WO2014181810A1 - Water vapor transmission rate evaluation method, water vapor transmission rate evaluation system, and gas barrier film production method - Google Patents

Abstract

The present invention addresses the problem of providing a non-destructive, non-contact water vapor transmission rate evaluation method for a gas barrier film that makes it possible to calculate the water vapor transmission rate for the entirety of a gas barrier film having a gas barrier layer. Further, the invention also addresses the problems of providing a water vapor transmission rate evaluation system and a gas barrier film production method that use said water vapor transmission rate evaluation method. The water vapor transmission rate evaluation method according to the present invention is a water vapor transmission rate evaluation method for evaluating the water vapor transmission rate of a gas barrier film (F) on the basis of the layer thickness and refractive index of a gas barrier layer (F4) of the gas barrier film (F) and is characterized by the inclusion of a measurement step for measuring the layer thickness and refractive index of the gas barrier layer (F4) and a water vapor transmission rate calculation step for calculating the overall water vapor transmission rate of the gas barrier film (F) within a measurement range.

Description

Water vapor permeability evaluation method, water vapor permeability evaluation system and gas barrier film manufacturing method

The present invention relates to a method for evaluating water vapor permeability. The present invention also relates to a 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.

Conventionally, 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. In addition to the above packaging applications, 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.

However, 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.

Conventionally used evaluation of water vapor permeability is the cup method (JIS Z 0208-1976), the so-called Mokon method (JIS K 7129-1992 B method), and the like. Among these methods, even the Mokon method, which has a wide measurable range, covers the range of water vapor permeability of 5 × 10 ⁻² to 5 × 10 ³ g / m ² · 24 h. However, liquid crystal substrates, organic EL substrates, and the like are required to evaluate water vapor permeability with higher sensitivity.

As a method for evaluating the gas barrier property of a gas barrier film, in addition to the above method, a calcium corrosion method (hereinafter also referred to as a calcium method or a Ca method) for measuring water vapor permeability is known. In this method, 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.

In addition, with respect to a method for evaluating water vapor permeability using a mass spectrometer or the like (for example, see Patent Document 1) and a functional element having a marker part, the superiority or inferiority of the gas barrier layer is determined based on the refractive index of the marker part. An inspection method (for example, see Patent Document 2) is known.

However, the method described in Patent Document 1 is a destruction method in which a part of a sample specimen is extracted as in the calcium corrosion method. The method described in Patent Document 2 is a partial evaluation based on the premise of the uniformity of the gas barrier film, and does not guarantee the water vapor permeability of the entire gas barrier film.

Patent Document 3 discloses a method for calculating a refractive index based on a measured film thickness of a gas barrier laminate film and determining a gas barrier property of the film from a relationship with a water vapor permeability measured by a differential pressure method. Are listed.

However, the method of Patent Document 3 roughly determines a gas barrier film failure from a correlation based on the measured values of water vapor permeability and refractive index, and does not calculate water vapor permeability.

Japanese Patent No. 4759096 JP 2005-317286 A JP 2013-44542 A

The present invention has been made in view of the above problems and situations, and a solution to the problem is water vapor that can be calculated non-destructively and non-contact, and the water vapor permeability of the entire gas barrier film having a gas barrier layer. It is to provide a transmittance evaluation method. 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.

In order to solve the above problems, the present inventor examined the cause of the above problems and the like, and based on the thickness and refractive index of the gas barrier film having the gas barrier layer, the water vapor permeation of the entire gas barrier film in the measurement range. The inventors have found that the problem of the present invention can be solved by calculating the degree, and have reached the present invention.

That is, the said subject which concerns on this invention is solved by the following means.
1. A water vapor permeability evaluation method for evaluating the water vapor permeability of a gas barrier film based on the thickness and refractive index of the gas barrier layer of the gas barrier film,
(1) a measuring step for optically measuring the thickness and refractive index of the gas barrier layer;
(2) 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 layer thickness and refractive index measured by the measuring step;
The water vapor permeability evaluation method characterized by including.

2. In the water vapor permeability calculation step, the water vapor permeability is estimated using a water vapor permeability estimation model created based on the water vapor permeability of the gas barrier film, the thickness of the gas barrier layer and the refractive index measured by the calcium corrosion method. The water vapor permeability evaluation method according to item 1, wherein the water vapor permeability is calculated.

3. The estimation model of water vapor permeability includes a preset water vapor permeability term, a preset water vapor permeability change amount based on a change amount from a predetermined layer thickness and refractive index, and a correction term. The water vapor permeability evaluation method according to item 2, characterized in that:

4. The gas barrier layer to be measured is a gas barrier layer formed by applying a coating liquid containing polysilazane to a substrate and drying the layer to modify it by irradiating with vacuum ultraviolet light. The water vapor permeability evaluation method according to any one of items 1 to 3, which is a characteristic.

5. The water vapor permeability evaluation method according to any one of claims 1 to 4, wherein in the measurement step, the layer thickness and the refractive index are measured using a spectral reflectometer or an ellipsometer. .

6). A water vapor permeability evaluation system for evaluating the water vapor permeability of a gas barrier film based on the thickness and refractive index of the gas barrier layer of the gas barrier film,
(1) measuring means for optically measuring the thickness and refractive index of the gas barrier layer;
(2) Water vapor permeability calculating means for calculating the water vapor permeability of the entire gas barrier film in the measurement range based on the layer thickness and refractive index measured by the measuring means;
A water vapor transmission rate evaluation system comprising:

7. The water vapor permeability evaluation system according to claim 6, which is used for evaluating the water vapor permeability of the gas barrier film in the step of producing the gas barrier film.

8. 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 5. Manufacturing method.

By the above means of the present invention, it is possible to provide a water vapor permeability evaluation method capable of calculating the water vapor permeability of the entire gas barrier film having a gas barrier layer in a nondestructive and non-contact manner. In addition, a water vapor permeability evaluation system using the water vapor permeability evaluation method and a gas barrier film manufacturing method can be provided.

In an electronic device such as an organic electroluminescence element using a film substrate, a film substrate having a high gas barrier property against water vapor is essential, and an increase in water vapor permeability due to non-uniformity of the film substrate leads to deterioration of the electronic device. Therefore, the thickness and refractive index of a gas barrier film having a gas barrier layer are measured, and the water vapor permeability of the entire gas barrier film is calculated using the layer thickness and refractive index, so that the film is non-destructive and non-contact. It was found that a highly reliable water vapor permeability can be obtained in this state.

Schematic configuration diagram showing an example of a water vapor permeability evaluation system according to the present invention The block diagram which shows the main structures of the water-vapor-permeation evaluation system based on this invention Sectional drawing which shows an example of the gas barrier film which concerns on this invention Conceptual diagram showing the relationship between layer thickness and water vapor permeability Conceptual diagram showing the relationship between refractive index and water vapor transmission rate Flow chart showing flow of 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 is a water vapor permeability evaluation method for evaluating the water vapor permeability of a gas barrier film based on the thickness and refractive index of the gas barrier layer of the gas barrier film, and the layer thickness of the gas barrier layer And a measuring step for optically measuring the refractive index, and a water vapor permeability calculating step for calculating the water vapor permeability of the entire gas barrier film in the measuring range based on the layer thickness and the refractive index measured by the measuring step. It is characterized by including. This feature is a technical feature common to the inventions according to claims 1 to 8.

As an embodiment of the present invention, in the water vapor permeability calculation step, the water vapor permeability of the gas barrier film measured by the calcium corrosion method, the layer thickness of the gas barrier layer, and the refraction in that the effect of the present invention can be expressed more. It is preferable to calculate the water vapor transmission rate using an estimation model of the water vapor transmission rate created based on the rate. Thereby, the water vapor transmission rate close to the actual measurement value can be calculated in a non-destructive and non-contact state.

Further, in the present invention, the estimation model of the water vapor transmission rate includes a predetermined water vapor transmission rate term and a change amount of water vapor transmission rate based on a change amount from a preset layer thickness and refractive index. And a correction term. Thereby, an accurate water vapor transmission rate can be calculated even for a portion where the layer thickness or the refractive index slightly deviates from the predetermined range.

Further, in the present invention, the gas barrier layer to be measured was formed by applying a coating liquid containing polysilazane to a substrate and drying the layer obtained by irradiation with vacuum ultraviolet light to modify the layer. A gas barrier layer is preferred. Thereby, an accurate water vapor permeability can be calculated for a gas barrier film having a high gas barrier property.

In the present invention, it is preferable that in the measurement step, the layer thickness and the refractive index are measured using a spectral reflectometer or an ellipsometer. Thereby, even if it is a multilayer film, a film thickness (layer thickness) and a refractive index can be simultaneously measured in a non-contact manner.

The water vapor permeability evaluation system of the present invention is a water vapor permeability evaluation system for evaluating the water vapor permeability of a gas barrier film based on the layer thickness and refractive index of the gas barrier layer of the gas barrier film,
(1) measuring means for optically measuring the thickness and refractive index of the gas barrier layer;
(2) Water vapor permeability calculating means for calculating the water vapor permeability of the entire gas barrier film in the measurement range based on the layer thickness and refractive index measured by the measuring means;
It is characterized by including. Based on the optically measured thickness and refractive index of the gas barrier layer, the water vapor permeability of the entire gas barrier film in the measurement range is calculated. Can do.

Moreover, the water vapor permeability evaluation system of 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.

In addition, as a method for producing the gas barrier film of the present invention, it is temporally and economically to have a step of evaluating the water vapor permeability of the gas barrier film using the water vapor permeability evaluation method of the gas barrier film. It is preferable from the viewpoint.

Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” 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.

<Outline of water vapor permeability evaluation method>
The method for evaluating water vapor permeability of the present invention comprises a measurement step for optically measuring the thickness and refractive index of a gas barrier layer based on the thickness and refractive index of the gas barrier layer of the gas barrier film, and a measurement step. And 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 layer thickness and the refractive index.
Specifically, for a gas barrier film used in an electronic device such as a solar cell, a liquid crystal display element, or an organic EL element, the thickness and refractive index of the gas barrier layer of the gas barrier film are measured. Next, based on the measured layer thickness and refractive index, the water vapor permeability of the entire gas barrier film in the measurement range is calculated.

In the measurement step, the thickness and refractive index of the gas barrier layer are preferably measured using a spectral reflectometer or an ellipsometer.
For example, the thickness of the layer and the refractive index may be calculated by measuring the surface of the gas barrier layer every 1 mm ² using a spectral reflectometer. It is more preferable to calculate the thickness and refractive index of the gas barrier layer together with the coordinate information of the gas barrier layer. Thereby, the layer thickness and refractive index of the gas barrier layer within a predetermined range can be obtained in association with the position information.

In the water vapor permeability calculation step, the water vapor permeability is calculated using an estimated model of water vapor permeability created based on the water vapor permeability of the gas barrier film measured by the calcium corrosion method, the layer thickness of the gas barrier layer, and the refractive index. It is preferable to calculate.
Specifically, in the water vapor permeability calculation step, an optimum water vapor permeability estimation model is created for the gas barrier film to be measured in accordance with the target water vapor permeability range.

The estimation model of water vapor permeability has a preset water vapor permeability term, a preset water vapor permeability change amount based on a change amount from the layer thickness and refractive index, and a correction term. Is preferred.
Specifically, since the water vapor permeability is correlated with the layer thickness and the refractive index, the water vapor permeability estimation model uses the water vapor permeability obtained by the calcium corrosion method to change the layer thickness and the refractive index. Can be obtained by performing multiple regression analysis. Multiple regression analysis yields an estimated model for water vapor transmission rate, which has a water vapor transmission rate term, a water vapor transmission rate change term based on a preset change in thickness and refractive index, and a correction term. It is done.

Next, it is determined whether or not the thickness and refractive index of the gas barrier layer measured by the measurement step are outside a predetermined range.
Specifically, it is determined whether or not the measured thickness and refractive index of the gas barrier layer are outside a predetermined range set in advance according to the type of the gas barrier film. For example, when it is determined that at least one of the thickness and refractive index of the gas barrier layer is outside a predetermined range, it is determined as an abnormal portion. Since at least one of the thickness and refractive index of the gas barrier layer is out of the predetermined range, the water vapor transmission rate is often lower than the practical value, so that it is practical by calculating the water vapor transmission rate. It is effective to check whether or not.
The predetermined thickness and refractive index ranges required for the gas barrier layer of the gas barrier film can be set for each gas barrier film.

Based on the thickness and refractive index of the gas barrier layer measured in the measuring step, the gas barrier layer portion having a layer thickness or refractive index outside the predetermined range, that is, the water vapor permeability of the abnormal portion is estimated. Calculate using the model.
The portion of the gas barrier layer whose layer thickness and refractive index are within the predetermined range (hereinafter referred to as a normal portion) is considered to satisfy the water vapor permeability required for a gas barrier film, and thus is a specified value. The above water vapor permeability can be obtained.

Next, in the water vapor permeability calculation step, the water vapor permeability of the entire gas barrier film in the measurement range is calculated by combining the water vapor permeability of the abnormal part calculated by the estimation model and the water vapor permeability of the normal part.
In the following description, it is assumed that the water vapor permeability of the normal part is equal to or higher than a specified value, but is not calculated using the estimation model, but can be appropriately set to calculate the water vapor permeability using the estimation model. .

<Configuration of water vapor permeability evaluation system>
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.
As shown in FIG. 1, the water vapor permeability evaluation system 100 for a gas barrier film according to the present invention includes a data processing device 1, a spectral reflectance meter adjustment device 2, a spectral reflectance meter 3, and a film observation table 4. Is preferred.

[Data processing device]
The data processing device 1 is connected to the spectral reflectometer adjusting device 2 and the spectral reflectometer 3 so that they can communicate with each other. Below, each structure of the data processor 1 is demonstrated.
As shown in FIG. 2, the data processing apparatus 1 includes a control unit 11, a recording unit 12, a communication unit 13, a data processing unit 14 (estimated model creation unit 14a, gas barrier layer determination unit 14b, water vapor permeability calculation unit 14c), and 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 data processing device 1, and a RAM (Random) that functions as a work memory for temporarily storing various data when the CPU 11a executes a program. (Access Memory) 11b, a program that is read and executed by the CPU 11a, a program memory 11c that stores fixed data, and the like. The program memory 11c is composed of a ROM or the like.

In addition to the layer thickness and refractive index values of the gas barrier layer of the gas barrier film measured by the spectral reflectometer 3, the recording unit 12 uses threshold data used in the data processing unit and the amount of irradiation light when producing the gas barrier layer. The water vapor permeability estimation model created according to the value of the water vapor permeability, the type of substrate, etc. is recorded.

The communication unit 13 includes a communication interface such as a network I / F, and transmits the measurement conditions input from the operation display unit 15 to the spectral reflectometer adjustment device 2 via a network such as an intranet. Further, the communication unit 13 receives the values of the thickness and refractive index of the gas barrier layer of the gas barrier film measured by the spectral reflectometer 3.

The data processing unit 14 analyzes the thickness and refractive index of the gas barrier layer of the gas barrier film measured by the spectral reflectometer 3 received by the communication unit 13.
The data processing unit 14 includes an estimated model creation unit 14a, a gas barrier layer determination unit 14b, and a water vapor permeability calculation unit 14c.
The layer thickness and refractive index of the gas barrier layer are exemplified by the configuration measured and calculated by the spectral reflectometer 3. However, based on the physical property values measured by the spectral reflectometer 3, the data processing unit 14 uses the gas thickness. The thickness and refractive index of the barrier layer may be calculated.

The estimation model creation unit 14a creates an estimation model for calculating the water vapor permeability of the gas barrier film.
Specifically, the estimated model creation unit 14a is determined to be an abnormal part by using the measured values of the gas barrier layer thickness and refractive index calculated by the spectral reflectometer 3 and the water vapor permeability by the calcium corrosion method. An estimation model for calculating the water vapor permeability of the gas barrier layer is created.
In creating the estimation model, the irradiation light quantity for modifying the polysilazane contained in the gas barrier layer described later greatly affects the refractive index of the gas barrier layer. You may create the database which shows a correspondence relationship with the actual value of the water vapor permeability by a calcium corrosion method.

For example, the estimated model creation unit 14a performs a multiple regression analysis using the water vapor permeability obtained by the calcium corrosion method, the layer thickness and the refractive index of the gas barrier layer as explanatory variables, and the water vapor permeability as an objective variable. Create an estimation model of transparency.
As an example, a graph showing the relationship between the layer thickness and the water vapor permeability is shown in FIG. FIG. 5 shows a graph showing the relationship between the refractive index and the water vapor transmission rate.
The estimation model for water vapor transmission rate is a multiple regression analysis based on the relationship between the layer thickness and water vapor transmission rate and the relationship between the refractive index and water vapor transmission rate. Looking for. The estimation model (A) of water vapor permeability is shown below.

(A) Water vapor transmission rate (WVTR) [g / m ² · 24h] = WVTR (d, n) + f (Δd, Δn) + k
WVTR (d, n): Normal value of water vapor transmission rate d: Layer thickness n: Refractive index f (Δd, Δn): Change in layer thickness and change in water vapor transmission rate due to change in refractive index Δd: Change in layer thickness Δn: Refractive index change k: Constant

The water vapor permeability estimation model (B) created by performing multiple regression analysis using the difference from the values of the thickness and refractive index of the gas barrier layer showing the normal value of water vapor permeability is shown. Here, the thickness of the gas barrier layer showing a normal value of water vapor permeability is 250 nm, the refractive index is 1.78, and the water vapor permeability is 1.0 × 10 ⁻⁶ g / m ² · 24 h.
(B) Water vapor transmission rate (WVTR) [g / m ² · 24h] = 1.0 × 10 ⁻⁶ −2.7 × 10 ⁻⁷ × Δd−1.7 × 10 ⁻⁴ × Δn + k
Here, the constant k is a correction term for the water vapor transmission rate obtained from an actual measurement value by a multiple regression analysis and a calcium corrosion method.

The gas barrier layer determination unit 14b determines whether any of the measured layer thickness and refractive index of the gas barrier layer is outside a predetermined range set in advance.
Here, if the gas barrier layer determination unit 14b determines that either the measured thickness or refractive index of the measured portion of the gas barrier layer is outside the predetermined range set in advance, the gas barrier layer determination unit 14b determines that it is an abnormal part. On the other hand, if the layer thickness and refractive index of the measured portion of the gas barrier layer are determined to be the layer thickness and refractive index within a predetermined range set in advance, the gas barrier layer determination unit 14b determines that it is a normal part.
Here, the predetermined ranges of the layer thickness and the refractive index can be appropriately set depending on the gas barrier film to be measured. For example, the range of the thickness of the gas barrier layer is in the range of 240 to 260 nm, and the range of the refractive index is in the range of 1.73 to 1.83 as a predetermined range in which the layer thickness and the refractive index are set in advance. can do. In that case, if it is determined that either the layer thickness or the refractive index is out of this range, it is determined as an abnormal part.

For example, when the thickness of the gas barrier layer is 270 nm and the refractive index is 1.70, it is determined to be out of the predetermined range and determined to be an abnormal part. In this case, in order to calculate the water vapor transmission rate, the change amount of the layer thickness (270−250 = 20 nm) is used as Δd. Further, as Δn, a refractive index change amount (1.70-1.78 = −0.08) is used. By substituting this value into (B), the water vapor permeability of the gas barrier layer determined to be an abnormal part can be calculated.

The water vapor transmission rate calculation unit 14 c calculates the water vapor transmission rate of the entire gas barrier film in the measurement range based on the thickness and refractive index of the gas barrier layer measured by the spectral reflectometer 3.
Specifically, the water vapor transmission rate calculation unit 14c calculates the water vapor transmission rate of the portion determined as an abnormal part by the gas barrier layer determination unit 14b using the estimation model.
The normal part is a practical gas barrier film, and the water vapor transmission rate does not have to be calculated using the water vapor transmission rate estimation model. That is, the normal part of the gas barrier layer having a layer thickness and a refractive index in a predetermined range has a water vapor permeability equal to or higher than a predetermined value, and the predetermined value is set as a part of the gas barrier layer having a practical water vapor permeability. It can be estimated as transmission. When the water vapor permeability of the normal part is calculated using the estimation model, the water vapor permeability can be calculated with the correction term k = 0.
Thereby, the water vapor permeability of the whole gas barrier film in the measurement range can be calculated by adding the water vapor permeability of the normal part and the water vapor permeability of the abnormal part calculated by the estimation model.
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 layer thickness and refractive index created by the spectral reflectometer 3.

The data processing unit 14 may further include a water vapor permeability distribution calculating unit that calculates a water vapor permeability distribution of the gas barrier film.
The water vapor permeability distribution calculating unit may calculate the water vapor permeability distribution of the gas barrier film from the water vapor permeability of the normal part and the abnormal part determined by the data processing unit 14.
Specifically, the water vapor transmission rate distribution calculation unit calculates the water vapor transmission rate calculated by the water vapor transmission rate calculation unit 14c and the normal portion water vapor for the portion of the gas barrier layer determined to be abnormal by the data processing unit 14. From the permeability, a water vapor permeability distribution corresponding to the position coordinates of the gas barrier film may be calculated.

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, an operation key group, 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.

[Spectral reflectometer adjustment device]
The spectral reflectance meter adjustment device 2 adjusts the spectral reflectance meter 3 based on the measurement conditions received from the data processing device 1.
Specifically, the spectral reflectance meter adjustment device 2 is configured to measure the measurement conditions received from the data processing device 1, such as the position (height) from the gas barrier film, the wavelength, the measurement interval of the spectral reflectance meter 3, and the moving speed. The spectral reflectometer 3 can be adjusted based on the above.

[Spectral reflectometer]
The spectral reflectometer 3 measures the thickness and refractive index of the gas barrier layer of the gas barrier film under the conditions adjusted by the spectral reflectometer adjusting device 2.
The spectral reflectometer 3 includes a light receiving unit 31 and a light source 32. The spectral reflectometer 3 is, for example, a spectral reflectometer or an ellipsometer, and can optically measure the gas barrier layer of the gas barrier film to calculate the layer thickness and the refractive index.
Specifically, the spectral reflectometer 3 is a gas barrier film according to the conditions adjusted by the spectral reflectometer adjusting device 2, such as the position (height) of the light receiving unit, the wavelength, the moving direction of the spectral reflectometer, etc. The spectral reflectance of the gas barrier layer is measured, and the layer thickness and refractive index are calculated based on the measured spectral reflectance.
For example, the spectral reflectometer 3 preferably measures the gas barrier layer of the gas barrier film every 1 mm ² . Thereby, the water vapor permeability of the gas barrier layer can be accurately calculated.
The spectral reflectometer 3 preferably measures the gas barrier layer at a wavelength in the range of 380 to 1050 nm, and particularly preferably in the range of 380 to 750 nm in the visible light region.
Then, the spectral reflectometer 3 transmits the obtained thickness and refractive index of the gas barrier layer to the data processing device 1 via the communication unit 13.
In determining the layer thickness and refractive index of the gas barrier layer, the layer thickness and refractive index of only the gas barrier layer can be determined by measuring the layer thickness and refractive index of the substrate and other layers in advance.
Moreover, a spectral reflectometer or an ellipsometer can be suitably selected according to the gas barrier film used as a measuring object. For example, when the gas barrier film is thinner than 10 μm, an ellipsometer may be used, and when it is 10 μm or more, a spectral reflectometer may be used.
The spectral reflectometer 3 functions as a measuring means for optically measuring the thickness and refractive index of the gas barrier layer.

[Film observation stand]
For example, 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 can fix the gas barrier film (see FIG. 3) as a sample by the film fixing table 41 and measure the thickness and refractive index of the gas barrier layer with the spectral reflectometer 3. Secure to. 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 range wider than the film observation table 4 can be measured with the spectral reflectometer 3.

In addition, the film observation stand 4 may be connected to the data processing apparatus 1 so as to be able to communicate. The data processing device 1 and the film observing table 4 are connected so that they can communicate with each other, so that the data processing device 1 may set the speed at which the gas barrier film is moved.

[External output device]
The data processing device 1 may include an external output device 5 that is communicably connected to the data processing device 1. The external output device 5 may be a general PC (Personal Computer), an image forming device, or the like. Further, the external output device 5 may function as an operation display unit instead of the operation display unit 15 of the data processing device 1.

<Method for evaluating water vapor permeability of gas barrier film>
[Estimated model creation process for water vapor permeability of gas barrier film]
Next, a method for evaluating the water vapor permeability of a gas barrier film will be described with reference to the flowcharts shown in FIGS.
Specifically, a process for creating an estimation model of the water vapor permeability of the gas barrier film shown in FIG. 6 and a water vapor permeability evaluation process for the gas barrier film shown in FIG. 7 will be described.
In the process of creating an estimated model of the water vapor permeability of the gas barrier film, first, the water vapor permeability is measured for a partial range of the sample by a method such as a calcium corrosion method using a sample equivalent to the sample to be measured. And based on the measured water vapor transmission rate, it is the process which creates the estimation model of the water vapor transmission rate used for the water vapor transmission rate calculation of a gas barrier film.

The control unit 11 sets the measurement conditions of the gas barrier layer of the gas barrier film recorded on the recording unit 12, the layer thickness of the normal part, and the refractive index range (step S1).
Specifically, the control unit 11 transmits the measurement conditions to the spectral reflectometer 3 via the communication unit 13, and sets a predetermined range of the layer thickness and the refractive index (the range of the normal portion layer thickness and the refractive index). The data is transmitted to the data processing unit 14 and set. The conditions such as the measurement conditions may be set in advance in the recording unit 12, or the user may select the operation display unit 15 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.

Next, the spectral reflectometer 3 measures the spectral reflectance of the gas barrier layer of the gas barrier film (step S2).
Specifically, the spectral reflectance meter 3 measures the spectral reflectance of the gas barrier layer of the gas barrier film under the measurement conditions and the like input from the data processing device 1.

Next, the spectral reflectometer 3 calculates the thickness and refractive index of the gas barrier layer based on the measured spectral reflectance (step S3).
Specifically, the film thickness and refractive index of the gas barrier film can be calculated by analyzing the reflection from the interface between the surface of the gas barrier film and the substrate. Since the layer thickness (film thickness) and refractive index of a layer (film) other than the gas barrier film substrate and the gas barrier layer can be measured in advance, the film thickness and refractive index of the entire gas barrier film should be calculated. Thus, the layer thickness and refractive index of the gas barrier layer alone can be obtained.

Next, the water vapor permeability of the gas barrier film is measured using a method such as a calcium corrosion method (step S4).
Specifically, the control part 11 records the measured value of the water vapor permeability of the gas barrier film by the calcium corrosion method in the recording part.
The method for measuring the 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 ⁻⁶ g / m ² · 24 h. Any method capable of measuring the water vapor permeability may be used. In the following description, as an example, an explanation will be given using an actual measured value of water vapor permeability obtained by the calcium corrosion method.

Next, the estimation model creation unit 14a creates a water vapor permeability estimation model using the multiple regression analysis from the measured values of the water vapor permeability obtained by the thickness and refractive index of the gas barrier layer and the calcium corrosion method. (Step S5).
Specifically, the estimation model creation unit 14a uses a multiple regression analysis method from the measured values of the water vapor permeability obtained by the layer thickness and refractive index of the gas barrier layer and the calcium corrosion method. For example, the estimated model creation unit 14a has a water vapor permeability term based on the normal value of the water vapor permeability set according to the type of the gas barrier film, and the water vapor permeability based on the amount of change in the layer thickness and the refractive index. An estimation model having a change amount term and a correction term is created.

[Evaluation of water vapor permeability of gas barrier film]
Next, the water vapor permeability evaluation process of the gas barrier film will be described with reference to the flowchart shown in FIG.
The water vapor permeability evaluation process of the gas barrier film is performed by calculating the water vapor permeability in the measurement range of the gas barrier film by using the water vapor permeability estimation model created by the water vapor permeability estimation model creation process. Is a process for evaluating

As for the processing in steps S11 to S13, the same processing as in steps S1 to S3 shown in FIG. 6 is performed on the sample to be measured.

The gas barrier layer determination unit 14b determines whether or not the layer thickness and the refractive index of the gas barrier layer calculated in step S13 are outside a predetermined range (step S14).
Specifically, when the gas barrier layer determination unit 14b determines that the thickness and refractive index of the gas barrier layer of the normal part transmitted to the data processing unit 14 are out of range (step S14; Yes), The relevant part of the gas barrier layer is determined as an abnormal part.
For example, in the gas barrier layer determination unit 14b, the thickness of the normal gas barrier layer transmitted to the data processing unit 14 is in the range of 240 to 260 nm, and the refractive index is in the range of 1.73 to 1.78. , The gas barrier layer portion having a layer thickness of 250 nm and a refractive index of 1.45 is determined as an abnormal portion.
On the other hand, when the thickness of the gas barrier layer is 250 nm and the refractive index is 1.75, the gas barrier layer determination unit 14b determines that the gas barrier layer is not outside the set range (step S14; No), and the gas barrier layer This part is determined as a normal part.

And when it is judged that it is an abnormal part in Step S14, water vapor permeability calculation part 14c is abnormal using an estimated model of water vapor permeability from the layer thickness and refractive index of the gas barrier layer calculated in Step S13. The water vapor permeability of the part is calculated (step S15).
Specifically, the water vapor permeability calculation unit 14c calculates the water vapor permeability of the abnormal part using the water vapor permeability estimation model created by the water vapor permeability estimation model creation process.

Next, the water vapor transmission rate calculation unit 14c calculates the water vapor transmission rate of the entire gas barrier film in the measurement range from the water vapor transmission rate of the normal part and the water vapor transmission rate of the abnormal part calculated in step S14 (step S16). .
Specifically, the water vapor transmission rate calculation unit 14c adds the water vapor transmission rate of the abnormal part calculated by the estimation model and the water vapor transmission rate of the normal part within a predetermined range, thereby obtaining a gas barrier in the measurement range. Calculate the water vapor permeability of the entire film.
Further, when the normal part is determined in step S14, the water vapor permeability of the normal part can be regarded as being equal to or less than a certain water vapor permeability because the calculated layer thickness and refractive index are within a predetermined range. Yes (step S16).
Note that the calculation of the water vapor transmission rate using the normal part estimation model can be omitted from the economical and temporal viewpoints, but the normal part water vapor transmission rate may also be calculated using the estimation model. However, when the water vapor permeability of the normal part is calculated using the estimation model, the correction term k of the estimation model is 0.

Moreover, as 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 manufacturing process of the gas barrier film. Can be evaluated.

<Configuration of gas barrier film>
An example of the gas barrier film to be measured is shown in FIG. As shown in FIG. 3, the gas barrier film F is comprised from the board | substrate F1, the bleed-out prevention layer F2, the smooth layer F3, and the gas barrier layer F4.
As shown in FIG. 3, 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.

Hereinafter, the main structure of the gas barrier film according to the present invention will be described in detail.

〔substrate〕
Examples of the substrate F1 constituting the gas barrier film F 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.

Of these resin films, films such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), and polycarbonate (PC) are preferably used from the viewpoints of economy and availability.

In addition, when high temperature treatment is required in the sealing process for sealing the device, 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 μm, but is preferably 25 to 250 μm in view of heat resistance and ease of conveyance.

The substrate F1 using the above resin material may be an unstretched film or a stretched film.

[Smooth layer]
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.

[Gas barrier layer]
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.

For example, 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 | coating and drying, a protective layer is laminated | stacked and the modification process of irradiating vacuum ultraviolet light from the coating-film side of the protective layer is performed. The polysilazane-containing layer can be formed by modifying it into a gas barrier layer.

(Application of gas barrier layer forming coating solution containing polysilazane)
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.

Here, “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 layer 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 μm, more preferably 10 nm to It is in the range of 10 μm, and most preferably in the range of 10 nm to 1 μm.

In addition, 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. For example, as described in JP-A-8-112879 Compounds are preferred.

(Polysilazane modification treatment: vacuum ultraviolet light irradiation treatment)
The polysilazane modification treatment refers to a treatment for converting a part or most of the polysilazane compound into silicon oxide or silicon oxynitride.

In this modification treatment, 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.

By this ultraviolet 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.

In the vacuum ultraviolet irradiation treatment, the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane layer coating is preferably in the range of 30 to 200 mW / cm ² , and in the range of 50 to 160 mW / cm ^2. Is more preferable. If it is 30 mW / cm ² or more, there is no concern that the reforming efficiency is lowered, and if it is 200 mW / cm ² or less, the coating film is not ablated and the substrate is not damaged, which is preferable.
In addition, since it is thought that there is a correlation between the irradiation amount of vacuum ultraviolet light and the refractive index of the gas barrier layer, the irradiation amount of vacuum ultraviolet light may be adjusted in accordance with the refractive index of the target gas barrier layer.

[Protective layer]
In the gas barrier film which concerns on this invention, you may provide a protective layer as needed. The protective layer is laminated on the gas barrier layer for the purpose of protecting the gas barrier layer formed on the smooth layer.

This protective layer can be formed by applying a protective layer-forming coating solution on the gas barrier layer and then drying. In addition, after applying and drying the coating liquid for forming the protective layer, the coating film formed 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. Examples of 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 | dissolving said compound material (resin) and various additives with the solvent and diluent etc. which were selected suitably, roll coat, gravure coat, knife coat, dip coat, 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).

(Lamination method of protective layer)
The protective layer is laminated on a gas barrier layer (polysilazane-containing layer) provided on the smooth layer.

As a method for forming the protective layer, when an inorganic compound reactive with moisture is used, 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. Here, since the humidity in the low humidity environment varies depending on the temperature, a preferable form is shown for the relationship between the temperature and the humidity by defining the dew point temperature. 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, and 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.

[Bleed-out prevention layer]
In the gas barrier film, as shown in FIG. 3, 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.

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.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
In the following examples, the thickness of the gas barrier layer is in the range of 240 to 260 nm, and the range of the gas barrier layer in which the refractive index is in the range of 1.73 to 1.78 is outside the normal range. The water vapor transmission rate was calculated using as an abnormal part.

[Creation of water vapor permeability estimation model]
(Production of substrate)
A polyethylene terephthalate (PET) substrate (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm that is easily bonded on both sides is used as the substrate F1, and the sheet-like substrate F1 has a temperature of 25 ° C. and a relative humidity of 55%. After storage and conditioning in the environment for 96 hours, 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.

(Formation of bleed-out prevention layer)
On one side of the substrate, 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 μm. 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.

(Formation of smooth 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: Thus, 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. Using these coating solutions, spin coating using Mikasa spin coater MS-A100 so that the layer thickness after drying is 2 μm, followed by drying at 80 ° C. for 3 minutes, followed by drying. And allowed to stand for 48 hours in an environment of 40 ° C.

(Formation of gas barrier layer)
Next, a 10% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, manufactured by AZ Electronic Materials Co., Ltd.) and amine catalyst N, N, N ′, N′-tetramethyl-1,6-diamino A (average) layer thickness after drying a liquid (first coating liquid) in which a 10% by mass dibutyl ether solution of hexane was mixed at a ratio of 99: 1 by spin coating using a Mikasa spin coater MS-A100. However, it was applied on the smooth layer F3 so as to have a thickness of 250 nm, and dried with dry air at a temperature of 50 ° C. and a dew point of −5 ° C. for 1 minute to obtain a coated sample. 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.

The surface of 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 system>
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% by volume 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 / Adjust to be cm ² .

(Measurement of layer thickness and refractive index)
While moving the gas barrier film on the XY stage, the thickness and refractive index of the gas barrier layer were measured every 1 mm ² . The measurement time per 1 mm ² was measured at about 1 second.
Equipment used: Film thickness measurement system F20 (manufactured by Filmetrics)
Software used: FILMeasure (Filmetrics)

(Evaluation of gas barrier properties by the calcium corrosion method)
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.
<Evaluation equipment>
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 (φ3-5mm, granular)
<Production of gas barrier evaluation cell>
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). Next, in a dry nitrogen gas atmosphere, 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. An evaluation cell was produced.

The 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.

(Preparation model of water vapor permeability from layer thickness and refractive index)
Multiple regression analysis was performed using the water vapor permeability obtained by the calcium corrosion method, the thickness of the gas barrier layer, and the refractive index as explanatory variables. Estimating the water vapor transmission rate with a normal gas barrier layer thickness of 250 nm, a refractive index of 1.78, and a water vapor transmission rate of 1.0 × 10 ⁻⁶ g / m ² · 24 h for calculating the amount of change The model was created as follows.
Water vapor permeability (g / m ² · 24h) = 1.0 × 10 ⁻⁶ −2.7 × 10 ⁻⁷ × Δd−1.7 × 10 ⁻⁴ × Δn + k
Δn is a difference in refractive index between the gas barrier layer of the normal part and the gas barrier layer of the gas barrier film to be measured. Δd is a difference in layer thickness between the gas barrier layer of the normal part and the gas barrier layer of the gas barrier film to be measured. The constant k is a correction term for the water vapor transmission rate obtained from an actual measurement value by a multiple regression analysis and a calcium corrosion method.

[Calculation of water vapor permeability by water vapor permeability estimation model]
(Production of gas barrier film)
The gas barrier film was produced in the same manner as the gas barrier film used for calculating the water vapor permeability estimation model by the calcium corrosion method.

(Measurement of layer thickness and refractive index)
As for the gas barrier film, the thickness and refractive index of the gas barrier layer were measured in the same manner as the gas barrier film used for calculating the water vapor permeability estimation model by the calcium corrosion method.

(Determination of gas barrier film)
It is determined whether or not the layer thickness and refractive index calculated by the spectroscopic reflectometer are outside the predetermined range, the portion of the gas barrier layer determined to be out of the predetermined range is determined as an abnormal portion, and within the predetermined range The portion of the gas barrier layer that was determined to be present was determined as the normal portion.
In this example, among the portions where the thickness and refractive index of the gas barrier layer were calculated, the portion determined to be a normal portion was designated as sample number 1, and the portion determined to be an abnormal portion was designated as sample numbers 2 to 4.

Based on the measured layer thickness and refractive index, using the difference between the gas barrier layer thickness of 250 nm and the refractive index of 1.78, the water vapor transmission rate was measured based on the estimated model for sample numbers 2 to 4. Calculated. The water vapor permeability (normal value of water vapor permeability) of the normal part (sample number 1) is 1.0 × 10 ⁻⁶ g / m ² · 24 h or less. The results are shown in Table 1.

(Comparison with water vapor permeability by calcium corrosion method)
The value of the water vapor permeability of the abnormal part (sample numbers 2 to 4) calculated by the estimation model is close to the actual measurement value obtained by the calcium corrosion method.
From the above, it has been found that the gas barrier performance can be evaluated over a wide range in a short time without contact and non-destructively using the method for evaluating the water vapor permeability of the gas barrier film of the present invention. By using the high-speed spectral reflectometer or ellipsometer, the water vapor permeability evaluation method of the present invention can be incorporated into the production process of the gas barrier film.

The water vapor permeability evaluation system for the gas barrier film of the present invention can calculate the water vapor permeability of the entire gas barrier film in a non-destructive and non-contact manner, and the water vapor permeability evaluation system is deteriorated by a gas such as water vapor. Therefore, it may be used in the field of inspecting the quality of gas barrier films used in electronic devices such as organic EL elements.

DESCRIPTION OF SYMBOLS 100 Water vapor permeability evaluation system 1 Data processor 11 Control part 12 Recording part 13 Communication part 14 Data processing part 14a Estimated model preparation part 14b Gas barrier layer determination part 14c Water vapor permeability calculation part 15 Operation display part 2 Spectral reflectometer adjustment Device 3 Spectral Reflectance Meter 31 Light Receiving Unit 32 Light Source 4 Film Observation Table 41 Film Fixing Table 42 Biaxial Motorized Stage 43 Device Frame F Gas Barrier Film F1 Substrate F2 Bleed-out Prevention Layer F3 Smooth Layer F4 Gas Barrier Layer

Claims (8)

1. A water vapor permeability evaluation method for evaluating the water vapor permeability of a gas barrier film based on the thickness and refractive index of the gas barrier layer of the gas barrier film,
   (1) a measuring step for optically measuring the thickness and refractive index of the gas barrier layer;
   (2) 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 layer thickness and refractive index measured by the measuring step;
   The water vapor permeability evaluation method characterized by including.
2. In the water vapor permeability calculation step, the water vapor permeability is estimated using a water vapor permeability estimation model created based on the water vapor permeability of the gas barrier film, the thickness of the gas barrier layer and the refractive index measured by the calcium corrosion method. The water vapor permeability evaluation method according to claim 1, wherein:
3. The estimation model of water vapor permeability includes a preset water vapor permeability term, a preset water vapor permeability change amount based on a change amount from a predetermined layer thickness and refractive index, and a correction term. The method for evaluating water vapor transmission rate according to claim 2.
4. The gas barrier layer to be measured is a gas barrier layer formed by applying a coating liquid containing polysilazane to a substrate and drying the layer to modify it by irradiating with vacuum ultraviolet light. The water vapor permeability evaluation method according to any one of claims 1 to 3, wherein the water vapor transmission rate is evaluated.
5. 5. The water vapor transmission rate evaluation method according to claim 1, wherein in the measurement step, the layer thickness and the refractive index are measured using a spectral reflectometer or an ellipsometer. .
6. A water vapor permeability evaluation system for evaluating the water vapor permeability of a gas barrier film based on the thickness and refractive index of the gas barrier layer of the gas barrier film,
   (1) measuring means for optically measuring the thickness and refractive index of the gas barrier layer;
   (2) Water vapor permeability calculating means for calculating the water vapor permeability of the entire gas barrier film in the measurement range based on the layer thickness and refractive index measured by the measuring means;
   A water vapor transmission rate evaluation system comprising:
7. The water vapor permeability evaluation system according to claim 6, which is used for evaluating the water vapor permeability of the gas barrier film in the step of producing the gas barrier film.
8. 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 claims 1 to 5. Manufacturing method.

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