WO2015182706A1 - 水蒸気透過度測定装置の校正用標準フィルム及びその製造方法、並びに校正用標準フィルムセット及びそれを利用した校正方法 - Google Patents
水蒸気透過度測定装置の校正用標準フィルム及びその製造方法、並びに校正用標準フィルムセット及びそれを利用した校正方法 Download PDFInfo
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- calibration
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
- G01N15/0806—Details, e.g. sample holders, mounting samples for testing
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
- G01N15/082—Investigating permeability by forcing a fluid through a sample
- G01N15/0826—Investigating permeability by forcing a fluid through a sample and measuring fluid flow rate, i.e. permeation rate or pressure change
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
- G01N2015/086—Investigating permeability, pore-volume, or surface area of porous materials of films, membranes or pellicules
Definitions
- the present invention relates to a standard film for calibration of a water vapor transmission rate measuring device for carrying out gas barrier property evaluation, a method for manufacturing the standard film set, a standard film set for calibration, and a calibration method using the standard film.
- organic electronic device elements such as organic electroluminescence (organic EL) elements or organic thin film solar cell elements
- a small amount of gas such as water vapor or oxygen entering from the outside is considered to be a factor that degrades element performance.
- Sealing for the purpose of blocking intrusion gas is generally performed.
- a barrier film using a polymer film as a base material is used as an element substrate or a sealing material instead of the conventional glass.
- a barrier film having a water vapor transmission rate (WVTR) on the order of 10 ⁇ 6 to 10 ⁇ 3 g / m 2 / day is required.
- WVTR water vapor transmission rate
- Patent Document 1 As a standard sample for calibration of a conventional apparatus, one in which a calibration sample is connected to a water vapor detection line of the apparatus has been proposed (for example, see Patent Document 1). This is characterized by having a stainless steel tube, a resin filled in the tube, and a joint for connecting to a water vapor permeability measuring device at both ends of the tube.
- a lift-off method is known as a method for forming a metal film pattern on a resin film (see, for example, Patent Document 2 or 3).
- a film-shaped sample is placed in a chamber called a permeation cell, so that the influence on water vapor permeability due to a difference in attachment mechanism or method can be considered.
- a calibration sample that can be evaluated including these effects is required.
- the object of the present invention is applicable to many water vapor permeability measuring devices without the need for a dedicated connection, and is a calibration standard sample that can be calibrated with the same mounting mechanism and measurement conditions as a normal film sample. Is to provide.
- the object of the present invention is to use a combination of a plurality of calibration standard films and correct the WVTR value, for example, to offset a change in water vapor transmission rate caused by the physical properties of the adhesive used for bonding the films. It is to provide a standard film set for calibration and a calibration method that can be performed.
- an object of the present invention is to provide a method for producing a standard film for calibration that can form a small hole having a fine size that can be controlled in the plating layer.
- the present inventor has prepared a standard sample used for calibration of a water vapor transmission rate measuring device in a film shape attached to the water vapor transmission rate measuring device, and having water vapor on a resin film as a substrate. It is possible to calibrate the water vapor permeability measurement device by making a film with a barrier layer to block and providing a small-diameter hole only in the barrier layer and changing the number of small holes to check the linearity of the water vapor permeability. I found out. That is, the standard film for calibration according to the present invention includes a barrier layer on a resin film, and the barrier layer has at least one small hole, and has a water vapor permeability of 10 ⁇ 3 g / m 2 / day or less.
- the thickness L of the resin film is preferably 5 to 500 ⁇ m. It can be expected that the durability is high and the change in water vapor transmission rate due to deterioration of the sample is small, and comparison between a plurality of apparatuses is possible. In addition, the calibration accuracy can be further increased.
- the barrier layer is preferably a deposited layer of metal, metal oxide or silicon oxide, metal foil or plated layer. It is possible to further improve the accuracy of calibration by further improving the barrier property of water vapor.
- the small holes are preferably provided by etching, electroforming, laser processing or polishing.
- the opening area can be controlled with higher accuracy, and the accuracy of calibration can be further increased.
- the standard film for calibration according to the present invention preferably has a plurality of the small holes, and the minimum value in the circle-equivalent radius of each small hole is in the range of 70% or more of the maximum value.
- the distance between the edges of adjacent small holes is preferably 2L or more. Calibration accuracy can be further increased.
- the calibration standard film set according to the present invention includes a plurality of calibration standard films according to the present invention, and the plurality of calibration standard films are combinations of films having different numbers of small holes in the test surface. And the minimum value in the circle-corresponding radius of each small hole provided in the plurality of calibration standard films is in the range of 70% or more of the maximum value.
- At least one of the plurality of calibration standard films is preferably a film whose absolute value of water vapor permeability is known.
- the absolute value can be calibrated.
- the calibration method according to the present invention is a calibration method using the calibration standard film set according to the present invention, the step of measuring the water vapor permeability of each calibration standard film, and each calibration Plotting the opening area [m 2 ] and the water vapor transmission rate [g / m 2 / day] of the small holes of the standard film for use on a log-log graph, and each plot is on a straight line with a slope of 1 ⁇ 5% And a step of confirming this.
- the method for producing a standard film for calibration comprises a barrier layer on a resin film, the barrier layer having at least one small hole, and water vapor permeation of 10 ⁇ 3 g / m 2 / day or less.
- a method for producing a standard film for calibration of a water vapor transmission rate measuring device for measuring the degree of the process comprising the step 1b of providing a seed layer on the surface of the resin film, and a small hole formation scheduled region on the surface of the seed layer Step 2b of masking with a resist, Step 3b of performing plating on the surface of the seed layer other than the region where the small holes are to be formed, and providing a plating layer as the barrier layer; And a step 4b for removing the resist and the seed layer immediately below the resist, wherein a circle-equivalent radius of the small hole is less than 100 ⁇ m.
- the seed layer in the step 1b is preferably an electroless plating layer.
- the seed layer can be removed more reliably.
- the method for producing a standard film for calibration comprises a barrier layer on a resin film, the barrier layer having at least one small hole, and water vapor permeation of 10 ⁇ 3 g / m 2 / day or less.
- a method for producing a standard film for calibration of a water vapor transmission rate measuring apparatus for measuring the degree wherein a step 1a of masking a small hole forming region on the surface of the resin film with a resist, the surface of the resist and the resist A step 2a of providing a seed layer on the surface of the resin film around the substrate; a step 3a of removing the resist together with the seed layer on the surface of the resist by lifting off; and remaining on the surface of the resin film
- a step 4a of performing plating on the surface of the seed layer and providing a plating layer having a small hole as the barrier layer, and the circle equivalent radius of the small hole is 100 ⁇ m. It characterized in that it is a fully.
- R / T ⁇ 3 where R is a circle equivalent radius of the small hole and R is a thickness of the plating layer.
- R is a circle equivalent radius of the small hole and R is a thickness of the plating layer.
- a standard film for calibration suitable for calibration in a region where the water vapor permeability is smaller (for example, 10 ⁇ 5 g / m 2 / day or less) can be obtained.
- the present invention provides a calibration standard sample that can be applied to many water vapor permeability measuring devices without requiring a dedicated connection, and can be calibrated with the same mounting mechanism and measurement conditions as a normal film sample. can do.
- the present invention uses a combination of a plurality of calibration standard films and corrects the WVTR value, so that it is possible to cancel the change in water vapor transmission rate due to, for example, the physical properties of the adhesive used for bonding the films.
- a standard film set for calibration and a calibration method can be provided.
- the standard film for calibration according to the present invention is a film shape, it can be applied to many water vapor permeability measuring devices.
- measurement under the same conditions as normal film measurement is possible. Since repeated durability is high with respect to a normal barrier film, it can be expected that there is little change in water vapor permeability due to deterioration of the sample, and comparison between a plurality of apparatuses is possible. Compared with a pinhole or the like of a barrier film, the size of the small holes is large and the structure is simple, so that the measurement time can be shortened.
- the standard film set for calibration and the calibration method according to the present invention correct the WVTR value with a plurality of samples, for example, it is possible to cancel the change in water vapor transmission rate due to the physical properties of the adhesive used for bonding. is there.
- the present invention can provide a method for producing a standard film for calibration that can form a small hole having a fine size that can be controlled in the plating layer.
- FIG. 1 is a schematic cross-sectional view of a first example of a calibration standard sample according to the present embodiment.
- FIG. 2 is a schematic top view of a first example of a calibration standard sample according to the present embodiment.
- the standard film for calibration 10 according to the present embodiment includes a barrier layer 12 on a resin film 11, the barrier layer 12 has at least one small hole 13, and is equal to or less than 10 ⁇ 3 g / m 2 / day.
- the equivalent circle radius means an equivalent area radius.
- the water vapor transmission rate means the water vapor transmission rate in a steady state.
- the conditions are 25 ° C. and relative humidity 50% RH.
- the resin film 11 is a base material that holds the barrier layer 12.
- the resin film 11 is not particularly limited as long as it can hold the barrier layer, but is preferably an organic material or an organic-inorganic hybrid material.
- the resin film 11 is made of, for example, acrylic ester, methacrylic ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene ( PE), Polypropylene (PP), Polystyrene (PS), Nylon (Ny), Aromatic polyamide, Polyetheretherketone, Polysulfone, Polyethersulfone, Polyimide, Polyetherimide, etc.
- Plastic film, Sil with organic-inorganic hybrid structure A heat-resistant transparent film (for example, product name Sila-DEC, manufactured by Chisso Corporation) having sesquioxane as a basic skeleton, and a laminated film formed by laminating two or more plastic films.
- a heat-resistant transparent film for example, product name Sila-DEC, manufactured by Chisso Corporation
- PAT polyethylene terephthalate
- PEN polyethylene naphthalate
- PC polycarbonate
- PCTFE Poly Chloro Trifuro Ethylene
- a heat resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure is preferably used.
- the thermal expansion coefficient of the resin film 11 is not particularly limited, but is preferably the same as the thermal expansion coefficient of the barrier layer 12 or 80 to 120% of the thermal expansion coefficient of the barrier layer 12. .
- the thickness L [ ⁇ m] of the resin film 11 is preferably 5 to 500 ⁇ m, more preferably 20 to 300 ⁇ m, and still more preferably 50 to 250 ⁇ m. If the thickness of the resin film 11 exceeds 500 ⁇ m, the opening area of the small hole 13 becomes too large, and the opening area of the small hole and the water vapor permeability may not satisfy the proportional relationship. If the thickness of the resin film 11 is less than 5 ⁇ m, the repeated durability may be insufficient. It is preferable that the thickness of the resin film 11 is 20 ⁇ m or more from the viewpoint of improving the handleability and preventing an unintended leak during measurement.
- the thickness of the resin film 11 By setting the thickness of the resin film 11 within the above range, it can be expected that the repetition durability is high, and the change in the water vapor transmission rate due to the deterioration of the sample is small, and comparison between a plurality of apparatuses is possible. In addition, the calibration accuracy can be further increased.
- the shape and dimensions of the resin film 11 can be adjusted to the standard of the measuring apparatus that performs calibration.
- the outer shape is a circular shape with a diameter of 100 mm and the test surface is a circular shape with a diameter of 80 to 90 mm. is there.
- the barrier layer 12 is preferably a deposited layer of metal, metal oxide or silicon oxide, metal foil or plated layer. It is possible to further improve the accuracy of calibration by further improving the barrier property of water vapor.
- the barrier layer 12 preferably covers a part or the whole of any one surface of the resin film 11.
- the form in which the barrier layer 12 covers a part of one surface of the resin film 11 is provided, for example, only in the region where the barrier layer 12 is at least the test surface of the standard film for calibration, and is attached to the apparatus. This is a form that is not provided in the region. More preferably, the barrier layer 12 preferably covers the entire surface of one of the resinous films 11.
- the vapor deposition layer is formed by, for example, physical vapor deposition or chemical vapor deposition.
- the metal is, for example, aluminum, chromium, zinc, gold, silver, copper, nickel, or titanium.
- the metal oxide include aluminum oxide, titanium oxide, zirconium oxide, and silicon oxide.
- the thickness of the vapor deposition layer is preferably 5 to 30 ⁇ m, and more preferably 10 to 20 ⁇ m. The present invention is not limited to the vapor deposition method and the material and thickness of the vapor deposition layer.
- the metal foil is, for example, an aluminum foil or a copper foil.
- the thickness of the metal foil is preferably 10 to 50 ⁇ m, more preferably 10 to 30 ⁇ m in consideration of repeated durability.
- the present invention is not limited to the material and thickness of the metal foil.
- the metal foil is bonded to the resin film 11 using, for example, an adhesive.
- the plating layer is formed by, for example, an electroplating method, an electroless plating method, or a hot dip galvanizing method.
- the type of plating is, for example, gold, silver, copper, zinc, tin, chromium, nickel, or titanium.
- the thickness of the plating layer is preferably 5 to 30 ⁇ m, and more preferably 10 to 20 ⁇ m. The present invention is not limited to the plating method and the material and thickness of the plating layer.
- the small hole 13 is a through hole penetrating the barrier layer 12.
- the shape of the small hole 13 is, for example, a polygonal shape such as a circular shape, an elliptical shape, a triangular shape, or a quadrangular shape when the surface of the barrier layer 12 opposite to the resin film 11 side is viewed in a plan view. It is preferable that the shape is a perfect circle.
- the small holes 13 are provided in a region to be a test surface in the surface of the barrier layer 12.
- the region to be the test surface is, for example, the central portion of the barrier layer 12.
- the small holes 13 are preferably provided by etching, electroforming, laser processing or polishing.
- the barrier layer 12 is a vapor deposition layer
- the small holes 13 can be processed by wet or dry etching.
- the barrier layer 12 is a metal foil
- the small holes 13 can be processed by wet or dry etching.
- the small holes 13 may be formed after the metal foil is bonded to the resin film 11 or the metal foil is bonded to the resin film 11.
- the small holes 13 are suitable for processing by electroforming. At this time, a small hole 13 is formed by applying a mask to a portion of the resin film 11 where the small hole 13 is to be provided and forming a plating layer by electroforming.
- the number of small holes 13 is arbitrary depending on the sensitivity of the measuring apparatus and the required water vapor permeability, and may be one or plural.
- the upper limit of the number of small holes is not particularly limited, but is preferably, for example, 100 or less, more preferably 50 or less, more preferably 10 or less, and particularly preferably 5 or less. preferable.
- FIG. 1 and FIG. 2 an embodiment in which there is one small hole 13 is shown as a first example.
- 3 and 4 show a form in which there are 25 small holes 23 as a second example.
- the interval between the edges of adjacent small holes 23 is preferably 2L or more.
- interval in the edge of adjacent small holes 23 means the shortest distance of the outer periphery of adjacent small holes 23.
- the interval between the adjacent small holes 23 is more preferably 3L or more.
- interval of adjacent small holes 23 is not specifically limited, It is preferable that it distributes equally in the center part in a test surface.
- the circle equivalent radius R [ ⁇ m] of the small hole 13 is appropriately selected according to the thickness L [ ⁇ m] of the resin film 11.
- the circle-equivalent radius R of the small hole 13 is preferably 500 ⁇ m (0.5 mm) or less, and more preferably 400 ⁇ m (0.4 mm) or less.
- the lower limit of the circle-equivalent radius R of the small hole 13 is not particularly limited as long as it can be processed. For example, it is preferably 0.01 ⁇ m or more, and more preferably 1 ⁇ m or more.
- the circle-equivalent radius of the small hole 13 means the circle-equivalent radius of the small hole 13 when the number of the small holes 13 is 1, and when the number of the small holes 13 is plural, The circle equivalent radius of the small hole 13 is said. Further, when the number of small holes 13 is plural, it is preferable that the minimum value in the circle-equivalent radius of each small hole 13 is in a range of 70% or more of the maximum value. More preferably, it is in the range of 75% or more, and particularly preferably in the range of 80% or more. Moreover, the opening area of the small hole 13 means the area of the opening part of the small hole 13 in the surface at the side of the resin film 11 of the barrier layer 12.
- the opening area of the small holes 13 can be rephrased as the area of the portion of the surface that becomes the test surface of the resin film 11 that is not covered with the barrier layer 12.
- the opening area of the small holes 23 is the sum of the areas of the plural small holes 23.
- the present inventor can perform calibration even in the range of R / L ⁇ 5 by combining a plurality of calibration standard films 10 and 20 in which the number of small holes 13 having the same area is changed. I found out that I can do it.
- R / L ⁇ 3 is more preferable, and R / L ⁇ 2 is particularly preferable.
- the standard film for calibration is a standard film for calibration of a water vapor permeability measuring apparatus that measures a water vapor permeability of 10 ⁇ 3 g / m 2 / day or less. More preferably, it is 10 ⁇ 4 g / m 2 / day or less.
- a PET film having an outer diameter of 100 mm ⁇ as a resin film 11, a diameter of 80 mm ⁇ and a thickness of 100 ⁇ m as a barrier layer 12 is provided with one small hole 13 having a diameter of 0.1 mm (radius 50 ⁇ m) as a 30 ⁇ m thickness.
- the WVTR is 4 ⁇ 10 ⁇ 5 to 7 ⁇ 10 ⁇ 5 g / m 2 / day under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH. .
- a method for performing calibration with a WVTR of 10 ⁇ 4 g / m 2 / day or less for example, a method for increasing the area of the test surface of the calibration standard film (for example, a diameter of 264 mm ⁇ or more), a resin film having a water vapor permeability of There are a method using a high film (for example, PCTFE) and a method for reducing the equivalent circle radius of the small holes (for example, 20 ⁇ m or less).
- the calibration standard film set according to the present embodiment includes a plurality of calibration standard films 10 and 20 according to the present embodiment, and the plurality of calibration standard films 10 and 20 include small holes 12 included in the test surface,
- the number of 23 is a combination of films different from each other, and the minimum value is 70% or more of the maximum value among the circle equivalent radii of the small holes 13 and 23 provided in the plurality of calibration standard films 10 and 20. It is in the range.
- the minimum and maximum values of the equivalent circle radius are for small holes in all the films of the standard film set for calibration.
- the minimum value of the circle equivalent radius is in the range of 70% or more of the maximum value. That means.
- the number of calibration standard films 10 and 20 is not particularly limited, but is preferably 2 to 20, more preferably 5 to 10.
- the number of the small holes 13 is n (where n is an integer of 1 or more), and the number of the small holes 23 is m. It is preferable that the second film 20 is included (where m is an integer greater than n).
- the first film 10 is a standard film for calibration shown in FIGS. 1 and 2, for example. In FIG. 1 and FIG. 2, the number of small holes 13 is one as an example, but the number n of small holes 13 is not limited to this and may be two or more.
- the second film 20 is, for example, a standard film for calibration shown in FIGS. 3 and 4, for example, the number of small holes 23 is 25. However, the number m of small holes 23 may be an integer larger than the number n of small holes 13 of the first film 10. The invention is not limited to this.
- At least one of the plurality of calibration standard films 10 and 20 is preferably a film whose absolute value of water vapor permeability is known.
- the film whose absolute value of water vapor transmission rate is known is a standard film for calibration, which is a film whose absolute value of water vapor transmission rate is measured with a pre-calibrated measuring device.
- the circle equivalent radius X of the virtual holes is X / L ⁇ 5.
- the film is 75.
- FIG. 5 is a schematic diagram for explaining an example of the calibration method according to the present embodiment.
- a calibration method using the calibration standard film set according to this embodiment will be described by taking as an example the case where the calibration standard film set includes the first film 10 and the second film 20 as the calibration standard film. explain.
- the calibration method includes a step of measuring the water vapor permeability of each calibration standard film 10, 20, the opening area [m 2 ] of the small holes of each calibration standard film 10, 20 and the water vapor permeability [ g / m 2 / day] on a log-log graph, and confirming that each plot is on a straight line with a slope of 1 ⁇ 5%. More specifically, as shown in FIG. 5, a plot 10 of the first film 10 and a plot 20 of the second film 20 are plotted on a log-log graph of the opening area of the small holes and the water vapor permeability, and the plot 10 A line g1 connecting the plots 20 is drawn.
- the water vapor permeability (WVTR 10 , WVTR 20 ) of the first film 10 and the second film 20 is proportional to the opening area (S 10 , S 20 ) (each plot has a slope of 1 ⁇ 5% (the slope is 0.95) Confirm that it is on the straight line in the range of .about.1.05). ⁇ 5% is an allowable range of measurement error with respect to slope 1.
- the opening area of the hole and the water vapor permeability are in a proportional relationship, but as shown in the graph g3 in FIG. 5, when R / L ⁇ 5. Since the opening area of the small hole 13 and the water vapor transmission rate deviate from the proportional relationship, it is difficult to calculate the water vapor transmission rate from the opening area. Since the standard film set for calibration according to the first embodiment changes the opening area of the small holes 13 by changing the number of small holes 13 having a small diameter satisfying R / L ⁇ 5, the standard film for calibration As shown in the graph g1 of FIG.
- the opening area of the small holes 13 and the water vapor permeability of the standard film for calibration have a proportional relationship with a slope of 1 ⁇ 5% in the log-log graph.
- FIG. 6 is a flowchart for explaining the calibration method according to the present embodiment.
- the water vapor permeability WVTR 10 of the first film 10 and the water vapor permeability WVTR 20 of the second film 20 are measured, and it is confirmed that Equation 1 is satisfied. Also good.
- the circle equivalent radius R of the small hole is sufficiently smaller than the thickness L of the resin film (for example, when R / L ⁇ 0.4), the circle equivalent radius of one small hole was changed.
- a plurality of films may be prepared, and the calibration may be performed by confirming that the opening area of the small holes and the water vapor permeability have a slope of 1/2 ⁇ 5% in a log-log graph.
- the manufacturing method described here is a method using a lift-off method (first embodiment) and a method using an etching method (second embodiment).
- the manufacturing method according to the first embodiment and the second embodiment is particularly effective when it is desired to set the circle-equivalent radius of the small hole to be less than 100 ⁇ m.
- the circle equivalent radius of the small holes is more preferably 50 ⁇ m or less.
- the lower limit of the circle-equivalent radius of the small hole is not particularly limited as long as it can be processed. For example, it is preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m or more.
- the first embodiment will be described.
- the difference between the method of the first embodiment and the conventional lift-off method is that the conventional lift-off method forms a fine structure of plating on the substrate, whereas the method of the first embodiment is based on the basic method. This is that a fine opening (small hole) having a circle-equivalent radius of less than 100 ⁇ m is provided in the plating film provided on the material.
- FIG. 8 is a diagram for explaining a method of manufacturing a calibration standard film according to the first embodiment.
- the calibration standard film manufacturing method according to the first embodiment includes a barrier layer 32 on a resin film 31, the barrier layer 32 having at least one small hole 33, and 10 ⁇ 3 g / m 2 /
- a method for manufacturing a standard film for calibration of a water vapor transmission rate measuring apparatus that measures a water vapor transmission rate less than or equal to a day, in which a small hole forming region 33a on the surface of a resin film 31 is masked with a resist 1a (masking process) ),
- a step 2 a seed layer forming step) of providing a seed layer 35 (35 a, 35 b) on the surface of the resist 34 and on the surface of the resin film 31 around the resist 34, and the resist 34 on the surface of the resist 34.
- the step 3a lift-off step of removing by lifting off together with the upper seed layer 35b, and the surface of the seed layer 35a remaining on the surface of the resin film 31
- a step 4a plating step of providing a plating layer having a small hole 33 as the barrier layer 32, and the circle equivalent radius of the small hole 33 is less than 100 ⁇ m.
- the pattern of the resist 34 is formed using, for example, a photolithography technique.
- the pattern of the resist 34 is appropriately designed according to the size, shape and number of small holes 33 to be formed.
- the pattern of the resist 34 is preferably a cylindrical shape having a radius of 50 ⁇ m and a height (thickness) of 30 ⁇ m or more.
- n resist patterns 34 are provided.
- the seed layer 35 (35a, 35b) is formed on the resist 34 and the resin film 31 around the resist 34.
- the formation method of the seed layer 35 is not particularly limited, but for example, an ion plating method, a sputtering method, or an electroless plating method.
- the thickness of the seed layer 35 is not particularly limited, but is preferably 0.1 to 0.5 ⁇ m.
- the seed layer 35 may have a single-layer structure or a stacked structure.
- a specific example of the case where the seed layer 35 has a laminated structure is a two-layer structure in which a layer made of Ti and a layer made of Cu are arranged in this order from the resin film 31 side.
- the present invention is not limited to this structure.
- Process 3a (lift-off process) will be described.
- the resist 34 is removed by dissolving or expanding using a resist stripping solution, and the seed layer 35b formed on the resist 34 is simultaneously removed.
- the lift-off process a laminate in which the seed layer 35a having an opening in the small hole forming region 33a is laminated on the resin film 31 is obtained.
- Process 4a (plating process) will be described.
- the barrier layer (plating layer) 32 is formed only on the conductive seed layer 35a, and is not formed in the small hole forming region 33a where the insulating resin film 31 is exposed.
- a plated resin film with a small hole (standard film for calibration according to this embodiment) 30 in which the plated layer 32 having the small hole 33 is laminated on the resin film 31 with the seed layer 35a interposed therebetween is obtained.
- the thickness of the plating layer 32 is preferably 5 to 30 ⁇ m, and more preferably 10 to 20 ⁇ m.
- the plating layer 32 having a desired thickness may be formed by one process, or the plating layer 32 having a desired thickness may be formed by two or more processes. In this embodiment, it is preferable to perform the plating process twice or more. As a result, the plating layer 32 can be made denser and the barrier property can be further enhanced.
- the method for producing a calibration standard film it is preferable to have a cleaning step of cleaning the surface of the resin film 31 on the side where the plating layer 32 is provided before the masking step.
- a polyethylene terephthalate (PET) film is wiped using an organic solvent such as acetone, ethanol, isopropyl alcohol or the like.
- the method of the second embodiment is different from the conventional etching method in that the conventional etching method forms a fine structure of plating on the substrate, whereas the method of the second embodiment is based on the basic method. This is that a fine opening (small hole) having a circle-equivalent radius of less than 100 ⁇ m is provided in the plating film provided on the material.
- the manufacturing method according to the second embodiment is more difficult to etch than conventional etching methods, and uses materials that are easy to etch or etch temperature conditions, etc. It is necessary to devise such as optimizing conditions.
- FIG. 9 is a diagram for explaining a method for manufacturing a calibration standard film according to the second embodiment.
- the method for producing a standard film for calibration according to the second embodiment includes a barrier layer 42 on a resin film 41, the barrier layer 42 has at least one small hole 43, and 10 ⁇ 3 g / m 2 / A method for producing a standard film for calibration of a water vapor transmission rate measuring device for measuring a water vapor transmission rate below day, wherein a seed layer 45 is provided on the surface of the resin film 41 (seed layer forming step), and a seed A step 2b (masking step) for masking the small hole formation planned region 43a on the surface of the layer 45 with a resist 44, and a plating process is performed on the surface of the seed layer 45 other than the small hole formation planned region 43a to form a barrier layer 42.
- Step 3b plating treatment step for providing a plating layer
- step 4 for removing the resist 44 provided in the small hole formation scheduled region 43a and the seed layer 45 immediately below the resist 44.
- b (removal step)
- the equivalent circle radius of the small hole 43 is less than 100 ⁇ m.
- the seed layer 45 is formed on the surface of the resin film 41.
- the formation method, thickness, and structure of the seed layer 45 are the same as those in the step 2a.
- the seed layer 45 is preferably an electroless plating layer.
- the electroless plating layer is, for example, an electroless nickel plating layer or an electroless copper plating layer, and more preferably an electroless copper plating layer.
- the seed layer 45 can be more reliably removed.
- Process 2b (masking process) will be described.
- the resist 44 is formed in the small hole formation scheduled region 43 a on the surface of the seed layer 45.
- the formation method and pattern of the resist 44 are the same as in step 1a.
- Process 3b (plating process) will be described.
- the plating layer 42 is formed on the seed layer 45 around the resist 44.
- the plating method and the thickness of the plating layer 42 are the same as in step 4a.
- the removal step includes a step 4b1 for removing the resist 44 provided in the small hole formation planned region 43a and a step 4b2 for removing the seed layer 45 just under the resist 44 removed in the step 4b1.
- step 4b1 the resist 44 is removed by, for example, dissolving or swelling using a resist stripping solution.
- the exposed seed layer 45 is removed by removing the resist 44 in step 4b1.
- the seed layer 45 is preferably removed by etching.
- the etching may be wet etching or dry etching.
- wet etching it is preferable to use a ferric chloride solution or a cupric chloride solution for etching the Cu layer of the seed layer 45. More preferably, it is a ferric chloride solution.
- the concentration of ferric chloride is usually 10 to 45% by mass, more preferably 30 to 40% by mass.
- etching the Ti layer in the seed layer 45 it is preferable to use hot sulfuric acid, hot nitric acid, hydrofluoric acid-based etching solution, hydrogen peroxide-based etching solution, or the like. More preferred is a hydrogen peroxide-based etching solution.
- the temperature of the etching solution during etching of the Ti layer is preferably 30 ° C. or higher, and more preferably 40 ° C. or higher. By performing the etching at a high temperature, the seed layer 45 can be more reliably removed.
- R / T ⁇ 3 is preferred. It can be used as a standard film for calibration more suitable for calibration in a region where the water vapor permeability is smaller (for example, 10 ⁇ 5 g / m 2 / day or less). R / T is more preferably less than 1.
- the lower limit of R / T is not particularly limited, but is preferably 0.001 or more, and more preferably 0.01 or more.
- substantially blocking water vapor means that the water vapor permeability (WVTR) of the portions not including the small holes 33 and 43 of the plating layers 32 and 42 is less than 10 ⁇ 6 g / m 2 / day.
- substantially blocking oxygen means that the oxygen transmission rate (OTR) of the portions of the plated layers 32, 42 not including the small holes 33, 43 is less than 10 ⁇ 3 cm 3 / m 2 / day.
- the oxygen permeability is a value obtained under the condition of a temperature of 23 ° C. according to JIS K 7126-1 or -2: 2006 “Plastic-Film and Sheet—Gas Permeability Test Method”. .
- the obtained calibration standard films 30 and 40 substantially block the gas such as water vapor or oxygen by the plating layers 32 and 42, and control the size of the small holes 33 and 43 to control the gas permeation amount of water vapor or oxygen. Can be controlled.
- the standard film for calibration obtained by the manufacturing method according to the present embodiment can be used as, for example, a gas flow rate filter in addition to the calibration use of the water vapor permeability measuring device.
- the gas flow rate filter is a filter whose flow rate is uniquely determined by pressure conditions when a standard mixed gas is introduced into a vacuum vessel, for example, as a “micropore filter” described in Patent Document 4.
- Example 1-1 Preparation of standard film for calibration
- a 100 ⁇ m-thick polyethylene terephthalate (PET) film was used as a resin film, and a 30 ⁇ m-thick aluminum foil was used as a barrier layer and bonded together using an adhesive as a standard film A for calibration.
- One circular small hole was provided in the barrier layer of the standard film for calibration by wet etching.
- Table 1 shows the opening area of the small holes in the calibration standard film A
- Table 2 shows the equivalent circle radius.
- the opening area measurement position of the small hole was the lowest part of the barrier layer (that is, the surface of the barrier layer on the side of the resin film, which is the exposed surface of the adhesive in this experimental example).
- the water vapor permeability at this time was about 1 ⁇ 10 ⁇ 4 g / m 2 / day under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH.
- the calibration standard film (correction multi-hole sample) was prepared as three types of films provided with two, five, and ten circular holes, which were designated as calibration standard films B, C, and D, respectively. These films were combined with the calibration standard film A to form a calibration standard film set. Table 1 shows the opening area of the small holes of the calibration standard films B, C, and D, and Table 2 shows the equivalent circle radius.
- FIG. 7 shows a graph g4 in which the water vapor transmission rate and the opening area are plotted for the calibration standard films A to D.
- the standard film for calibration in which the small holes are changed to 1, 2, 5, and 10 has an inclination of 0.97, and the error is within ⁇ 5% with respect to the inclination 1.
- the proportional relationship between the water vapor permeability and the opening area was confirmed.
- calibration of water vapor permeability up to about 1 ⁇ 10 ⁇ 4 g / m 2 / day was established by using this standard film for calibration.
- FIG. 7 shows a graph g5 in which the water vapor transmission rate and the opening area are plotted for six types of films each having one large hole.
- the water vapor transmission rate and the opening area have a proportional relationship of 1 ⁇ 5% in the logarithmic graph, and when the opening area is small, the inclination is 1 ⁇ 5 in the logarithmic graph. It was confirmed that it deviates from the proportionality of%. Further, it was confirmed that the proportional relationship is shifted when R / L ⁇ 5. The proportional relationship is determined by R / L regardless of the material of the resin film of the base material.
- Example 2 A calibration standard film was produced by the method for producing a calibration standard film according to the first embodiment.
- a cylindrical resist pattern having a radius of 50 ⁇ m and a height of 56 ⁇ m was formed on a polyethylene terephthalate (PET) sheet having a thickness of 100 ⁇ m as a resin film using a photolithography technique.
- PET polyethylene terephthalate
- a film-type photoresist was attached, and ultraviolet light passed through a mask having a patterned opening was irradiated using an exposure apparatus.
- Masking was performed by dissolving an unexposed portion using an aqueous sodium hydroxide solution.
- a layer made of Ti (thickness 0.1 ⁇ m) and a layer made of Cu (thickness 0.3 ⁇ m) are arranged in this order from the resin film side on the resinous film on which the resist pattern obtained in the masking process is formed.
- a two-layer seed layer was formed. Specifically, a vapor deposition material (Ti (purity 99.9%), Cu (purity 99.99%)) and a resin film are placed in an ion plating apparatus, and a high vacuum of about 10 ⁇ 3 to 10 ⁇ 4 Pa. After making the state, Ar gas was introduced. Thereafter, the vapor deposition material was heated with an electron gun, a bias voltage was applied to the resin film, and films were formed in the order of Ti (film formation rate 0.1 nm / sec) and Cu (film formation rate 1 nm / sec).
- the resist was removed by lifting off with the seed layer on the resist. Specifically, the resist was dissolved or expanded by immersion in an aqueous sodium hydroxide solution and removed. The seed layer formed on the resist was simultaneously removed in the above process.
- plating process A plating layer (thickness 20 ⁇ m) made of Cu was formed on the seed layer of the laminate obtained in the lift-off process to obtain a standard film for calibration. Specifically, a copper sulfate plating bath was used, the treatment conditions were room temperature, current value: 1.5 A / dm 2 , and the treatment time was 60 minutes.
- the opening area of the small holes was 4.8509 ⁇ 10 ⁇ 9 m 2 , and the equivalent circle radius was 39.29 ⁇ m.
- the opening area measurement position of the small holes was the lowest part of the barrier layer (that is, the surface of the barrier layer on the side of the resin film, which is the exposed surface of the resin film in this experimental example). From the result of Experimental Example 2, it was confirmed that the manufacturing method according to the first embodiment can perform finer hole processing.
- the water vapor permeability of the calibration standard film was about 2 ⁇ 10 ⁇ 5 g / m 2 / day under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH. By using this calibration standard film, it is possible to calibrate the water vapor permeability up to about 1 ⁇ 10 ⁇ 5 g / m 2 / day.
- a layer made of Ti (thickness 0.1 ⁇ m) and a layer made of Cu (thickness 0.3 ⁇ m) are arranged in this order from the resin film side on the resinous film on which the resist pattern obtained in the masking process is formed.
- a two-layer seed layer was formed. Specifically, a vapor deposition material (Ti (purity 99.9%), Cu (purity 99.99%)) and a resin film are placed in an ion plating apparatus, and a high vacuum of about 10 ⁇ 3 to 10 ⁇ 4 Pa. After making the state, Ar gas was introduced. Thereafter, the vapor deposition material was heated with an electron gun, a bias voltage was applied to the resin film, and films were formed in the order of Ti (film formation rate 0.1 nm / sec) and Cu (film formation rate 1 nm / sec).
- a cylindrical resist pattern having a radius of 50 ⁇ m and a height of 56 ⁇ m was formed on the seed layer by photolithography. Specifically, a film-type photoresist was attached, and ultraviolet light passed through a mask having a patterned opening was irradiated using an exposure apparatus. Masking was performed by dissolving an unexposed portion using an aqueous sodium hydroxide solution.
- plating process A plating process (thickness 20 ⁇ m) made of Cu was formed by plating on the seed layer. Specifically, a copper sulfate plating bath was used, the treatment conditions were room temperature, current value: 1.5 A / dm 2 , and the treatment time was 60 minutes.
- the resist formed in the small hole forming region was removed. Specifically, the resist was dissolved or expanded by immersion in an aqueous sodium hydroxide solution and removed.
- the seed layer exposed by removing the resist was removed by etching. Specifically, the Cu layer was etched by being immersed in a 40 mass% ferric chloride solution at room temperature for 1 minute. Thereafter, the Ti layer was etched by immersing in a hydrogen peroxide etchant (ADEKA Tech W, manufactured by ADEKA) heated to 50 ° C. for 5 minutes.
- ADEKA Tech W manufactured by ADEKA
- the opening area of the small holes was 8.4553 ⁇ 10 ⁇ 9 m. 2 and the equivalent circle radius was 51.88 ⁇ m.
- the position of measuring the opening area of the small holes was the same as in Experimental Example 2.
- the water vapor permeability of the calibration standard film obtained in Experimental Example 3-1 was about 4 ⁇ 10 ⁇ 5 g / m 2 / day under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH.
- Example 3-2 A standard film for calibration was obtained in the same manner as in Experimental Example 3-1, except that the resist pattern was changed to a cylindrical resist pattern having a radius of 10 ⁇ m and a height of 30 ⁇ m in the masking step of Experimental Example 3-1.
- the opening area of the small holes was 2.49 ⁇ 10 ⁇ 11 m 2.
- the equivalent circle radius was 2.82 ⁇ m.
- the position of measuring the opening area of the small holes was the same as in Experimental Example 2.
- the water vapor permeability of the calibration standard film obtained in Experimental Example 3-2 was about 3 ⁇ 10 ⁇ 6 g / m 2 / day under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH.
Abstract
Description
(校正用標準フィルムの作製)
厚さ100μmのポリエチレンテレフタレート(PET)フィルムを樹脂製フィルムとし、厚さ30μmのアルミニウム箔をバリア層として接着材を用いて貼り合わせたフィルムを校正用標準フィルムAとした。校正用標準フィルムのバリア層には、円形状の小孔をウェットエッチングによって1個設けた。校正用標準フィルムAの小孔の開口面積を表1に、円相当半径を表2に示す。なお、小孔の開口面積測定位置は、バリア層の最下部(すなわち、バリア層の樹脂製フィルム側の表面であって、本実験例では接着材露出面)とした。このときの水蒸気透過度は、温度40℃及び相対湿度90%RHの条件で、約1×10-4g/m2/dayであった。
校正用標準フィルム(補正用多穴試料)は円形状の小孔を2個、5個、10個設けた3種類のフィルムを作製し、それぞれ校正用標準フィルムB,C,Dとした。これらのフィルムを校正用標準フィルムAと合わせて校正用標準フィルムセットとした。校正用標準フィルムB,C,Dの小孔の開口面積を表1に、円相当半径を表2に示す。
各校正用標準フィルムについて、API-MS又はCRDS(Cavity Ring Down Spectroscopy)を検出器として使用した水蒸気透過度測定装置によってWVTRを測定した。測定条件は温度40℃、水蒸気供給側の相対湿度90%とした。校正用標準フィルムA~Dについて水蒸気透過度と開口面積とをプロットしたグラフg4を図7に示す。図7に示すように、小孔を1個、2個、5個、10個と変化させた校正用標準フィルムでは傾きが0.97であり、傾き1に対して誤差±5%の範囲内で水蒸気透過度と開口面積の比例関係を確認した。また、本校正用標準フィルムを使用することによって約1×10-4g/m2/dayまでの水蒸気透過度の校正が確立した。
R/Lと、水蒸気透過度及び小孔の開口面積の比例関係との関係を確認した。厚さ100μmのポリエチレンテレフタレート(PET)フィルムを樹脂製フィルムとし、厚さ30μmのアルミニウム箔をバリア層として接着材を用いて貼り合わせ、バリア層に円形状の大孔を1個ずつ設けた6種類の試料を用意した。各フィルムの大孔の円相当半径は、それぞれ116.79μm、209.14μm、575.08μm、988.45μm、2468.59μm、4821.95μmであった。この6種類の試料についてWVTRを測定した。測定条件は温度40℃、水蒸気供給側の相対湿度90%とした。大孔を1個ずつ設けた6種類のフィルムについて水蒸気透過度と開口面積とをプロットしたグラフg5を図7に示す。図7に示すように、開口面積が大きい領域では水蒸気透過度と開口面積とが両対数グラフにおいて傾き1±5%の比例関係があること、開口面積が小さくなると両対数グラフにおいて傾き1±5%の比例関係からずれてくることが確認された。さらに、R/L≦5では、比例関係がずれてくることが確認された。比例関係がずれてくるのは基材の樹脂フィルムの材質に拘わらずR/Lで決まる。
校正用標準フィルムAの作製において、レジストに設ける開口部の半径を50μmとしてウェットエッチングを行った以外は校正用標準フィルムAと同様にして校正用標準フィルムを得た。得られた校正用標準フィルムの小孔を含む表面領域を、レーザー顕微鏡を用いて倍率1080倍で観察したところ、小孔の開口面積は、7.5928×10-9m2であり、円相当半径は49.16μmであった。小孔の開口面積測定位置は、実験例1-1と同様とした。また、この校正用標準フィルムの水蒸気透過度は温度40℃及び相対湿度90%RHの条件で、約6×10-5g/m2/dayであった。
第一実施形態に係る校正用標準フィルムの製造方法で、校正用標準フィルムを作製した。
まず、樹脂製フィルムとして厚さ100μmのポリエチレンテレフタレート(PET)シート上に、フォトリソグラフィ技術を用いて、半径50μm、高さ56μmの円柱形のレジストパターンを形成した。具体的には、フィルムタイプのフォトレジストを貼り付け、開口部をパターニングしたマスクを通した紫外光を、露光装置を用いて照射した。水酸化ナトリウム水溶液を用いて、未露光部分を溶解することでマスキングした。
マスキング工程で得たレジストパターンが形成された樹脂性フィルム上に、樹脂製フィルム側から順に、Tiからなる層(厚さ0.1μm)及びCuからなる層(厚さ0.3μm)が配置された2層構造のシード層を形成した。具体的にはイオンプレーティング装置内に蒸着材(Ti(純度99.9%)、Cu(純度99.99%))および樹脂製フィルムを入れ、10-3~10-4Pa程度の高真空状態にした後、Arガスを導入した。その後、電子銃にて蒸着材を加熱し、樹脂製フィルムにバイアス電圧を印加し、Ti(成膜レート0.1nm/sec)、Cu(成膜レート1nm/sec)の順に成膜した。
レジストを、レジスト上のシード層とともにリフトオフして除去した。具体的には、水酸化ナトリウム水溶液中に浸漬することでレジストを溶解又は膨張させて除去した。レジスト上に形成されたシード層は上記工程において同時に除去された。
リフトオフ工程で得られた積層体のシード層上にメッキ処理を施してCuからなるメッキ層(厚さ20μm)を形成して校正用標準フィルムを得た。具体的には、硫酸銅メッキ浴を使用し、処理条件は室温で電流値:1.5A/dm2で、処理時間は60分とした。
第二実施形態に係る校正用標準フィルムの製造方法で、校正用標準フィルムを作製した。
マスキング工程で得たレジストパターンが形成された樹脂性フィルム上に、樹脂製フィルム側から順に、Tiからなる層(厚さ0.1μm)及びCuからなる層(厚さ0.3μm)が配置された2層構造のシード層を形成した。具体的にはイオンプレーティング装置内に蒸着材(Ti(純度99.9%)、Cu(純度99.99%))および樹脂製フィルムを入れ、10-3~10-4Pa程度の高真空状態にした後、Arガスを導入した。その後、電子銃にて蒸着材を加熱し、樹脂製フィルムにバイアス電圧を印加し、Ti(成膜レート0.1nm/sec)、Cu(成膜レート1nm/sec)の順に成膜した。
シード層上に、フォトリソグラフィ技術を用いて、半径50μm、高さ56μmの円柱形のレジストパターンを形成した。具体的には、フィルムタイプのフォトレジストを貼り付け、開口部をパターニングしたマスクを通した紫外光を、露光装置を用いて照射した。水酸化ナトリウム水溶液を用いて、未露光部分を溶解することでマスキングした。
シード層上にメッキ処理を施してCuからなるメッキ層(厚さ20μm)を形成した。具体的には、硫酸銅メッキ浴を使用し、処理条件は室温で電流値:1.5A/dm2で、処理時間は60分とした。
小孔形成領域に形成されたレジストを除去した。具体的には、水酸化ナトリウム水溶液中に、浸漬することでレジストを溶解又は膨張させて除去した。
レジストの除去で露出したシード層をエッチングで除去した。具体的には、常温で40質量%の塩化第二鉄液に1分間浸漬することで、Cu層をエッチングした。その後、50℃に加熱した過酸化水素エッチング液(ADEKA社製、アデカテックW)に5分間浸漬することで、Ti層をエッチングした。
実験例3-1のマスキング工程において、レジストパターンを、半径10μm、高さ30μmの円柱形のレジストパターンに変更した以外は、実験例3-1と同様にして校正用標準フィルムを得た。
11 基材
12 バリア層
13 小孔
20 校正用標準フィルム(補正用多穴試料)
21 基材
22 バリア層
23 小孔
30,40 校正用標準フィルム
31,41 樹脂製フィルム
32,42 バリア層(メッキ層)
33,43 小孔
33a,43a 小孔形成領域
34,44 レジスト
35(35a,35b),45 シード層
Claims (13)
- 樹脂製フィルム上にバリア層を備え、該バリア層が少なくとも1個の小孔を有し、10-3g/m2/day以下の水蒸気透過度を測定する水蒸気透過度測定装置の校正用標準フィルムであって、
前記小孔の円相当半径をR[μm]、前記樹脂製フィルムの厚さをL[μm]としたとき、R/L≦5であることを特徴とする校正用標準フィルム。 - 前記樹脂製フィルムの厚さLが5~500μmであることを特徴とする請求項1に記載の校正用標準フィルム。
- 前記バリア層は、金属、金属酸化物若しくは酸化ケイ素の蒸着層、金属箔又はメッキ層であることを特徴とする請求項1又は2記載の校正用標準フィルム。
- 前記小孔はエッチング、エレクトロフォーミング、レーザー加工又は研磨によって設けられることを特徴とする請求項1~3のいずれか一つ記載の校正用標準フィルム。
- 前記小孔を複数個有し、前記各小孔の円相当半径のうち最小値が最大値の70%以上の範囲にあることを特徴とする請求項1~4のいずれか一つに記載の校正用標準フィルム。
- 隣り合う小孔同士の縁における間隔は2L以上であることを特徴とする請求項5に記載の校正用標準フィルム。
- 請求項1~6のいずれか一つに記載の校正用標準フィルムを複数枚備え、
該複数枚の校正用標準フィルムは、被験面内に有する小孔の個数が相互に異なるフィルムの組み合わせであり、かつ、前記複数枚の校正用標準フィルムに設けられた各小孔の円相当半径のうち最小値が最大値の70%以上の範囲にあることを特徴とする校正用標準フィルムセット。 - 前記複数枚の校正用標準フィルムのうち少なくとも1枚は、水蒸気透過度の絶対値が判明しているフィルムであることを特徴とする請求項7に記載の校正用標準フィルムセット。
- 請求項7又は8に記載の校正用標準フィルムセットを用いたことを特徴とする校正方法であって、
前記各校正用標準フィルムの水蒸気透過度を測定する工程と、
前記各校正用標準フィルムの小孔の開口面積[m2]と水蒸気透過度[g/m2/day]とを両対数グラフ上にプロットする工程と、
各プロットが傾き1±5%の直線上にあることを確認する工程と、を含むことを特徴とする校正方法。 - 樹脂製フィルム上にバリア層を備え、該バリア層が少なくとも1個の小孔を有し、10-3g/m2/day以下の水蒸気透過度を測定する水蒸気透過度測定装置の校正用標準フィルムの製造方法であって、
前記樹脂製フィルムの表面上にシード層を設ける工程1bと、
該シード層の表面上の小孔形成予定領域をレジストでマスキングする工程2bと、
前記シード層の前記小孔形成予定領域以外の表面上にメッキ処理を施し、前記バリア層としてメッキ層を設ける工程3bと、
前記小孔形成予定領域に設けられたレジスト及び該レジストの直下の前記シード層を除去する工程4bと、を有し、
前記小孔の円相当半径が、100μm未満であることを特徴とする校正用標準フィルムの製造方法。 - 前記工程1bのシード層が、無電解メッキ層であることを特徴とする請求項10に記載の校正用標準フィルムの製造方法。
- 樹脂製フィルム上にバリア層を備え、該バリア層が少なくとも1個の小孔を有し、10-3g/m2/day以下の水蒸気透過度を測定する水蒸気透過度測定装置の校正用標準フィルムの製造方法であって、
前記樹脂製フィルムの表面上の小孔形成領域をレジストでマスキングする工程1aと、
該レジストの表面上及び該レジストの周囲の前記樹脂製フィルムの表面上にシード層を設ける工程2aと、
前記レジストを、該レジストの表面上のシード層とともにリフトオフして除去する工程3aと、
前記樹脂製フィルムの表面上に残った前記シード層の表面上にメッキ処理を施し、前記バリア層として小孔を有するメッキ層を設ける工程4aと、を有し、
前記小孔の円相当半径が、100μm未満であることを特徴とする校正用標準フィルムの製造方法。 - 前記小孔の円相当半径をR[μm]、前記メッキ層の厚さをT[μm]としたとき、R/T<3であることを特徴とする請求項10~12のいずれか一つに記載の校正用標準フィルムの製造方法。
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KR1020167003183A KR101667907B1 (ko) | 2014-05-29 | 2015-05-28 | 수증기 투과도 측정 장치의 교정용 표준 필름 및 그 제조 방법, 및 교정용 표준 필름 세트 및 그것을 이용한 교정 방법 |
US14/910,212 US20170074771A1 (en) | 2014-05-29 | 2015-05-28 | Standard film for correction of water vapor permeability measurement device, method for manufacturing same, standard film set for correction, and correction method using same |
EP15800196.6A EP3035029A1 (en) | 2014-05-29 | 2015-05-28 | Standard film for correction of water vapor permeability measurement device, method for manufacturing same, standard film set for correction, and correction method using same |
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WO2021199560A1 (ja) * | 2020-03-31 | 2021-10-07 | 株式会社Moresco | 水蒸気透過度測定装置を校正するための標準試料 |
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CN107271345B (zh) * | 2017-06-15 | 2019-07-19 | 中国食品药品检定研究院 | 一种两法联合标定氧气透过量标准膜及其制备方法 |
US11467053B2 (en) * | 2018-05-31 | 2022-10-11 | Goertek Inc. | Test device and calibrating method |
KR102624426B1 (ko) * | 2021-10-27 | 2024-01-12 | 한국표준과학연구원 | 가스 투과 측정용 표준 재료 |
CN114577697A (zh) * | 2022-02-21 | 2022-06-03 | 中国食品药品检定研究院 | 三法联合标定水蒸气透过量标准膜及其制备方法 |
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US20170074771A1 (en) | 2017-03-16 |
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