying the concentration of an acidic or alkaline component in a gas, characterized in that... include: The capture step employs the capture method described in claim 4 to capture the acid or alkaline components in the gas. The elution step involves passing a solvent through the adsorption column used for capturing the acidic or alkaline components, thereby eluting the captured acidic or alkaline components into the solvent to obtain an eluent. as well as The determination step involves measuring the concentration of the acidic or alkaline component in the eluent.

7. A management method for managing the cleanliness of a space, characterized in that... include: The quantitative step involves using the quantitative method described in claim 6 to quantify the concentration of acid or alkali components in the gas within the space. as well as The exclusion step involves identifying and excluding the source of the acid or alkali component in the gas inside the space if the concentration of the acid or alkali component quantified in the quantitative step exceeds a threshold.

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