JP6453042B2 - Transmission amount measuring method and transmission amount measuring apparatus - Google Patents

Description

  The present invention relates to a permeation amount measuring method and a permeation amount measuring device, and more particularly to a permeation amount measuring method and a permeation amount measuring device capable of measuring a permeation amount when a component in a liquid permeates a film-like material.

  Film-like materials are used in a wide variety of applications due to various functions. One of the major features among various functions is the permeability of the substance. For example, when the permeable substance is a gas, a film that is easy to permeate is used as an air filter, and a film that is difficult to permeate is used as a gas barrier film.

  For example, Patent Document 1 uses an air permeability called the Gurley method of JIS-P-8117 as an index indicating the ease of passing a film-like material. This is a method for evaluating the time by which a predetermined volume of air passes through the film-like material. If the use application is an air filter or the like, it can be assumed that the ease of passing air is directly reflected in the performance. For example, in the case of an application that allows liquid to permeate as described in Patent Document 2 and Patent Document 3, However, the air permeability is also used for the evaluation of permeability.

  Air permeability is advantageous in that it can easily measure film-like materials in a dry state, but it does not take into account interactions such as adsorption between the substance that actually permeates and the film material. May not have been properly evaluated. For example, in battery separator applications such as those described in Patent Document 3, ion transmission characteristics are considered to be important characteristic values that directly affect performance. Evaluation methods have been sought.

JP 2014-094501 A JP 2010-167384 A JP 2006-183008 A

  The present invention has been made in view of the above problems, and a permeation amount measuring method capable of appropriately evaluating the amount of a substance in a liquid that actually passes through a film-like material, and a permeation amount that can easily realize the method. It aims at providing a measuring device.

  In order to achieve the above-mentioned object, the permeation amount measuring method of the present invention includes the opening of the first container having a flanged opening, the opening of the first container, and the opening having the target flange. A sandwiching step in which the openings of the second container provided are overlapped with each other with a film-like material interposed therebetween and fixed in a state of sandwiching the film-like material; and at least one component amount Two different kinds of liquids are respectively injected into the first and second containers, and the film-like material is immersed, and after the film-like material is immersed for a certain time, the two kinds of liquids are With respect to at least one type of liquid extracted from the first and second containers and at least one of the two types of liquid extracted, the amount of the component before and after immersion in the film-like material is determined. Constant, and characterized in that it comprises a measuring step from the amount of change determining a permeation amount of the film-like material of said components, a.

  Further, the permeation amount measuring apparatus of the present invention is a liquid holding first container having a liquid holding first container having a flanged opening, and an opening having a flange of the first container and a target flange. A first container, and the first container and the second container are formed so as to be fixable in a state where the film-like material is sandwiched by overlapping the respective openings. And the second container includes a dipping part that holds the liquid when dipping the film-like material, and a storage part that holds the liquid in a state where the film-like material is not dipped in communication with the dipping part, By tilting the first and second containers, the liquid is formed so as to be movable between the immersion part and the storage part.

  According to the permeation amount measuring method of the present invention, by removing all the liquid after immersion, it is possible to equalize the difference in the concentration of the permeate at the position close to and away from the film-like material and eliminate the influence of the sampling position. it can. For this reason, the amount of transmission can be analyzed accurately.

  Moreover, according to the transmission amount measuring apparatus of the present invention, the method can be easily realized.

It is a perspective view of the permeation | transmission amount measuring apparatus which concerns on one Embodiment of this invention, (a) is the state before an assembly, (b) is the state after an assembly. It is a figure which shows the 1st container of the permeation amount measuring apparatus which concerns on one Embodiment of this invention, (a) is a top view, (b) is a side view. It is the schematic which shows the permeation | transmission amount measuring method which concerns on one Embodiment of this invention, (a) is the state which injected the liquid into the storage part of the 1st and 2nd container, (b) is the 1st and 2nd A state in which the liquid is moved to the immersion part of the container, (c) is a state in which the liquid is returned to the storage part of the first and second containers.

  In the permeation amount measuring method of the present embodiment, a liquid containing the target permeating substance is present on one side of the film-like material, and a liquid not containing the permeating substance or having a different concentration is present on the other side, for a certain period of time. After that, the change in the amount of the target substance is examined. Specifically, it is measured by the following steps (A) to (D).

(A) The opening of the first container having a flanged opening, and the opening of the second container having an opening having a flange of the first container and a target flange are formed in a film shape. They are overlapped with each other with the material interposed, and fixed in a state where the film-like material is sandwiched (pinch step).

(B) Two types of liquids having at least one different component amount are injected into the first and second containers, respectively, and the film-like material is immersed (immersion step).

(C) After immersing the film-like material for a certain period of time, the two kinds of liquids are taken out from the first and second containers (extraction step).

(D) With respect to at least one of the two types of liquids taken out, the amount of the component before and after the immersion of the target component in the film-like material is measured, and from the amount of change, the film-like material of the component is measured The permeation amount is determined (measurement process).

[A. Nipping process]
In the nipping process, the opening of the first container and the opening of the second container are overlapped with each other with the film-like material interposed therebetween, and are fixed with the film-like material being nipped. As the first and second containers and the means for fixing used in the holding process, the containers and clips shown in the embodiments described later can be used.

  Examples of film-like materials include separators used in various batteries, semi-permeable membranes such as ion permeable membranes, filters such as oil filters, biological membranes such as corneas, or artificial polymer membranes that replace them, etc. These component permeability can be evaluated. Moreover, as a method for evaluating that the liquid does not leak, the method of the present invention can be applied to, for example, a film material for a liquid storage bag.

  The film-like material is preferably provided so as to cover the entire opening of the first and second containers.

[B. Immersion process]
In the dipping process, two kinds of liquids having different amounts of at least one kind of components are used as liquids to be injected into the container.

[C. Extraction process]
After immersing the film-like material for a certain period of time, the two kinds of liquids are taken out from the container. By taking out the entire amount of the liquid after immersion, the difference in the concentration of the permeating substance between the vicinity of the film-like material and the distant position is made uniform, so that the influence of the sampling position can be eliminated. Therefore, the transmission amount can be accurately known.

[D. Measurement process]
For at least one of the two types of liquids taken out, the amount of the component before and after the immersion of the target component in the film-like material is measured, and from the change, the amount of the film-like material permeated is determined. Ask.

  The change in the amount of the permeated target component can be obtained by analyzing the liquid before and after immersion. The analysis method is appropriately selected depending on the target component. For example, gas chromatograph, liquid chromatograph, nuclear magnetic resonance, ion chromatograph if it is ionic, ICP (high frequency inductively coupled plasma) if it contains a specific element, GPC (gel permeation chromatograph if it is a polymer) Graph).

  Here, if the immersion time is known, it is possible to calculate the permeation speed from the permeation amount. For this reason, it is important to set the immersion time accurately. However, when two kinds of liquids are successively brought into contact with the film-like material, the immersion of the liquid starts simultaneously with the contact, so that not only the accurate start time of immersion can be set, but the results may differ depending on the order of contact. This is a problem that is also a concern when taking out the liquid after immersion.

  For this reason, in the dipping process, it is preferable to simultaneously pour two kinds of liquids having different amounts of at least one kind of ingredient into the first container and the second container, respectively. Moreover, also in a taking-out process, it is preferable to take out two types of liquid simultaneously from a 1st container and a 2nd container, respectively.

  In this way, the immersion time can be controlled more accurately by simultaneously injecting (contacting) two types of liquid into the film-like material and simultaneously taking out the two liquids.

  As described above, in order to simultaneously inject (contact) and simultaneously take out the film-like material, it is preferable that both the first container and the second container have the following configurations. For example, a space (hereinafter referred to as `` immersion part '') that holds liquid when the film-like material is immersed, and a liquid storage part (hereinafter referred to as `` reservoir part '' that can hold the liquid in a state where the film-like material is not immersed in the immersion part ”). By tilting both the first container and the second container having such a structure, two kinds of liquids can be moved simultaneously from the storage part to the immersion part or from the immersion part to the storage part. It becomes possible.

  As described above, by providing the liquid storage portion in the container, the simultaneous movement operation of the liquid can be performed more simply and reliably.

  If the area of the opening of the container is known, the component permeation amount per unit area of the film-like material can be calculated. Or the shielding area which opened the hole of the shape smaller than an opening part on either surface of a film-form material may be pinched | interposed, and a permeation | transmission area may be limited.

  On the other hand, when the liquid is brought into contact with the film-like material, there is a risk that wrinkles or tears may occur due to the degree of contact of the liquid with the film-like material, or the manner of contact may promote the effect of permeation of the substance.

  To solve this problem, by arranging the porous material over the entire container opening on both sides of the film-like material, the momentum of the poured liquid is relaxed by the porous material, The occurrence of tears can be prevented. In addition, since the liquid can contact the film-like material more uniformly, the immersion start time can be set more clearly.

  The porous material is not particularly limited as long as it is a material that does not dissolve in the liquid or does not react with the liquid and can circulate the liquid quickly. Examples thereof include a glass filter, glass wool, metal mesh, and the like. In addition, if the material has a considerable strength, it also functions as a support for the film-like material, which contributes to the improvement of workability, such as prevention of wrinkling of the film-like material in the holding process. .

  The porous material may be sandwiched between the first container and the second container after the film-like material is sandwiched from both sides, or is fixed in advance and integrated with the entire opening of the first container and the second container. May be. In the former case, the outer edge of the film-like material includes the outer edge of the porous material over the entire circumference so that the target component does not move through the film-like material, and the outer edge of the porous material is the first container. And it is preferable to arrange | position so that the outer edge of the opening part of a 2nd container may be included in an inside over a perimeter.

[Electrochemical reaction by voltage application or energization]
When the permeation component of interest is a product of an electrochemical reaction, an electrode is introduced into the first container and / or the second container, and the liquid in the first container and the second container It is possible to generate a state in which the amount of components in the liquid is different.

  That is, in the liquid in the first container and in the liquid in the second container by an electrochemical reaction by applying a voltage between the two electrodes inserted in the container or energizing before or during the immersion in the immersion process. The state in which the amount of the components of the different may occur.

  Moreover, when the permeation | transmission component used as object is electrically charged like ion, the permeation | transmission amount can be promoted, suppressed, or controlled by providing a potential gradient to both surfaces of a film-form material.

  The electrochemical reaction requires at least two types of electrodes, cathode and anode, but the place where the electrodes are introduced can be divided into the first container and the second container through the film material, respectively. Alternatively, both the cathode and the anode may be installed in one container without sandwiching the film-like material.

  Moreover, when the immersion part and the storage part are provided in the first container and the second container, the electrode may be installed in the immersion part or the storage part. In this case, the electrode can be divided and installed in the first container and the second container with the film-like material sandwiched in the immersion part. However, in the case where the electrode is installed in the storage part, the pair of the cathode and the anode that performs the reaction is the first container. Install together in the reservoir of either the container or the second container. Furthermore, a plurality of pairs of cathodes and anodes may be prepared and the electrochemical reaction may be performed simultaneously or sequentially at a plurality of locations in the first container and / or the second container.

[Structure of transmission measurement device]
1 and 2 show the structure of a transmission amount measuring apparatus according to an embodiment of the present invention.
The permeation amount measuring apparatus according to the present embodiment includes a first container 1a, a second container 1b, a clip 8 that fixes the first container 1a and the second container 1b in an overlapped state, It has the lids 6a and 7a of the container 1a and the lids 6b and 7b of the second container 1b. In the present embodiment, since the first container 1a and the second container 1b are formed symmetrically, only the first container 1a will be described below.

  The first container 1a communicates via an opening 9a having a flange 4a, an immersion part 2a capable of holding a liquid following the opening 9a, a communication part 5a communicating with the immersion part 2a, and a communication part 5a. And a storage portion 3a capable of storing the liquid without contacting the opening 9a.

  The immersion part 2a and the storage part 3a of the first container 1a are formed so as to be able to move liquids through the communication part 5a by inclining the first container 1a.

  Also, the opening 9a of the first container 1a and the opening 9b of the second container 1b are overlapped with each other with a film material (not shown) interposed therebetween, and fastened with a clip 8 to fix the film-like material. It can be fixed in a pinched state.

[Transmission measurement method using transmission measurement device]
Next, a transmission amount measuring method using the transmission amount measuring apparatus having the above configuration will be described with reference to FIG.
First, for example, an electrolyte solution 11 containing an electrolyte salt is injected into the reservoir 3a of the first container 1a, and only the solvent 12 is injected into the reservoir 3b of the second container 1b. 6a, 6b, 7a, 7b are closed (see FIG. 3A).

  Next, the entire container is tilted to the right in the figure, the electrolyte solution 11 containing the electrolyte salt is moved to the immersion part 2a of the first container 1a, and the solvent 12 is moved to the immersion part 2b of the second container 1b. (See FIG. 3B).

  After a certain period of time, the entire container is tilted to the left in the figure, the electrolyte solution 11 containing electrolyte salt is returned to the storage part 3a of the first container 1a, and the solvent 12 is returned to the storage part 3b of the second container 1b. (See FIG. 3C).

  By sampling the solvent 12 and measuring the concentration of the electrolyte salt, the permeation amount of the electrolyte salt film-like material can be determined.

  In the permeation amount measuring apparatus of this embodiment, since the first container 1a and the second container 1b are formed symmetrically, the amount of the electrolyte solution 11 containing the electrolyte salt and the amount of the solvent 12 are the same amount. Then, by inclining the first and second containers 1a and 1b, the electrolyte solution 11 containing the electrolyte salt and the solvent 12 are simultaneously put into the other space (ie, from the storage portions 3a and 3b to the immersion portions 2a and 2b, or It can be moved from the immersion parts 2a, 2b to the storage parts 3a, 3b).

  In addition, the liquid is first injected into the storage units 3a and 3b, moved to the immersion units 2a and 2b, immersed in the film-like material, and then returned to the storage units 3a and 3b. The entire amount can be taken out from 3a and 3b. For this reason, the difference in the density | concentration of the permeation | transmission substance in the vicinity position of a film-form material and the distant position can be equalize | homogenized, and the influence of a sampling position can be excluded. For this reason, the amount of transmission can be analyzed accurately.

[Other embodiments]
(1) In the above embodiment, the clip 8 is used as the fixing means for the flange portions 4a and 4b. However, other fixing means such as an adhesive tape and a fastener may be used, and the overlapping flange portions 4a, A case imitating the outer shape of 4b may be prepared, and the flange portions 4a and 4b may be accommodated in the case to be fixed.

(2) In the above embodiment, the opening 9a of the first container 1a and the opening 9b of the second container 1b are circular, but other shapes such as a polygonal shape can also be used. Further, the shape and area of the opening 9a and the opening 9b may be substantially the same as well as the case where they are the same.

(3) In the above embodiment, the immersion part 2a and the storage part 3a of the first container 1a are configured to communicate with each other via the communication part 5a. However, the immersion part 2a and the storage part are provided without providing the communication part 5a. It can also be set as the structure which made the part 3a contact directly. In this case, it is preferable to provide a valve that opens in a predetermined direction when the container is inclined at the opening portion at the boundary between the immersion part 2a and the storage part 3a. The same applies to the second container 1b.

(4) Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. These embodiments and their modifications are included in the scope and gist of the invention, and are also included in the invention described in the claims and the equivalents thereof.

DESCRIPTION OF SYMBOLS 1a ... 1st container 1b ... 2nd container 2a, 2b ... immersion part 3a, 3b ... storage part 4a, 4b ... flange part 5a, 5b ... communication part 6a, 6b ... lid 7a, 7b ... lid 8 ... clip 9a , 9b ... opening 11 ... electrolyte solution 12 containing electrolyte salt ... solvent

Claims (5)

A film-like material is interposed between the opening of the first container having a flanged opening and the opening of the second container having an opening having a flange symmetrical to the flange of the first container. A sandwiching process in which the film-like material is sandwiched and fixed in a sandwiched state,
An immersion step of immersing the film-like material by simultaneously injecting two kinds of liquids having different component amounts of at least one kind into the first and second containers, respectively ,
After the film-like material is immersed for a certain period of time, an extraction step of taking out the entire amount of the two types of liquid from the first and second containers;
For at least one of the two types of liquids taken out, the amount of the component before and after immersion in the film-like material of the target component is measured, and the amount of permeation of the film-like material of the component from the amount of change look including a measurement step of obtaining a,
Both the first and second containers include an immersion part that holds the liquid when the film-like material is immersed, and a storage part that communicates with the immersion part and holds the liquid in a state where the film-like material is not immersed. Prepared,
By inclining the first and second containers, in the immersion step, the two kinds of liquids are simultaneously moved from the storage portion toward the immersion portion . A film-like material is interposed between the opening of the first container having a flanged opening and the opening of the second container having an opening having a flange symmetrical to the flange of the first container. A sandwiching process in which the film-like material is sandwiched and fixed in a sandwiched state,
An immersion step of injecting at least one type of two or more kinds of liquids having different component amounts into the first and second containers and immersing the film-like material,
After the film-like material is immersed for a certain period of time, an extraction step of taking out all the two types of liquid from the first and second containers at the same time,
For at least one of the two types of liquids taken out, the amount of the component before and after immersion in the film-like material of the target component is measured, and the amount of permeation of the film-like material of the component from the amount of change look including a measurement step of obtaining a,
Both the first and second containers include an immersion part that holds the liquid when the film-like material is immersed, and a storage part that communicates with the immersion part and holds the liquid in a state where the film-like material is not immersed. Prepared,
The permeation amount measuring method, wherein the two kinds of liquids are simultaneously moved from the immersion part toward the storage part in the extraction step by inclining the first and second containers . The permeation amount measuring method according to claim 1 or 2 , wherein a porous material is disposed on both surfaces of the film-like material so as to cover the entire opening in the nipping step. A first container for holding liquid with a flanged opening; and a second container for holding liquid with an opening having a flange symmetrical to the flange of the first container;
The first container and the second container are formed so that they can be fixed in a state where the film-like material is sandwiched by overlapping the openings.
Both the first and second containers include an immersion part that holds the liquid when the film-like material is immersed, and a storage part that communicates with the immersion part and holds the liquid in a state where the film-like material is not immersed. And a permeation amount measuring device, wherein the liquid is formed to be movable between the immersion part and the storage part by inclining the first and second containers. The permeation amount measuring apparatus according to claim 4 , wherein a porous material is disposed in the openings of the first and second containers so as to cover the entire opening.

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