JP2021043125A - Method and device for cleaning sampling bags and liquid used therefor - Google Patents

Abstract

To clean the inside of a sampling bag so that it is in an even cleaner state than that in the conventional art.SOLUTION: A sampling bag cleaning method is provided, comprising a step of supplying a humidifying gas obtained by evaporating a liquid containing water and an organic solvent into a sampling bag.SELECTED DRAWING: Figure 1

Description

The present invention relates to a sampling bag cleaning method, a sampling bag cleaning device, and a liquid used in the method and device.

Sampling bags are used to collect gas and analyze its quantity and composition. This sampling bag is used not only for collecting and analyzing gas in the environmental atmosphere, but also for collecting, inspecting and analyzing gas emitted from parts such as automobile interior materials.

For example, if a volatile organic compound (hereinafter referred to as "VOC") is emitted from a substance constituting an interior material of an automobile, so-called sick car syndrome may be caused. For this reason, the types and amounts of VOCs emitted from automobile interior materials are strictly regulated, and when an interior material manufacturer delivers interior materials to an automobile manufacturer, it is possible to inspect the gas emitted from the interior materials. Desired. When inspecting the gas emitted from parts such as automobile interior materials, the parts to be inspected are placed in a sampling bag, sealed, set in a heating device such as a dryer, and heated at a predetermined temperature for a predetermined time. Then, the gas emitted from the inspection parts is collected in the sampling bag. Then, by analyzing the gas collected in the sampling bag with an analyzer such as a gas chromatograph, it is possible to inspect the gas such as VOC emitted from the inspection parts.

Here, the sampling bag is made of various resin films such as a polyvinyl alcohol-based film, a polyvinylidene fluoride film, a polyester film, and a polyvinyl fluoride (Tedlar: registered trademark) film. If gas is emitted from the resin film constituting the sampling bag, this gas may be mixed with the gas to be inspected. Especially when inspecting parts such as automobile interior materials, cut the sampling bag, put the parts to be inspected, seal the cut part with heat seal, clip stopper, tape stopper, etc., and then put the sampling bag in a dryer etc. The gas is dissipated by putting it in a heating device and heating the inspection parts in the sampling bag. Therefore, the gas is likely to be dissipated from the resin film constituting the sampling bag by this heating, and this gas may be mixed with the gas to be inspected, making it impossible to perform an accurate inspection.

Therefore, the sampling bag is washed before the inspection for collecting and analyzing the gas in the sampling bag. Patent Documents 1 and 2 disclose the technique invented by the present inventor among the techniques for cleaning sampling bags. Patent Document 1 describes a humidifying gas tube for supplying a humidified gas into a sampling bag to clean the sampling bag with the humidifying gas, and supplying dry gas into the sampling bag to expel the humidified gas and inside the sampling bag. A dry gas tube to be dried and a connection attachment formed by attaching a humidifying gas tube and / or a dry gas tube and used by connecting to a connection port provided in the sampling bag are provided, and the connection attachment is provided in the sampling bag. Each tip of the humidified gas tube or dry gas tube protrudes from the connection attachment so that the humidified gas tube or dry gas tube is inserted into the sampling bag while connected to the connection port. Disclosed is a cleaning device characterized in that the connection attachment is provided with an exhaust port in which the inside of the sampling bag communicates with the outside through the connection port in a state of being connected to, and a cleaning method of the sampling bag using such a mechanism. There is.

Further, Patent Document 2 fills a sampling bag with a cleaning gas, heats the sampling bag to volatilize volatile chemical substances from the sampling bag into the cleaning gas, and samples the cleaning gas containing the volatile gas of the chemical substance. When cleaning the sampling bag by discharging it from the inside of the bag, the cleaning gas is continuously supplied into the sampling bag through the connection port provided in the sampling bag while heating the sampling bag. Discloses a method for cleaning a sampling bag, which comprises filling the gas with a cleaning gas and continuously discharging the filled cleaning gas through a connection port by extruding the filled cleaning gas with the cleaning gas supplied later into the sampling bag. doing.

Japanese Unexamined Patent Publication No. 2016-166851 Japanese Unexamined Patent Publication No. 2017-142082

By the above technique developed by the present inventor, a high cleaning effect of the sampling bag is obtained. On the other hand, if the amount of VOCs and the like (hereinafter referred to as “cleaning target”) in the sampling bag before being used in the measurement can be further reduced by washing, the VOC and the like using the sampling bag (hereinafter referred to as “measurement target”) can be further reduced. ”) Can be performed more accurately. Further, even if the sampling bag is once used for inspection, if the inside of the sampling bag can be cleaned to a cleaner state by a method having a higher cleaning effect, the reuse of the sampling bag can be further promoted. Therefore, such a technique having a higher cleaning effect has been desired.

As a result of diligent studies by the present inventors, it has been found that the above problems can be solved by a method having a specific step, an apparatus for carrying out the method, and a liquid used in the method and the apparatus, and the present invention has been reached. ..
That is, the present invention
[1] A method for cleaning a sampling bag, which comprises a step of supplying a humidifying gas obtained by evaporating a liquid containing water and an organic solvent into the sampling bag.
[2] The cleaning method according to [1], wherein the organic solvent contained in the liquid is one or more polar solvents.
[3] The cleaning method according to [1] or [2], wherein the organic solvent contained in the liquid is one or more solvents selected from ketones or monohydric alcohols.
[4] The cleaning method according to any one of [1] to [3], wherein the amount of the organic solvent with respect to water in the liquid is 3 to 50 parts by mass with respect to 100 parts by mass of water.
[5] The cleaning method according to any one of [1] to [4], which comprises a step of supplying the drying gas into the sampling bag after the step of supplying the humidifying gas.
[6] A humidifying device that generates a humidifying gas by evaporating a liquid containing water and an organic solvent, and a humidifying device.
It is connected to a humidifying gas tube for supplying the humidifying gas obtained from the humidifying device into the sampling bag and a connection port provided in the sampling bag, and the humidifying gas tube is attached to the connection port of the sampling bag. A connection attachment with an exhaust port that allows the inside of the sampling bag to communicate with the outside through the connection port while connected to
Sampling bag cleaning device, characterized by having
[7] The cleaning apparatus according to [6], which further has a dry gas tube for supplying a dry gas, and [8] any of [1] to [5] containing water and an organic solvent. The cleaning method described or the liquid for use in the apparatus of [6] or [7],
Regarding.

INDUSTRIAL APPLICABILITY According to the present invention, a higher cleaning effect of a cleaning object, which can be an obstacle when performing an analysis using a sampling bag, can be obtained.

It is a drawing explaining one form of the cleaning apparatus of this invention. It is a drawing explaining the humidifying apparatus provided with the dew condensation liquid trap. It is a drawing explaining one embodiment which heats a humidifying bottle. It is a drawing explaining one form of the connection attachment used in the apparatus of FIG. It is a drawing explaining the connection attachment of FIG. 4 through which a humidifying gas tube is inserted. It is a drawing explaining the flow of the humidifying gas when the humidifying gas is supplied to the sampling bag by the apparatus of FIG. Further, it is a drawing explaining one form of the cleaning apparatus of this invention provided with a dry gas tube. It is a drawing explaining another form of the cleaning apparatus of this invention provided with a dry gas tube. It is a drawing explaining one form of the connection attachment used in the apparatus of FIG. It is a drawing explaining the connection attachment of FIG. 9 through which a dry gas tube and a humidifying gas tube are inserted. It is a drawing explaining the flow of the humidifying gas and the drying gas when the humidifying gas and then the drying gas are supplied to the sampling bag by the apparatus of FIG. It is a drawing explaining the cleaning system using the cleaning apparatus of this invention. It is a drawing which graphed the numerical values of Examples 1-6, Comparative Example 1 and Reference Example 1. It is a drawing which graphed the numerical values of Comparative Example 2 and Examples 7-12. It is a drawing which shows the example of a sampling bag. It is a drawing explaining the flow of air in a sampling bag.

Hereinafter, embodiments of the present invention will be described. It goes without saying that the present invention is not limited to the following embodiments as they are, and various modifications can be made within the technical scope of the invention described in the claims.

FIG. 1 shows a mode of an apparatus for carrying out the method of the present invention. The cleaning device 1 of FIG. 1 is
A humidifying device 2 that generates a humidifying gas by evaporating a liquid containing water and an organic solvent.
The humidifying gas tube 3 for supplying the humidifying gas obtained from the humidifying device 2 into the sampling bag X and the connecting port X1 provided in the sampling bag X are connected to the humidifying gas tube 3. , A connection attachment 4 having an exhaust port in which the inside of the sampling bag X communicates with the outside through the connection port X1 in a state of being connected to the connection port X1 of the sampling bag X.
Have.

Humidifier 2
In the present invention, the humidifying gas is obtained by evaporating a liquid containing water and an organic solvent, which will be described later, in a gas such as air or nitrogen gas. The method for evaporating the liquid is not particularly limited, and the liquid is evaporated by direct or indirect heating using a heat source, a method of physically evaporating using ultrasonic waves or the like, or a gas such as nitrogen or air. Any means commonly used in evaporating a liquid, such as bubbling and evaporating, can be used. In the embodiment of FIG. 1, the cleaning device 1 has a humidifying device 2 formed of a humidifying bottle 21 or the like. The humidifying bottle 21 contains a liquid 22 to be described later and is sealed with a lid 23. One end of the humidifying bottle 21 is inserted into the connection attachment 4 and the other end of the humidified gas tube 3 is inserted into the lid 23. It is attached. The end of the humidifying gas tube 3 is located in the humidifying bottle 21 in a space above the water surface of the liquid 22. A gas tube 24 for supplying a gas such as nitrogen gas or air is connected to the humidifying device 2. The gas tube 24 is inserted through the lid 23 and attached, and the tip portion thereof is immersed in the liquid 22. Then, when the gas is sent through the gas tube 24, the gas dives into the liquid 22 from the tip of the gas tube 24 and is supplied into the humidifying device 2. By submerging the gas in the liquid 22 and bubbling it in this way, the water and the organic solvent contained in the liquid 22 are evaporated and contained in the gas as vapor, and a humidifying gas is obtained. This humidifying gas is sent from the humidifying device 2 to the humidifying gas tube 3.

The liquid 22 used in the present invention is a liquid containing water and an organic solvent. The organic solvent is not particularly limited as long as it is a solvent that does not excessively deteriorate the material of the sampling bag and can wash the object to be washed existing inside the sampling bag and / or emitted from the film forming the sampling bag. Can be used.

Specific examples of such organic solvents include polar solvents. By using a polar solvent, the cleaning effect of the humidifying gas obtained by evaporating the liquid 22 containing the polar solvent can be further improved. As these polar solvents, one or two or more polar solvents may be used in combination.
Specific examples of such polar solvents include solvents selected from ketones or monohydric alcohols. By selecting these solvents as the polar solvents, the effect of cleaning the object to be cleaned is further improved. Specific examples of the ketone include acetone, ethyl methyl ketone, diethyl ketone and the like. Specific examples of the monohydric alcohol include methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, ter-butyl alcohol and the like.

The amount of the organic solvent with respect to water in the liquid 22 is not particularly limited, and is not particularly limited as long as a humidifying gas capable of cleaning the object to be washed in the sampling bag can be obtained. Specifically, the amount of the organic solvent with respect to water is, for example, 3 to 50 parts by mass, preferably 5 to 50 parts by mass, more preferably 5 to 30 parts by mass, still more preferably 5 parts by mass, based on 100 parts by mass of water. It is 10 to 30 parts by mass. By setting the amount of the organic solvent with respect to water in the above range, it is possible to further enhance the effect of cleaning the object to be washed in the sampling bag while avoiding the use of an excessive amount of the organic solvent.

In the embodiment of FIG. 1, a backflow prevention container 25 formed of a backflow prevention bottle or the like is provided in the middle of the gas tube 24. That is, the middle of the gas tube 24 is cut, and each cut end is inserted into the backflow prevention container 25 through the lid 26 of the backflow prevention container 25 and attached. When the humidifying gas supplied to the sampling bag X through the humidifying gas tube 3 flows back through the humidifying gas tube 3, the pressure inside the humidifying bottle 21 increases, so that the liquid 22 in the humidifying bottle 21 may flow back into the gas tube 24. There is. In this way, even if the liquid 22 flows back through the gas tube 24, the liquid 22 flows into and accumulates in the backflow prevention container 25, and it is possible to prevent the gas tube 24 from flowing back any further. If activated carbon or the like is placed in the backflow prevention container 25, the impure components in the gas supplied through the gas tube 24 can be adsorbed on the activated carbon, and the humidified gas tube 3 can be filled with the gas in a purified state. Can be sent.

The vapor generated by the humidifying device 2 may condense in response to changes in temperature and atmospheric pressure, and the liquid generated by the dew condensation (hereinafter referred to as “condensation liquid”) may flow into the sampling bag X. When the dew condensation liquid is supplied into the sampling bag X, the measurement target may be absorbed by the water contained in the dew condensation liquid, or the organic solvent contained in the dew condensation liquid may become measurement noise. May interfere. In such a case, the humidifying device 2 may include, for example, a trap for such a dew condensation liquid (hereinafter, referred to as a “condensation liquid trap”). By providing the dew condensation liquid trap in this way, even if the vapor generated in the humidifying bottle 21 condenses inside the gas tube 24, the dew condensation liquid is recovered by the dew condensation liquid trap. Therefore, the dew condensation liquid is not supplied to the sampling bag X, and only the humidifying gas can be supplied to the sampling bag X. FIG. 2 shows an example of a humidifying device 2 provided with such a dew condensation liquid trap. The humidifying device 2 of FIG. 2 includes a backflow prevention container 25, a humidifying bottle 21, and a dew condensation liquid trap 27 connected by a gas tube 24. The humidifying bottle 21 and the backflow prevention container 25 are as described above. In FIG. 2, the dew condensation liquid trap 27 is a bottle-shaped container similar to the humidifying bottle 21 and the backflow prevention container 25, and is sealed by a lid 28.

In the form of FIG. 1, the humidifying gas tube 3 is inserted into the humidifying bottle 21 through the lid 23. On the other hand, in the humidifying device 2 of FIG. 2, one end of the gas tube 24 is inserted into the humidifying bottle 21 instead of the humidifying gas tube 3 through the lid 23 of the humidifying bottle 21. The end opposite to the end inserted into the humidifying bottle 21 of the gas tube 24 is inserted into the dew condensation liquid trap 27 through the lid 28. The end of the gas tube 24 inserted into the dew condensation liquid trap 27 is inserted close to the bottom of the dew condensation liquid trap 27. Further, one end of the humidifying gas tube 3 is inserted into the dew condensation liquid trap 27 through the lid 28 of the dew condensation liquid trap 27. The end of the humidifying gas tube 3 inserted into the dew condensation liquid trap 27 does not protrude from the back surface of the lid 28, in other words, the lower end of the humidifying gas tube 3 is aligned with the lower end of the back surface of the lid 28, or the humidifying gas tube 3 It is preferable that the lower end of the lid 28 stays inside the lid 28. With such a structure, even if the dew condensation liquid collected in the dew condensation liquid trap 27 evaporates and condenses on the back surface of the lid 28 again, the possibility that the dew condensation liquid enters the humidifying gas tube 3 can be reduced as much as possible. Further, as shown in FIG. 2, by keeping the distance between the lower end of the gas tube 24 and the lower end of the humidifying gas tube 3 in the dew condensation liquid trap 27 as long as possible, the dew condensation liquid flowing from the gas tube 24 enters the humidifying gas tube 3. The possibility of getting in can be reduced as much as possible.

Further, when the humidifying device 2 is used in an environment where the temperature is low, for example, the amount of evaporation of the liquid 22 may be reduced and the cleaning effect of the humidifying gas may be reduced. In addition, there are cases where it is desired to obtain more steam and improve the cleaning effect by the humidifying gas even if it is not in a low temperature environment. In such a case, a means for heating the humidifying device 2 may be provided. FIG. 3 shows a specific example of such a heating means. FIG. 3 describes a heating tool 29 for heating the humidifying bottle 21. The heater 29 is formed by attaching a ring-shaped electric heater 292 to the heating container 291 and its inner circumference. The humidifying bottle 21 is set by inserting the lower portion of the humidifying bottle 21 into the inner circumference of the electric heater 292 so that the liquid 22 in the humidifying bottle 21 can be heated by the electric heater 292. By adjusting the heating temperature of the electric heater 292 using such a heating tool 29, the amount of evaporation of the liquid 22 can be increased and the amount of vapor of the liquid 22 in the humidifying gas can be increased, resulting in sampling. The cleaning effect inside the bag X can be further enhanced. The form of the heater 29 is not limited to that shown in FIG. 3, and for example, a heater may be built in the humidifying bottle 21 to directly heat the liquid 22.

Humidifying gas tube 3
The humidifying gas tube 3 is inserted into the sampling bag X from the humidifying device 2 via a connection attachment 4 described later. The humidifying gas tube 3 has a diameter of about 1.5 to 3 mm and is formed into a flexible circular tube made of a flexible resin (for example, a fluororesin or a polyolefin resin such as polypropylene or polyethylene). Can be used.

Connection attachment 4
FIG. 4 shows an example of the connection attachment 4, which is formed of a fluororesin or the like in a columnar shape as a whole as shown in FIG. 4A. As shown in FIG. 4B, one end of the connection attachment 4 is formed as a cylindrical tubular connection 41 having a cavity 41a that opens only on one end surface on the inner circumference. Further, the tip portion of the tubular connecting portion 41 is formed as a connecting flange 42 having a small diameter. A hole is bored in one place of the connection attachment 4 in the radial direction, and this hole communicates with the hollow portion 41a on the inner circumference of the tubular connection portion 41, and serves as an exhaust port 43 of the connection attachment 4. It is open to the outer peripheral surface.

Further, a tube insertion hole 44 having a circular cross section is formed at an end portion of the connection attachment 4 opposite to the tubular connection portion 41. The tube insertion hole 44 is provided so as to be arranged at the center of the connection attachment 4 as shown in FIG. 4 (c). One end of the tube insertion hole 44 is the end face of the connection attachment 4, and the other end is. It is formed so as to open at the end face of the cavity portion 41a of the tubular connection portion 41.

In the embodiment of FIG. 4, a circular O-ring accommodating recess 45 is recessed in the end surface of the connection attachment 4, and the tube insertion hole 44 is opened at the center of the bottom surface of the O-ring accommodating recess 45. ..

Here, the inner diameter of the tube insertion hole 44 is formed to be slightly larger than the diameter of the humidifying gas tube 3, and the inner diameter of the cavity 41a of the tubular connecting portion 41 is the diameter of the humidifying gas tube 3. It is formed to a larger size.

Then, the humidifying gas tube 3 is attached to the connection attachment 4 as shown in FIG. 5 by inserting the humidifying gas tube 3 into the tube insertion hole 44, inserting the humidifying gas tube 3 through the tubular connecting portion 41, and guiding the humidifying gas tube 3 through the inside of the tubular connecting portion 41. The humidifying gas tube 3 can be moved in the longitudinal direction of the tube as shown by the arrow in FIG. 5 by sliding in the tube insertion hole 44. At this time, the elastic O-ring 46 is fitted into the O-ring accommodating recess 45, the humidifying gas tube 3 is passed through the inner circumference of the O-ring 46, and the outer periphery of the humidifying gas tube 3 is formed on the O-ring 46. It is in contact elastically. Therefore, when the humidifying gas tube 3 is slid along the inside of the tube insertion hole 44, the resistance due to this impact is received, so that the humidifying gas tube 3 can be prevented from inadvertently sliding and moving. Further, the O-ring 46 ensures airtightness between the humidifying gas tube 3 and the tube insertion hole 44.

The method of cleaning the sampling bag X using the apparatus of FIG. 1 will be described below. The method of the present invention is characterized by comprising a step of supplying a humidifying gas obtained by evaporating a liquid containing water and an organic solvent into a sampling bag.

Any commercially available sampling bag X can be used as the sampling bag X. The sampling bag X may be the one before use or the one used for measurement once. Examples of the object to be washed include a solvent used in producing the film forming the sampling bag X and the like. For example, an amide-based solvent such as dimethylacetamide may be used when preparing a polyvinyl fluoride film. In the method of the present invention, such an amide-based solvent can be washed as a washing target.

Since sampling bags X of various sizes and shapes are commercially available, the length of the humidifying gas tube 3 protruding from the tubular connection portion 41 of the connection attachment 4 according to the size and shape of the sampling bag X. Adjust the gas. In the drawings of the present specification, a case where the rectangular sampling bag X is washed will be described as an example. As described above, the humidifying gas tube 3 can be moved in the longitudinal direction of the tube by sliding in the tube insertion hole 44. Therefore, the length of the humidifying gas tube 3 protruding from the tubular connection portion 41 of the connection attachment 4 can be easily adjusted. It is desirable that the length to be adjusted substantially matches the distance from the connection port X1 of the sampling bag X to the end of the farthest corner from the connection port X1 of the sampling bag X formed in a rectangular shape. It is sufficient to adjust the length so that the tip of the humidifying gas tube 3 is inserted into the vicinity of the center of the sampling bag X or deeper than the center of the sampling bag X. That is, the humidifying gas tube 3 may have its tip protruding from the connection attachment 4 with a length located at least in the center of the sampling bag X. In this way, the humidifying gas tube 3 itself has a sufficient length so that the length of the sampling bags X of various sizes can be adjusted so as to substantially match the distance from the connection port X1 to the end of the farthest corner. It is necessary to use the humidifying gas tube 3 in a dimension longer than the diagonal line of the largest sampling bag X to be used.

Then, first, the humidifying gas tube 3 is inserted into the sampling bag X through the inner circumference of the cylindrical connection port X1 of the sampling bag X. Here, when the length of the humidifying gas tube 3 protruding from the connection attachment 4 is short or too long, the humidifying gas tube 3 is inserted into the sampling bag X, and the humidifying gas tube 3 is slid to connect the connection attachment 4. The length of protrusion from the surface may be adjusted.

With the humidifying gas tube 3 inserted into the sampling bag X in this way, the connection attachment 4 is connected and fixed to the connection port X1 of the sampling bag X. For the connection between the connection port X1 and the connection attachment 4, a joint cylinder 6 formed in a cylindrical shape with an elastic material such as silicon is used, and as shown in FIG. 1B, the connection ports X1 are formed on the inner circumferences of both sides of the joint cylinder 6. And the connection flange 42 of the cylindrical connection portion 41 of the connection attachment 4 can be inserted and combined with each other. Since the outer diameter of the connection port X1 of the sampling bag X is slightly different for each manufacturer, the connection port X1 and the tubular connection portion 41 of the connection attachment 4 are connected while absorbing the difference in the outer diameter of the connection port X1. In order to do so, an elastic joint cylinder 6 is used.

Here, when cleaning the sampling bag X provided with one connection port X1 as shown in FIG. 15A, the inside of the sampling bag X is sealed by connecting the connection attachment 4 to the connection port X1. However, when cleaning the sampling bag X provided with a plurality of connection ports X1 as shown in FIG. 15B, the connection port X1 to which the connection attachment 4 is not connected may be closed by plugging the connection port X1 or the like. The inside of the sampling bag X is sealed.

Next, a gas such as nitrogen gas or air is sent out through the gas tube 24. When this gas passes through the humidifying bottle 21 of the humidifying device 2, the liquid 22 containing water and an organic solvent is bubbled in the humidifying bottle 21 to evaporate the liquid 22 and become a humidifying gas. It is sent through the tube 3 and supplied into the sampling bag X. The humidifying gas is blown into the sampling bag X from the tip of the humidifying gas tube 3. Since the tip of the humidifying gas tube 3 is deeply inserted into the sampling bag X, the humidifying gas is blown into a portion far away from the connection port X1 of the sampling bag X. When the humidifying gas is blown deep into the sampling bag X from the tip of the humidifying gas tube 3, the humidifying gas is sent to the end of the sampling bag X, the end of the sampling bag X swells, and then the connection port. The humidifying gas flows in the sampling bag X so that the portion that bulges toward the side of X1 spreads. That is, as shown by the solid arrow in FIG. 6, the humidifying gas flows through the entire area of the sampling bag X from the inner end of the sampling bag X toward the connection port X1. Then, when an amount of humidifying gas exceeding the capacity of the sampling bag X is blown in, the amount of humidifying gas exceeding the capacity flows out from the connection port X1 into the cavity 41a of the tubular connection portion 41 of the connection attachment 4 to the connection attachment 4. It is exhausted through the provided exhaust port 43.

By continuing to blow the humidifying gas into the sampling bag X through the humidifying gas tube 3 while discharging the humidifying gas from the exhaust port 43, the humidifying gas can be continuously flowed into the sampling bag X, and the humidification flowing into the sampling bag X can be continued. The inside of the sampling bag X can be cleaned with gas. Here, the humidifying gas contains a large amount of water vapor and vapor of an organic solvent, and the cleaning target in the sampling bag X is easily adsorbed by these vapors. Therefore, the humidifying gas is in a state where the cleaning target in the sampling bag X is adsorbed on the humidifying gas. At the same time, it can be discharged from the exhaust port 43. Therefore, by humidifying and cleaning the sampling bag X with the above-mentioned humidifying gas as the gas for cleaning, the cleaning can be performed efficiently and with high effect.

Moreover, by blowing the humidifying gas from the humidifying gas tube 3 toward the back of the sampling bag X as described above, the humidifying gas is directed from the back of the sampling bag X to the connection port X1 as shown by the solid arrow in FIG. After flowing toward, it is discharged through the connection port X1. Therefore, as shown by the broken line arrow c in FIG. 16A, the humidifying gas flowing into the sampling bag X from the connection port X1 is not immediately discharged from the connection port X1 in a short circuit. Therefore, the humidifying gas flows through the entire surface of the sampling bag X and then is discharged, so that the sampling bag X can be filled with the humidifying gas. Therefore, the humidifying gas uniformly humidifies the entire surface of the sampling bag X. Can be washed.

When the humidifying gas is passed through the sampling bag X for cleaning as described above, the sampling bag X may be heated as described later. Then, for example, in the case of the sampling bag X having a capacity of 10 L, for example, when the humidifying cleaning is performed by setting the heating temperature to 80 ° C. and the flow rate of the humidifying gas to 200 to 600 mL / min, the humidifying gas is sampled for about 1 to 5 hours. Humidifying cleaning can be completed by passing it through X.

After the humidification cleaning is completed, the humidifying gas in the sampling bag X is discharged to the outside of the sampling bag X. There is no particular limitation on the method of discharging the humidified gas from the sampling bag X. For example, a method of forcibly discharging by pushing the outside of the sampling bag X, a tube connected to the discharge port X1 of the sampling bag X, and suction by a pump or the like. A method, and as will be described later, a method of expelling the humidified gas from the sampling bag X1 by connecting a tube to the discharge port X1 of the sampling bag X and supplying a gas such as a dry gas can be adopted.

Dry gas tube 5
The cleaning device 1 of the present invention may have a dry gas tube 5 if necessary. The dry gas tube 5 is inserted into the sampling bag X via the connection attachment 4. The dry gas tube 5 has a diameter of about 1.5 to 3 mm and is formed into a flexible circular tube made of a flexible resin (for example, a fluororesin or a polyolefin resin such as polypropylene or polyethylene). Can be used.

When the sampling bag X has two or more connection ports X1 as shown in FIG. 15B, the connection attachment 4 in which the humidifying gas tube 3 is inserted is connected to one connection port X1 as shown in FIG. Then, another connection attachment 4 through which the dry gas tube 5 is inserted may be connected to another connection port X1.

On the other hand, when the sampling bag X has only one connection port X1 as shown in FIG. 15A, or even if there are two or more connection ports X1, in order to further improve the work efficiency, the dry gas tube 5 May be inserted into the same connection attachment 4 as the connection attachment 4 into which the humidifying gas tube 3 is inserted. FIG. 8 shows a form of the cleaning device 1 in which the humidifying gas tube 3 and the drying gas tube 5 are inserted into the same connection attachment 4. The embodiment of FIG. 8 is the same as the embodiment of FIG. 1 except that the dry gas tube 5 is inserted into the same connection attachment 4 as the insertion attachment 4 of the humidifying gas tube 3.

FIG. 9 is a diagram illustrating a form of a connection attachment 4 into which both the humidifying gas tube 3 and the dry gas tube 5 can be inserted. In the embodiment of FIG. 9, a pair of tube insertion holes 44 are provided in the connection attachment 4, and the tube insertion holes 44a and 44b are arranged in parallel in close proximity to each other. A pair of circular O-ring accommodating recesses 45 and 45 are recessed on the end surface of the connection attachment 4, and the tube insertion holes 44a and 44b are opened at the center of the bottom surface of the O-ring accommodating recesses 45 and 45. There is.

Here, the inner diameters of the tube insertion holes 44a and 44b are formed to be slightly larger than the diameters of the humidifying gas tube 3 and the dry gas tube 5. Further, the inner diameter of the hollow portion 41a of the tubular connecting portion 41 is formed to be larger than the total size of the diameter of the humidifying gas tube 3 and the diameter of the dry gas tube 5.

Then, the humidifying gas tube 3 is inserted into the tube insertion hole 44a and the dry gas tube 5 is inserted into the tube insertion hole 44b and led out through the tubular connection portion 41, whereby the humidifying gas is inserted into the connection attachment 4 as shown in FIG. The tube 3 and the dry gas tube 5 are attached. The humidifying gas tube 3 and the drying gas tube 5 can be moved in the longitudinal direction of the tube as shown by the arrow in FIG. 10 by sliding the inside of the tube insertion holes 44a and 44b. At this time, the elastic O-rings 46, 46 are fitted into the respective O-ring accommodating recesses 45, 45, and the humidifying gas tube 3 and the drying gas tube 5 are passed through the inner circumference of the O-rings 46, 46. The outer circumferences of the humidifying gas tube 3 and the drying gas tube 5 are in elastic contact with the O-rings 46 and 46. Therefore, when the humidifying gas tube 3 or the drying gas tube 5 is slid along the inside of the tube insertion holes 44a and 44b, the humidifying gas tube 3 and the drying gas tube 5 are inadvertently moved due to the resistance due to the impact. It is possible to prevent it from happening. Further, the O-rings 46 and 46 ensure the airtightness between the humidifying gas tube 3 and the dry gas tube 5 and the tube insertion holes 44a and 44b.

The method of the present invention may further include a step of supplying a drying gas after supplying a humidifying gas. Hereinafter, a cleaning method including a step of supplying a humidifying gas will be described using the embodiment of FIG.

After cleaning the inside of the sampling bag X with the humidifying gas as described above, the supply of the humidifying gas by the humidifying gas tube 3 is stopped, and then the dry gas is supplied to the sampling bag X through the dry gas tube 5. The dry gas may be supplied after the humidifying gas is discharged from the sampling bag X (batch type), or may be performed in a state where the humidifying gas remains in the sampling bag X (continuous type). Hereinafter, the method of the present invention will be described based on an example in which the dry gas is continuously supplied.

Since the dry gas is blown into the sampling bag X from the tip of the dry gas tube 5 and the tip of the dry gas tube 5 is inserted into the back of the sampling bag X, the dry gas is inserted into the connection port X1 of the sampling bag X. It is blown into a position far from. When the dry gas is blown into the sampling bag X from the tip of the dry gas tube 5, the dry gas is sent to the end of the sampling bag X, and as shown by the solid line arrow in FIG. 11, the end of the sampling bag X It flows from the portion toward the side of the connection port X1. Then, the humidifying gas in the sampling bag X is pushed toward the connection port X1 by the flow of the dry gas as shown by the chain line arrow in FIG. 11, and passes through the tubular connection portion 41 of the connection attachment 4 from the connection port X1. Then, it is discharged from the exhaust port 43. At this time, the dry gas flows from the back of the sampling bag X toward the connection port X1 as shown by the solid line arrow, and then is discharged through the connection port X1 as shown by the broken line arrow f in FIG. 16B. The dry gas that has flowed into the sampling bag X from the connection port X1 is not immediately and short-circuited and discharged from the connection port X1. Therefore, the humidifying gas can be expelled from the sampling bag X by the drying gas and discharged without leaving the humidifying gas in the sampling bag X, and the inside of the sampling bag X can be dried more efficiently.

Further, since the dry gas is blown from the tip of the dry gas tube 5 inserted into the back of the sampling bag X, the gas pressure of the dry gas in the end of the sampling bag X is high. When the gas pressure in the end of the sampling bag X is low, the swelling at the end of the sampling bag X disappears and the inner surfaces overlap each other, and the condensed moisture generated from the humidifying gas permeates into the overlapping and intimate part by capillarity. , It may be difficult to dry the inside of the sampling bag X. However, as described above, by blowing the dry gas from the tip of the dry gas tube 5 inserted into the back of the sampling bag X, the gas pressure of the dry gas in the end of the sampling bag X can be secured high, so that sampling can be performed. It is possible to prevent the inner surfaces of the bag X from overlapping and adhering to each other, and it is possible to prevent the dew condensation moisture from remaining due to the capillary phenomenon.

When the drying gas is passed through the sampling bag X to dry the inside of the sampling bag X as described above, the sampling bag X may be heated. Then, for example, in the case of a sampling bag X having a capacity of 10 L, when drying is performed by setting the heating temperature to 80 ° C. and the flow rate of the drying gas to 200 to 600 mL / min, the drying gas is kept in the sampling bag X for about 20 to 40 minutes. Drying can be completed by passing it through. As described above, the cleaning step of the sampling bag X using the humidifying gas and the drying gas can be completed.

FIG. 12 shows a cleaning system using the sampling bag cleaning device 1 of the present invention. Reference numeral 7 denotes a control device, which incorporates a gas pipe, a control valve, a control unit, and the like, and a gas cylinder and the like can be connected to the gas pipe. The humidifying gas tube 3 and the drying gas tube 5 are connected to the gas pipe of the control device 7, and cleaning is performed by supplying the humidifying gas to the sampling bag X through the humidifying gas tube 3 as described above, or through the drying gas tube 5. The cleaning performed by supplying the drying gas to the sampling bag X can be automatically controlled by the control device 7.

Further, in this system, the heating device 8 is used. As the heating device 8, a commonly used dryer can be used as it is. Since the side wall of the dryer is usually provided with an opening for taking in pipes, the connection attachment 4 can be arranged in the heating device 8 by opening the opening and passing the humidifying gas tube 3 and the drying gas tube 5. it can. Then, by connecting the sampling bag X to the connection attachment 4 in the heating device 8, the sampling bag X can be washed with the above-mentioned humidifying gas and drying gas while heating to a predetermined temperature in the heating device 8. it can. When the sampling bag X is heated in this way, gas is easily dissipated from the sampling bag X, so that the cleaning efficiency of the sampling bag X can be improved.

Here, in the embodiment of FIG. 12, the humidifying device 2 is arranged outside the heating device 8, but the humidifying device 2 may be arranged inside the heating device 8. When the humidifying device 2 is arranged in the heating device 8 in this way, the liquid 22 in the humidifying device 2 is heated and the liquid 22 evaporates, and the vapor content in the humidifying gas generated in the humidifying device 2 is increased. Humidifying gas containing steam can be generated at a high concentration, and the cleaning effect of the humidifying gas can be further improved. Although the use of the backflow prevention container 25, the dew condensation liquid trap 27 and the heating tool 29 is omitted in the embodiment of FIG. 12, it goes without saying that the humidifying device 2 may further have these. ..

1. 1. Confirmation of cleaning effect depending on the type of solvent Using the cleaning system of FIG. 12 having a humidifying device 2 in which the heating tool 29 is attached to the humidifying bottle 21, a polyvinyl fluoride bag (Tedlar (registered trademark) bag) that has not been cleaned and has not been used A 10 L cleaning test was performed. The polyvinyl fluoride bag was placed in a dryer set at 80 ° C., and a humidifying gas was continuously flowed for 90 minutes and then a drying gas for 30 minutes at a gas flow rate of 0.5 mL / min. The heating temperature of the humidifying bottle 21 that generates the humidifying gas was set to 30 ° C. The humidifying gas is water in a humidifying bottle, acetone (Example 1), tert-butanol (Example 2), methanol (Example 3), ethanol (Example 4), 2-propanol (Example 5) or acetone. A liquid containing a 1: 1 mixed solvent of ethanol and ethanol (Example 6) was added and bubbling was performed to evaporate the liquid to generate it. The amount of the organic solvent added to 100 parts by mass of water was 10 parts by mass. Further, only water was put into the humidifying bottle 21 to generate a humidifying gas (without adding an organic solvent), and the same washing was performed to obtain Comparative Example 1.

4 L of nitrogen gas was supplied to the washed polyvinyl fluoride bag, and the mixture was allowed to stand in a dryer set at 65 ° C. in a closed state for 2 hours, and then the amount of dimethylacetamide in the polyvinyl fluoride bag was measured. .. The amount of dimethylacetamide in the unused polyvinyl fluoride bag before washing was measured and used as Reference Example 1.

The test results are shown in the table below and in the graph of FIG.

As is clear from the above table and graph, Comparative Example 1 washed with a humidifying gas obtained from water containing no organic solvent was in a polyvinyl fluoride bag as compared with Reference Example 1 not washed. The amount of dimethylacetamide is decreasing. However, in Examples 1 to 6 washed by the method of the present invention, the amount of dimethylacetamide in the polyvinyl fluoride bag is further reduced as compared with Comparative Example 1. Therefore, it is clear that the method of the present invention has an excellent cleaning effect.

2. Confirmation of cleaning effect by concentration of solvent Using ethanol as a solvent, the amount of ethanol added was 0 parts by mass (Comparative Example 2), 1 part by mass (Example 7), and 3 parts by mass (Example 7) with respect to 100 parts by mass of water. Examples 1 to 6 except for Example 8), 5 parts by mass (Example 9), 10 parts by mass (Example 10), 30 parts by mass (Example 11), and 50 parts by mass (Example 12). A similar test was performed. The results of the test are shown in the graphs in Table 2 and FIG. 14 below.

From the above table and graph, it can be seen that the cleaning effect of dimethylacetamide is higher when the amount of the organic solvent added to 100 parts by mass of water exceeds 3 parts by mass.

1: Cleaning device 2: Humidifying device, 21: Humidifying bottle, 22: Liquid, 23: Lid, 24: Gas tube, 25: Backflow prevention container, 26: Lid, 27: Condensation liquid trap, 28: Lid, 29: Heating Tool, 291: Heating container, 292: Electric heater 3: Humidifying gas tube 4: Connection attachment, 41: Cylindrical connection part, 41a: Cavity part, 42: Connection flange, 43: Exhaust port, 44: Tube insertion hole, 45: O-ring accommodating recess, 46: O-ring 5: Dry gas tube 6: Joint cylinder 7: Control device 8: Heating device X: Sampling bag, X1: Connection port

Claims (8)

A method for cleaning a sampling bag, which comprises a step of supplying a humidifying gas obtained by evaporating a liquid containing water and an organic solvent into the sampling bag. The cleaning method according to claim 1, wherein the organic solvent contained in the liquid is one or more polar solvents. The cleaning method according to claim 1 or 2, wherein the organic solvent contained in the liquid is one or more solvents selected from ketones and monohydric alcohols. The washing method according to any one of claims 1 to 3, wherein the amount of the organic solvent with respect to water in the liquid is 3 to 50 parts by mass with respect to 100 parts by mass of water. The cleaning method according to any one of claims 1 to 4, further comprising a step of supplying a dry gas into the sampling bag after the step of supplying the humidifying gas. A humidifier that generates a humidifying gas by evaporating a liquid containing water and an organic solvent,
It is connected to a humidifying gas tube for supplying the humidifying gas obtained from the humidifying device into the sampling bag and a connection port provided in the sampling bag, and the humidifying gas tube is attached to the connection port of the sampling bag. A connection attachment with an exhaust port that allows the inside of the sampling bag to communicate with the outside through the connection port while connected to
A sampling bag cleaning device characterized by having. The cleaning device according to claim 6, further comprising a dry gas tube for supplying a dry gas. A liquid for use in the cleaning method according to any one of claims 1 to 5 or the apparatus according to claim 6 or 7, which comprises water and an organic solvent.

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