JP6261682B2 - Manufacturing method of electronic device - Google Patents

Description

  The present invention relates to an electronic device.

  In various electronic devices, the element material is easily deteriorated by oxygen or water vapor. For this reason, electronic devices usually have a sealing structure that suppresses intrusion of oxygen and water vapor into the inside in order to suppress performance degradation due to element degradation.

  In recent years, as a material applicable to a sealing structure of an electronic device, a gas barrier film in which a barrier layer of an inorganic compound is formed on the surface of a plastic film or the like has been proposed. An electronic device using such a gas barrier film can be reduced in weight by replacing the substrate made of glass or an inorganic oxide with a gas barrier film to form a sealing structure. Further, it is expected that an electronic device having flexibility as a whole is formed by forming an element on a flexible film.

  For example, organic electroluminescence (hereinafter abbreviated as organic EL) has been proposed as an electronic device having flexibility. An organic EL element has a structure in which a light emitting layer is disposed between a pair of electrodes, is a self-luminous element, and has low power consumption. Therefore, the organic EL element is applied to a lighting device or a display device. By forming such an organic EL element on a gas barrier film and making it flexible, it is expected to realize a lighting device installed on a curved wall, a portable display that can be bent, and the like. Yes.

  On the other hand, in an organic EL element, when an electrode is exposed to oxygen or water vapor, a light emitting failure portion called a dark spot may occur due to oxidation or corrosion of the electrode. In addition, the light emitting layer may be deteriorated by contact with oxygen or water vapor, and the light emission characteristics may be deteriorated. Therefore, in order to avoid these inconveniences, an apparatus including an organic EL element has a sealing structure that suppresses the electrodes and the light emitting layer from coming into contact with oxygen or water vapor.

  As a sealing structure of a device including an organic EL element, an organic EL element is formed on a first substrate having a gas barrier property, and the organic EL element is covered with a second substrate having a gas barrier property. There is known a structure in which a composition called a sealing material (or a sealing material) is disposed so as to surround the substrate and the two substrates are bonded together. Therefore, there are two possible routes for oxygen and water vapor intrusion: (1) transmission through the substrate and (2) transmission through the sealing material.

  In the study of the conventional sealing structure, many studies have been made on improving the gas permeability and water vapor permeability of the gas barrier film. Therefore, when the gas barrier film is applied to the organic EL element, the sealing performance has been improved with respect to the intrusion route of (1) above, so that the above (2) rather than the intrusion route of (1) above. It is conceivable that the intrusion route has a greater influence on the performance of the entire device. However, in the past, studies on improving the performance of gas barrier films have preceded, and studies on improving the sealing performance of the entire organic EL element in which a sealing structure is formed using the gas barrier film have not always been sufficient.

Such circumstances include not only organic EL elements but also various electronic devices that form a sealing structure using a gas barrier film, specifically, liquid crystal display elements, electrophoretic display elements, photoelectric conversion elements, and battery elements. Common to devices that have.

As a sealing method or sealing structure, it is disclosed by patent document 1 or patent document 2, for example.
Patent Document 1 discloses a method of sealing an environment sensitive device with a gas barrier film having a barrier layer including an organic region and an inorganic region through an adhesive layer including a hygroscopic agent.
In Patent Document 2, a gas barrier sheet having a hygroscopic film formed on the surface so as to cover the upper surface and side surfaces of the object to be sealed is used, and the object to be sealed is formed on the moisture absorbing surface side of the gas barrier sheet. There is disclosed a sealing body that covers the upper surface and side surfaces of the upper surface, and further adheres to the substrate in a region where the hygroscopic film of the gas barrier sheet is not formed.

JP 2009-76436 A JP 2011-20335 A

However, since the method described in Patent Document 1 is provided at a position where the moisture absorption layer is in contact with the outside air, water vapor enters the moisture absorption layer from the side surface, and the capability of the moisture absorption layer is rapidly lost.
In the method described in Patent Document 2, the moisture absorption film of the gas barrier sheet is in direct contact with the cathode of the organic EL, which is a functional element, and there is a concern about the influence on the durability of the element.

  Further, in the conventional gas barrier film, there is a problem that the gas barrier property against oxygen and water vapor is lowered when the film is bent, and as a gas barrier film that requires flex resistance like a flexible liquid crystal display, When the film is bent, the gas barrier property is not always sufficient.

  The present invention has been made in view of such circumstances, and it is an object of the present invention to provide an electronic device that is less likely to deteriorate in performance and has high reliability.

  As a result of intensive studies to achieve the above object, the present inventors have achieved high sealing using a gas barrier film excellent in barrier properties and flexibility and a sealing portion excellent in sealing performance. By realizing the performance, it has been found that an electronic device with low performance degradation and high reliability can be obtained, and the present invention has been completed.

That is, the present invention includes a first substrate, a functional element provided on a surface of the first substrate, a second substrate facing the surface of the first substrate, and the first substrate. And a sealing portion that is disposed along a peripheral edge of the first substrate and the second substrate and bonds the first substrate and the second substrate between the first substrate and the second substrate. Wherein at least one of the first substrate and the second substrate includes a film and at least one barrier layer formed on at least one surface of the film. The gas barrier film has a water vapor permeability of 10 ⁻² g / (m ² · day) or less, and at least one of the barrier layers contains silicon atoms, oxygen atoms, and carbon atoms. And the thickness of the barrier layer The distance from the surface of the barrier layer in the direction and the ratio of the number of silicon atoms to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the barrier layer at the point located at the distance (ratio of the number of silicon atoms) In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve respectively showing the relationship between the ratio of the number of oxygen atoms (the ratio of the number of oxygen atoms) and the ratio of the number of carbon atoms (the ratio of the number of carbon atoms), the following conditions ( i) to (iii):
(I) The atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition represented by the following formula (1) in a region of 90% or more in the film thickness direction of the barrier layer. about,
(Oxygen atomic ratio)> (Si atomic ratio)> (Carbon atomic ratio) (1)
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve is 5 at% or more,
Satisfy all
The average value of the carbon atom number ratio determined from the carbon distribution curve is 11 at% or more and 21 at% or less,
The average density of the barrier layer is 1.8 g / cm ³ or more, and the sealing portion is composed of a moisture absorbing layer and an adhesive layer, and the moisture absorbing layer surrounds the functional element inside the adhesive layer. The gas barrier film is formed by forming a barrier layer on the film using a plasma chemical vapor deposition method, satisfying that the moisture absorption capacity of the moisture absorption layer is 10 mg / cc or more. A film forming step, the film forming step being opposed to the first film forming roll on which the film is wound and the first film forming roll, and downstream of the film transport path with respect to the first film forming roll. And a second film forming roll on which the film is wound, and the barrier layer is formed in an endless tunnel shape in a space where the first roll and the second roll are opposed to each other To form a magnetic field Further, it is formed by a plasma chemical vapor deposition method using discharge plasma formed along the tunnel-like magnetic field, and the flow rate (sccm) of the source gas is taken as the horizontal axis and the flow rate (sccm) of the oxygen gas is taken as the vertical axis. In the two-dimensional coordinates, the film is formed by controlling the flow rate of the source gas and the flow rate of the oxygen gas within the range surrounded by the line segments represented by the following formulas (1) to (4). An electronic device manufacturing method.
Formula (1) y = 250
Formula (2) y = 14.7x-235
Formula (3) y = 500
Formula (4) y = 6.25x-93.75

In the electronic device of the present invention, at least one of the barrier layers contains silicon, oxygen, and hydrogen, and the bonding state with oxygen atoms, which is obtained in ²⁹ Si solid state NMR measurement of the barrier layer, is Based on the abundance ratio of different silicon atoms, it is preferable that the ratio of the sum of the peak areas of Q ¹ , Q ² , and Q ^{3 to} the peak area of Q ⁴ satisfies the following conditional expression (I).
(A value obtained by summing peak areas of Q ¹ , Q ² , and Q ³ ) / (peak area of Q ⁴ ) <10 (I)
(Q ¹ represents a silicon atom bonded to one neutral oxygen atom and three hydroxyl groups, Q ² represents a silicon atom bonded to two neutral oxygen atoms and two hydroxyl groups, and Q ³ represents 3 (It shows a silicon atom bonded to one neutral oxygen atom and one hydroxyl group, and Q ⁴ represents a silicon atom bonded to four neutral oxygen atoms.)

  In the electronic device of the present invention, it is preferable that the barrier layer is formed on a surface of the gas barrier film facing the functional element.

  In the electronic device of the present invention, it is preferable that both the first substrate and the second substrate are the gas barrier film.

  In the electronic device of the present invention, it is preferable that the gas barrier film has the barrier layer formed on both surfaces of the film.

  In the electronic device of the present invention, it is preferable that the hygroscopic layer of the sealing portion includes a desiccant and a binder, and the desiccant includes an alkali metal oxide and / or an alkaline earth metal oxide.

  In the electronic device of the present invention, it is preferable that the adhesive layer of the sealing portion is made of a thermosetting resin or a photocurable resin.

  In the electronic device of the present invention, it is preferable that the film forming material includes at least one resin material selected from a polyester resin, a polyolefin resin, and a polyimide resin.

  According to the present invention, it is possible to provide an electronic device with little performance degradation and high reliability.

It is the schematic which shows 1st Embodiment of the electronic device of this invention, (a) is a perspective view, (b) is a sectional side view along the AA line of (a). It is a schematic diagram which shows the example of the gas barrier film used for this embodiment. It is a schematic diagram which shows an example of the gas barrier film manufacturing apparatus used for this embodiment. It is explanatory drawing of the method of calculating | requiring the film-forming conditions at the time of manufacture of the gas barrier film used for this embodiment. It is explanatory drawing of the method of calculating | requiring the film-forming conditions at the time of manufacture of the gas barrier film used for this embodiment. It is a sectional side view which shows 2nd Embodiment of the electronic device of this invention.

Embodiments of the electronic device of the present invention will be described.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

<First Embodiment>
1A and 1B are schematic views showing a first embodiment of the electronic device of the present invention, in which FIG. 1A is a perspective view and FIG. 1B is a side sectional view taken along line AA in FIG. In addition, in order to make the drawing easy to see, the dimensions and ratios of the respective constituent elements are appropriately changed.

  The electronic device 70 of this embodiment includes a first substrate 71, a functional element 72 provided on the surface 71a of the first substrate 71, a second substrate 63 facing the surface 71a, and a first substrate. The first substrate 71 and the second substrate 63 are disposed along the peripheral edges of the first substrate 71 and the second substrate 63 so as to surround the functional element 72 between the first substrate 71 and the second substrate 63. The sealing part 84 which bonds together is comprised roughly.

  That is, in the electronic device 70, the first substrate 71 and the second substrate 63 are stacked via the sealing portion 84 in the thickness direction, and the first substrate 71 and the second substrate 63 are sealed. The functional element 72 is stored in the space formed by the portion 84.

  At least one of the first substrate 71 and the second substrate 63 is a film and a gas barrier film formed on at least one surface of the film.

≪First board≫
In the present embodiment, the first substrate 71 is a gas barrier film. That is, the first substrate 71 includes the film 73 and the barrier layer 74. From the viewpoint of eliminating the influence of water vapor permeation from the film edge to the inside of the electronic device and protecting the functional element, the barrier layer is preferably formed on the side facing the functional element of the gas barrier film. In the form, the barrier layer 74 is formed on the surface 73 a of the film 73. From the viewpoint of further enhancing the protective function of the functional element, barrier layers may be formed on both sides of the film. That is, a barrier layer may also be formed on the surface 73 b of the film 73.

As the material of the barrier layer 74, metal oxides such as silicon oxide and aluminum oxide; metal nitrides such as silicon nitride and aluminum nitride; metal oxynitrides such as silicon oxynitride and the like can be used.
Among these barrier layer materials, it is preferable to use silicon oxide as a main component from the viewpoint of the balance between transparency and gas barrier properties of the obtained gas barrier film, and a general formula: SiOx (wherein X is 1 in the above general formula) It is more preferable to use silicon oxide represented by the general formula A: SiOx (in the general formula A, X represents a number of 1.5 to 2.0). It is particularly preferable to use silicon oxide represented by
In this specification, the term “used as a main component” means that the content of the component is 50% by weight or more (preferably 70% by weight or more) with respect to the mass of all the components of the material.
Further, these barrier layers containing silicon oxide as a main component may contain elements other than silicon and oxygen. An example of such an element is carbon. The barrier layer containing silicon, oxygen, and carbon has a general formula B: SiOxCy (in the general formula B, X represents a number from 0 to 2 and Y represents a number from 0 to 2). -It is preferable to use a carbon compound as a main component.
These barrier layers may contain hydrogen as an element other than silicon, oxygen, and carbon.

Hereinafter, details of the gas barrier film used as the first substrate 71 in this embodiment will be described.
[Gas barrier film]
The gas barrier film used for the electronic device 70 of the present embodiment includes a film and at least one barrier layer formed on at least one surface of the film, and has a water vapor permeability of 10 ⁻² g / m ^2. and at least one of the barrier layers contains a silicon atom, an oxygen atom, and a carbon atom, and is located at the distance from the surface of the barrier layer in the film thickness direction of the barrier layer and the distance. The ratio of the number of silicon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the barrier layer at the point (ratio of silicon atoms), the ratio of oxygen atoms (oxygen atom ratio), the number of carbon atoms In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve that show the relationship with the ratio (the atomic ratio of carbon), the following conditions (i) to (iii):
(I) the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy a condition represented by the following formula (1) in a region of 90% or more in the film thickness direction of the barrier layer;
(Oxygen atomic ratio)> (Si atomic ratio)> (Carbon atomic ratio) (1)
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve is 5 at% or more,
And the average value of the carbon atom number ratio determined from the carbon distribution curve is 3 at% or more and 30 at% or less, and the average density of the barrier layer is 1.8 g / cm ³ or more.

  Hereinafter, a description will be given with reference to FIG. In all the drawings below, the dimensions and ratios of the constituent elements are appropriately changed in order to make the drawings easy to see.

FIG. 2 is a schematic diagram of an example of a gas barrier film used in the present embodiment. The gas barrier film used in the present embodiment is formed by laminating a barrier layer H that ensures gas barrier properties on the surface of the film F. The film F corresponds to the film 73 in FIG. 1, and the barrier layer H corresponds to the barrier layer 74 in FIG.
The barrier layer H includes at least one of the barrier layers H containing silicon, oxygen, and hydrogen, and a first layer Ha containing a large amount of SiO ₂ generated by a complete oxidation reaction of a deposition gas described later, incomplete oxidation It includes a second layer Hb containing a large amount of SiO _x C _y produced by the reaction, and has a three-layer structure in which the first layer Ha and the second layer Hb are alternately stacked.

  However, FIG. 2 schematically shows that there is a distribution in the film composition. Actually, there is no clear interface between the first layer Ha and the second layer Hb. Is changing continuously. The barrier layer H may be formed by laminating a plurality of units with the above three-layer structure as one unit. The method for producing the gas barrier film shown in FIG. 2 will be described in detail later.

(the film)
The film F included in the gas barrier film used in this embodiment is flexible and uses a polymer material as a forming material.
The formation material of the film F is, for example, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN); a polyethylene (PE), polypropylene (PP), cyclic polyolefin, etc. Polyamide resin; Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyether sulfone resin; Polyimide resin. Among these resins, from the viewpoint of a balance between heat resistance and transparency, it is preferable to include one or more resin materials selected from polyester resins, polyolefin resins, and polyimide resins. Moreover, these resin can be used individually by 1 type or in combination of 2 or more types.
Further, when the light transmittance of the gas barrier film is not regarded as important, for example, a composite material in which a filler or an additive is added to the resin can be used as the film F.

  The thickness of the film F is appropriately set in consideration of stability and the like when producing a gas barrier film, but is preferably 5 μm to 500 μm because the film can be easily conveyed even in a vacuum. Furthermore, when the barrier layer H is formed using a plasma chemical vapor deposition method (plasma CVD method), since the discharge is performed through the film F, the thickness of the film F is more preferably 50 μm to 200 μm, It is especially preferable that it is 50 micrometers-100 micrometers.

  The film F may be subjected to a surface activation treatment for cleaning the surface in order to increase the adhesion with the barrier layer to be formed. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

(Barrier layer)
The barrier layer H included in the gas barrier film used in the present embodiment is a layer formed on at least one surface of the film F, and at least one layer contains silicon atoms, oxygen atoms, and carbon atoms. The barrier layer H may further contain nitrogen and aluminum. In addition, the barrier layer H is good also as forming on both surfaces of the film F from a viewpoint of further improving the protective function of a functional element.

(Barrier layer density)
The barrier layer H provided in the gas barrier film used in the present embodiment has an average density of 1.8 g / cm ³ or higher. In this specification, the “average density” of the barrier layer H is the number of silicon atoms, the number of carbon atoms, the number of oxygen atoms, and the hydrogen forward scattering method determined by Rutherford Backscattering Spectrometry (RBS). The weight of the barrier layer in the measurement range is calculated from the number of hydrogen atoms determined by Hydrogen Forward Scattering Spectrometry (HFS), and the volume of the barrier layer in the measurement range (product of the irradiation area of the ion beam and the film thickness) It is calculated by dividing by.

When the barrier layer H has a density of 1.8 g / cm ³ or more, the gas barrier film exhibits high gas barrier properties. When the barrier layer H is made of silicon, oxygen, carbon, and hydrogen, the average density of the barrier layer is less than 2.22 g / cm ³ .

(Distribution of silicon, carbon and oxygen in the barrier layer)
The barrier layer H has a distance from the surface of the barrier layer H in the film thickness direction of the barrier layer H and a ratio of the number of silicon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms at points located at the distance ( Silicon distribution curve, oxygen distribution curve, and carbon distribution curve showing the relationship among silicon atom ratio, oxygen atom ratio (oxygen atom ratio), and carbon atom ratio (carbon atom ratio), respectively. The above-mentioned conditions (i) to (iii) are all satisfied.

  Hereinafter, the distribution curve of each element will be described first, and then the conditions (i) to (iii) will be described.

  The silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen-carbon distribution curve, which will be described later, are used in combination with X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon. Thus, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample.

In the distribution curve obtained by XPS depth profile measurement, the vertical axis represents the atomic ratio of elements (unit: at%), and the horizontal axis represents the etching time. In such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and an etching rate (etching rate) is 0.05 nm / sec (in terms of SiO ₂ thermal oxide film). Value).

However, _SiO x _{C y} which is abundant in the second layer, to be etched faster than the SiO ₂ thermal oxide film, an etching rate of the SiO ₂ thermal oxide film 0.05 mm / sec is used as a measure of the etching conditions . That is, the product of the etching rate of 0.05 mm / sec and the etching time to the film F does not strictly represent the distance from the surface of the barrier layer H to the film F.

  Therefore, the film thickness of the barrier layer H is separately measured, and from the obtained film thickness and the etching time from the surface of the barrier layer H to the film F, the etching time “barrier layer in the film thickness direction of the barrier layer H” is determined. "Distance from the surface of H".

  Thereby, the vertical axis is the atomic ratio (unit: at%) of each element, and the horizontal axis is the distance (unit: nm) from the surface of the barrier layer H in the film thickness direction of the barrier layer H. A curve can be created.

  First, the film thickness of the barrier layer H is obtained by TEM observation of a section of the barrier layer slice produced by FIB (Focused Ion Beam) processing.

  Next, from the obtained film thickness and the etching time from the surface of the barrier layer H to the film F, the “distance from the surface of the barrier layer H in the film thickness direction of the barrier layer H” is made to correspond to the etching time.

In the XPS depth profile measurement, when the etching region moves from the barrier layer H made of SiO ₂ or SiO _x C _y to the film F made of a polymer material, the carbon atom ratio measured is Increases rapidly. Therefore, in the present invention, the time during which the slope is maximum corresponds to the boundary between the barrier layer H and the film F in the XPS depth profile measurement in the above-mentioned region where the number ratio of carbon atoms increases rapidly in the XPS depth profile. Etching time to be used.

  When the XPS depth profile measurement is performed discretely with respect to the etching time, the time at which the difference between the measured values of the carbon atom number ratio between the two adjacent measurement times is maximized is extracted. The midpoint is an etching time corresponding to the boundary between the barrier layer H and the film F.

  Further, when XPS depth profile measurement is continuously performed in the film thickness direction, the time derivative of the graph of the carbon atom number ratio with respect to the etching time in the above-mentioned region where the carbon atom number ratio increases rapidly. The point where the value is maximized is defined as the etching time corresponding to the boundary between the barrier layer H and the film F.

  In other words, the thickness of the barrier layer obtained by TEM observation of the section of the barrier layer section is made to correspond to the “etching time corresponding to the boundary between the barrier layer H and the film F” in the XPS depth profile. It is possible to create a distribution curve of each element, where is the atomic ratio of each element, and the horizontal axis is the distance from the surface of the barrier layer H in the film thickness direction of the barrier layer H.

The condition (i) with which the barrier layer H is provided is that the barrier layer H has the following formula in a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer. (1) is satisfied.
(Oxygen atomic ratio)> (Si atomic ratio)> (Carbon atomic ratio) (1)

  The barrier layer H preferably satisfies the above formula (1) in a region of 95% or more of the thickness of the barrier layer H, and particularly preferably in a region of 100% of the thickness of the barrier layer H.

  When the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon in the barrier layer H satisfy the condition (i), the resulting gas barrier film has sufficient gas barrier properties.

  The condition (ii) included in the barrier layer H is that the barrier layer H has a carbon distribution curve having at least one extreme value.

  In the barrier layer H, the carbon distribution curve preferably has at least two extreme values, and more preferably has at least three extreme values. When the carbon distribution curve does not have an extreme value, the gas barrier property is lowered and insufficient when the obtained gas barrier film is bent.

  Further, in the case of having at least three extreme values as described above, one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value from the surface of the barrier layer H in the film thickness direction of the barrier layer H. The absolute value of the difference in distance is preferably 200 nm or less, and more preferably 100 nm or less.

  In the present specification, the “extreme value” refers to the maximum value or the minimum value of the atomic ratio of the element to the distance from the surface of the barrier layer H in the film thickness direction of the barrier layer H in the distribution curve of each element. Say.

  In this specification, the “maximum value” is a point where the value of the atomic ratio of an element changes from increasing to decreasing when the distance from the surface of the barrier layer H is changed, and the element at that point The value of the atomic ratio of an element at a position where the distance from the surface of the barrier layer H in the film thickness direction of the barrier layer H from the point is further changed by 20 nm is reduced by 3 at% or more. I mean.

  Furthermore, in this embodiment, the “minimum value” is a point where the value of the atomic ratio of an element changes from a decrease to an increase when the distance from the surface of the barrier layer H is changed, and the element at that point The value of the atomic ratio of the element at a position where the distance from the surface in the thickness direction of the barrier layer H from the point to the surface of the barrier layer H is further changed by 20 nm is increased by 3 at% or more than the atomic ratio value. That means.

  The condition (iii) with which the barrier layer H is provided is that the barrier layer H has an absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve of 5 at% or more.

  In the barrier layer H, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is preferably 6 at% or more, and more preferably 7 at% or more. When the absolute value is less than 5 at%, the gas barrier property when the obtained gas barrier film is bent is insufficient.

(Carbon atom ratio in the barrier layer)
Moreover, the barrier layer H with which the gas barrier film used for this embodiment is provided has an average value of the carbon atom number ratio determined from the carbon distribution curve of 3 at% or more and 30 at% or less.

  Here, as the “average value of the carbon atom number ratio determined from the carbon distribution curve” in this specification, a value obtained by averaging the carbon atom number ratio included in the region between the following two points was adopted.

First, in the gas barrier film used in the present embodiment, the barrier layer H is, the first layer in a thickness direction including many SiO ₂ Ha, second layer Hb containing a large amount of _SiO x _{C y,} that the first layer Ha A layer structure is formed. Therefore, it is expected that the carbon distribution curve has the minimum value of the carbon atom number ratio corresponding to the first layer Ha in the vicinity of the film surface and in the vicinity of the film F.

  Therefore, when the carbon distribution curve has such a minimum value, the above average value is calculated from the local minimum value on the surface side (origin side) of the barrier layer in the carbon distribution curve, in the carbon distribution curve. The value obtained by averaging the atomic ratio of carbon included in the region up to the minimum value before moving to the region where the number ratio increases rapidly is adopted.

  Moreover, in the laminated film of the other structure used as the comparison object of the gas barrier film used in the present embodiment, either or both of the surface side and the film side may not have the above-described minimum value. . Therefore, when the carbon distribution curve does not have such a minimum value, a reference point for calculating an average value is obtained on the surface side and the film side of the barrier layer H as follows.

  On the surface side, when the distance from the surface of the barrier layer H is changed, in a region where the value of the carbon atom number ratio decreases, a certain point (first point) and the film thickness of the barrier layer H from the point. The second point is the reference point when the absolute value of the difference in the carbon atom number ratio from the point where the distance from the surface of the barrier layer H in the direction is further changed by 20 nm (second point) is 5 at% or less It was.

  On the film side, when the distance from the surface of the barrier layer H is changed in the vicinity of the region where the carbon atom number ratio increases rapidly, which is a region including the boundary between the barrier layer and the film. In the region where the value of the carbon atom number ratio is increasing, a point (first point) and a point from which the distance from the surface of the barrier layer H in the thickness direction of the barrier layer H is further changed by 20 nm ( The first point was used as the reference point when the absolute value of the difference in the carbon atom number ratio from the second point) was 5 at% or less.

  The “average” of the atomic ratio of carbon is obtained by arithmetically averaging each measured value when XPS depth profile measurement in creating the carbon distribution curve is performed discretely in the film thickness direction. Further, when the XPS depth profile measurement is continuously performed in the film thickness direction, the integral value of the carbon distribution curve in the region for which the average is obtained is obtained, and the length of the region is regarded as one side and corresponds to the integral value. It is obtained by calculating the other side of the rectangle having the area.

  When the average value of the atomic ratio of carbon in the barrier layer H is 3 at% or more and 30 at% or less, high gas barrier properties can be maintained even after the gas barrier film is bent. This average value is preferably 5 at% or more and 25 at% or less, and more preferably 11 at% or more and 21 at% or less.

  When the gas barrier film has transparency, if the difference between the refractive index of the gas barrier film and the refractive index of the barrier layer is large, reflection and scattering will occur at the interface between the film and the barrier layer. And transparency may be reduced. In this case, it is possible to improve the transparency of the gas barrier film by adjusting the carbon atom ratio of the barrier layer within the above numerical range and reducing the difference in refractive index between the film and the barrier layer.

  For example, when PEN is used as the film, the average value of the atomic ratio of carbon is 3 at% or more and 30 at% or less, and the gas barrier property is compared with the case where the average value of the carbon atomic ratio is larger than 30 at%. The light transmittance of the film is high and the film has good transparency.

  Furthermore, in the gas barrier film used in this embodiment, it is preferable that the average value of the atomic ratio of carbon and oxygen obtained from the carbon-oxygen distribution curve is 63.7 at% or more and 70.0 at% or less.

  In the present specification, the “average value of the carbon and oxygen atom ratio” is the closest to the surface side (origin side) of the barrier layer in the carbon distribution curve, similarly to the “average value of the carbon atom ratio” described above. A value obtained by arithmetically averaging the atomic ratio of carbon and oxygen contained in a region from a certain minimum value to a minimum value before moving to the film region in the carbon distribution curve was adopted.

  In the gas barrier film used in the present embodiment, the position where the atomic ratio of silicon is 29 at% or more and 38 at% or less in the silicon distribution curve is 90% or more in the film thickness direction of the barrier layer. Preferably. If the atomic ratio of silicon is within this range, the gas barrier property of the resulting gas barrier film tends to be improved. In the silicon distribution curve, it is more preferable that the position where the atomic ratio of silicon is 30 at% or more and 36 at% or less occupies a region of 90% or more in the film thickness direction of the barrier layer.

  At this time, the distance from the surface of the barrier layer in the thickness direction of the barrier layer and the ratio of the total number of oxygen atoms and carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms at the points located at the distance (oxygen) In the oxygen carbon distribution curve showing the relationship with the atomic ratio of carbon and carbon), the position where the atomic ratio of oxygen and carbon shows a value of 62 at% or more and 71 at% or less is 90% or more in the film thickness direction of the barrier layer. It is preferable to occupy this area.

  In the gas barrier film used in this embodiment, the carbon distribution curve has a plurality of extreme values, and the absolute value of the difference between the maximum extreme value and the minimum extreme value is 15% at or more. Preferably there is.

  In the gas barrier film used in the present embodiment, the oxygen distribution curve preferably has at least one extreme value, more preferably has at least two extreme values, and has at least three extreme values. Particularly preferred. When the oxygen distribution curve does not have an extreme value, the gas barrier property when the obtained gas barrier film is bent tends to be lowered.

  Further, in the case of having at least three extreme values as described above, one extreme value of the oxygen distribution curve and the extreme value adjacent to the extreme value from the surface of the barrier layer H in the film thickness direction of the barrier layer H. The absolute value of the difference in distance is preferably 200 nm or less, and more preferably 100 nm or less.

  Further, in the gas barrier film used in the present embodiment, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the barrier layer H is preferably 5 at% or more, and 6 at%. More preferably, it is more preferably 7 at% or more. If the absolute value is less than the lower limit, the gas barrier property tends to decrease when the resulting gas barrier film is bent.

  In the gas barrier film used in the present embodiment, the absolute value of the difference between the maximum value and the minimum value is preferably less than 5 at% with respect to the silicon atomic ratio in the silicon distribution curve of the barrier layer H, and less than 4 at%. More preferably, it is more preferably less than 3 at%. When the absolute value exceeds the upper limit, the gas barrier property of the obtained gas barrier film tends to be lowered.

  In the gas barrier film used in the present embodiment, the absolute value of the difference between the maximum value and the minimum value is preferably less than 5 at% with respect to the atomic ratio of oxygen and carbon in the oxygen-carbon distribution curve. More preferably, it is more preferably less than 3 at%. When the absolute value exceeds the upper limit, the gas barrier property of the obtained gas barrier film tends to be lowered.

  Further, in the gas barrier film used in the present embodiment, the barrier layer H is formed in the film surface direction (the surface of the barrier layer H) from the viewpoint of forming the barrier layer H having a uniform and excellent gas barrier property over the entire film surface. In a direction parallel to the surface). In this specification, that the barrier layer H is substantially uniform in the film surface direction means that an oxygen distribution curve, a carbon distribution curve, and an arbitrary two measurement points on the film surface of the barrier layer H by XPS depth profile measurement, and When the oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the maximum value of the carbon atomic ratio in each carbon distribution curve and The absolute value of the difference between the minimum values is the same as each other or within 5 at%.

Furthermore, in the gas barrier film used in this embodiment, the carbon distribution curve is preferably substantially continuous. In this specification, that the carbon distribution curve is substantially continuous means that it does not include a portion in which the carbon atomic ratio in the carbon distribution curve changes discontinuously. Specifically, the film of the barrier layer H In the relationship between the distance from the surface of the layer in the thickness direction (x, unit: nm) and the atomic ratio of carbon (C, unit: at%), the following formula (F1):
| DC / dx | ≦ 0.5 (F1)
This means that the condition represented by

( ²⁹ Si-solid NMR peak area)
The barrier layer H of the gas barrier film comprises used in the present embodiment, at least one layer of silicon, oxygen, and includes a hydrogen, obtained in ^{29 Si-} solid NMR measurement of the barrier layer H, the Q ⁴ It is preferable that the ratio of the sum of the peak areas of Q ¹ , Q ² , and Q ^{3 to} the peak area satisfies the following conditional expression (I).
(A value obtained by summing peak areas of Q ¹ , Q ² , and Q ³ ) / (peak area of Q ⁴ ) <10 (I)

Here, Q ¹ , Q ² , Q ³ , and Q ⁴ indicate the silicon atoms constituting the barrier layer H by distinguishing them according to the nature of oxygen bonded to the silicon atoms. That is, each symbol of Q ¹ , Q ² , Q ³ , and Q ⁴ is bonded to a silicon atom when an oxygen atom that forms a Si—O—Si bond is a “neutral” oxygen atom with respect to a hydroxyl group. Indicates that the oxygen atom is as follows.
Q ¹ : silicon atom bonded to one neutral oxygen atom and three hydroxyl groups Q ² : silicon atom bonded to two neutral oxygen atoms and two hydroxyl groups Q ³ : three neutral oxygen atoms and 1 Silicon atom bonded to two hydroxyl groups Q ⁴ : Silicon atom bonded to four neutral oxygen atoms

Here, when measuring “ ²⁹ Si-solid NMR of the barrier layer H”, the film F may be included in the test piece used for the measurement.

  The peak area of solid-state NMR can be calculated as follows, for example.

First, the spectrum obtained by ²⁹ Si-solid NMR measurement is subjected to a smoothing treatment. Specifically, the spectrum obtained by ²⁹ Si-solid NMR measurement is Fourier-transformed, and after removing a high frequency of 100 Hz or more, smoothing processing is performed by inverse Fourier transform (low-pass filter processing). ^The spectrum obtained by the ²⁹ Si-solid NMR measurement contains noise having a frequency higher than that of the peak signal, and these noises are removed by smoothing by the low-pass filter process.
In the following description, the spectrum after smoothing is referred to as “measured spectrum”.

Next, the measured spectrum ^is separated into peaks of ^{Q 1, Q 2, Q 3} , Q 4. That is, it is assumed that the peaks of Q ¹ , Q ² , Q ³ , and Q ⁴ each show a Gaussian (normal distribution) curve centered on a specific chemical shift, and Q ¹ , Q ² , Q ³ , Q Parameters such as the height and half-value width of each peak are optimized so that the model spectrum obtained by summing ⁴ matches the one after the smoothing of the measured spectrum.

  Parameter optimization is performed by using an iterative method. That is, an iterative method is used to calculate a parameter such that the sum of the squares of the deviation between the model spectrum and the measured spectrum converges to a minimum value.

Next, each peak area is calculated by integrating the peaks of Q ¹ , Q ² , Q ³ , and Q ⁴ thus obtained. Using the peak area thus obtained, the left side of the above formula (I) (the sum of the peak areas of Q ¹ , Q ² , and Q ³ ) / (peak area of Q ⁴ ) is obtained to evaluate the gas barrier properties. Used as an indicator.

Gas barrier film used in the present embodiment, about 9% of the silicon atoms constituting the barrier layer H was quantified by solid-state NMR measurements (1 / (10 + 1)) be greater than the proportion is a silicon atom of Q ⁴ preferable.

The silicon atom of Q ⁴ is surrounded by four neutral oxygen atoms around the silicon atom, and the four neutral oxygen atoms are bonded to the silicon atom to form a network structure. On the other hand, since the silicon atoms of Q ¹ , Q ² , and Q ³ are bonded to one or more hydroxyl groups, there are fine voids in which no covalent bond is formed between adjacent silicon atoms. . Therefore, as the number of silicon atoms of Q ⁴ increases, the barrier layer H becomes a dense layer, and a gas barrier film that realizes high gas barrier properties can be obtained.

In the gas barrier film used in this embodiment, as shown in the above formula (I), (the sum of the peak areas of Q ¹ , Q ² , Q ³ ) / (peak area of Q ⁴ ) is less than 10. If it exists, it is preferable because it shows a high gas barrier property.

The value of (the sum of the peak areas of Q ¹ , Q ² , Q ³ ) / (peak area of Q ⁴ ) is preferably 8 or less, and more preferably 6 or less.

In addition, when the material containing a silicone resin or glass is used as the film F, in order to avoid the influence of silicon in the film in the solid NMR measurement, the barrier layer H is separated from the film F, and the barrier layer H It is preferable to measure solid-state NMR of silicon alone.
As a method of separating the barrier layer H and the film F, for example, a method of scraping off the barrier layer H with a metal spatula or the like and collecting it in a sample tube in solid NMR measurement can be mentioned. Alternatively, the film F may be removed using a solvent that dissolves only the film, and the barrier layer H remaining as a residue may be collected.

  In the gas barrier film used in the present embodiment, the thickness of the barrier layer H is preferably in the range of 5 nm to 3000 nm, more preferably in the range of 10 nm to 2000 nm, and in the range of 100 nm to 1000 nm. It is particularly preferred. When the thickness of the barrier layer H is 5 nm or more, gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are further improved. Moreover, the still higher effect which suppresses the fall of the gas-barrier property at the time of making it bend because it is 3000 nm or less is acquired.

In addition, the gas barrier film used in this embodiment contains (a) silicon atoms, oxygen atoms, and carbon atoms, (b) an average density of 1.8 g / cm ³ or more, and (c) the above condition ( Although all of i) to (iii) are satisfied, and (d) the average value of the atomic ratio of carbon obtained from the carbon distribution curve includes at least one barrier layer H of 3 at% or more and 30 at% or less, the condition (a ) To (d) may be provided with two or more barrier layers. Furthermore, when two or more such barrier layers H are provided, the materials of the plurality of barrier layers H may be the same or different. When two or more such barrier layers H are provided, such a barrier layer H may be formed on one surface of the film F, or may be formed on both surfaces of the film F. May be.

  In addition, when the gas barrier film used in the present embodiment has a layer in which two or more barrier layers H are laminated, the total thickness of the barrier layers H (the film of the barrier film in which the barrier layers H are laminated) (Thickness) is preferably larger than 100 nm and not larger than 3000 nm. When the total thickness of the barrier layer H is 100 nm or more, gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are further improved. In addition, when the total thickness of the barrier layer H is 3000 nm or less, a higher effect of suppressing a decrease in gas barrier properties when bent is obtained.

(Other configurations)
The gas barrier film used in the present embodiment includes the film F and the barrier layer H, but may further include a primer coat layer, a heat sealable resin layer, an adhesive layer, and the like as necessary. . Such a primer coat layer can be formed using a known primer coat agent capable of improving the adhesion to the gas barrier film. Moreover, such a heat-sealable resin layer can be suitably formed using a well-known heat-sealable resin. Further, such an adhesive layer can be appropriately formed using a known adhesive, and a plurality of gas barrier films may be adhered to each other by such an adhesive layer.
Gas barrier film used in the present embodiment has a configuration as described above, the water vapor permeability, under conditions of 40 ° C. RH ^90%, or less ^{10 -2 g / m 2 · day} , 10 - ³ g / m ² · day or less is preferable, and 10 ⁻⁴ g / m ² · day or less is more preferable.

(Method for producing gas barrier film)
Subsequently, the manufacturing method of the gas barrier film which has a barrier layer which satisfy | fills all the above-mentioned conditions (a)-(d) is demonstrated.

  FIG. 3 is a diagram showing an example of an apparatus for producing a gas barrier film used in the present embodiment, and is a schematic view of an apparatus for forming a barrier layer by a plasma chemical vapor deposition method. In FIG. 3, the dimensions and ratios of the constituent elements are appropriately changed in order to make the drawing easier to see.

  3 includes a feed roll 11, a take-up roll 12, transport rolls 13 to 16, a first film forming roll 17, a second film forming roll 18, a gas supply pipe 19, a plasma generating power source 20, and electrodes. 21, an electrode 22, a magnetic field forming device 23 installed inside the first film forming roll 17, and a magnetic field forming device 24 installed inside the second film forming roll 18.

  Among the constituent elements of the manufacturing apparatus 10, at least the first film forming roll 17, the second film forming roll 18, the gas supply pipe 19, the magnetic field forming apparatus 23, and the magnetic field forming apparatus 24 are illustrated when the gas barrier film is manufactured. Arranged in an approximate vacuum chamber. This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.

  When this apparatus is used, the discharge of the film forming gas supplied from the gas supply pipe 19 to the space between the first film forming roll 17 and the second film forming roll 18 is controlled by controlling the plasma generating power source 20. Plasma can be generated, and plasma CVD film formation can be performed by a continuous film formation process using the generated discharge plasma.

  The delivery roll 11 is installed in a state where the film F before film formation is wound up, and the film F is delivered while being unwound in the longitudinal direction. Moreover, the winding roll 12 is provided in the edge part side of the film F, winds up the film F after film-forming, pulling up, and accommodates in roll shape.

  The first film-forming roll 17 and the second film-forming roll 18 extend in parallel and face each other. Both rolls are formed of a conductive material and convey the film F while rotating. It is preferable to use the 1st film-forming roll 17 and the 2nd film-forming roll 18 with the same diameter, for example, it is preferable to use the thing of 5 cm or more and 100 cm or less.

  The first film-forming roll 17 and the second film-forming roll 18 are insulated from each other and connected to a common plasma generation power source 20. When applied from the plasma generating power source 20, an electric field is formed in the space SP between the first film forming roll 17 and the second film forming roll 18. The plasma generating power source 20 is preferably one that can apply applied power to 100 W to 10 kW and that can set the AC frequency to 50 Hz to 500 kHz.

  The magnetic field forming device 23 and the magnetic field forming device 24 are members that form a magnetic field in the space SP, and are stored in the first film forming roll 17 and the second film forming roll 18. The magnetic field forming device 23 and the magnetic field forming device 24 are fixed so as not to rotate together with the first film forming roll 17 and the second film forming roll 18 (that is, the relative posture with respect to the vacuum chamber does not change). .

  The magnetic field forming device 23 and the magnetic field forming device 24 are arranged around the center magnets 23a and 24a extending in the same direction as the extending directions of the first film forming roll 17 and the second film forming roll 18 and the center magnets 23a and 24a. It has annular outer magnets 23b and 24b arranged extending in the same direction as the extending direction of the first film forming roll 17 and the second film forming roll 18 while being enclosed. In the magnetic field forming device 23, magnetic lines (magnetic field) connecting the central magnet 23a and the external magnet 23b form an endless tunnel. Similarly, in the magnetic field forming device 24, the magnetic field lines connecting the central magnet 24a and the external magnet 24b form an endless tunnel.

  A discharge plasma of the film forming gas is generated by the magnetron discharge in which the magnetic field lines intersect with the electric field formed between the first film forming roll 17 and the second film forming roll 18. That is, as will be described in detail later, the space SP is used as a film formation space for performing plasma CVD film formation, and is a surface that does not contact the first film formation roll 17 and the second film formation roll 18 (film formation surface). ) Forms a barrier layer in which the deposition gas is deposited via the plasma state.

  In the vicinity of the space SP, a gas supply pipe 19 that supplies a film forming gas G such as a plasma CVD source gas to the space SP is provided. The gas supply pipe 19 has a tubular shape extending in the same direction as the extending direction of the first film forming roll 17 and the second film forming roll 18, and the space SP is opened from openings provided at a plurality of locations. A film forming gas G is supplied to the substrate. In FIG. 3, the state in which the film forming gas G is supplied from the gas supply pipe 19 toward the space SP is indicated by arrows.

  The source gas can be appropriately selected and used according to the material of the barrier film to be formed. As the source gas, for example, an organosilicon compound containing silicon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Silane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, dimethyldisilazane, trimethyldisilazane, Examples include tetramethyldisilazane, pentamethyldisilazane, and hexamethyldisilazane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling of the compound and gas barrier properties of the resulting barrier film. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types. Further, as the source gas, monosilane may be contained in addition to the above-described organosilicon compound, and the resultant gas may be used as a silicon source for the barrier film to be formed.

  As the film forming gas, a reactive gas may be used in addition to the source gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for

  The film forming gas may contain a carrier gas as necessary in order to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate discharge plasma. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon, etc .; hydrogen can be used.

  The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas and the like, but the pressure in the space SP is preferably 0.1 Pa to 50 Pa. When plasma CVD is a low pressure plasma CVD method for the purpose of suppressing gas phase reaction, it is usually 0.1 Pa to 10 Pa. The power of the electrode drum of the plasma generator can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, and the like, but is preferably 0.1 kW to 10 kW.

  Although the conveyance speed (line speed) of the film F can be suitably adjusted according to the kind of source gas, the pressure in a vacuum chamber, etc., it is preferable that it is 0.1m / min-100m / min. More preferably, it is 5m / min-20m / min. If the line speed is less than the lower limit, wrinkles due to heat tend to be easily generated in the film F. On the other hand, if the line speed exceeds the upper limit, the thickness of the formed film F tends to be thin.

  In the manufacturing apparatus 10 as described above, film formation is performed on the film F as follows.

First, prior to film formation, a pretreatment may be performed so that outgas generated from the film F is sufficiently reduced. The amount of outgas generated from the film F can be determined using the pressure when the film F is attached to the production apparatus and the inside of the apparatus (inside the chamber) is decompressed. For example, if the pressure in the chamber of the manufacturing apparatus is 1 × 10 ⁻³ Pa or less, it can be determined that the amount of outgas generated from the film F is sufficiently reduced.

  Examples of the method for reducing the amount of outgas generated from the film F include vacuum drying, heat drying, drying by a combination thereof, and drying by natural drying. Regardless of the drying method, in order to accelerate the drying of the film F wound up in a roll shape, the roll F is repeatedly wound (unwinding and winding) during drying, and the entire film F is dried. Exposure to the environment is preferred.

  The vacuum drying is performed by placing the film F in a pressure-resistant vacuum container and evacuating the vacuum container using a decompressor such as a vacuum pump. The pressure in the vacuum vessel during vacuum drying is preferably 1000 Pa or less, more preferably 100 Pa or less, and even more preferably 10 Pa or less. The exhaust in the vacuum vessel may be continuously performed by continuously operating the decompressor, and intermittently by operating the decompressor intermittently while managing the internal pressure so that it does not exceed a certain level. It is good also to do. The drying time is preferably at least 8 hours or more, more preferably 1 week or more, and further preferably 1 month or more.

  Heat drying is performed by exposing the film F to an environment of 50 ° C. or higher. The heating temperature is preferably 50 ° C. or higher and 200 ° C. or lower, and more preferably 70 ° C. or higher and 150 ° C. or lower. If the temperature exceeds 200 ° C., the film F may be deformed. Moreover, when an oligomer component elutes from the film F and precipitates on the surface, defects may occur. The drying time can be appropriately selected depending on the heating temperature and the heating means used.

  The heating means is not particularly limited as long as the film F can be heated to 50 ° C. or higher and 200 ° C. or lower under normal pressure. Among the generally known apparatuses, an infrared heating apparatus, a microwave heating apparatus, and a heating drum are preferably used.

  Here, the infrared heating device is a device that heats an object by emitting infrared rays from an infrared ray generating means.

  A microwave heating device is a device that heats an object by irradiating microwaves from microwave generation means.

  A heating drum is a device that heats a drum surface by heat conduction by heating the drum surface and bringing an object into contact with the drum surface.

  Natural drying is performed by placing the film F in a low-humidity atmosphere and maintaining a low-humidity atmosphere by passing a dry gas (dry air, dry nitrogen). When performing natural drying, it is preferable to place a desiccant such as silica gel together in a low humidity environment where the film F is placed. The drying time is preferably at least 8 hours or more, more preferably 1 week or more, and further preferably 1 month or more.

These dryings may be performed separately before the film F is mounted on the manufacturing apparatus, or may be performed in the manufacturing apparatus after the film F is mounted on the manufacturing apparatus.
As a method for drying the film F after it is mounted on the production apparatus, the inside of the chamber can be decompressed while the film F is fed out and conveyed from the feeding roll. Moreover, the roll to pass shall be provided with a heater, and it is good also as heating this roll as the above-mentioned heating drum by heating a roll.

  Another method for reducing outgas from the film F is to form an inorganic film on the surface of the film F in advance. Examples of the film formation method for the inorganic film include physical film formation methods such as vacuum vapor deposition (heat vapor deposition), electron beam (EB) vapor deposition, sputtering, and ion plating. Alternatively, the inorganic film may be formed by a chemical deposition method such as thermal CVD, plasma CVD, or atmospheric pressure CVD. Furthermore, the influence of outgas may be further reduced by subjecting the film F having an inorganic film formed on the surface to a drying treatment by the above-described drying method.

  Next, a vacuum chamber (not shown) is set in a reduced pressure environment and applied to the first film forming roll 17 and the second film forming roll 18 to generate an electric field in the space SP.

  At this time, since the magnetic field forming device 23 and the magnetic field forming device 24 form the above-described endless tunnel-like magnetic field, by introducing the film forming gas, the magnetic field and the electrons emitted into the space SP are used. Then, a discharge plasma of a doughnut-shaped film forming gas is formed along the tunnel. Since this discharge plasma can be generated at a low pressure in the vicinity of several Pa, the temperature in the vacuum chamber can be in the vicinity of room temperature.

  On the other hand, since the temperature of electrons captured at high density in the magnetic field formed by the magnetic field forming device 23 and the magnetic field forming device 24 is high, discharge plasma is generated due to collision between the electrons and the deposition gas. That is, electrons are confined in the space SP by a magnetic field and an electric field formed in the space SP, so that high-density discharge plasma is formed in the space SP. More specifically, a high-density (high-intensity) discharge plasma is formed in a space overlapping with an endless tunnel-like magnetic field, and a low-density (low An intense (discharged) plasma is formed. The intensity of these discharge plasmas changes continuously.

  When the discharge plasma is generated, a large amount of radicals and ions are generated and the plasma reaction proceeds, and a reaction between the source gas contained in the film forming gas and the reactive gas occurs. For example, an organic silicon compound that is a raw material gas reacts with oxygen that is a reactive gas, and an oxidation reaction of the organic silicon compound occurs. Here, in a space where high-intensity discharge plasma is formed, a large amount of energy is given to the oxidation reaction, so that the reaction is likely to proceed, and a complete oxidation reaction of the organosilicon compound can be caused mainly. On the other hand, in a space where low-intensity discharge plasma is formed, since the energy given to the oxidation reaction is small, the reaction does not proceed easily, and an incomplete oxidation reaction of the organosilicon compound can be caused mainly.

In this specification, “complete oxidation reaction of an organosilicon compound” means that a reaction between an organosilicon compound and oxygen proceeds, and the organosilicon compound is oxidized and decomposed into silicon dioxide (SiO ₂ ), water, and carbon dioxide. Refers to that.

For example, when the film forming gas contains hexamethyldisiloxane (HMDSO: (CH ₃ ) ₆ Si ₂ O) as a raw material gas and oxygen (O ₂ ) as a reactive gas, a “complete oxidation reaction” Then, the reaction as described in the following reaction formula (1) occurs, and silicon dioxide is produced.

Further, in the present specification, the "incomplete oxidation reactions of organic silicon compounds", organosilicon compounds without the complete oxidation reaction, SiO x C _{y (0} containing carbon in the SiO ₂ without structure _{<x <2} , 0 <y <2).

As described above, in the manufacturing apparatus 10, the discharge plasma is formed in a donut shape on the surfaces of the first film forming roll 17 and the second film forming roll 18. The film F transported on the surface alternately passes through the space where the high-intensity discharge plasma is formed and the space where the low-intensity discharge plasma is formed. For this reason, the surface of the film F passing through the surfaces of the first film-forming roll 17 and the second film-forming roll 18 has a layer containing a large amount of SiO ₂ (first layer Ha in FIG. 2) generated by the complete oxidation reaction. A layer (a second layer Hb in FIG. 2) containing a large amount of SiO _x C _y generated by the complete oxidation reaction is sandwiched and formed.

  In addition to these, high-temperature secondary electrons are prevented from flowing into the film F due to the action of the magnetic field, so that high power can be input while the temperature of the film F is kept low, and high-speed film formation is achieved. . Film deposition mainly occurs only on the film-forming surface of the film F, and the film-forming roll is covered with the film F and is not easily soiled.

Next, a method for controlling the average value of the atomic ratio of carbon in the barrier layer will be described.
In order to set the average value of the atomic ratio of carbon contained in the barrier layer to, for example, 11 at% or more and 21 at% or less for the barrier layer formed using the above-described apparatus, for example, the following is determined. A film is formed using a film forming gas in which a source gas and a reaction gas are mixed within a range.

  FIG. 4 is a graph showing the average value of the ratio of the number of carbon atoms contained in the barrier layer with respect to the amount of source gas. In the graph of the figure, the horizontal axis shows the amount of raw material gas (sccm: Standard Cubic Centimeter per Minute), the vertical axis shows the average value of atomic ratio of carbon (unit: at%), and HMDSO is used as the raw material gas. The relationship when oxygen is used as the reaction gas is shown.

  FIG. 4A shows a graph (indicated by reference numeral O1) showing the relationship of the average value of the atomic ratio of carbon to the amount of HMDSO when the amount of oxygen is fixed at 250 sccm, and the amount of oxygen at 500 sccm. The graph (it shows with the code | symbol O2) which shows the relationship of the average value of the atomic ratio of carbon with respect to the quantity of HMDSO at the time of fixing is shown. The graph of FIG. 4B is obtained by measuring and plotting the average value of the atomic ratio of carbon for three points where the amount of HMDSO is changed for each oxygen amount, and then performing a linear regression on each point with a spline curve. It is.

The film forming conditions other than the amounts of oxygen and HMDSO are as follows.
(Deposition conditions)
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min

  The following can be said qualitatively from the graph of FIG.

  First, when the flow rate of oxygen is constant, when the flow rate of HMDSO is increased, the average value of the atomic ratio of carbon in the barrier layer is increased. This can be explained as the amount of carbon contained in the barrier layer increases as a result of the reaction conditions under which HMDSO undergoes incomplete oxidation because the amount of HMDSO increases relative to the amount of oxygen.

  Further, when the flow rate of HMDSO is constant, when the flow rate of oxygen is increased, the average value of the atomic ratio of carbon in the barrier layer is decreased. This is because the amount of HMDSO decreases relative to the amount of oxygen, and as a result, the amount of carbon contained in the barrier layer decreases as a result of approaching the reaction conditions under which HMDSO undergoes complete oxidation.

  Even if the ratio between HMDSO and oxygen is the same, the average value of the ratio of the number of carbon atoms in the barrier layer increases when the total amount of the deposition gas is large. This is because, when the flow rate of the entire film forming gas is large, the energy that HMDSO obtains from the discharge plasma is relatively reduced. As a result, HMDSO becomes a reaction condition that causes incomplete oxidation, resulting in the amount of carbon contained in the barrier layer. Can be explained as increasing.

  FIG. 4B is a partially enlarged view of the graph shown in FIG. 4A, in which the vertical axis is 11 at% or more and 21 at% or less. From the coordinates of the contact point X1 between the graph O1 and the lower horizontal axis in FIG. 4B, the flow rate of HMDSO when the average value of the carbon atom number ratio is 11 at% under the condition of the oxygen flow rate of 250 sccm, It turns out that it is about 33 sccm. Further, from the contact X2 between the graph O1 and the upper horizontal axis, the flow rate of HMDSO is about 55 sccm when the average value of the atomic ratio of carbon is 21 at% under the condition of an oxygen flow rate of 250 sccm. I understand. That is, under the condition of an oxygen flow rate of 250 sccm, it can be seen that if the HMDSO flow rate is about 33 sccm to about 55 sccm, the average value of the carbon atom number ratio can be 11 at% or more and 21 at% or less.

  Similarly, from the coordinates of the contacts X3 and X4 between the graph O2 and the upper and lower horizontal axes, the condition of HMDSO for setting the average value of the atomic ratio of carbon to 11 at% or more and 21 at% or less under the condition of an oxygen flow rate of 500 sccm. It can be seen that the upper limit value and the lower limit value of the flow rate can be read and are about 51 sccm and about 95 sccm, respectively.

  FIG. 5 is a graph obtained by converting the HMDSO flow rate and the oxygen flow rate obtained from the points X1 to X4 in FIG. 4 into a graph in which the horizontal axis represents the HMDSO flow rate and the vertical axis represents the oxygen flow rate. It is. In FIG. 5, the area AR surrounded by the line segments when the line segments are connected in the order of symbols X1, X2, X4, X3, and X1 has an average value of the carbon atom number ratio of 11 at% or more and 21 at% or less. The flow rate of HMDSO and the flow rate of oxygen are shown. That is, when plotted in FIG. 5, the average value of the carbon atom ratio of the barrier layer obtained is 11 at% by controlling the flow rate of HMDSO and oxygen so as to be contained in the region AR. It can be made 21 at% or less.

  In the above description, the oxygen flow rate is 250 sccm and 500 sccm. However, the relationship between the flow rate of HMDSO and the flow rate of oxygen when the oxygen flow rate is lower than 250 sccm or higher than 500 sccm is the same operation. It can be determined by doing.

  In this way, it is possible to determine the reaction conditions by controlling the amounts of HMDSO and oxygen, and to form a barrier layer having an average value of the carbon atom number ratio of 11 at% or more and 21 at% or less.

  In the above description, plotting and graphing is performed for three points where the amount of HMDSO is changed with respect to each oxygen flow rate, but even if the level where the amount of HMDSO is changed with respect to the oxygen flow rate is two points, When the average value of the carbon number ratio of the two points is less than 11 at% and greater than 21 at%, a graph corresponding to FIG. 4 may be created from the results of the two points. Of course, a graph corresponding to FIG. 4 may be created from the results of four or more points.

  In addition, for example, when the amount of film forming gas is fixed and the applied voltage applied to the first film forming roll 17 and the second film forming roll 18 is changed, the ratio of the number of carbon atoms to the change in the voltage is changed. It is good also as calculating | requiring the relationship of an average value and calculating | requiring the applied voltage used as the average value of the atomic ratio of desired carbon similarly to the above-mentioned description.

  The gas barrier film used in the present embodiment can be manufactured by defining the film forming conditions in this manner and forming a barrier layer on the surface of the film by plasma CVD using discharge plasma.

Moreover, in the gas barrier film used for this embodiment, the average density of the barrier layer formed is 1.8 g / cm ³ or more.

In the barrier layer, a layer containing a large amount of _SiO x _{C y} caused by incomplete oxidation reactions, SiO ₂ (Density: 2.22g / cm ³⁾ from the network of the oxygen atom has been substituted with structure carbon atoms It is thought that. In a layer containing a large amount of SiO _x C _y , when the structure has a structure in which oxygen atoms of SiO ₂ are substituted with many carbon atoms (that is, when the average value of the carbon atom number ratio of the barrier layer increases), Si—O The average density of the barrier layer decreases because the molecular volume increases due to the difference between the bond length of the sp3 bond (about 1.63 Å) and the bond length of the sp3 bond of Si-C (about 1.86 Å). However, when the average value of the carbon atom number ratio of the barrier layer is 3 at% or more and 30 at% or less, the average density of the barrier layer is 1.8 g / cm ³ or more.

  According to the gas barrier film satisfying the conditions (a) to (d) as described above, a film capable of maintaining a high gas barrier property even when bent.

≪Second board≫
In the present embodiment, as the second substrate 63, the above-described polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin; Polyamide resin; Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyether sulfone resin; Polyimide resin, etc .; Glass; Aluminum, Copper, etc. Or the like.

  The thickness of the second substrate 63 is not particularly limited, and is preferably 10 μm to 700 μm, and more preferably 50 μm to 200 μm.

≪Sealing part≫
In the present embodiment, in order to block the influence of water vapor or the like from the outside of the electronic device 70, the first substrate 71 and the first substrate 71 surround the functional element 72 provided on the one surface 71 a of the first substrate 71. The sealing part 84 which is arrange | positioned along the peripheral part of the 2nd board | substrate 63 and bonds the 1st board | substrate 71 and the 2nd board | substrate 63 is provided.

The sealing portion 84 includes a hygroscopic layer 85 and an adhesive layer 86, and the hygroscopic layer 85 is formed inside the adhesive layer 86 so as to surround the functional element 72.
The adhesive layer 86 serves to bond the first substrate 71 and the second substrate 63.
The moisture absorption layer 85 plays a role of absorbing water vapor that has entered from the adhesive layer 86. In order to fulfill this role, the moisture absorption layer 85 may be in contact with at least one of the first substrate and the second substrate, and a space may be formed between the other substrate. In order to exhibit the performance of the moisture absorption layer more, it is preferable that the moisture absorption layer is in contact with both the first substrate and the second substrate, is in close contact with one substrate, and is in contact with the other substrate. More preferably, it is particularly preferable that it is in close contact with both substrates. In the present embodiment, the moisture absorption layer 85 is in close contact with both the first substrate 71 and the second substrate 63 together with the adhesive layer 86.

Examples of the material constituting the adhesive layer 86 include a thermosetting resin, a photocurable resin, a silicone resin, and a thermoplastic resin. Among them, it is preferable to form a thermosetting resin or a photocurable resin from the viewpoint that layer formation and curing are relatively easy and appropriate adhesion to the substrate can be obtained.
Thermosetting resins include one-pack type and two-pack type, and any of them can be used as an adhesive layer.
Although the main thing of photocurable resin is UV curable resin, an acrylate compound, an epoxy compound, an oxetane compound, a polyfunctional vinyl ether compound etc. are mentioned as the typical compound.
As the material used for the adhesive layer 86, it is desirable to select and use a material having excellent moisture resistance. In addition, as a material used for the adhesive layer 86, it is desirable to select a material having high adhesive strength with the substrate to be used.

It is preferable that the moisture absorption layer 85 consists of a desiccant and a binder. The binder plays a role of promoting the formation of the structure of the moisture absorption layer and the adhesion of the moisture absorption layer to the substrate by enclosing the desiccant, particularly when the desiccant is in a powder form.
Examples of the binder material include a thermosetting resin, a photocurable resin, and a silicone resin.
As the desiccant constituting the moisture absorption layer 85, either a chemical reaction desiccant or a physical adsorption desiccant may be used.
Examples of the physical adsorption desiccant include molecular sieve and silica gel.
Examples of the chemical reaction type desiccant include alkali metal oxides, alkaline earth metal oxides, alkaline earth metal halides, phosphorus pentoxide, and the like.
Examples of the alkali metal oxide include lithium oxide (Li ₂ O) and sodium oxide (Na ₂ O).
Examples of the alkaline earth metal oxide include magnesium oxide (MgO), calcium oxide (CaO), strontium oxide (SrO), and barium oxide (BaO).
An example of the alkaline earth metal halide is calcium chloride.
Among these desiccants, since they are highly reactive with water (H ₂ O) and have excellent performance as desiccants, they contain oxides of alkali metals and / or alkaline earth metals. It is preferable. That is, the desiccant may contain either an alkali metal oxide or an alkaline earth metal oxide, or may contain both. Further, a plurality of alkali metal oxides and / or alkaline earth metal oxides may be included.

The moisture absorption capacity of the moisture absorption layer is defined by the weight of moisture that can absorb moisture with respect to its volume.
For example, barium oxide alone as a desiccant reacts with 0.117 (g / g) of water relative to its own weight, and its moisture absorption capacity is 669 (mg / cc) from its density of 5.72.
Moreover, the moisture absorption capability of calcium oxide alone is 1,075 (mg / cc).

For example, when other conditions are constant and (i) the water vapor permeability of the adhesive layer is low, (ii) the adhesive layer is wide, (iii) the moisture absorbent layer is wide, or the moisture absorbent layer When the area is large, the moisture absorption capacity of the moisture absorption layer can be set low.
On the other hand, (i) When the water vapor permeability of the adhesive layer is high, (ii) When the width of the adhesive layer is narrow, (iii) When the width of the hygroscopic layer is narrow, or When the area of the hygroscopic layer is small, (iv) Electrons When setting the lifetime of the device to be long, it is necessary to set the moisture absorption capacity of the moisture absorption layer high.

If the moisture-absorbing layer is composed of a desiccant and a binder, and the proportion of the desiccant in the moisture-absorbing layer is too high, the viscosity becomes too high, and it may be difficult to form the moisture-absorbing layer or the moisture-absorbing layer may become a porous body. .
On the other hand, when the proportion of the desiccant in the moisture absorption layer is too low, the moisture remaining in the binder increases the rate at which the moisture absorption capability of the desiccant is lost during mixing, and the moisture absorption capability of the initial moisture absorption layer increases. May decrease.

The moisture absorption capacity of the moisture absorbing layer is 10 mg / cc or more, preferably 20 mg / cc or more, more preferably 50 mg / cc or more, and particularly preferably 80 mg / cc or more. The upper limit of the moisture absorption capacity of the moisture absorption layer is limited by the usage form of the binder.
Moreover, the material which comprises the moisture absorption layer 85 may each differ with the position in which the moisture absorption layer 85 in the electronic device 70 is provided.

Examples of the method for forming the sealing portion 84 on the substrate include a method using a dispenser; a method using a printing method such as screen printing, flexographic printing, and gravure printing. Specifically, the following method is mentioned, for example.
First, the sealing portion 84 is formed in a frame shape along the outer periphery of the first substrate 71 on the one surface 71a of the first substrate 71 provided with the functional element 72 by the above method. Next, the second substrate 63 is placed and stacked on the surface 71a. In the case of using a thermosetting resin or a photocurable resin as the adhesive layer 86, these resins are cured by heating or light irradiation.
When the first substrate 71 on which the sealing portion 84 is formed and the second substrate 63 are bonded, when the second substrate 63 is a flexible substrate such as a film or a metal foil, A laminator can be used.

≪Functional element≫
In the present embodiment, the functional element 72 is not particularly limited, and examples thereof include an organic EL element, a liquid crystal display element, an electrophoretic display element, and an organic thin film solar cell. Due to the characteristics of the materials constituting these functional elements, the electronic device 70 of the present embodiment using the functional elements is required to have extremely low water vapor transmission characteristics.

  According to the present embodiment, by using a gas barrier film excellent in barrier properties and flexibility suitability and a sealing portion excellent in sealing performance, high sealing performance can be realized. An electronic device with little deterioration and high reliability can be provided.

Second Embodiment
FIG. 6 is a cross-sectional side view showing a second embodiment of the electronic device of the present invention. In addition, in order to make the drawing easy to see, the dimensions and ratios of the respective constituent elements are appropriately changed.
In the present embodiment, the same components as those shown in the first embodiment are denoted by the same reference numerals and description thereof is omitted.

  The electronic device 80 of this embodiment includes a first substrate 71, a functional element 72 provided on one surface 71a of the first substrate 71, a second substrate 93 facing the surface 71a, The first substrate 71 and the second substrate 93 are disposed along the peripheral edges of the first substrate 71 and the second substrate 93 so as to surround the functional element 72. The sealing part 84 which bonds the board | substrate 93 together is roughly comprised.

  That is, in the electronic device 80, the first substrate 71 and the second substrate 93 are stacked via the sealing portion 84 in the thickness direction, and the first substrate 71 and the second substrate 93 are sealed. The functional element 72 is stored in the space formed by the portion 84.

≪Second board≫
In the present embodiment, both the first substrate 71 and the second substrate 93 are gas barrier films. That is, the second substrate 93 includes the film 94 and the barrier layer 95. From the viewpoint of protecting the functional element, the barrier layer is preferably formed on the side facing the functional element of the gas barrier film. In this embodiment, the barrier layer 95 is formed on the surface 94a of the film 94. ing. From the viewpoint of further enhancing the protective function of the functional element, barrier layers may be formed on both sides of the film. That is, a barrier layer may also be formed on the surface 94b of the film 94.

  The gas barrier film used in the present embodiment has the above-described configuration, and the film 73 constituting the first substrate 71 and the film 94 constituting the second substrate 93 are formed of the same material. Well, it can be different.

  According to the present embodiment, since both the first substrate and the second substrate are gas barrier films, in addition to the effects of the first embodiment, there is flexibility and weight reduction. Electronic devices can be provided.

  Hereinafter, although the present invention will be described more specifically based on experimental examples, the present invention is not limited to the following experimental examples.

(Experimental example 1)

The materials used in Experimental Example 1 are shown below.
(A-1) Film Biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”)

A gas barrier film was produced using the production apparatus shown in FIG.
That is, A-1 was used as a base material (base material F), and this was mounted on the delivery roll 11.
Then, an endless tunnel-like magnetic field is formed in the space between the first film-forming roll 17 and the second film-forming roll 18, and power is supplied to the first film-forming roll 17 and the second film-forming roll 18, respectively. Supplying and discharging between the first film-forming roll 17 and the second film-forming roll 18, a film-forming gas (mixed gas of source gas (HMDSO) and reaction gas (oxygen gas)) is supplied to such a discharge region. Then, a thin film was formed by plasma CVD under the following conditions. By performing this process three times, a gas barrier film in which a SiO _X C _Y barrier layer composed of silicon, oxygen, and carbon elements was laminated was obtained.

(Deposition conditions)
Source gas supply: 50 sccm
Supply amount of oxygen gas: 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min

  The thickness of the barrier layer in the gas barrier film thus obtained was 0.3 μm.

(Measurement of water vapor permeability)
With respect to the water vapor permeability of the obtained gas barrier film, a water vapor permeability measuring machine (GTR Tech, manufactured by GTR Tech Co., Ltd.) was used at a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side. It was 2 * 10 < ^-4 > g / (m < ² > * day) when measured using -30XASC.

(Distribution curve of each element in the barrier layer)
The obtained gas barrier film was subjected to XPS depth profile measurement under the following conditions to create distribution curves of silicon atoms, oxygen atoms and carbon atoms. From the obtained silicon distribution curve, oxygen distribution curve and carbon distribution curve The carbon distribution curve is substantially continuous; the carbon distribution curve has at least one extreme value; and the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve is 5 at%. It was confirmed that the above were satisfied.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: VG Theta Probe, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot shape and spot diameter: 800 × 400 μm ellipse.

(Experimental example 2)
The materials used in Experimental Example 2 are shown below.
(A-2) Substrate Two sheets of the gas barrier film (film: polyethylene naphthalate (PEN), barrier layer: SiO _X C _Y ) prepared in Experimental Example 1 were prepared by UV ozone cleaning.
(C-1) Photocurable resin UV curable resin (epoxy acrylate, viscosity at 25 ° C .: 7720 (mPa · s), manufactured by Hitachi Chemical Co., Ltd., trade name “Hitaroid 7851”)
(C-2) Photopolymerization initiator Photopolymerization initiator (2,2-dimethoxy-1,2-diphenylethane-1-one, melting point: 63 to 67 ° C., manufactured by BASF, trade name “IRGACURE651”)

97 wt% C-1 and 3 wt% C-2 were heated to 80 ° C. and stirred and mixed to prepare an adhesive (hereinafter referred to as D-1). The first A-2 was used as the first substrate, and D-1 was applied to a thickness of about 250 μm on the barrier layer surface of A-2 using a bar coater.
Next, the second A-2 was used as the second substrate, and the D-1 coating surface of the first substrate and the barrier layer surface of the second substrate were bonded together.
Subsequently, UV irradiation was performed for 100 seconds with the intensity | strength of 10 mW / cm < ² > on the bonded surface using UV irradiation apparatus. D-1 was cured to form an adhesive layer, which was confirmed to be in close contact with the gas barrier film.

(Experimental example 3)
The materials used in Experimental Example 3 are shown below.
(A-3) Substrate Two films (polyethylene terephthalate (PET)) were prepared.
(C-1) Photocurable resin UV curable resin (epoxy acrylate, viscosity at 25 ° C .: 7720 (mPa · s), manufactured by Hitachi Chemical Co., Ltd., trade name “Hitaroid 7851”)
(C-2) Photopolymerization initiator Photopolymerization initiator (2,2-dimethoxy-1,2-diphenylethane-1-one, melting point: 63 to 67 ° C., manufactured by BASF, trade name “IRGACURE651”)
(E) Desiccant Desiccant (barium oxide, average particle size by BET specific surface area method: 0.9 μm)

48.5% by weight of C-1 and 1.5% by weight of C-2 were heated to 80 ° C., stirred and mixed, and after C-2 was sufficiently dissolved, 50 wt. % Was added and mixed to obtain a hygroscopic agent (hereinafter F-1).
On the surface of the first A-3, F-1 was applied to a thickness of about 250 μm using a bar coater, and then the second A-3 was bonded to the coated surface. Next, after UV irradiation was performed on the bonded surfaces with an intensity of 10 mW / cm ² for 100 seconds using a UV irradiation apparatus, the formed moisture absorbing layer was peeled off from A-3, and used as a sample for measuring moisture absorption capacity. Using.

(Measurement of moisture absorption capacity of moisture absorption layer)
Using a high-temperature, high-humidity TG / DTA measuring device (manufactured by SSI Technology Co., Ltd.), the weight increase due to moisture absorption of the moisture-absorbing layer 12.28 (mg) under a certain temperature and humidity was measured. The measurement conditions are shown below.

(Measurement condition)
The sample was supersaturated at 50 ° C. and 60% RH, and after 2.5 hours, the sample was switched to the condition of 50 ° C. and 0% RH, and the weight increase asymptotically measured after 1 hour or more was defined as the moisture absorption capacity of the sample.

  Weight increase amount (g) / sample amount (g) × 100 = 4.8 (wt%), and from the specific gravity of the moisture absorption layer 1.85, the moisture absorption layer has a moisture absorption capacity of 89 (mg / cc). I found out.

  Using the barrier film substrate obtained in Experimental Example 1, the adhesive layer obtained in Experimental Example 2, and the moisture-absorbing layer obtained in Experimental Example 3, it has high sealing performance and is highly reliable with little deterioration in performance. It is clear that an electronic device can be provided.

  DESCRIPTION OF SYMBOLS 10 ... Manufacturing apparatus, 11 ... Sending roll, 12 ... Winding roll, 13-16 ... Conveyance roll, 17 ... 1st film-forming roll, 18 ... 2nd film-forming roll, 19 ... Gas supply pipe, 20 ... For plasma generation Power source, 21, 22 ... Electrode, 23, 24 ... Magnetic field forming device, 63 ... Second substrate, 70, 80 ... Electronic device, 71 ... First substrate, 72 ... Functional element, 73, 94, F ... Film, 74, 95, H ... barrier layer, 84 ... sealing part, 85 ... hygroscopic layer, 86 ... adhesive layer, 93 ... second substrate, SP ... space (film formation space).

Claims (8)

A first substrate; and a functional element provided on a surface of the first substrate;
A second substrate facing the surface of the first substrate;
The first substrate and the second substrate are disposed between the first substrate and the second substrate, and are disposed along a peripheral portion of the first substrate and the second substrate, and the first substrate and the second substrate are attached to each other. A method for manufacturing an electronic device having a sealing portion to be combined,
At least one of the first substrate and the second substrate is a gas barrier film including a film and at least one barrier layer formed on at least one surface of the film, and water vapor of the gas barrier film The transmittance is 10 ⁻² g / (m ² · day) or less,
At least one of the barrier layers contains silicon, oxygen and carbon atoms;
The distance from the surface of the barrier layer in the thickness direction of the barrier layer, and the ratio of the number of silicon atoms to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the barrier layer at the point located at the distance ( Silicon distribution curve, oxygen distribution curve, and carbon distribution curve showing the relationship among silicon atom ratio), oxygen atom ratio (oxygen atom ratio), and carbon atom ratio (carbon atom ratio), respectively. In the following conditions (i) to (iii):
(I) The atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition represented by the following formula (1) in a region of 90% or more in the film thickness direction of the barrier layer. about,
(Oxygen atomic ratio)> (Si atomic ratio)> (Carbon atomic ratio) (1)
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve is 5 at% or more,
Satisfy all
The average value of the carbon atom number ratio determined from the carbon distribution curve is 11 at% or more and 21 at% or less,
The barrier layer has an average density of 1.8 g / cm ³ or more;
The sealing portion includes a moisture absorption layer and an adhesive layer, and the moisture absorption layer is formed inside the adhesion layer so as to surround the functional element, and the moisture absorption capacity of the moisture absorption layer is 10 mg / cc or more. Be satisfied,
Using a plasma chemical vapor deposition method, having a film forming step of forming a gas barrier film by forming a barrier layer on the film;
The film forming step is performed by facing the first film forming roll on which the film is wound and the first film forming roll, and the film is wound on the first film forming roll downstream of the film transport path. A second film forming roll, and a film forming apparatus comprising:
Using the discharge plasma formed along the tunnel-like magnetic field by forming an endless tunnel-like magnetic field in the space where the first roll and the second roll face the barrier layer Formed by plasma enhanced chemical vapor deposition ,
In a two-dimensional coordinate system in which the flow rate of the source gas (sccm) is the horizontal axis and the flow rate of the oxygen gas (sccm) is the vertical axis, the flow rate of the source gas and the flow rate of the oxygen gas are expressed by the following equations (1) to (4). A method of manufacturing an electronic device, characterized in that film formation is controlled within a range surrounded by a line segment represented .
Formula (1) y = 250
Formula (2) y = 14.7x-235
Formula (3) y = 500
Formula (4) y = 6.25x-93.75 At least one of the barrier layers contains silicon, oxygen, and hydrogen;
Based on the abundance ratio of silicon atoms having different bonding states with oxygen atoms, as determined in ²⁹ Si solid state NMR measurement of the barrier layer, the peak areas of Q ¹ , Q ² , and Q ³ are totaled with respect to the peak area of Q ⁴ The method for manufacturing an electronic device according to claim 1, wherein the ratio of the measured values satisfies the following conditional expression (I).
(A value obtained by summing peak areas of Q ¹ , Q ² , and Q ³ ) / (peak area of Q ⁴ ) <10 (I)
(Q ¹ represents a silicon atom bonded to one neutral oxygen atom and three hydroxyl groups, Q ² represents a silicon atom bonded to two neutral oxygen atoms and two hydroxyl groups, and Q ³ represents 3 (It shows a silicon atom bonded to one neutral oxygen atom and one hydroxyl group, and Q ⁴ represents a silicon atom bonded to four neutral oxygen atoms.)   The method of manufacturing an electronic device according to claim 1, wherein the barrier layer is formed on a surface of the gas barrier film facing the functional element.   4. The method of manufacturing an electronic device according to claim 1, wherein both of the first substrate and the second substrate are the gas barrier films. 5.   The said gas barrier film is a manufacturing method of the electronic device of any one of Claim 1 to 4 in which the said barrier layer is formed in both surfaces of the said film.   The hygroscopic layer of the sealing part is made of a desiccant and a binder, and the desiccant contains an alkali metal oxide and / or an alkaline earth metal oxide. Electronic device manufacturing method.   The method for manufacturing an electronic device according to claim 1, wherein the adhesive layer of the sealing portion is made of a thermosetting resin or a photocurable resin.   The method for manufacturing an electronic device according to any one of claims 1 to 7, wherein the film forming material includes one or more resin materials selected from a polyester resin, a polyolefin resin, and a polyimide resin.

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