WO2014163039A1 - Procédé et système d'évaluation du taux de transmission de vapeur d'eau d'un film barrière aux gaz, et procédé de production dudit film barrière aux gaz - Google Patents
Procédé et système d'évaluation du taux de transmission de vapeur d'eau d'un film barrière aux gaz, et procédé de production dudit film barrière aux gaz Download PDFInfo
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- WO2014163039A1 WO2014163039A1 PCT/JP2014/059459 JP2014059459W WO2014163039A1 WO 2014163039 A1 WO2014163039 A1 WO 2014163039A1 JP 2014059459 W JP2014059459 W JP 2014059459W WO 2014163039 A1 WO2014163039 A1 WO 2014163039A1
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- water vapor
- gas barrier
- vapor permeability
- barrier film
- defect
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Images
Classifications
-
- 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
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/88—Investigating the presence of flaws or contamination
- G01N21/89—Investigating the presence of flaws or contamination in moving material, e.g. running paper or textiles
- G01N21/892—Investigating the presence of flaws or contamination in moving material, e.g. running paper or textiles characterised by the flaw, defect or object feature examined
- G01N21/894—Pinholes
-
- 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
- G01N2015/0846—Investigating permeability, pore-volume, or surface area of porous materials by use of radiation, e.g. transmitted or reflected light
Definitions
- the present invention relates to a method for evaluating water vapor permeability of a gas barrier film.
- the present invention also relates to a gas barrier film water vapor permeability evaluation system and a gas barrier film manufacturing method using the water vapor permeability evaluation method. More specifically, the present invention relates to a method for evaluating water vapor permeability with improved inspection efficiency.
- a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film prevents deterioration due to various gases such as water vapor and oxygen. For this reason, it is widely used in applications for packaging articles that require blocking of various gases.
- the present invention in order to prevent deterioration due to various gases, the present invention is also used for sealing electronic devices such as solar cells, liquid crystal display elements or organic electroluminescent elements (hereinafter also referred to as organic EL elements). in use.
- a gas barrier film is superior in flexibility to a glass substrate, and is superior in terms of roll-type production suitability, weight reduction and handling of electronic devices.
- a film substrate such as a transparent plastic has a problem that gas barrier properties are inferior to a glass substrate. It has been found that when a substrate with inferior gas barrier properties is used, water vapor or oxygen penetrates and, for example, the function in the electronic device is deteriorated.
- a calcium corrosion method for measuring water vapor permeability.
- Ca method a calcium corrosion method for measuring water vapor permeability.
- a film having a calcium film formed on the inside is used as a test piece, placed in a constant temperature and humidity environment, and the amount of calcium corroded by reacting with water vapor that has passed through the film is measured by image processing or the like.
- the water vapor permeability is calculated.
- the calcium corrosion method can calculate the water vapor transmission rate with higher sensitivity than the conventional mocon method or the like, but is a destruction method in which a part of a sample is extracted. Further, the calcium corrosion method measures the water vapor permeability of a part extracted, and does not guarantee the water vapor permeability of the entire gas barrier film.
- a method for evaluating the water vapor barrier performance of a gas barrier film using an electric capacity type moisture sensor for example, see Patent Document 1
- a method for evaluating water vapor permeability using a mass spectrometer for example, a patent) Reference 2
- a method of detecting a defect in a gas barrier film by introducing gas into a sample holder and detecting pressure for example, see Patent Document 3
- any method is a destruction method in which a sample is partially extracted, and does not guarantee the water vapor permeability of the entire gas barrier film.
- JP 2011-242354 A International Publication No. 2010/117012 JP-A-10-73527
- the present invention has been made in view of the above problems and situations, and its solution is a water vapor permeability evaluation method capable of calculating the water vapor permeability of the entire gas barrier film in a short time in a non-destructive and non-contact manner. Is to provide. Moreover, it is providing the manufacturing method of the water vapor permeability evaluation system and gas barrier film which used the said water vapor permeability evaluation method.
- the present inventor examined the cause of the above problems, etc., detected a film defect, calculated the local water vapor permeability for each defect based on the feature quantity of the defect, The present inventors have found that the subject of the present invention can be solved by calculating the water vapor permeability of the entire gas barrier film from the degree.
- a water vapor transmission rate evaluation method for a gas barrier film that evaluates water vapor transmission rate based on information about defects in the film, (1) a defect detection step for detecting a defect in the gas barrier film; (2) a local water vapor permeability calculating step for calculating a local water vapor permeability for each defect detected by the defect detecting step using a feature amount of the defect; (3) a water vapor permeability calculating step for calculating the water vapor permeability of the entire gas barrier film in the measurement range based on the local water vapor permeability calculated by the local water vapor permeability calculating step;
- a method for evaluating a water vapor permeability of a gas barrier film comprising:
- the local water vapor permeability calculation step the local water vapor permeability for each defect detected in the defect detection step is calculated using an estimation model of the local water vapor permeability prepared in advance based on the feature amount of the defect. 2.
- the water vapor transmission rate per unit area is converted from the total value of the measurement range of the local water vapor transmission rate calculated in the local water vapor transmission rate calculation step, and the water vapor transmission rate per unit area is further converted. 3.
- a defect detection means for detecting a defect in the gas barrier film;
- Local water vapor permeability calculating means for calculating the local water vapor permeability for each defect detected by the defect detecting means using the feature amount of the defect;
- Water vapor permeability calculating means for calculating the water vapor permeability of the entire gas barrier film in the measurement range based on the local water vapor permeability calculated by the local water vapor permeability calculating means;
- a water vapor permeability evaluation system for a gas barrier film comprising:
- defect detection means detects a defect from image data of an image of the gas barrier film obtained by being optically imaged by an area sensor camera or a line sensor camera.
- Film water vapor permeability evaluation system
- Water vapor permeability distribution calculating means for calculating the water vapor permeability distribution of the gas barrier film from the defects detected by the defect detecting means and the water vapor permeability per unit area calculated by the water vapor permeability calculating means.
- a gas barrier film comprising a step of evaluating the water vapor permeability of a gas barrier film using the method for evaluating the water vapor permeability of a gas barrier film according to any one of items 1 to 3. Manufacturing method.
- a gas barrier film comprising a step of evaluating the water vapor permeability of a gas barrier film using the water vapor permeability evaluation system for a gas barrier film according to any one of items 4 to 7. Manufacturing method.
- a film substrate having a high gas barrier property against water vapor is essential, and an increase in water vapor permeability due to a defect of the film substrate leads to deterioration of the electronic device. Therefore, image the film, detect the film defect using the captured image, calculate the local water vapor permeability for each defect, and calculate the water vapor permeability of the entire film in a short time from the local water vapor permeability
- the inventors have found that a highly reliable water vapor transmission rate can be obtained in a non-destructive and non-contact state of the film.
- Schematic configuration diagram showing an example of a water vapor permeability evaluation system of the present invention The block diagram which shows the main structures of the water vapor permeability evaluation system of this invention Sectional drawing which shows an example of the gas barrier film which concerns on this invention Graph showing the relationship between defect diameter and water vapor transmission rate Flow chart showing the flow of local water vapor permeability estimation model creation process Flow chart showing the flow of water vapor permeability evaluation processing by the water vapor permeability evaluation system
- the water vapor permeability evaluation method of the present invention includes a defect detection step for detecting a defect in a gas barrier film, and a local water vapor permeability calculation for calculating the local water vapor permeability for each detected defect using the feature amount of the defect. And a water vapor transmission rate calculating step for calculating a water vapor transmission rate of the entire gas barrier film in the measurement range based on the calculated local water vapor transmission rate.
- the local water vapor permeability estimation model created in advance based on the feature amount of the defect It is preferable to calculate the local water vapor permeability for each defect detected by the defect detection step. Thereby, the local water vapor permeability closer to the actually measured value can be calculated in a non-destructive / non-contact state.
- the water vapor permeability per unit area is converted from the total value of the measurement range of the local water vapor permeability calculated in the local water vapor permeability calculation step, It is preferable to correct the water vapor permeability per unit area using an actual measured value of the water vapor permeability obtained by the calcium corrosion method. Thereby, a slight error due to a minute defect that is difficult to detect by defect detection can be corrected.
- a defect detection means for detecting a defect of the gas barrier film, and a local water vapor permeability for calculating the local water vapor permeability for each defect detected by the defect detection means using the feature amount of the defect. It is preferable to include a calculation unit and a water vapor transmission rate calculation unit that calculates the water vapor transmission rate of the entire gas barrier film in the measurement range based on the local water vapor transmission rate calculated by the local water vapor transmission rate calculation unit. Since the water vapor transmission rate of the entire gas barrier film in the measurement range is calculated based on the local water vapor transmission rate for each defect, the water vapor transmission rate can be obtained over a wide range in a non-destructive and non-contact manner.
- the defect detection means detect a defect from image data of an image of the gas barrier film obtained by being optically imaged by an area sensor camera or a line sensor camera.
- An optimal optical system can be selected according to the state of the gas barrier film, and defects can be detected from the image data of the gas barrier film captured over a wide range. Furthermore, if a camera with a high pixel and a high scan rate is used, this evaluation method can be inlined.
- the water vapor transmission rate for calculating the water vapor transmission rate distribution of the gas barrier film from the defects detected by the defect detection unit and the water vapor transmission rate per unit area calculated by the water vapor transmission rate calculation unit It is preferable to provide a degree distribution calculation means. Thereby, the water vapor permeability of the gas barrier film can be visually grasped.
- the present invention is preferably used for evaluating the water vapor permeability of the gas barrier film in the step of producing the gas barrier film. Since the evaluation of the water vapor permeability of the gas barrier film is incorporated in the production process, it becomes easy to associate the water vapor permeability with the production conditions.
- the method for evaluating the water vapor permeability of the gas barrier film of the present invention is preferably provided from the viewpoint of time and economy, as a process for evaluating the water vapor permeability of the gas barrier film in the method for producing a gas barrier film. .
- the water vapor permeability evaluation system for a gas barrier film of the present invention is preferably provided as a step of evaluating the water vapor permeability of the gas barrier film in the method for producing a gas barrier film from the viewpoint of time and economy. .
- ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
- the water vapor transmission rate evaluation method of the present invention is a water vapor transmission rate evaluation method for a gas barrier film that evaluates water vapor transmission rate based on information about defects in the film, and (1) a defect detection step for detecting a defect in the gas barrier film. And (2) a local water vapor permeability calculating step for calculating a local water vapor permeability for each defect detected by the defect detecting step using a feature quantity of the defect, and (3) a local water vapor permeability calculating step. And a water vapor transmission rate calculating step for calculating a water vapor transmission rate of the entire gas barrier film in the measurement range based on the local water vapor transmission rate calculated by.
- the defect of a gas barrier film is detected about the gas barrier film used for electronic devices, such as a solar cell, a liquid crystal display element, or an organic EL element.
- the local water vapor permeability of the detected defect is calculated using the feature amount of the defect, for example, the area of the defect such as a crack, the aspect ratio, the long diameter, the density, and the like. Then, based on the calculated local water vapor permeability, the water vapor permeability of the entire gas barrier film in the measurement range is calculated.
- the local water vapor permeability calculation step it is preferable to calculate the local water vapor permeability for each defect detected in the defect detection step using an estimation model of the local water vapor permeability prepared in advance based on the feature amount of the defect. Specifically, an estimation model of local water vapor permeability is created in advance using the feature amount of the optimum defect according to the material of the film to be measured. Then, the local water vapor permeability for each defect detected by the defect detection step can be calculated based on the estimation model.
- the selection of the optimal feature quantity of the defect according to the material of the film to be measured is the estimation of the feature quantity of the defect among the estimation models created by the multiple regression analysis based on the feature quantity appropriately selected from a plurality of feature quantities. You can choose the one with the highest contribution.
- the selection of the optimum feature amount of defects according to the material of the film to be measured may be performed once for one type of film.
- the water vapor permeability per unit area is converted from the total value of the measurement range of the local water vapor permeability calculated in the local water vapor permeability calculation step, and the water vapor permeability per unit area is further converted to calcium. Correction is made using the actual measured value of water vapor permeability obtained by the corrosion method. Specifically, based on the local water vapor permeability calculated in the local water vapor permeability calculation step, the total value of the water vapor permeability of the entire gas barrier film in the measurement range is calculated.
- This total value is converted into a water vapor permeability per unit area, and the water vapor permeability per unit area can be corrected using, for example, an actual value of the water vapor permeability obtained by the calcium corrosion method.
- a correction term can be used when correcting the calculated water vapor permeability per unit area on the basis of actual measurement values such as the calcium corrosion method. This correction term is a value for adjustment so as to match the actual measurement value when the estimation model is created.
- FIG. 1 shows an example of the configuration of a gas barrier film water vapor permeability evaluation system 100 that uses the gas barrier film water vapor permeability evaluation method of the present invention.
- a functional block diagram of the water vapor permeability evaluation system 100 of the gas barrier film is shown in FIG.
- the water vapor permeability evaluation system 100 for a gas barrier film of the present invention preferably includes an image processing device 1, an imaging adjustment device 2, an imaging device 3, and a film observation table 4.
- the image processing device 1 is connected to the imaging adjustment device 2 and the imaging device 3 so as to communicate with each other.
- the image processing apparatus 1 includes a control unit 11, a recording unit 12, a communication unit 13, a data processing unit 14 (defect detection unit 14a, local water vapor permeability calculation unit 14b, water vapor transmission rate calculation unit 14c, water vapor A transmission distribution calculation unit 14d), an operation display unit 15 and the like are provided, and each unit is connected to be communicable with each other by a bus 16.
- the control unit 11 includes a CPU (Central Processing Unit) 11a that performs overall control of the operation of the image processing apparatus 1, and a RAM (Random) that functions as a work memory for temporarily storing various data when the CPU 11a executes a program.
- CPU Central Processing Unit
- RAM Random
- the program memory 11c is composed of a ROM or the like.
- the recording unit 12 records, in addition to the image data of the gas barrier film imaged by the imaging device 3, the threshold value data used in the data processing unit, the data processed by the data processing unit regarding the water vapor transmission rate, and the like. Specifically, the recording unit 12 records the image data received by the communication unit 13, the local water vapor transmission rate analyzed by the data processing unit 14 from the image data, the water vapor transmission rate per unit area of the gas barrier film, and the like. To do.
- the communication unit 13 includes a communication interface such as a network I / F, and transmits the imaging condition input from the operation display unit 15 to the imaging adjustment device 2 via a network such as an intranet.
- the communication unit 13 receives image data of the gas barrier film imaged by the imaging device 3.
- the data processing unit 14 analyzes the image data of the gas barrier film received by the communication unit 13 and imaged by the imaging device 3.
- the data processing unit 14 includes a defect detection unit 14a, a local water vapor transmission rate calculation unit 14b, and a water vapor transmission rate calculation unit 14c, and further preferably includes a water vapor transmission rate distribution calculation unit 14d.
- the defect detection unit 14a detects a defect in the gas barrier film. Moreover, it is preferable that a defect detection part detects a defect from the image data of the image of the obtained gas barrier film optically imaged with an area sensor camera or a line sensor camera. Specifically, the defect detection unit optically images the gas barrier film with an area sensor camera or a line sensor camera, and receives image data of the obtained image via the communication unit 13. And the image data of a gas barrier film are analyzed by image processing, and a defect is detected. As a method for image processing of image data, various known methods can be used. For example, a defect such as a crack can be detected by binarizing the image data with a preset threshold value. The threshold value can be appropriately changed depending on the material and thickness of the gas barrier film to be measured.
- the defect detection unit 14a functions as a defect detection unit that detects a defect in the gas barrier film.
- the local water vapor transmission rate calculation unit 14b calculates the local water vapor transmission rate for each defect detected by the defect detection unit 14a using the feature amount of the defect.
- the local water vapor permeability calculation unit 14b can select, for example, the defect feature amount from the defect diameter, area, aspect ratio, center of gravity, circularity, and the like.
- the local water vapor permeability calculation unit 14b can select a feature amount of a defect according to the material of the gas barrier film, and can calculate a local water vapor permeability for each defect using the feature amount of the defect.
- the local water vapor permeability calculator 14b functions as a local water vapor permeability calculator that calculates the local water vapor permeability for each defect detected by the defect detector 14a using the feature amount of the defect.
- the water vapor transmission rate calculation unit 14c calculates the water vapor transmission rate of the entire gas barrier film in the measurement range based on the local water vapor transmission rate calculated by the local water vapor transmission rate calculation unit 14b. Specifically, the water vapor permeability calculator 14c calculates the water vapor permeability of the entire gas barrier film in the measurement range by summing the local water vapor permeability for each defect calculated by the local water vapor permeability calculator 14b. be able to. Moreover, since the defect size which can be detected changes with the resolution
- the value based on the estimation model is lower than the actual measurement value obtained by the conventional method such as the calcium corrosion method due to the influence of undetected defects, and it has been empirically known that the estimated value and the actual measurement value have a correlation.
- the water vapor permeability evaluation method of the present invention it is possible to correct an error between the actually measured value and the estimated value obtained by actually measuring the water vapor permeability by the calcium corrosion method. .
- the water vapor permeability calculator 14c functions as a water vapor permeability calculator that calculates the water vapor permeability of the entire gas barrier film in the measurement range based on the local water vapor permeability calculated by the local water vapor permeability calculator 14b.
- the water vapor permeability distribution calculating unit 14d calculates the water vapor permeability distribution of the gas barrier film from the defects detected by the defect detecting unit 14a and the water vapor permeability per unit area calculated by the water vapor permeability calculating unit 14c. Specifically, the water vapor transmission rate distribution calculating unit 14d calculates the position of the defect in the gas barrier film from the defects detected by the defect detecting unit 14a and the water vapor transmission rate per unit area calculated by the water vapor transmission rate calculating unit 14c. It is possible to calculate the water vapor permeability distribution corresponding to the above.
- the water vapor permeability distribution calculating unit 14d calculates the water vapor permeability distribution of the gas barrier film from the defects detected by the defect detecting unit 14a and the water vapor permeability per unit area calculated by the water vapor permeability calculating unit 14c. It functions as a transmittance distribution calculation means.
- the operation display unit 15 may include, for example, an LCD (Liquid Crystal Display), a touch panel provided so as to cover the LCD, various switches and buttons, a numeric keypad, a group of operation keys, and the like (not shown).
- the operation display unit 15 receives an instruction from the user and outputs an operation signal to the control unit 11.
- the operation display unit 15 displays on the LCD an operation screen for displaying various setting instructions for inputting various operation instructions and setting information, various processing results, and the like, in accordance with a display signal output from the control unit 11.
- the imaging adjustment device 2 adjusts the imaging device 3 based on the imaging conditions received from the image processing device 1. Specifically, the imaging adjustment device 2 is based on the imaging conditions received from the image processing device 1, for example, the position from the gas barrier film, the amount of light at the time of imaging, the shutter speed, the imaging interval of the imaging device 3, the moving speed, and the like. Thus, the imaging device 3 can be adjusted.
- the imaging device 3 images the surface of the gas barrier film under the conditions adjusted by the imaging adjustment device 2.
- the imaging device 3 includes an imaging camera 31 and an illumination light source 32.
- the imaging camera 31 can optically image the surface of the gas barrier film with an area sensor camera or a line sensor camera, for example.
- an area sensor camera that can image a wide area at a time is suitable.
- a line sensor camera that is not easily affected by the shadow of the roll is suitable.
- the area of a gas barrier film is narrow, it can also image with an optical microscope provided with an imaging device.
- the imaging camera 31 can be appropriately selected according to the size and state of the gas barrier film.
- the imaging device 3 images the surface of the gas barrier film according to the conditions adjusted by the imaging adjustment device 2, such as the position of the imaging camera, the amount of light, the moving direction of the imaging camera, etc., and obtains image data.
- the imaging device 3 transmits the obtained image data to the image processing device 1 via the communication unit 13.
- the film observation table 4 preferably includes a film fixing table 41, a biaxial electric stage 42, and an apparatus frame 43. Specifically, the film observation table 4 fixes the gas barrier film as a sample by the film fixing table 41 and fixes the surface so that it can be imaged by the imaging camera. Even when the gas barrier film as a sample is wound in a roll shape, for example, the minor axis direction is fixed by the film fixing base 41, the two-axis electric stage is moved at a predetermined speed, and the gas barrier film is By moving the film in the long axis direction, a wider range than the film observation table 4 can be imaged by the imaging camera 31.
- the film observation stand 4 may be connected to the image processing apparatus 1 so as to be communicable.
- the speed at which the gas barrier film is moved may be set by the image processing apparatus 1 by connecting the image processing apparatus 1 and the film observation stand 4 so that they can communicate with each other.
- the image processing device 1 may include an external output device 5 that is communicably connected to the image processing device 1.
- the external output device 5 may be a general PC (Personal Computer), an image forming device, or the like.
- the external output device 5 may function as an operation display unit instead of the operation display unit 15 of the image processing apparatus 1.
- the process for creating an estimation model for the local water vapor permeability of the gas barrier film is performed by measuring the water vapor permeability of a part of the sample by a method such as the calcium corrosion method using a sample equivalent to the sample to be measured, and measuring the measured water vapor.
- This is a process of creating an estimation model of local water vapor permeability used for calculation of local water vapor permeability of the gas barrier film based on the permeability.
- the control unit 11 performs settings for imaging and image processing on the surface of the gas barrier film, such as imaging conditions recorded in the recording unit 12, image processing threshold values, and detection parameters (step S1). Specifically, the control unit 11 transmits the imaging condition to the imaging device 3 via the communication unit 13, and transmits the threshold value and detection parameter of the image processing to the defect detection unit 14a.
- the imaging conditions and the like may be set using conditions recorded in the recording unit 12 in advance, or the operation display unit 15 may be selected by the user according to the state of the sample to be measured and the accuracy of the desired water vapor transmission rate. Can be entered or changed.
- the imaging device 3 images the surface of the gas barrier film and acquires image data of the surface (step S2). Specifically, the imaging device 3 images the surface of the gas barrier film under the imaging conditions input from the image processing device 1, and the obtained image is sent as image data to the defect detection unit 14a via the communication unit 13. Send.
- the data processing unit 14 of the image processing apparatus 1 performs image processing such as binarization processing on the image data received from the communication unit 13 based on the image processing threshold value set in step S1 (step S3). ).
- the data processing unit 14 may perform a general binarization process on the image data. Based on a predetermined threshold, the data processing unit 14 is white when the luminance value of the image is equal to or higher than the threshold, and is black when the luminance is lower than the threshold.
- Image processing can be performed.
- the threshold value to be set can be appropriately set according to the material and thickness of the gas barrier film to be measured.
- noise removal may be performed in advance using a known smoothing filter, median filter, or the like.
- the defect detection part 14a detects the defect of a gas barrier film (step S4). Specifically, for example, a portion of the image data on the surface of the gas barrier film binarized based on a predetermined threshold value in step S3 is detected as a defect.
- the data processing unit 14 acquires a defect feature amount from the defect detected in step S4 (step S5).
- the defect feature amount of the defect detected from the binarized image data for example, the maximum ferret diameter, area, area ratio, aspect ratio, center of gravity, circularity, circumscribed rectangle length, circumscribed rectangle of the defect Width, outer circumference, equivalent ellipse major axis, equivalent ellipse minor axis, equivalent rectangle long side, equivalent rectangle short side, equivalent rectangle diagonal, maximum horizontal width, peak concentration, average concentration, density, Hu moment, etc. can be calculated.
- the defect feature amount to be calculated one or a plurality of preset defect features can be calculated.
- the water vapor permeability of the gas barrier film is measured using a method such as a calcium corrosion method (step S6).
- a control part memorize stores the measured value of the water vapor permeability of the gas barrier film by a calcium corrosion method in a recording part.
- the method for measuring the local water vapor permeability of the gas barrier film equivalent to the sample to be measured in advance is not limited to the calcium corrosion method, and is less than 1.0 ⁇ 10 ⁇ 4 g / m 2 ⁇ 24 h. Any method can be used as long as the water vapor permeability can be measured. In the following description, as an example, an explanation will be given using an actual measurement value of local water vapor permeability obtained by the calcium corrosion method.
- the local water vapor transmission rate calculation unit 14b creates a water vapor transmission rate estimation model from the defect feature amount by multiple regression analysis (step S7). Specifically, the local water vapor permeability calculation unit 14b uses, as an explanatory variable, an appropriate variable having a high contribution rate among the defect feature values acquired in step S5, and the local water vapor permeability for each defect as an objective variable. Multiple regression analysis is performed to create a local water vapor permeability estimation model for each defect. As the defect feature amount, one defect feature amount may be used, or a local water vapor permeability estimation model for each defect may be created using a plurality of defect feature amounts. As an example, a graph showing the relationship between the diameter of the detected defect and the water vapor permeability is shown in FIG.
- a local water vapor permeability estimation model created by multiple regression analysis using the defect diameter as the defect feature amount is shown.
- C 40 ⁇ m ⁇ Defect diameter 9.0 ⁇ 10 ⁇ 8 g / point ⁇ 24h
- the defect diameter is the maximum ferret diameter of the image of the defect binarized by image processing (the maximum length of the vertical or horizontal side of the rectangle circumscribing the defect image).
- the local water vapor permeability for each defect can be calculated. For example, when 10 defects having a defect diameter of 3 ⁇ m are confirmed in the measurement range of the gas barrier film, the defect diameter is 0 ⁇ m by setting the defect to 3.0 ⁇ 10 ⁇ 11 ⁇ 10 using a local water vapor permeability estimation model. The total value of the local water vapor permeability of defects that are larger and within a range of 5 ⁇ m or less is calculated. Similarly, when the defect diameter is larger than 40 ⁇ m, the total value of the local water vapor permeability can be calculated.
- the defect diameter can be calculated using the average value of the defect diameters of the defects in the range.
- the local water vapor permeability in the range may be calculated by substituting the defect diameter for each detected defect into the estimation model and summing the obtained values. Note that the number and type of defect feature quantities suitable for the layer structure and the like are different and are not limited to the defect diameter.
- the water vapor permeability evaluation process of the gas barrier film is performed by calculating the water vapor permeability of the entire gas barrier film of the measurement sample using the water vapor permeability estimation model created by the local water vapor permeability estimation model creation process. This is a process for evaluating the transparency.
- steps S11 to S15 For the processing of steps S11 to S15, the same processing as that of steps S1 to S5 shown in FIG. 5 is performed on the sample to be measured.
- the local water vapor permeability calculation unit 14b calculates the local water vapor permeability for each defect detected in step S14 using the feature amount of the defect (step S16). Specifically, the local water vapor permeability calculator 14b calculates the local water vapor permeability using the local water vapor permeability estimation model created by the local water vapor permeability estimation model creation process. For example, when the defect diameter is used as the defect feature amount, the local water vapor permeability for each defect is determined by using the water vapor permeability estimation model corresponding to one of the above estimated models (A) to (C). Can be calculated.
- the water vapor permeability calculation unit 14c calculates the water vapor permeability of the entire gas barrier film in the measurement range based on the local water vapor permeability calculated in step S16 (step S17). Specifically, the water vapor permeability calculation unit 14c calculates the water vapor permeability of the entire gas barrier film in the measurement range as a total value based on the local water vapor permeability for each detected defect in the measurement range. For example, when the defect diameter is used as the defect feature amount, the number of defects corresponding to the defect diameter is calculated, and the total value of the local water vapor permeability is calculated using the local water vapor permeability estimation model.
- the number of defects is X within the range of the defect diameter of (A), the number of defects is Y within the range of the defect diameter of (B), and the defect diameter of (C). It is assumed that the number of defects is Z within the range.
- the water vapor permeability of the gas barrier film can be calculated by the sum of the products of the local water vapor permeability and the number of defects for each defect. it can. Therefore, the following equation (D) can be obtained using the estimated model and the number of defects.
- Formula (D): Water vapor permeability within measurement range (before correction) [g / 24h] 3.0 ⁇ 10 ⁇ 11 ⁇ X + (3.0 ⁇ 10 ⁇ 9 ⁇ average value of defect diameter ⁇ 1 ⁇ 10 ⁇ 8 ) ⁇ Y + 9. 0 ⁇ 10 ⁇ 8 ⁇ Z
- the data processing unit 14 corrects the water vapor permeability calculated using the measured value of the water vapor permeability by the calcium corrosion method for a sample equivalent to the gas barrier film to be measured (step S18). Specifically, the data processing unit 14 obtains a correction value by comparing the measured value of water vapor permeability by the calcium corrosion method with the local water vapor permeability calculated by the local water vapor permeability estimation model. In addition, prepare multiple samples equivalent to the gas barrier film to be measured, perform the calcium corrosion method on the sample for which the water vapor permeability in the measurement range was calculated by the water vapor permeability evaluation process, and average the error from the estimated model The correction term may be obtained in advance. The equation (D) is corrected as follows using the correction term.
- the data processing unit 14 calculates the water vapor transmission rate per unit area using the water vapor transmission rate corrected in step S18 (step S19). Specifically, the data processing unit 14 can calculate the water vapor permeability per unit area by dividing the water vapor permeability corrected from the actually measured value by the calcium corrosion method by the measurement range.
- the image processing apparatus calculates a water vapor permeability distribution for calculating a water vapor permeability distribution of the gas barrier film from a defect detected by the defect detection unit and a water vapor permeability per unit area calculated by the water vapor permeability calculation unit. It is preferable to provide the part 14d.
- the gas barrier film defects detected by the defect detector for example, from the water vapor permeability per unit area calculated by the water vapor permeability calculator corresponding to the position, size, range, etc.
- the water vapor permeability distribution of the gas barrier film can be reflected in the image data obtained by the imaging device.
- the water vapor permeability distribution may be calculated using the water vapor permeability of the entire gas barrier film in the measurement range.
- a manufacturing method of a gas barrier film it is preferable to have the process of evaluating the water vapor permeability of a gas barrier film using the water vapor permeability evaluation method or water vapor permeability evaluation system of a gas barrier film. Since the water vapor permeability evaluation method and the water vapor permeability evaluation system of the gas barrier film measure the water vapor permeability of the entire gas barrier film in a non-destructive and non-contact manner, the water vapor permeability is incorporated into the gas barrier film manufacturing process. Can be evaluated.
- FIG. 3 An example of the gas barrier film to be measured is shown in FIG.
- the gas barrier film F is comprised from the board
- the gas barrier film F includes a smooth layer F3 on one surface of the substrate F1, and the gas barrier layer F4 is laminated on the smooth layer F3. Further, a bleed-out prevention layer F2 is provided on the other surface side of the substrate F1.
- the gas barrier film shown in FIG. 3 is an example, and does not limit the gas barrier film to be measured.
- the substrate F1 constituting the gas barrier film F examples include a flexible and bendable resin film, but it may be a glass substrate or the like.
- the substrate F1 is not particularly limited as long as it is a material that can hold the gas barrier layer F4 having gas barrier properties, the smooth layer F3 according to the present invention, and other various functional layers.
- Examples of the resin material applicable to the substrate F1 include acrylic acid ester, methacrylic acid 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.
- Resin film heat-resistant transparent film (product name: Silplus, manufactured by Nippon Steel Chemical Co., Ltd.) based on silsesquioxane having an organic / inorganic hybrid structure, and two or more layers of the above film materials Can be used consists resin film by.
- films such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), and polycarbonate (PC) are preferably used from the viewpoints of economy and availability.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PC polycarbonate
- a transparent polyimide film having both heat resistance and transparency for example, a transparent polyimide film (for example, type HM) manufactured by Toyobo Co., Ltd.
- a transparent polyimide film for example, Neoprim L L-3430 manufactured by Mitsubishi Gas Chemical Co., Ltd. can be preferably used.
- the thickness of the substrate F1 applied to the present invention is preferably in the range of 5 to 500 ⁇ m, but the imaging conditions by the imaging device and the setting conditions in the image processing of the surface of the imaged gas barrier film can be adjusted. There is no particular limitation.
- the substrate F1 using the above resin material may be an unstretched film or a stretched film.
- the smooth layer F3 flattens the rough surface of the substrate F1 where minute protrusions and the like are present, so that irregularities and pinholes are not generated in the gas barrier layer F4 and the like formed on the substrate F1 by the protrusions on the surface of the substrate F1. Therefore, it has a function of trapping the amine catalyst and ammonia diffusing from the gas barrier layer as described above, or moisture diffusing from the substrate F1 to the gas barrier layer F4, and the adhesion between each layer is improved. It is a layer that has been given a role to improve.
- Such a smooth layer F3 may be a compound having at least one urethane bond in the polymer skeleton, for example, and a known polyol compound having at least two hydroxy groups in one molecule and an isocyanate group in one molecule. It is preferable that it is a urethane-cured cured resin using a known polyfunctional isocyanate having two or more. Such a range includes a phenoxy resin crosslinked with isocyanate and a copolymer thereof, and a polyvinyl acetal resin.
- the gas barrier layer F4 is formed by applying a coating liquid for forming a gas barrier layer containing polysilazane on the smooth layer F3 formed by the above method and drying to form a coating film, and then applying vacuum ultraviolet light to the formed coating film. It is preferable to form it by irradiating and subjecting it to a modification treatment.
- Coating reforming layer as a gas barrier layer As a method of coating a coating film modifying layer, which is a thin film for forming a gas barrier layer on a substrate and a smooth layer, for example, a gas barrier layer forming coating solution containing polysilazane is applied and dried on the smooth layer.
- the coating film (polysilazane-containing layer) formed in this manner is subjected to an ultraviolet irradiation treatment that irradiates vacuum ultraviolet light, and converted to a gas barrier layer, which is a polysilazane modified layer having gas barrier properties.
- the gas barrier layer is formed by subjecting a polysilazane-containing layer formed by applying and drying a gas barrier layer-forming coating solution containing polysilazane to a smooth layer and subjecting the polysilazane-containing layer to a vacuum ultraviolet light irradiation. It can be formed by modifying the gas barrier layer. Moreover, on the polysilazane content layer (gas barrier layer) formed by application
- the gas barrier layer is preferably formed by a wet coating method in which a coating solution for forming a gas barrier layer containing polysilazane is applied to form a coating film.
- polysilazane is a polymer having a silicon-nitrogen bond, SiO 2 having a bond such as Si—N, Si—H, N—H, etc., Si 3 N 4 and both intermediate solid solutions SiO x N y. It is a ceramic precursor inorganic polymer composed of, and the like.
- the wet coating method for coating the gas barrier layer-forming coating solution containing polysilazane can be appropriately selected from conventionally known methods. Specific examples of coating methods include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, cast film formation, bar coating, and gravure printing. It is done.
- the thickness of the polysilazane-containing layer formed on the smooth layer is appropriately set according to the purpose, but the thickness after drying is preferably in the range of 1 nm to 100 ⁇ m, more preferably 10 nm to It is in the range of 10 ⁇ m, and most preferably in the range of 10 nm to 1 ⁇ m.
- the polysilazane to be applied is preferably a compound that is converted to silica by being ceramicized at a relatively low temperature condition so as to be applied so as not to impair the properties of the substrate to be used.
- a compound that is converted to silica by being ceramicized at a relatively low temperature condition so as to be applied so as not to impair the properties of the substrate to be used.
- Compounds are preferred.
- the polysilazane modification treatment refers to a treatment for converting a part or most of the polysilazane compound into silicon oxide or silicon oxynitride.
- a conversion reaction using ultraviolet light capable of a conversion reaction at a lower temperature is suitably used from the viewpoint of adapting to a plastic substrate when producing a gas barrier film.
- the polysilazane coating film (polysilazane-containing layer) from which moisture has been removed is modified by ultraviolet light irradiation treatment.
- Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures. It is.
- UV light irradiation O 2 and H 2 O, UV absorbers, polysilazane itself, etc. that contribute to ceramics are excited and activated. And the ceramicization of the excited polysilazane is promoted, and the resulting ceramic film becomes dense. Irradiation with ultraviolet light is effective at any time after the formation of the coating film.
- This protective layer can be formed by applying a protective layer-forming coating solution on the gas barrier layer and then drying.
- the coating liquid for forming the protective layer is subjected to a predetermined modification treatment (for example, an ultraviolet irradiation treatment for irradiating vacuum ultraviolet light similar to that used for forming a gas barrier layer, A method of forming a protective layer by applying a heat treatment with irradiation with heat rays may be applied.
- the compound used for forming the protective layer is an organic or inorganic compound, and is preferably a transparent film in the ultraviolet to visible light region.
- the organic resin include polyester resins, isocyanate resins, urethane resins, An acrylic resin, an ethylene vinyl alcohol resin, a vinyl modified resin, an epoxy resin, a modified styrene resin, a modified silicon resin, an acetal resin, or the like can be used alone or in combination. Conventionally known additives can be added to these resins. And after preparing the coating liquid for protective layer formation by melt
- the protective layer can be formed by coating on the gas barrier layer by a known wet coating method such as spray coating, and then drying and removing the solvent, diluent and the like.
- the coating amount is preferably within a range of 0.01 to 1 g / m 2 (dry state).
- the protective layer is laminated on a gas barrier layer (polysilazane-containing layer) provided on the smooth layer.
- a protective layer-forming coating solution prepared by dissolving and dispersing the compound in a solvent having a low moisture content is used in a low humidity environment. It is preferable to form by applying and drying.
- a preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%)
- a more preferable dew point temperature is ⁇ 8 ° C. (temperature 25 ° C./humidity 10%) or lower
- a more preferable dew point temperature is ⁇ 31 ° C. (temperature 25 ° C./temperature). Humidity 1%) or less.
- the thickness of the protective layer is usually in the range of 1 to 1000 nm, preferably in the range of 10 to 500 nm. In the present invention, if the thickness of the protective layer is within the range specified above, it is easy to ensure the uniformity of the protective layer coating film to be formed, and the gas barrier layer is protected from scratches and stress during bending. Can be protected.
- a bleed-out prevention layer F2 may be formed on the opposite side of the substrate F1 from the smooth layer.
- the bleed-out prevention layer F2 is for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the substrate F1 to the surface of the substrate F1 when the substrate (film) having the smooth layer F3 is heated to contaminate the film surface. And provided on the opposite surface of the substrate F1 having the smooth layer F3.
- the bleed-out prevention layer F2 may basically have the same configuration as the smoothing layer F3 as long as it has this function.
- the molecule As an unsaturated organic compound having a polymerizable unsaturated group (hereinafter also referred to as a hard coat agent) that can be included in the bleed-out prevention layer F2, the molecule has two or more polymerizable unsaturated groups. Examples thereof include polyunsaturated organic compounds and unit price unsaturated organic compounds having one polymerizable unsaturated group in the molecule.
- a 100 ⁇ m-thick polyester film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) that is easily bonded on both sides is used as the substrate F1, and the sheet-like substrate F1 is 96 in an environment of a temperature of 25 ° C. and a relative humidity of 55%. After storing for a period of time and adjusting the humidity, a bleed-out prevention layer F2 on one side and a smooth layer F3 on the opposite side were prepared and used as described below.
- a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation was applied by spin coating using a spin coater MS-A100 manufactured by Mikasa so that the layer thickness after drying was 4 ⁇ m. Then, using a high-pressure mercury lamp under air, curing and drying were performed under a curing condition of 1.0 J / cm 2 and a drying condition of 80 ° C. for 3 minutes to form a bleed-out prevention layer.
- Two-component polyurethane resin paint Washin Coat MP-6103A (normal butyl acetate solution with a solid content of 40% by mass); Tolylene diisocyanate modified isocyanate resin (Material having an isocyanate group) and Washin Coat MP-6103B (a toluene / methyl ethyl ketone mixed solution having a solid content concentration of 30% by mass); a modified polyester resin (polyol) having a mass ratio of hydroxy groups to isocyanate groups in the polyol of 1:
- a coating solution diluted with a 1/1 mixed solvent of methyl ethyl ketone / methyl isobutyl ketone was prepared so that the solid content concentration as the coating solution was 10% by mass.
- the obtained coated sample was treated with dry air at a temperature of 95 ° C. and a dew point of ⁇ 5 ° C. for 2 minutes to obtain a sample in which a polysilazane-containing layer was formed on the smooth layer F3 on the upper surface of the substrate F1.
- each sample was irradiated with vacuum ultraviolet light (excimer modification treatment) under the following apparatus and conditions to modify the polysilazane-containing layer to form a gas barrier layer.
- Excimer modification treatment The sample after the polysilazane coating film was dried and the polysilazane-containing layer was formed was subjected to an excimer modification treatment with the following apparatus and conditions to modify the polysilazane-containing layer to form a gas barrier layer F4.
- Excimer irradiation device MODEL MECL-M-1-200 manufactured by M.D.Com Wavelength: 172nm Lamp filled gas: Xe ⁇ Reforming treatment conditions> Average excimer light intensity: 130 mW / cm 2 (172 nm) Distance between sample and light source: 2mm Stage heating temperature: 95 ° C Oxygen concentration in the irradiation apparatus: Maintaining 0.1% or less Stage transport speed during excimer light irradiation: 10 mm / sec Number of stage transport times during excimer light irradiation: Accumulated amount of excimer light exposure on the sample surface is 5000 mJ / cm Adjust to be 2 .
- a substrate (gas barrier film) on which the above gas barrier layer was formed was further prepared in order to obtain an actual measurement value by the calcium corrosion method. evaluated.
- Vapor deposition equipment JEOL-made vacuum vapor deposition equipment JEE-400
- Constant temperature and humidity oven Yamato Humidic Chamber IG47M Metal that reacts with water and corrodes: Calcium (granular)
- Water vapor impermeable metal Aluminum ( ⁇ 3-5mm, granular)
- Metallic calcium was vapor-deposited on the surface of the protective layer of the gas barrier film sample using a vacuum evaporation apparatus (JEOL-made vacuum evaporation apparatus JEE-400).
- the metal calcium vapor deposition surface is bonded and bonded to quartz glass having a thickness of 0.2 mm via a sealing ultraviolet curable resin (manufactured by Nagase ChemteX) and irradiated with ultraviolet rays.
- a sealing ultraviolet curable resin manufactured by Nagase ChemteX
- An evaluation cell was produced.
- test piece described in Japanese Patent Application Laid-Open No. 2005-283561 is imaged under a constant temperature and humidity environment, and the obtained image is subjected to image processing to calculate corroded calcium and obtained based on a method of measuring water vapor permeability.
- the obtained sample (evaluation cell) was stored under conditions of 60 ° C. and 90% RH, and the amount of moisture permeated into the cell was evaluated from the corrosion amount of metallic calcium.
- a local water vapor permeability estimation model was obtained as follows. 0 ⁇ m ⁇ Defect diameter ⁇ 5 ⁇ m 3.0 ⁇ 10 ⁇ 11 g / point ⁇ 24h 5 ⁇ m ⁇ defect diameter ⁇ 40 ⁇ m 3.0 ⁇ 10 ⁇ 9 ⁇ defect diameter ⁇ 1.0 ⁇ 10 ⁇ 8 g / point ⁇ 24h 40 ⁇ m ⁇ Defect diameter 9.0 ⁇ 10 ⁇ 8 g / point ⁇ 24h
- Table 1 shows the number of defects corresponding to the detected defect diameter.
- the local water vapor permeability for each detected defect is calculated using the local water vapor permeability estimation model. Specifically, when the water vapor permeability of the number of defects shown in Table 1 (total value of the local water vapor permeability) is calculated using the local water vapor permeability model, it is as follows.
- Water vapor permeability within measurement range (before correction) [g / 24h] 3.0 ⁇ 10 ⁇ 11 ⁇ X + (3.0 ⁇ 10 ⁇ 9 ⁇ average value of defect diameter ⁇ 1.0 ⁇ 10 ⁇ 8 ) ⁇ Y + 9.0 ⁇ 10 ⁇ 8 ⁇ Z
- an average value of the defect diameter an average value of defect diameters of defects in the range of 5 ⁇ m or more and 40 ⁇ m or less is used.
- a gas barrier film was prepared by the method of this example, extracted at 5 locations at 10 cm 2 , and after calculating water vapor permeability using an estimated model, an actual measurement value by the calcium corrosion method was obtained for the same gas barrier film.
- the slopes of the regression curves obtained by the least square method were almost equal, and the constant term had an actually measured value 1.1 times the estimated value.
- the water vapor permeability of the gas barrier film according to the present invention by the water vapor permeability evaluation method was 8.79 ⁇ 10 ⁇ 5 [g / m 2 ⁇ 24 h] with a measurement time of 12 hours and a measurement range of 150 mm 2 .
- the water vapor permeability by the calcium corrosion method was 9.00 ⁇ 10 ⁇ 5 [g / m 2 ⁇ 24 h] at a measurement time of 320 hours, a measurement range of 15 mm 2 , a measurement temperature of 60 ° C., and a relative humidity of 90% RH. It was.
- the obtained water vapor permeability value is close to the actually measured value obtained by the calcium corrosion method. From the above, it was found that the water vapor permeability of the gas barrier film according to the present invention can be measured in a non-contact, non-destructive, short time, wide range and highly reliable water vapor permeability.
- the water vapor permeability evaluation system for a gas barrier film of the present invention With the water vapor permeability evaluation system for a gas barrier film of the present invention, the water vapor permeability of the entire gas barrier film can be calculated in a short time in a non-destructive and non-contact manner. Therefore, it may be used in the field of inspecting the quality of a gas barrier film used in an electronic device such as an organic EL element that deteriorates due to the above.
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Abstract
Le problème décrit par la présente invention est de pourvoir à un procédé d'évaluation du taux de transmission de vapeur d'eau d'un film barrière aux gaz, le procédé étant capable de calculer le taux de transmission de vapeur d'eau du film barrière aux gaz entier en un court laps de temps en mode non destructeur et sans contact et de pourvoir en outre à un système d'évaluation du taux de transmission de vapeur d'eau et à un procédé de production d'un film barrière aux gaz qui utilisent ledit procédé d'évaluation du taux de transmission de vapeur d'eau.
La solution selon l'invention porte sur un procédé d'évaluation du taux de transmission de vapeur d'eau d'un film barrière aux gaz caractérisé en ce qu'il comprend : une étape de détection de défauts qui consiste à détecter les défauts dans un film barrière aux gaz ; une étape de calcul du taux de transmission de vapeur d'eau local qui consiste à calculer les taux de transmission de vapeur d'eau locaux des défauts respectifs détectés dans l'étape de détection de défauts à l'aide des quantités caractéristiques des défauts respectifs ; et une étape de calcul du taux de transmission de vapeur d'eau qui consiste à calculer, sur la base des taux de transmission de vapeur d'eau locaux calculés dans l'étape de calcul du taux de transmission de vapeur d'eau local, le taux de transmission de vapeur d'eau du film barrière aux gaz entier dans une plage de mesures.
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Cited By (5)
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FR3037400A1 (fr) * | 2015-06-15 | 2016-12-16 | Arkema France | Procede et dispositif de caracterisation d'un schema d'encapsulation transparent |
WO2017013050A1 (fr) * | 2015-07-23 | 2017-01-26 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Dispositif pour déterminer le taux de perméation d'un échantillon |
JP2018116545A (ja) * | 2017-01-19 | 2018-07-26 | オムロン株式会社 | 予測モデル作成装置、生産設備監視システム、及び生産設備監視方法 |
JP2018155548A (ja) * | 2017-03-16 | 2018-10-04 | コニカミノルタ株式会社 | 欠陥検査方法、欠陥検査プログラム、および欠陥検査装置 |
WO2019034888A1 (fr) * | 2017-08-18 | 2019-02-21 | Oxford University Innovation Limited | Perméabilité à la vapeur d'eau |
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WO2019034888A1 (fr) * | 2017-08-18 | 2019-02-21 | Oxford University Innovation Limited | Perméabilité à la vapeur d'eau |
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