JP2005233943A - Device and method for measuring gas permeability of film material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas permeability measuring device capable of accurately measuring gas permeability of a specific gas constituent (water and/or oxygen) for a film material. <P>SOLUTION: Gas flow chambers 10 and 12 opening to the opposite end faces 9 and 11 are formed in device main bodies 1 and 2. The film material 22 to be subjected to measurement of specific gas constituent permeability is clamped and pressed between the opposite end faces 9 and 11 having central parts exposed to the gas flow chambers 10 and 12. Between the opposite end faces 9 and 11, a seal chamber 23 surrounding the outer circumference of the film material 22 is formed. Seal gas 36 is fed to the seal chamber 23, while exposure gas 24 containing the specific gas constituent is fed to the flow chamber 10, and carrier gas 30 including no specific gas constituent is fed to the flow chamber 12. For measuring the specific gas constituent permeability of the film material 22, an amount of the specific gas constituent included in the carrier gas 30a flowing out from the gas flow chamber 12 is measured. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  For film materials (films, sheets, membranes made of plastics, etc.) used for packaging foods, medicines, precision electronic components, etc., determine the superiority or inferiority of permeability (gas barrier properties) of specific gas components such as moisture and oxygen In order to achieve this, it is necessary to accurately measure the amount of a specific gas component that permeates the film material. The present invention relates to a gas permeability measuring device and a gas permeability measuring method for a film material for measuring the permeability of (or oxygen) with high accuracy.

As a conventional gas permeability measuring device for a film material, a film material is sandwiched between an upper container having a vacuum exhaust chamber and a lower container having a gas inflow chamber through an O-ring, and then the gas inflow Known to measure the permeability of specific gas components (water, oxygen, etc.) in the film material by measuring the amount of gas that permeates the film material from the chamber and exhausts it to the vacuum exhaust chamber. (For example, refer to FIG. 7 of Patent Document 1).
JP 2004-157035 (FIG. 7)

  In such a gas permeability measuring device for film material (hereinafter referred to as “conventional device”), only the vacuum exhaust chamber and the gas inflow chamber and the film material are sealed by an O-ring. There was a problem that the seal between them was insufficient and unstable, and it was difficult to accurately measure the gas permeability. That is, in the conventional apparatus, there is a possibility that the specific gas component that has passed through the film material leaks out of the apparatus, or conversely, the atmospheric component outside the apparatus may be mixed into the specific gas component that has passed through the film material. Therefore, it is difficult to equalize the specific gas component amount permeated through the film material and the specific gas component amount discharged from the vacuum exhaust chamber, and it is difficult to accurately measure the specific gas component permeability in the film material. It was. Such a problem is particularly remarkable when the permeability of a specific gas component is very small in a film material having a high gas barrier property.

  By the way, as a method for measuring the moisture permeability of a film material, generally, a water vapor permeability test method defined in JIS K7129 is well known, which includes a wet / dry sensor method (A method) and an infrared sensor method (B Law). JIS Z0208 defines a moisture permeability test method for moisture-proof packaging materials. As a method for measuring the oxygen permeability of a film material, an oxygen permeability test method defined in JIS K7126 is well known, and a differential pressure method (A method) and an isobaric method (B method) are presented. Has been.

  However, in these methods, since the measurement lower limit value of water vapor or oxygen permeability is high, the gas permeability cannot be accurately measured for a film material having a high gas barrier property (low gas permeability). That is, the dry / wet sensor method of JIS K7129 is not suitable when the moisture sensitivity is 0.05% RH and the moisture permeability is very small. In addition, the infrared sensor method of JIS K7129 is a measurement method with a moisture sensitivity of about 1 ppm (parts per million by volume), and in principle, moisture permeation at the level of ppb (parts per billion by volume). Degree measurement is difficult. Further, the moisture permeability test method of JIS Z0208 has a detection limit of about 0.5 g / m 2 · day, and is difficult to deal with a film material having a very small moisture permeability. In addition, the oxygen permeability test method defined in JIS K7126 uses a film material having a low gas barrier property (high oxygen permeability) (a film material having an oxygen permeability of 0.5 cc / m 2 · day · atm or more). This was intended, and the oxygen permeability of a film material having a high gas barrier property could not be measured. For example, in a galvanic cell type oximeter used for the isobaric method, the measurement limit value (the measurement lower limit value of the oxygen amount) is about 0.1 to 1 ppm (parts per million by volume ratio), and the fluctuation of the zero level is Therefore, it is difficult to measure a small amount of oxygen permeability. Furthermore, these methods cannot measure the gas permeability of a plurality of gas components (for example, moisture and oxygen) at the same time. Therefore, when measuring the gas permeability of a plurality of gas components, an apparatus is required for each component. It was necessary to prepare and measure each.

  The present invention can appropriately and accurately measure the permeability of a specific gas component (for example, moisture and / or oxygen) in the film material regardless of the gas barrier property of the film material without causing such a problem. An object of the present invention is to provide a gas permeability measuring device and a gas permeability measuring method for a film material.

  In order to achieve the above object, the present invention provides a first and second apparatus main bodies formed with gas flow chambers that open oppositely on opposite end faces, and a film material whose permeability of a specific gas component is to be measured. Between the opposing end surfaces, a seal mechanism that is removably loaded between the two device bodies with the central portion exposed to both gas flow chambers and the outer peripheral portion sandwiched and sealed between the opposing end surfaces. A sealed chamber surrounding the outer peripheral portion of the film material, an exposure gas supply mechanism for supplying an exposure gas containing a specific gas component to the gas flow chamber of the first apparatus body, The carrier gas supply mechanism that supplies a carrier gas that does not contain a specific gas component to the gas flow chamber of the second apparatus main body, the seal gas supply mechanism that supplies the seal gas to the seal chamber, and the gas flow chamber of the second apparatus main body. Do Suggest gas permeability measuring device of the film material characterized by comprising: a gas concentration measuring mechanism for measuring the specific gas component concentration in Yariagasu. In the preferred embodiment, the sealing mechanism includes a first annular seal member concentrically held on one of the opposing end faces of the two apparatus main bodies, a second annular seal member having a larger diameter than the first annular seal member, A clamp that fastens both device bodies to clamp both annular seal members between the opposing end faces in a state where the annular seal member is in contact with the outer peripheral portion of the film material, and is sealed by both annular seal members. Configured to hermetically seal the chamber.

  Thus, in such a gas permeability measuring device, when the specific gas component whose gas barrier property is to be determined is moisture, the gas concentration measuring mechanism has a carrier gas that flows out from the gas flow chamber of the second device body. It is preferable that the moisture concentration in the is measured by a quartz oscillation type moisture meter. In a preferred embodiment, a quartz oscillation type moisture meter having a moisture measurement limit value of 1 ppb to 0.1 ppm is used. Generally, nitrogen containing moisture is used as the exposure gas, and nitrogen containing no moisture is used as the carrier gas and the seal gas.

  When the specific gas component is oxygen, the gas concentration measuring mechanism separates the oxygen concentration in the carrier gas flowing out from the gas flow chamber of the second device body from the argon component contained in the carrier gas. It is preferable to measure by a discharge ionization gas chromatograph. In a preferred embodiment, a pulse discharge ionization gas chromatograph having an oxygen measurement limit value of 1 ppb to 0.1 ppm is used as the discharge ionization gas chromatograph. In general, oxygen is used as the exposure gas, and nitrogen containing no oxygen is used as the carrier gas and the seal gas.

  In addition, when the specific gas components are moisture and oxygen, the gas concentration measurement mechanism analyzes the moisture concentration and oxygen concentration contained in the carrier gas flowing out from the gas flow chamber of the second device body by atmospheric pressure ionization mass spectrometry. It is preferable to measure by a meter (APIMS). In a preferred embodiment, an atmospheric pressure ionization mass spectrometer having a measurement limit value of water concentration and oxygen concentration of 1 ppt to 0.1 ppb is used. In general, oxygen or air containing moisture is used as the exposure gas, and nitrogen that does not contain moisture and oxygen is used as the carrier gas and the seal gas. In addition to moisture and oxygen, for specific gas components (for example, one or more gas components selected from carbon dioxide, methane, etc.) whose concentration can be measured by an atmospheric pressure ionization mass spectrometer, a gas concentration measurement mechanism It is possible to measure the permeability of the specific component in the film material with the gas permeability measuring device (and the gas permeability measuring method described later using the same) using an atmospheric pressure ionization mass spectrometer as is there.

  Further, the present invention uses the gas permeability measuring device described above to measure the concentration of the specific gas component contained in the carrier gas flowing out from the gas flow chamber of the second device body, thereby identifying the specific material in the film material. A method for measuring the gas permeability of a film material, characterized in that the permeability of a gas component is measured.

  According to the gas permeability measuring apparatus and the gas permeability measuring method using the same according to claim 1, the seal between the gas flow chambers of the first and second apparatus bodies and the film material is highly and stable. It is possible to accurately measure the gas permeability. In particular, by configuring the seal mechanism as described in claim 11, a more sophisticated and stable seal function can be exhibited.

  In addition, according to the gas permeability measuring device and the gas permeability measuring method using the gas permeability measuring device according to claims 2 to 4, in combination with the excellent sealing function as described above, a trace amount of moisture in the film material is used. The permeability can also be accurately measured, and the gas barrier property against moisture of the film material can be accurately determined regardless of its level.

  In addition, according to the gas permeability measuring apparatus and the gas permeability measuring method using the same according to claims 5 to 7, in combination with the excellent sealing function as described above, oxygen in a very small amount of film material is used. The permeability can also be accurately measured, and the gas barrier property against oxygen of the film material can be accurately determined regardless of its level.

  In addition, according to the gas permeability measuring apparatus and the gas permeability measuring method using the same according to claims 8 to 10, in combination with the excellent sealing function as described above, a very small amount of moisture in the film material is used. The permeability and oxygen permeability can be accurately measured, and the gas barrier property against moisture and oxygen of the film material can be accurately determined regardless of its level. Furthermore, according to the gas permeability measuring apparatus and the gas permeability measuring method using the same according to claims 8 to 10, the gas permeability of a plurality of gas components (for example, moisture and oxygen) can be measured at a time. Therefore, it is not necessary to prepare an apparatus for each component and measure each of them, and the gas barrier property against moisture and oxygen of the film material can be determined easily and efficiently.

  FIG. 1 is a longitudinal front view showing an example of a gas permeability measuring device according to the present invention (hereinafter referred to as “first gas permeability measuring device M1”) when the specific gas component is moisture, and FIG. 2 is a specific gas. FIG. 3 is a longitudinal front view showing an example of a gas permeability measuring apparatus according to the present invention when the component is oxygen (hereinafter referred to as “second gas permeability measuring apparatus M2”), and FIG. 3 shows the specific gas component as moisture and oxygen. Is a longitudinal front view showing an example of a gas permeability measuring device according to the present invention (hereinafter referred to as “third gas permeability measuring device M3”), and FIG. 4 shows each gas permeability measuring device M1, M2, FIG. 5 is a cross-sectional bottom view of M3 (the cross section is taken along line IV-IV in FIG. 1, FIG. 2 or FIG. 3), and FIG. 5 is a cross-sectional plan view of each gas permeability measuring device M1, M2, M3. , Along the line VV in FIG. 2 or FIG.

  As shown in FIG. 1, FIG. 2 or FIG. 3, each gas permeability measuring device M 1, M 2, M 3 includes a first and second device main bodies 1, 2 and a seal mechanism 3 provided between the device main bodies 1, 2. And an exposure gas supply mechanism 4, a carrier gas supply mechanism 5, a seal gas supply mechanism 6, and a gas concentration measurement mechanism 7.

  As shown in FIG. 1, FIG. 2 or FIG. 3, and FIG. 4 and FIG. 5, the device main bodies 1 and 2 in each gas permeability measuring device M1, M2 and M3 are metal disks having the same diameter and facing each other. The upper first apparatus main body 1 is formed with a first gas flow chamber 10 that opens to the lower end surface 9 thereof. The lower second apparatus main body 2 is formed with a second gas flow chamber 12 that opens to the upper end surface 11 thereof. Each of the gas flow chambers 10 and 12 has a circular cross section that is concentric with the apparatus main bodies 1 and 2, and the openings of the gas flow chambers 10 and 12 face each other directly.

  The sealing mechanism 3 in each of the gas permeability measuring devices M1, M2, and M3 includes the first and second members held on the upper end surface of the second device body 2 as shown in FIG. 1, FIG. 2 or FIG. 3, and FIG. The second annular seal members 13 and 14 and the clamp 15 that fastens both the apparatus main bodies 1 and 2 in a state in which the annular seal members 13 and 14 are clamped between the opposed end surfaces 9 and 11 are provided. In this example, O-rings made of natural rubber, fluororubber, Kalrez, fluororesin, various metals, etc. are used as the annular seal members 13, 14, but C-rings made of various metals, various materials, and shapes are used. Gaskets can also be used. The first O-ring 13 has a diameter slightly larger than the opening diameter of the second gas flow chamber 12, and the second O-ring groove 16 formed in the upper end surface 11 of the second device body 2 has a second gas flow chamber 12. It is engaged and held concentrically with the opening. The second O-ring 14 has a larger diameter than the first O-ring 13 by a predetermined amount, and is engaged with the second O-ring groove 17 formed in the upper end surface 11 concentrically with the first O-ring 13. Are held together. The clamp 15 is inserted through the plurality of bolt insertion holes 18, 19, which are formed at equal intervals in the circumferential direction in the outer peripheral portions of the apparatus main bodies 1, 2, and through the bolt insertion holes 18, 19. And a plurality of nuts 21 screwed into the respective fastening bolts 20. By tightening each nut 21, both the apparatus main bodies 1 and 2 are placed between the opposed end surfaces 9 and 11. The two O-rings 13 and 14 can be fastened while being clamped.

  Thus, the film material to be attached to each gas permeability measuring device M1, M2, M3, that is, the film material 22 for which the permeability of a specific gas component (water and / or oxygen) is to be measured is shown in FIGS. Alternatively, as shown in FIGS. 3, 4, and 5, the first O-ring 13 has a circular shape having the same outer diameter as that of the first O-ring 13, and the central portion is exposed to both gas flow chambers 10 and 12. In this state, the outer peripheral portion is loaded between the two apparatus main bodies 1 and 2 with the first O-ring 13 being sandwiched and sealed between the opposed end faces 9 and 11 of the both apparatus main bodies 1 and 11. The loading is performed according to the following procedure. That is, first, after removing each nut 21 and removing the first apparatus main body 1 from the second apparatus main body 2, the film material 22 is placed on the first O-ring 13 in the outer peripheral portion thereof. Set on the second device body 2. Next, the first device main body 1 is set on the second device main body 2 in a state where the bolts 20 are inserted into the respective bolt insertion holes 18, and nuts 21 are screwed into the respective bolts 20. Tighten all nuts 21 evenly. By tightening the nuts 21, the outer peripheral portion of the film material 22 and the first O-ring 13 are sandwiched between the opposed end surfaces 9 and 11 of both the apparatus main bodies 1 and 2. At the same time, the second O-ring 14 is also sandwiched between the opposed end surfaces 9 and 11. Therefore, by tightening the nuts 21 until the both O-rings 13 and 14 are properly compressed, the film material 22 is moved between its outer peripheral portion and the opposed end surfaces 9 and 11 as shown in FIG. It is loaded between both apparatus main bodies 1 and 2 in a state where the space is sealed by the first O-ring 13 and the front and back surfaces of the central portion of the film material 22 are exposed to the gas flow chambers 10 and 12, respectively. Can do. Further, in such a loaded state of the film material 22, as shown in FIG. 1, a seal chamber 23 sealed by both O-rings 13 and 14 is formed between the opposed end surfaces 9 and 11 of the apparatus main bodies 1 and 2. The That is, the seal chamber 23 is an annular sealed space that surrounds the outer peripheral portion of the film material 22, is sealed off from the gas flow chambers 10 and 12 by the first O-ring 13, and is externally enclosed by the second O-ring 14 ( It is shielded from the atmosphere.

  The exposure gas supply mechanism 4 in each of the gas permeability measuring devices M1, M2, and M3 uses the exposure gas 24 containing the specific gas component as the first gas, as shown in FIG. 1, FIG. 2, or FIG. 3, and FIG. The exposure gas 24 is exposed (contacted) to the surface (upper surface) of the film material 22 by supplying a fixed amount to the flow chamber 10, and is formed in the first apparatus main body 1 and communicates with the first gas flow chamber 10. Exposure gas supply / exhaust ports 25, 26, an exposure gas supply channel 27 connected to the exposure gas supply port 25, an exposure gas discharge channel 28 connected to the exposure gas discharge port 26, and an exposure gas 24 of a predetermined pressure are exposed. An exposure gas supply device 29 for supplying a fixed amount from the gas supply path 27 to the first gas flow chamber 10 is provided.

  Thus, in the first gas permeability measuring device M1, nitrogen that does not contain moisture is used as the exposure gas 24, and the exposure gas supply device 29 supplies high-pressure nitrogen in the high-pressure nitrogen cylinder to a predetermined pressure by a pressure reducing valve. (Exposure gas, for example, 0.01 MPa · G), which is humidified to a saturated water content at about 40 ° C. by storing pure water and passing through a humidification pot kept at a constant temperature of 40 ° C. as exposure gas 24 The exposure gas supply path 27 is configured to supply a fixed amount (for example, 1 to 1000 mL / min).

  Further, in the second gas permeability measuring device M2, oxygen that does not contain moisture is used as the exposure gas 24, and the exposure gas supply device 29 supplies high-pressure oxygen in the high-pressure oxygen cylinder to a predetermined pressure (for example, by a pressure reducing valve). The pressure is reduced to 0.01 MPa · G), and the exposure gas 24 is supplied in a fixed amount (for example, 1 to 1000 mL / min) as the exposure gas supply path 27.

  Further, in the third gas permeability measuring device M3, oxygen containing moisture is used as the exposure gas 24, and the exposure gas supply device 29 supplies high-pressure oxygen in the high-pressure oxygen cylinder to a predetermined pressure (for example, by a pressure reducing valve). The pressure is reduced to 0.01 MPa · G), and the water that has been humidified to the saturated water content at about 40 ° C. by storing pure water and passing through a humidification pot kept at a constant temperature of 40 ° C. is used as the exposure gas 24. The gas supply path 27 is configured to supply a fixed amount (for example, 1 to 1000 mL / min).

  The carrier gas supply mechanism 5 in each of the gas permeability measuring devices M1, M2, and M3 supplies a specific gas that has passed through the film material 22 by quantitatively supplying a carrier gas 30 that does not contain a specific gas component to the second gas flow chamber 12. The component gas is entrained with the carrier gas 30 and transferred to the permeate gas measurement region outside the second gas flow chamber 12, and the carrier gas inflow formed in the second device body 2 and communicated with the second gas flow chamber 12 The carrier gas inflow passage 33 connected to the outlets 31 and 32, the carrier gas inflow port 31, the carrier gas outflow passage 34 connected to the carrier gas outflow port 32, and the carrier gas 30 having a predetermined pressure are supplied to the carrier gas inflow passage 33. And a carrier gas supply device 35 for supplying a fixed amount to the second gas flow chamber 12.

  Thus, in the first gas permeability measuring device M1, nitrogen that does not contain moisture is used as the carrier gas 30, and the carrier gas supply device 35 supplies the high-pressure nitrogen in the high-pressure nitrogen cylinder to the pressure reducing valve. Then, the pressure is reduced to the same pressure as the exposure gas (nitrogen) 24 to be supplied to the first gas flow chamber 10, and after dehumidification treatment with synthetic zeolite, a fixed amount is supplied to the carrier gas inflow passage 33 as the carrier gas 30 (for example, 1 ˜1000 mL / min).

  Further, in the second gas permeability measuring device M2, nitrogen not containing oxygen is used as the carrier gas 30, and the carrier gas supply device 35 is configured to supply high-pressure nitrogen in the high-pressure nitrogen cylinder with a pressure reducing valve. The pressure is reduced to the same pressure as the exposure gas (oxygen) 24 to be supplied to the first gas flow chamber 10 and the oxygen removal treatment is performed in the oxygen removal tower, and then the carrier gas 30 is quantitatively supplied to the carrier gas inflow passage 33 (for example, 1 ˜1000 mL / min).

  Further, in the third gas permeability measuring device M3, nitrogen that does not contain moisture and oxygen is used as the carrier gas 30, and the carrier gas supply device 35 supplies the high-pressure nitrogen in the high-pressure nitrogen cylinder to the pressure reducing valve. Thus, the pressure is reduced to the same pressure as the exposure gas (oxygen) 24 to be supplied to the first gas flow chamber 10, and the moisture and oxygen removal treatment by the purifier is performed, and then the carrier gas 30 is supplied to the carrier gas inflow path 33. It is comprised so that fixed supply (for example, 1-1000 mL / min) may be carried out.

  The seal gas supply mechanism 6 in each of the gas permeability measuring devices M1, M2, and M3 supplies a seal gas 36 that does not contain a specific gas component to the seal chamber 23 as shown in FIG. 1, FIG. 2, or FIG. The gas flow chambers 10 and 11 are more reliably sealed by the first O-ring 13, and the first apparatus main body 1 is opened in an annular space (seal chamber 23) between the O-rings 13 and 14. An annular groove 37 formed in the lower end surface 9, seal gas supply / exhaust ports 38 and 39 formed in the first apparatus body 1, opened in the annular groove 37 and communicating with the seal chamber 12, and a seal gas supply port A seal gas supply path 40 connected to 38, a seal gas discharge path 41 connected to a seal gas discharge port 39, and a seal that supplies a predetermined amount of seal gas 36 of a predetermined pressure from the seal gas supply path 40 to the seal chamber 23. Formed by and a scan feeder 42.

  Thus, in the first gas permeability measuring device M1, nitrogen that does not contain moisture is used as the sealing gas 36, and the sealing gas supply device 42 converts the high-pressure nitrogen in the high-pressure nitrogen cylinder into a pressure reducing valve. Thus, the pressure is reduced to the same pressure as the carrier gas (nitrogen) 30 to be supplied to the second gas flow chamber 12, and after dehumidification treatment with synthetic zeolite, a fixed amount is supplied as the seal gas 36 to the seal gas supply path 40 ( For example, it is configured to be 1 to 1000 mL / min). The supply sources (high-pressure nitrogen cylinders) for the gases 24, 30, and 36 may be provided individually or in common.

  Further, in the second gas permeability measuring device M2, nitrogen not containing oxygen is used as the sealing gas gas 36, and the sealing gas supply device 42 is configured to supply high-pressure nitrogen in the high-pressure nitrogen cylinder by a pressure reducing valve. The pressure is reduced to the same pressure as the carrier gas (nitrogen) 30 to be supplied to the second gas flow chamber 12 and the oxygen removal treatment is performed in the oxygen removal cylinder, and then a fixed amount is supplied as the seal gas 36 to the seal gas supply path 40 (for example, 1 ˜1000 mL / min). The supply sources (high-pressure nitrogen cylinders) for the carrier gas 30 and the seal gas 36 may be provided individually or in common.

  Further, in the third gas permeability measuring device M3, nitrogen that does not contain moisture and oxygen is used as the sealing gas gas 36, and the sealing gas supply device 42 converts the high-pressure nitrogen in the high-pressure nitrogen cylinder into a pressure reducing valve. Thus, the pressure is reduced to the same pressure as that of the carrier gas (nitrogen) 30 to be supplied to the second gas flow chamber 12, and after the moisture and oxygen removal treatment by the purifier, the seal gas 36 is supplied to the seal gas supply path 40. It is comprised so that fixed supply (for example, 1-1000 mL / min) may be carried out. The supply sources (high-pressure nitrogen cylinders) of the gases 30 and 36 may be provided individually or in common.

  According to each gas permeability measuring device M1, M2, M3 configured as described above and the gas permeability measuring method using the same, the sealing gas 36 having the same pressure as the carrier gas 30 (and the exposure gas 24) is sealed. By supplying the fixed amount to the seal chamber 23 by the gas supply mechanism 6, the seal portion by the first O-ring 13 of the second gas flow chamber 12 (and the first gas flow chamber 10) becomes a seal gas layer (the seal gas 36 is Since it is surrounded by the filled seal chamber 23), the second gas flow chamber 12 (and the first gas flow chamber 10) and the outside are reliably shut off (seal effect). Therefore, leakage of the carrier gas from the second gas flow chamber 12 and entry of air into the second gas flow chamber 12 from the outside are surely prevented, and the specific gas component that has permeated the film material 22 (first gas permeability measurement). The device M1 is water, the second gas permeability measuring device M2 is oxygen, and the third gas permeability measuring device M3 is moisture and oxygen). 30 or a specific gas component corresponding to a specific gas component in the atmosphere (in the first gas permeability measuring device M1, it is moisture and second gas permeation) In the degree measuring device M2, it is oxygen, and in the third gas permeability measuring device M3, it is not mixed with water and oxygen) and flows out from the second gas flow chamber 12. Carry The specific gas component amount contained in the gas 30 and the specific gas component amount permeated through the film material 22 can be equivalent, and the specific gas component permeability of the film material 22 can be accurately detected by the gas concentration measuring mechanism 7 described later. Can be measured.

Thus, the gas concentration measuring mechanism 7 in the first gas permeability measuring device M1 is separated from the second gas flow chamber 12 by the crystal oscillation moisture meter 43 disposed in the carrier gas outflow passage 34 as shown in FIG. Measures the moisture concentration (moisture amount) as the specific gas component concentration in the carrier gas (hereinafter referred to as “gas permeability measuring gas 30a”) flowing out along with the permeating gas (moisture as the specific gas component that has passed through the film material 22). To do. The moisture concentration is obtained in advance based on a calibration curve created by measuring a standard gas with a known moisture concentration or a gas prepared using a moisture generator that dynamically generates moisture with a known concentration. By the way, the crystal oscillator used in the crystal oscillation moisture meter 43 causes a phenomenon that the oscillation frequency decreases in inverse proportion to the increase in mass. The quartz oscillation type moisture meter 43 utilizes such a phenomenon, and a functional thin film (a coating film having strong hygroscopicity) sensitive to moisture is provided on the quartz vibrator, and the quartz vibration due to moisture adsorbed on the film is provided. It is configured to measure the frequency change of the child to obtain the water concentration (water content). As the quartz oscillation type moisture meter 43, it is preferable to use a moisture measurement limit value of 1 ppb to 0.1 ppm. The moisture content (g / m ² · day) contained in the gas permeability measurement gas 30a is determined by the moisture concentration (ppm) of the gas permeability measurement gas 30a, the flow rate (mL / min) of the carrier gas 30 and the film. Calculated and measured from the moisture permeation area (m ² ) of the material 22.

  Further, as shown in FIG. 2, the gas concentration measuring mechanism 7 in the second gas permeability measuring device M2 includes an argon separation device 44 and a discharge ionization gas chromatograph 45 located downstream thereof in the carrier gas outflow passage 34. Set up.

  The argon separation device 44 includes argon contained in a carrier gas (hereinafter referred to as “oxygen-entrained gas”) 30 b that flows out from the second gas flow chamber 12 with a permeating gas (oxygen that is a specific gas component that has permeated the film material 22). It separates and removes components. As the argon separation device 44, a known device that generally separates oxygen and argon by a low temperature column can be used. In this example, the oxygen-entrained gas 30 b is cooled to −200 ° C. to 20 ° C. The argon component contained therein is separated by a 1-20 m molecular sieve column.

The discharge ionization gas chromatograph 45 is configured such that an oxygen concentration (amount of oxygen permeating the film material 22) in a carrier gas (hereinafter referred to as “gas permeability measuring gas”) 30c obtained by separating an argon component by an argon separation device 44. ). The oxygen concentration is obtained in advance based on a calibration curve created by measuring a standard gas with a known oxygen concentration. Specifically, the discharge ionization gas chromatograph 45 uses light energy (13.5 to 17.7 eV) generated when excited helium molecules generated by pulse discharge return to the ground helium atom. A pulse discharge ionization gas chromatograph configured to ionize and detect molecules to be measured (oxygen molecules) is used, and an oxygen measurement limit value of 1 ppb to 0.1 ppm is used. Yes. Note that the oxygen amount (cc / m ² · day · atm) contained in the gas permeability measurement gas 30c is the oxygen concentration (ppm) of the gas permeability measurement gas 30c and the flow rate (mL / min) of the carrier gas 30. And the oxygen transmission area (m ² ) of the film material 22 are calculated and measured.

  Further, as shown in FIG. 3, the gas concentration measuring mechanism 7 in the third gas permeability measuring device M3 includes a second gas flow chamber by an atmospheric pressure ionization mass spectrometer (APIMS) 46 disposed in the carrier gas outflow passage 34. The specific gas component concentration of the carrier gas (hereinafter referred to as “gas permeability measuring gas 30d”) flowing out from the gas 12 along with the permeating gas (moisture and oxygen as the specific gas components that have passed through the film material 22) Permeated water and oxygen). The moisture concentration is determined in advance based on a calibration curve created by measuring a standard gas with a known moisture concentration or a gas prepared using a moisture generator that dynamically generates moisture with a known concentration. Is obtained in advance based on a calibration curve prepared by measuring a standard gas with a known oxygen concentration. This atmospheric pressure ionization mass spectrometer 46 is a gas analyzer characterized by high-sensitivity analysis capable of highly efficient ionization of impurities by performing ionization under atmospheric pressure. It is preferable to use one having a value of 1 ppt to 0.1 ppb. Note that the moisture and oxygen permeability (g / m 2 · day) are the moisture concentration (ppb) and oxygen concentration (ppb) of the gas permeability measurement gas 30d, the flow rate (mL / min) of the carrier gas 30, and the film material 22. Is calculated and measured from the moisture and oxygen permeation area (m2). The atmospheric pressure ionization mass spectrometer 46 is an analyzer capable of measuring various components (for example, carbon dioxide, methane, etc.) in addition to moisture and oxygen, and can be measured by the atmospheric pressure ionization mass spectrometer 46. If possible, the permeability of components other than moisture and oxygen can be measured using the third gas permeability measuring device M3. That is, in the third gas permeability measuring apparatus M3, for example, carbon dioxide or methane or a mixed gas of carbon dioxide and methane is used as the exposure gas 24, and carbon dioxide and / or methane is used as the carrier gas 30 and the seal gas 36. Carbon that is a carrier gas that flows out from the second gas flow chamber 12 with the permeating gas (carbon dioxide and / or methane that has permeated the film material 22) from the second gas flow chamber 12 using nitrogen that is not contained. And by measuring the methane concentration, the permeability of these components (specific gas components) can be measured.

  In each gas permeability measuring device M1, M2, M3, the gas flow paths (piping, gas flow chambers, etc.) of the exposure gas 24, the carrier gas 30, and the seal gas 36 have a dead volume as much as possible so that gas replacement can be performed quickly. In particular, the gas contact surface of the carrier gas 30 is subjected to a surface treatment such as mechanical polishing or electrolytic polishing so that a minute amount of a specific gas component is adsorbed and desorbed and does not affect the measured value. It is preferable. In order to improve the adsorption / desorption characteristics of a small amount of a specific gas component and reach an equilibrium state in a short time, the surface roughness Ry of the gas contact surface is preferably 5 μm or less, and more preferably the surface roughness Ry is 1 μm or less. preferable.

  The configuration of the gas permeability measuring apparatus according to the present invention is not limited to the above-described embodiments, and can be appropriately improved and changed without departing from the basic principle of the present invention.

  As Example 1, three types of films A, B, and C, which are film materials 22 formed by depositing a silicon oxide film on a polyethylene terephthalate film and having different moisture permeability (gas barrier properties), are used. The water permeability of B and C was measured using the first gas permeability measuring device M1 described above. That is, moisture-containing nitrogen 24 that is an exposure gas of 100 mL / min is input to the first gas flow chamber 10, dry nitrogen 30 that is a carrier gas of 400 mL / min is transferred to the second gas flow chamber 12, and 20 mL / min is transferred to the seal chamber 23. Dry nitrogen 36, which is a sealing gas, is continuously supplied, and the moisture permeability of each film A, B, C, that is, the moisture content contained in the gas permeability measurement gas 30a is measured until the moisture concentration is stabilized after the gas supply is started. It waited and measured with the quartz oscillation type moisture meter 43. The results were as shown in Table 1.

That is, for film A, the water concentration (22.5 ppm) was stable in about 10 hours, and the water permeability was 1.440 g / m ² · day. As for film B, the water concentration (3.63 ppm) was stable in about 10 hours, and the water permeability was 0.232 g / m ² · day. Furthermore, as for film C, the water concentration (0.134 ppm) was stable in about 10 hours, and the water permeability was 0.0086 g / m ² · day.

  In the first embodiment, each of the apparatus main bodies 1 and 2 is formed of a disk made of SUS304 having an outer diameter of 185 mm, each gas flow chamber 10 and 12 is formed with a recess having an inner diameter of 96 mm and a depth (vertical height) of 3 mm. did. The inner and outer diameters of the annular groove 37 formed in the first apparatus main body 1 were 112 mm and 118 mm, and the inner diameters of the O-ring grooves 16 and 17 were 110 mm and 120 mm, respectively. Further, as the quartz oscillation type moisture meter 43, MAH-2 manufactured by Shimadzu Corporation was used. The apparatus main bodies 1 and 2 were heated and maintained at 40 ° C. by a heater. The supply pressure of each gas 24, 30, 36 to each chamber 10, 12, 23 was set to 0.01 MPa · G.

  Moreover, in order to confirm the measurement accuracy of the water permeability by the first gas permeability measuring device M1, as a comparative example 1, an infrared absorption type gas permeability measuring device (PERMATRAN-W 3/31) manufactured by MOCON. Was used to measure the moisture permeability of films A, B, and C under the same conditions as above. The results were as shown in Table 1.

As understood from Table 1, in Example 1 and Comparative Example 1, almost the same measured values of moisture permeability were obtained for films A and B having low gas barrier properties (high moisture permeability). There is a great difference in the measurement of moisture permeability for the film C having high properties (low moisture permeability). That is, in Comparative Example 1, the measured value of moisture permeability for film C is negative, which indicates that the measurement limit of the gas permeability measuring device used in Comparative Example 1 is exceeded. On the other hand, in the examples, the measured value of moisture permeability for film C is appropriate. From these points, according to the first gas permeability measuring device M1, it is possible to measure the moisture permeability of the film material with high accuracy regardless of the moisture permeability. It was also confirmed that it can be measured appropriately and with high accuracy. From the measurement results, it is considered that the lower limit value of the water permeability measured by the comparative apparatus is about 0.14 g / m ² · day. On the other hand, the measurement limit value of the moisture permeability by the first gas permeability measuring device M1 is 0.0086 g / m ² · day or less, and further considering the sensitivity of the crystal oscillation moisture meter 43, the measurement limit value is Estimated to be 0.0010 g / m ² · day, there is a significant difference between the two devices.

  As Example 2, a film material 22 formed by depositing a silicon oxide film on a polyethylene terephthalate film and using four types of films A, B, C, and D having different oxygen permeability (oxygen barrier properties), The oxygen permeability of the films A, B, C, and D was measured using the second gas permeability measuring device M2 described above. That is, oxygen 24 as an exposure gas of 10 mL / min is supplied to the first gas flow chamber 10, nitrogen (nitrogen not containing oxygen) 30 as a carrier gas of 5 mL / min is supplied to the second gas flow chamber 12, and Nitrogen (nitrogen not containing oxygen) 36 as a seal gas of 20 mL / min is continuously supplied, and the oxygen permeability of each film A, B, C, D, that is, the amount of oxygen contained in the gas permeability measuring gas 30c is determined. After the start of gas supply, the oxygen concentration was stabilized and measured by a pulse discharge ionization gas chromatograph 45. The results were as shown in Table 2.

That is, for film A, the oxygen concentration (24.1 ppm) was stable in about 6 hours, and the oxygen permeability was 24.0 cc / m ² · day · atm. For film B, the oxygen concentration (2.37 ppm) was stable in about 10 hours, and the oxygen permeability was 2.36 cc / m ² · day · atm. As for film C, the oxygen concentration (0.37 ppm) was stable in about 10 hours, and the oxygen permeability was 0.37 cc / m ² · day · atm. Furthermore, as for film D, the oxygen concentration (0.23 ppm) was stable in about 10 hours, and the oxygen permeability was 0.23 cc / m ² · day · atm.

  In Example 2, each of the apparatus main bodies 1 and 2 is formed of a disk made of SUS304 having an outer diameter of 185 mm, each of the gas flow chambers 10 and 12 is formed with a recess having an inner diameter of 96 mm and a depth (vertical height) of 3 mm. did. The inner and outer diameters of the annular groove 37 formed in the first apparatus main body 1 were 112 mm and 118 mm, and the inner diameters of the O-ring grooves 16 and 17 were 110 mm and 120 mm, respectively. Further, as the pulse discharge ionization gas chromatograph 45, GC-14B manufactured by Shimadzu Corporation (detector: D-4-I-SH14-R manufactured by Valco Instrument) was used. The apparatus main bodies 1 and 2 were heated and maintained at 40 ° C. by a heater. The supply pressure of each gas 24, 30, 36 to each chamber 10, 12, 23 was almost atmospheric pressure (0.01 MPa · G).

  Moreover, in order to confirm the measurement accuracy of the oxygen permeability by the second gas permeability measuring device M2, as a comparative example 2, a Hersh type galvanic cell type oxygen permeability measuring device (OXTRAN 2/20) manufactured by MOCON is used. Then, the oxygen permeability of the films A, B, C, and D was measured under the same conditions as described above. The results were as shown in Table 2.

By the way, since the evaluation temperature in Comparative Example 2 using the apparatus manufactured by MOCON was performed at room temperature (23 ° C.), the evaluation result in Example 2 using the second gas permeability measuring apparatus M2 (evaluation temperature 40 However, from Table 2, in Example 2, as in Comparative Example 2, a film having a high oxygen permeability has a high measured value of oxygen permeability, and a film having a low oxygen permeability has a low data. It was a certain result. As described above, according to the second gas permeability measuring device M2, the oxygen permeability of 24.0 to 0.23 cc / m ² · day · atm can be measured, and further estimated from the sensitivity of the gas chromatograph 45. The measurement limit value of oxygen permeability by the second gas permeability measuring device M2 is 0.01 cc / m ² · day · atm.

  As Example 3, the moisture permeability and oxygen permeability of the film material 22 formed by depositing a silicon oxide film on the polymer film were measured using the third gas permeability measuring device M3 described above. . That is, the first gas flow chamber 10 is sealed with an exposure gas (moisture-containing air) 24 of 100 mL / min, the second gas flow chamber 12 is sealed with a carrier gas (nitrogen containing no moisture and oxygen) 30 of 400 mL / min. 100 mL / min of sealing gas (nitrogen containing no moisture and oxygen) 36 is continuously supplied to the chamber 23, and the moisture and oxygen permeability in the film, that is, the concentration of moisture and oxygen contained in the gas permeability measurement gas 30d. Was measured by an atmospheric pressure ionization mass spectrometer (APIMS) 46 after the gas supply was started until the concentration became stable. As a result, the water concentration (33 ppb) was stable in about 48 hours, and the water permeability was 0.0027 g / m 2 · day. The oxygen concentration (0.62 ppb) was stable in about 24 hours, and the oxygen permeability was 0.063 cc / m 2 · day · atm.

  In Example 3, the apparatus main bodies 1 and 2 are configured by SUS304 disks having an outer diameter of 185 mm, the gas flow chambers 10 and 12 are recessed with an inner diameter of 96 mm and a depth (vertical height) of 3 mm. did. Further, the inner and outer diameters of the annular groove 37 formed in the first apparatus main body 1 were 112 mm and 118 mm, and the inner diameters of the O-ring grooves 16 and 17 were 100 mm and 120 mm, respectively. As the atmospheric pressure ionization mass spectrometer 46, UG240-APNS manufactured by Hitachi Tokyo Electronics was used. The apparatus main bodies 1 and 2 were heated and maintained at 40 ° C. by a heater. The supply pressure of each gas 24, 30, 36 to each chamber 10, 12, 23 was set to 0.01 MPa · G.

  From these points, the third gas permeability measuring device M3 can measure the moisture and oxygen permeability of the film material with high accuracy regardless of the moisture and oxygen permeability, and in particular, a very small amount of moisture. It was also confirmed that the oxygen permeability can be measured appropriately and with high accuracy. Furthermore, since the third gas permeability measuring device M3 can measure moisture and oxygen permeability at the same time, it is not necessary to prepare devices for each component and measure each of them, easily and efficiently. It was confirmed that the gas barrier properties against moisture and oxygen can be determined. In addition, the lower limit of measurement of moisture permeability by the third gas permeability measuring device M3 is estimated from the measurement sensitivity (0.1 ppb) of the atmospheric pressure ionization mass spectrometer 46 at the time of measurement is 0.000006 g / m 2 · The measurement limit value of the day and oxygen permeability is 0.007 cc / m 2 · day · atm.

It is a vertical front view which shows a 1st gas permeability measuring apparatus. It is a vertical front view which shows a 2nd gas permeability measuring apparatus. It is a vertical front view which shows a 3rd gas permeability measuring apparatus. FIG. 4 is a transverse bottom view taken along line IV-IV in FIG. 1, FIG. 2 or FIG. 3. FIG. 5 is a transverse plan view taken along line VV in FIG. 1, FIG. 2 or FIG. 3.

Explanation of symbols

M1 first gas permeability measuring device M2 second gas permeability measuring device M3 third gas permeability measuring device 1 first device body 2 second device body 3 seal mechanism 4 exposure gas supply mechanism 5 carrier gas supply mechanism 6 seal gas Supply mechanism 7 Gas concentration measurement mechanism 9 Lower end surface of the first device body (opposite end surfaces of both device bodies)
10 First gas flow chamber 11 Upper end surface of second device main body (opposing end surfaces of both device main bodies)
12 Second gas flow chamber 13 First O-ring (first annular seal member)
14 Second O-ring (second annular seal member)
DESCRIPTION OF SYMBOLS 15 Clamp 22 Film material 23 Seal chamber 24 Exposure gas 25 Exposure gas supply port 26 Exposure gas discharge port 27 Exposure gas supply channel 28 Exposure gas discharge channel 29 Exposure gas supply device 30 Carrier gas 30a Gas permeability measurement gas 30c Gas permeability Measurement gas 30d Gas permeability measurement gas 31 Carrier gas inlet 32 Carrier gas outlet 33 Carrier gas inflow path 34 Carrier gas outflow path 35 Carrier gas supply device 36 Seal gas 38 Seal gas supply port 39 Seal gas discharge port 40 Seal Gas supply passage 41 Seal gas discharge passage 42 Seal gas supply device 43 Crystal oscillation type moisture meter 44 Argon separation device 45 Discharge ionization gas chromatograph 46 Atmospheric pressure ionization mass spectrometer

Claims (12)

A first and a second apparatus main body formed with gas flow chambers that open oppositely on the opposite end faces;
The film material whose permeability of a specific gas component is to be measured is in a state in which the central part is exposed to both gas flow chambers and the outer peripheral part is sandwiched and sealed between the opposed end surfaces. A seal mechanism that can be removably loaded into the
An annular sealed space formed between the opposing end faces, and a seal chamber surrounding an outer peripheral portion of the film material;
An exposure gas supply mechanism for supplying an exposure gas containing a specific gas component to the gas flow chamber of the first apparatus body;
A carrier gas supply mechanism that supplies a carrier gas that does not contain a specific gas component to the gas flow chamber of the second device body;
A seal gas supply mechanism for supplying seal gas to the seal chamber;
A gas concentration measurement mechanism for measuring a specific gas component concentration in the carrier gas flowing out of the gas flow chamber of the second device body;
An apparatus for measuring a gas permeability of a film material, comprising: When the specific gas component is moisture, the gas concentration measuring mechanism measures the moisture concentration in the carrier gas flowing out from the gas flow chamber of the second apparatus main body with a crystal oscillation moisture meter. A gas permeability measuring device for a film material according to claim 1. The apparatus for measuring gas permeability of a film material according to claim 2, wherein the quartz oscillation type moisture meter has a moisture measurement limit value of 1 ppb to 0.1 ppm. The apparatus for measuring gas permeability of a film material according to claim 2 or 3, wherein the exposure gas is nitrogen containing moisture, and the carrier gas and the seal gas are nitrogen not containing moisture. When the specific gas component is oxygen, the gas concentration measuring mechanism separates the oxygen concentration in the carrier gas flowing out from the gas flow chamber of the second device body from the argon component contained in the carrier gas, and then discharge ionization The apparatus for measuring a gas permeability of a film material according to claim 1, wherein the apparatus is measured by a type gas chromatograph. 6. The apparatus for measuring gas permeability of a film material according to claim 5, wherein the discharge ionization gas chromatograph is a pulse discharge ionization gas chromatograph having an oxygen measurement limit value of 1 ppb to 0.1 ppm. The apparatus for measuring oxygen permeability of a film material according to claim 5 or 6, wherein the exposure gas is oxygen, and the carrier gas and the seal gas are nitrogen not containing oxygen. When the specific gas components are moisture and oxygen, the gas concentration measurement mechanism measures the moisture concentration and oxygen concentration contained in the carrier gas flowing out from the gas flow chamber of the second device body with an atmospheric pressure ionization mass spectrometer. The apparatus for measuring a gas permeability of a film material according to claim 1, wherein: The apparatus for measuring gas permeability of a film material according to claim 8, wherein the atmospheric pressure ionization mass spectrometer has a measurement limit value of water concentration and oxygen concentration of 1 ppt to 0.1 ppb. The gas permeability of the film material according to claim 8 or 9, wherein the exposure gas is oxygen or air containing moisture, and the carrier gas and the sealing gas are nitrogen containing no moisture and oxygen. measuring device A first annular seal member concentrically held on one of the opposing end faces of the two apparatus main bodies, a second annular seal member having a larger diameter than the first annular seal member, and an outer peripheral portion of the film material. In order to clamp both annular seal members between the opposed end surfaces in a state of being in contact with each other, a clamp for fastening both apparatus main bodies is provided, and the seal chamber is hermetically sealed by both annular seal members. The present invention is described in claim 1, claim 2, claim 3, claim 4, claim 5, claim 6, claim 7, claim 8, claim 9 or claim 10. A device for measuring the gas permeability of film materials. Gas permeability measurement according to claim 1, claim 2, claim 3, claim 4, claim 5, claim 6, claim 7, claim 8, claim 9, claim 10, or claim 11. Using the device, the permeability of the specific gas component in the film material was measured by measuring the concentration of the specific gas component contained in the carrier gas flowing out from the gas flow chamber of the second device body. A method for measuring the gas permeability of a film material.

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