WO2014097997A1 - Electronic device - Google Patents

Abstract

[Problem] To provide an electronic device which has excellent long-term reliability. [Solution] An electronic device which comprises: a gas barrier film that has a base, a barrier layer that is formed on one surface of the base and contains silicon, oxygen and carbon, and a hard coat layer that is formed on the other surface of the base, contains a curable resin, and has a film thickness of 5 μm or more and a pencil hardness of HB or more; and an electronic element main body that is arranged on the barrier layer side of the gas barrier film. The barrier layer satisfies conditions (i)-(iv).

Description

Electronic devices

The present invention relates to an electronic device.

Conventionally, various studies have been made on a film having a property of blocking permeation of water vapor and oxygen, that is, a gas barrier property. In such studies, a technique for forming an inorganic layer by a method such as sputtering or a plasma CVD method has been proposed in order to improve the gas barrier property of the film (see JP-A-6-234186).

In recent years, in addition to demands for weight reduction and size increase, long-term reliability, high degree of freedom in shape, and the ability to display curved surfaces have been added, resulting in a glass substrate that is heavy, easily broken, and difficult to increase in area. Instead, film base materials such as transparent plastics are beginning to be adopted.

However, film substrates such as transparent plastics have a problem that the gas barrier property is inferior to glass. If a base material with inferior gas barrier properties is used, water vapor or air will permeate, and for example, the function in the electronic device will be degraded.

Gas barrier films used for packaging materials and liquid crystal display elements are known in which silicon oxide is vapor-deposited on a plastic film or aluminum oxide is vapor-deposited. However, in those techniques, only a water vapor barrier property of about 1 g / m ² / day is obtained. On the other hand, in recent years, the liquid crystal display has been increased in size, developed as a high-definition display, etc., and the gas barrier performance to the film substrate is about 0.1 g / m ² / day for water vapor permeability. ^The demand has risen to the order of ⁻⁵ to 10 ⁻⁶ g / m ² / day.

In response to the above problem, Japanese Patent Application Laid-Open No. 2005-288851 describes a polymer multilayer (PML) technique. This technique applies a coating consisting of a polymer layer and an aluminum oxide layer to a flexible substrate and seals the substrate. Both deposition processes can be operated at very high speeds using web processing equipment. It has been disclosed that the resistance to water and oxygen permeability is improved by 3 to 4 orders of magnitude compared to uncoated PET membranes.

In such polymer multilayer techniques, the polymer layer may work to mask any defects in adjacent ceramic layers and reduce the diffusion rate of oxygen and water vapor through the channels created by these defects in the barrier layer. Has been suggested. However, since the interface between the polymer layer and the aluminum oxide layer is generally weak due to the incompatibility of adjacent materials, there is a problem that it is easy to peel off and sufficient barrier ability cannot be obtained during long-term storage. It was.

On the other hand, Japanese Patent Application Laid-Open No. 2012-84306 reports an organic EL device having a gas barrier layer containing silicon, oxygen, and carbon with a specific composition. It is disclosed that the gas barrier layer has a high gas barrier property, and the gas barrier property is hardly lowered even when the film is bent, and can be formed in a simple process and in a short time.

However, in the technique described in Japanese Patent Application Laid-Open No. 2012-84306, in order to obtain a high gas barrier property, a barrier layer must be provided so as to have a film thickness exceeding at least 900 nm. Further, it was found that when this gas barrier film was applied to an electronic device, the electronic device deteriorated with time.

The present invention has been made in view of the above problems, and an object thereof is to provide an electronic device having excellent long-term reliability.

The present inventor conducted intensive research to solve the above problems. As a result, it has been found that an electronic device including a gas barrier film having a barrier layer containing silicon, oxygen, and carbon that satisfies specific conditions and a hard coat layer is excellent in long-term reliability. Based on the above findings, the present invention has been completed.

That is, the present invention includes a base material, a barrier layer containing silicon, oxygen, and carbon formed on one surface of the base material, and a curable resin formed on the other surface of the base material. An electronic device having a gas barrier film having a hard coat layer having a film thickness of 5 μm or more and a pencil hardness of HB or more, and an electronic element body disposed on the barrier layer side of the gas barrier film In this electronic device, the barrier layer satisfies the following conditions (i) to (iv).

(I) The distance (L) from the surface of the barrier layer in the thickness direction of the barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atom ratio of silicon) A silicon distribution curve showing a relationship, an oxygen distribution curve showing a relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), and the L and silicon atoms In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of oxygen atoms, and carbon atoms (the atomic ratio of carbon),
In the region of 90% or more of the film thickness of the barrier layer, (atomic ratio of oxygen), (atomic ratio of silicon), (atomic ratio of carbon) in this order,
(Ii) the carbon distribution curve has at least two extreme values;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.
(Iv) The film thickness exceeds 900 nm.

It is a schematic diagram which shows an example of the manufacturing apparatus which can be utilized suitably in order to manufacture the barrier layer which concerns on this invention, 1 is a gas-barrier film, 2 is a base material, 3 is a barrier layer Yes, 31 is a manufacturing apparatus, 32 is a delivery roller, 33, 34, 35 and 36 are transport rollers, 39 and 40 are film forming rollers, 41 is a gas supply pipe, 42 is A power source for generating plasma, 43 and 44 are magnetic field generators, and 45 is a winding roller. 2 is a graph of a carbon distribution curve, an oxygen distribution curve, and a silicon distribution curve of the barrier layer of Example 1. FIG.

The present invention comprises a base material, a barrier layer containing silicon, oxygen, and carbon formed on one surface of the base material, and a curable resin formed on the other surface of the base material, An electronic device having a gas barrier film having a hard coat layer having a film thickness of 5 μm or more and a pencil hardness of HB or more, and an electronic element body disposed on the barrier layer side of the gas barrier film. . The barrier layer satisfies the following conditions (i) to (iv).

(I) The distance (L) from the surface of the barrier layer in the thickness direction of the barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atom ratio of silicon) A silicon distribution curve showing a relationship, an oxygen distribution curve showing a relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), and the L and silicon atoms In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of oxygen atoms, and carbon atoms (the atomic ratio of carbon),
In the region of 90% or more of the film thickness of the barrier layer, (atomic ratio of oxygen), (atomic ratio of silicon), (atomic ratio of carbon) in this order,
(Ii) the carbon distribution curve has at least two extreme values;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.
(Iv) The film thickness exceeds 900 nm.

An electronic device having such a configuration is excellent in long-term reliability. The detailed reason why the electronic device of the present invention has excellent long-term reliability is unknown, but as the barrier layer thickness increases, physical stress is applied to non-uniform defects in the barrier layer. It is easy to cause cracks and the like, and the gas barrier performance is considered to deteriorate with time. In the gas barrier film according to the present invention, it is considered that by providing a hard coat layer on the surface opposite to the barrier layer of the substrate, cracks and the like of the barrier layer are suppressed and the long-term reliability of the electronic device is improved. . In addition, the said mechanism is based on estimation and this invention is not limited to the said mechanism at all.

Hereinafter, preferred embodiments of the present invention will be described. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

In the present specification, “X to Y” indicating a range means “X or more and Y or less”, “weight” and “mass”, “weight%” and “mass%”, “part by weight” and “weight part”. “Part by mass” is treated as a synonym. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

[Base material]
In the gas barrier film according to the present invention, a plastic film is usually used as a substrate. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a barrier layer, a hard coat layer, and the like, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

When the gas barrier film according to the present invention is used as a substrate for an electronic device such as an organic EL element, the base material is preferably made of a heat resistant material. Specifically, a resin base material having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) of 100 ° C. or more and 300 ° C. or less is used. The base material satisfies the requirements for use as a laminated film for electronic parts and displays. That is, when the gas barrier film of the present invention is used for these applications, the gas barrier film may be exposed to a process at 150 ° C. or higher. In this case, when the coefficient of linear expansion of the base material in the gas barrier film exceeds 100 ppm / K, the substrate dimensions are not stable when the gas barrier film is passed through the temperature process as described above, and thermal expansion and contraction occur. Inconvenience that the shut-off performance is deteriorated or a problem that the thermal process cannot withstand is likely to occur. If it is less than 15 ppm / K, the film may break like glass and the flexibility may deteriorate.

The Tg and linear expansion coefficient of the substrate can be adjusted by additives. More preferable specific examples of the thermoplastic resin that can be used as the substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic. Polyolefin (for example, ZEONOR (registered trademark) 1600: 160 ° C, manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C), polyethersulfone (PES: 220 ° C), polysulfone (PSF: 190 ° C), cycloolefin copolymer (COC: Compound described in JP-A No. 2001-150584: 162 ° C.), polyimide (for example, Neoprim (registered trademark): 260 ° C. manufactured by Mitsubishi Gas Chemical Co., Ltd.), fluorene ring-modified polycarbonate (BCF-PC: JP In 2000-227603 Listed compound: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound described in JP 2000-227603 A: 205 ° C.), acryloyl compound (compound described in JP 2002-80616 A: 300 ° C.) And the like) (Tg is shown in parentheses).

When the gas barrier film according to the present invention is used in combination with a polarizing plate, the gas barrier film is preferably disposed on the innermost side (adjacent to the element) so that the barrier layer of the gas barrier film faces the inner side of the cell. At this time, since the gas barrier film is disposed inside the cell from the polarizing plate, the retardation value of the gas barrier film is important. The usage form of the gas barrier film in such an embodiment includes a gas barrier film using a base film having a retardation value of 10 nm or less and a circularly polarizing plate (¼ wavelength plate + (½ wavelength plate) + straight line. It is preferable to use a linear polarizing plate in combination with a gas barrier film using a base film having a retardation value of 100 nm to 180 nm that can be used as a quarter wavelength plate. .

Examples of the substrate film having a retardation of 10 nm or less include, for example, cellulose triacetate (Fuji Film Co., Ltd .: Fujitac (registered trademark)), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace (registered trademark), Kaneka Corporation): Elmec (registered trademark)), cycloolefin polymer (manufactured by JSR Corporation: Arton (registered trademark), Nippon Zeon Corporation: ZEONOR (registered trademark)), cycloolefin copolymer (manufactured by Mitsui Chemicals, Inc .: APPEL (registered trademark)) (Pellets), manufactured by Polyplastics Co., Ltd .: Topas (registered trademark) (pellets)), polyarylate (manufactured by Unitika Co., Ltd .: U100 (pellets)), transparent polyimide (manufactured by Mitsubishi Gas Chemical Co., Ltd .: Neoprim (registered trademark)) Etc.

Further, as the quarter wavelength plate, a film adjusted to a desired retardation value by appropriately stretching the above film can be used.

Since the gas barrier film according to the present invention is used as an electronic device such as an organic EL element, the plastic film is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.

However, even when the gas barrier film according to the present invention is used for display, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.

The thickness of the plastic film used for the gas barrier film according to the present invention is not particularly limited because it is appropriately selected depending on the use, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. As the functional layer, in addition to those described above, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably used.

The substrate preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.

In addition, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

The base material used in the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. Further, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

At least on the side of the substrate on which the barrier layer according to the present invention is provided, various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and lamination of a primer layer described later Etc. are preferably performed, and it is more preferable to perform the above treatment in combination as necessary.

[Barrier layer]
The barrier layer according to the present invention is a layer formed on one surface of the substrate and is a layer containing silicon, oxygen, and carbon. The barrier layer satisfies the above conditions (i) to (iii).

First, the barrier layer comprises (i) a distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer, and a ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon An oxygen distribution curve indicating the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), And 90% or more of the thickness of the barrier layer in a carbon distribution curve showing a relationship between the L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (carbon atomic ratio) ( In the range of (upper limit: 100%), (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) increase in this order (atomic ratio is O> Si> C). When the above condition (i) is not satisfied, the gas barrier property and flexibility of the obtained gas barrier film are insufficient. Here, in the carbon distribution curve, the relationship of the above (atomic ratio of oxygen), (atomic ratio of silicon) and (atomic ratio of carbon) is at least 90% or more (upper limit: 100%) of the thickness of the barrier layer. ) And more preferably at least 93% or more (upper limit: 100%). Here, “at least 90% or more of the thickness of the barrier layer” does not need to be continuous in the barrier layer, and only needs to satisfy the above-described relationship at a portion of 90% or more.

In the barrier layer, (ii) the carbon distribution curve has at least two extreme values. The barrier layer preferably has at least three extreme values in the carbon distribution curve, more preferably at least four extreme values, but may have five or more extreme values. When the extreme value of the carbon distribution curve is 1 or less, the gas barrier property when the obtained gas barrier film is bent is insufficient. The upper limit of the extreme value of the carbon distribution curve is not particularly limited, but is preferably 30 or less, more preferably 25 or less, for example. Since the number of extreme values is also caused by the film thickness of the barrier layer, it cannot be specified unconditionally.

Here, in the case of having at least three extreme values, the distance from the surface of the barrier layer in the film thickness direction of the barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value. The absolute value of the difference of (L) (hereinafter, also simply referred to as “distance between extreme values”) is preferably 200 nm or less, more preferably 100 nm or less, and particularly preferably 75 nm or less. preferable. With such a distance between extreme values, there are portions having a large carbon atom ratio (maximum value) in the barrier layer at an appropriate period, so that appropriate flexibility is imparted to the barrier layer, and the gas barrier film Generation of cracks during bending can be more effectively suppressed / prevented. In this specification, the “extreme value” refers to the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer. Further, in this specification, the “maximum value” is a point where the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from an increase to a decrease when the distance from the surface of the barrier layer is changed, Further, the value of the atomic ratio of the element at the position where the distance from the point in the film thickness direction of the barrier layer from the point in the thickness direction of the barrier layer is further changed in the range of 4 to 20 nm than the value of the atomic ratio of the element at that point. It means a point that decreases by 3 at% or more. That is, it is sufficient that the atomic ratio value of the element is reduced by 3 at% or more in any range when changing in the range of 4 to 20 nm. Similarly, the “minimum value” in this specification is a point in which the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from decrease to increase when the distance from the surface of the barrier layer is changed. In addition, the atomic ratio value of the element at a position where the distance from the point in the film thickness direction of the barrier layer from the point in the film thickness direction of the barrier layer to the surface of the barrier layer is further changed by 4 to 20 nm is 3 at%. This is the point that increases. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is particularly high because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation when the gas barrier film is bent. Although not limited, in consideration of the flexibility of the barrier layer, the effect of suppressing / preventing cracks, thermal expansion, and the like, the thickness is preferably 10 nm or more, and more preferably 30 nm or more.

Further, the barrier layer has (iii) the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter, also simply referred to as “C _max −C _min difference”) of 3 at% or more. . When the absolute value is less than 3 at%, the gas barrier property is insufficient when the obtained gas barrier film is bent. The C _max -C _min difference is preferably 5 at% or more, more preferably 7 at% or more, and particularly preferably 10 at% or more. By setting the C _max −C _min difference, the gas barrier property can be further improved. In the present specification, the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in this specification, the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values. Here, the upper limit of the C _max -C _min difference is not particularly limited, but it is preferably 50 at% or less in consideration of the effect of suppressing / preventing crack generation during bending of the gas barrier film, and is preferably 40 at% or less. It is more preferable that

In addition, (iv) the thickness of the barrier layer exceeds 900 nm. In the case of 900 nm or less, the gas barrier properties are insufficient. The thickness of the barrier layer is preferably 950 to 2000 nm, more preferably 1000 to 1500 nm.

In the present invention, the oxygen distribution curve of the barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and more preferably has at least three extreme values. When the oxygen distribution curve has at least one extreme value, the gas barrier property when the obtained gas barrier film is bent is further improved. The upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the thickness of the barrier layer, and it cannot be defined unconditionally. In the case of having at least three extreme values, a difference in distance from the surface of the barrier layer in the film thickness direction of the barrier layer at one extreme value of the oxygen distribution curve and an extreme value adjacent to the extreme value. Are preferably 200 nm or less, more preferably 100 nm or less. With such a distance between extreme values, the occurrence of cracks during bending of the gas barrier film can be more effectively suppressed / prevented. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is not particularly limited, but considering the improvement effect of crack generation suppression / prevention when the gas barrier film is bent, the thermal expansion property, etc. The thickness is preferably 10 nm or more, and more preferably 30 nm or more.

In addition, in the present invention, 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 (hereinafter also simply referred to as “O _max −O _min difference”) is 3 at% or more. It is preferably 5 at% or more, more preferably 6 at% or more, and particularly preferably 7 at% or more. When the absolute value is 3 at% or more, the gas barrier property when the obtained gas barrier film is bent is further improved. Here, the upper limit of the O _max -O _min difference is not particularly limited, but is preferably 50 at% or less, and is preferably 40 at% or less in consideration of the effect of suppressing / preventing crack generation when the gas barrier film is bent. It is more preferable that

In the present invention, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of the barrier layer (hereinafter also simply referred to as “Si _max -Si _min difference”) is 10 at% or less. Is preferable, 7 at% or less is more preferable, and 3 at% or less is further preferable. When the absolute value is 10 at% or less, the gas barrier property of the obtained gas barrier film is further improved. The lower _limit of Si max _{-Si min difference,} because the effect of improving the crack generation suppression / prevention during bending of Si max _{-Si min} as gas barrier property difference is small film is high, is not particularly limited, and gas barrier property In consideration, it is preferably 1 at% or more, and more preferably 2 at% or more.

In the present invention, the total amount of carbon and oxygen atoms with respect to the thickness direction of the barrier layer is preferably substantially constant. Thereby, a barrier layer exhibits moderate flexibility, and the crack generation at the time of bending of a gas barrier film can be more effectively suppressed / prevented. More specifically, the ratio of the total amount of oxygen atoms and carbon atoms to the distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer and the total amount of silicon atoms, oxygen atoms, and carbon atoms ( In the oxygen-carbon distribution curve showing a relationship with the atomic ratio of oxygen and carbon, the absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon in the oxygen-carbon distribution curve (hereinafter simply referred to as “OC _max ”). -OC _min difference ") is preferably less than 5 at%, more preferably less than 4 at%, and even more preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier property of the obtained gas barrier film is further improved. _The lower limit of the OC max _{-OC min difference,} since preferably as OC max _{-OC min} difference is small, but is 0 atomic%, it is sufficient if more than 0.1 at%.

The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. 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. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time in this way, the etching time generally correlates with the distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer in the film thickness direction. Therefore, “Distance from the surface of the barrier layer in the film thickness direction of the barrier layer” is the distance from the surface of the barrier layer calculated from the relationship between the etching rate and the etching time adopted in the XPS depth profile measurement. can do. In the present invention, the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve were prepared under the following measurement conditions.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ );
Etching rate (converted to SiO ₂ thermal oxide film): 0.05 nm / sec;
Etching interval (SiO ₂ equivalent value): 10 nm;
X-ray photoelectron spectrometer: Model name "VG Theta Probe", manufactured by Thermo Fisher Scientific;
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 × 400 μm oval.

In addition, when a barrier layer is comprised from two or more layers, it is preferable that each barrier layer has the above thickness. In addition, the thickness of the entire barrier layer when the barrier layer is composed of two or more layers is not particularly limited, but the thickness of the entire barrier layer (dry film thickness) is preferably about 1000 to 2000 nm. With such a thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending.

In the present invention, the barrier layer is substantially uniform in the film surface direction (direction parallel to the surface of the barrier layer) from the viewpoint of forming a barrier layer having a uniform and excellent gas barrier property over the entire film surface. Preferably there is. Here, the barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon are measured at any two measurement points on the film surface of the barrier layer by XPS depth profile measurement. When a distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the maximum and minimum values of the carbon atomic ratio in each carbon distribution curve The absolute values of the differences are the same as each other or within 5 at%.

Furthermore, in the present invention, it is preferable that the carbon distribution curve is substantially continuous. Here, the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the carbon distribution curve is calculated from the etching rate and the etching time. In the relationship between the distance (x, unit: nm) from the surface of the barrier layer in the film thickness direction of at least one of the barrier layers, and the atomic ratio of carbon (C, unit: at%), It means satisfying the condition represented by the following formula (1).

In the gas barrier film according to the present invention, the barrier layer satisfying all of the above conditions (i) to (iii) may include only one layer or two or more layers. Furthermore, when two or more such barrier layers are provided, the materials of the plurality of barrier layers may be the same or different.

In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the silicon atomic ratio, the oxygen atomic ratio, and the carbon atomic ratio are in the region of 90% or more of the thickness of the barrier layer (i ), The atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier layer is preferably 20 to 45 at%, More preferably, it is 25 to 40 at%. Further, the atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier layer is preferably 45 to 75 at%, and more preferably 50 to 70 at%. . Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier layer is preferably 1 to 25 at%, and more preferably 2 to 20 at%. .

In the present invention, the method for forming the barrier layer is not particularly limited, and the conventional method and the method can be applied in the same manner or appropriately modified. The barrier layer is preferably formed by a chemical vapor deposition (CVD) method, in particular, a plasma chemical vapor deposition method (plasma CVD, PECVD (plasma-enhanced chemical vapor deposition), hereinafter also simply referred to as “plasma CVD method”). It is more preferable that the substrate is formed by a plasma CVD method in which a base material is disposed on a pair of film forming rollers and a plasma is generated by discharging between the pair of film forming rollers.

Further, the arrangement of the barrier layer is not particularly limited, but may be arranged on the substrate.

Hereinafter, a method of forming a barrier layer using the plasma CVD method preferably used in the present invention will be described below.

[Method for forming barrier layer]
Next, a preferred method for forming the barrier layer according to the present invention will be described. The gas barrier film according to the present invention can be produced by forming the barrier layer on one surface of the substrate and forming a hard coat layer to be described later on the other surface of the substrate. As a method of forming such a barrier layer according to the present invention on the surface of the substrate, it is preferable to employ a plasma CVD method from the viewpoint of gas barrier properties. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

Further, when plasma is generated in the plasma CVD method, it is preferable to generate plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and each of the pair of film forming rollers is used. More preferably, the substrate is disposed and discharged between a pair of film forming rollers to generate plasma. In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller It is possible not only to produce a thin film efficiently because it is possible to form a film on the surface part of the base material existing in the film while simultaneously forming a film on the surface part of the base material present on the other film forming roller. The film formation rate can be doubled compared to the plasma CVD method without using any roller, and a film having substantially the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled. It is possible to form a layer that satisfies all of the above conditions (i) to (iii).

Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma CVD method preferably includes an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation. In the gas barrier film of the present invention, the barrier layer is preferably a layer formed by a continuous film forming process.

Moreover, the gas barrier film according to the present invention preferably forms the barrier layer on the surface of the substrate by a roll-to-roll method from the viewpoint of productivity. Further, an apparatus that can be used when manufacturing the barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and the pair of film forming processes. It is preferable that the apparatus has a configuration capable of discharging between rollers. For example, when the manufacturing apparatus shown in FIG. 1 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It is also possible.

Hereinafter, the method for forming a barrier layer according to the present invention will be described in more detail with reference to FIG. FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the barrier layer according to the present invention. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

1 includes a feed roller 32, transport rollers 33, 34, 35, and 36, film forming rollers 39 and 40, a gas supply pipe 41, a plasma generating power source 42, and a film forming roller 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45. In such a manufacturing apparatus, at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge into the space between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 39 and 40) so that the central axis may become substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 39 and 40), the film forming rate can be doubled and a film having the same structure can be formed. Can be at least doubled. And according to such a manufacturing apparatus, it is possible to form the barrier layer 3 on the surface of the base material 2 by the CVD method, and the barrier layer component is formed on the surface of the base material 2 on the film forming roller 39. While depositing, the barrier layer component can also be deposited on the surface of the substrate 2 also on the film forming roller 40, so that the barrier layer can be efficiently formed on the surface of the substrate 2.

In the film forming roller 39 and the film forming roller 40, magnetic field generators 43 and 44 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

The magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 are respectively a magnetic field generating device 43 provided on one film forming roller 39 and a magnetic field generating device provided on the other film forming roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between them and the magnetic field generators 43 and 44 form a substantially closed magnetic circuit. By providing such magnetic field generators 43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell near the opposing surface of each film forming roller 39 and 40, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.

The magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity. By providing such magnetic field generators 43 and 44, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the magnetic field generators 43 and 44 are opposed. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be converged on the magnetic field, so that a wide base wound around the roller width direction can be obtained. The material 2 is excellent in that the barrier layer 3 that is a deposited film can be efficiently formed.

As the film formation roller 39 and the film formation roller 40, known rollers can be used as appropriate. As such film forming rollers 39 and 40, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameter of the film forming rollers 39 and 40 is preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.

In such a manufacturing apparatus 31, the base material 2 is disposed on a pair of film forming rollers (the film forming roller 39 and the film forming roller 40) so that the surfaces of the base material 2 face each other. By disposing the base material 2 in this manner, when the plasma is generated by performing discharge in the facing space between the film formation roller 39 and the film formation roller 40, the base existing between the pair of film formation rollers is present. Each surface of the material 2 can be formed simultaneously. That is, according to such a manufacturing apparatus, a barrier layer component is deposited on the surface of the substrate 2 on the film forming roller 39 and further deposited on the film forming roller 40 by plasma CVD. Therefore, the barrier layer can be efficiently formed on the surface of the substrate 2.

As the feed roller 32 and the transport rollers 33, 34, 35, and 36 used in such a manufacturing apparatus, known rollers can be appropriately used. The winding roller 45 is not particularly limited as long as it can wind the gas barrier film 1 having the barrier layer 3 formed on the substrate 2, and a known roller may be used as appropriate. it can.

Further, as the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging the raw material gas at a predetermined speed can be appropriately used.

The gas supply pipe 41 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 39 and the film formation roller 40, and is a vacuum as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. As described above, by providing the gas supply pipe 41 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 39 and the film formation roller 40. It is excellent in that the film formation efficiency can be improved.

Furthermore, as the plasma generating power source 42, a known power source of a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge. Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used. In addition, since the plasma generating power source 42 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. More preferably, it is possible to do this. As the magnetic field generators 43 and 44, known magnetic field generators can be used as appropriate. Furthermore, as the base material 2, in addition to the base material used in the present invention, a material in which the barrier layer 3 is previously formed can be used. As described above, the barrier layer 3 can be thickened by using the substrate 2 having the barrier layer 3 formed in advance.

Using such a manufacturing apparatus 31 shown in FIG. 1, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport of the film (base material) The barrier layer according to the present invention can be produced by appropriately adjusting the speed. That is, using the manufacturing apparatus 31 shown in FIG. 1, a discharge is generated between a pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber. Thus, the film-forming gas (raw material gas or the like) is decomposed by plasma, and the barrier layer 3 is formed on the surface of the base material 2 on the film-forming roller 39 and the surface of the base material 2 on the film-forming roller 40 by plasma CVD. Formed by law. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the film forming rollers 39 and 40, and the plasma is converged on the magnetic field. For this reason, when the base material 2 passes A point of the film-forming roller 39 and B point of the film-forming roller 40 in FIG. 1, the maximum value of the carbon distribution curve is formed in the barrier layer. On the other hand, when the substrate 2 passes through the points C1 and C2 of the film forming roller and the points C3 and C4 of the film forming roller 40 in FIG. 1, the minimum value of the carbon distribution curve is formed in the barrier layer. Is done. For this reason, five extreme values are usually generated for two film forming rollers. Further, the distance between the extreme values of the barrier layer (the difference between the distance (L) from the surface of the barrier layer in the thickness direction of the barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value) (Absolute value) can be adjusted by the rotation speed of the film forming rollers 39 and 40 (base material transport speed). In such film formation, the substrate 2 is conveyed by the delivery roller 32, the film formation roller 39, and the like, respectively, so that the surface of the substrate 2 is formed by a roll-to-roll continuous film formation process. Thus, the barrier layer 3 is formed.

As the film forming gas (raw material gas or the like) supplied from the gas supply pipe 41 to the facing space, a raw material gas, a reactive gas, a carrier gas, or a discharge gas can be used alone or in combination of two or more. The source gas in the film-forming gas used for forming the barrier layer 3 can be appropriately selected and used according to the material of the barrier layer 3 to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting barrier layer. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the barrier layer 3.

Further, as the film forming gas, a reactive gas may be used in addition to the raw material 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, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.

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

When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. By not excessively increasing the ratio of the reactive gas, the barrier layer 3 formed is excellent in that excellent barrier properties and bending resistance can be obtained. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

Hereinafter, as the film forming gas, hexamethyldisiloxane (organosilicon compound, HMDSO, (CH ₃ ) ₆ Si ₂ O) as a raw material gas and oxygen (O ₂ ) as a reactive gas are used. Taking a case of producing a silicon-oxygen-based thin film as an example, the preferred ratio of the raw material gas to the reactive gas in the film forming gas will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reactive gas is reacted by plasma CVD to form a silicon-oxygen-based system When the thin film is produced, a reaction represented by the following reaction formula (1) occurs by the film forming gas, and silicon dioxide is generated.

In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, a uniform silicon dioxide film is formed when oxygen is contained in the film forming gas in an amount of 12 moles or more per mole of hexamethyldisiloxane and a uniform silicon dioxide film is formed (a carbon distribution curve exists). Therefore, it becomes impossible to form a barrier layer that satisfies all of the above conditions (i) to (iii). Therefore, in the present invention, when the barrier layer is formed, the stoichiometric ratio of oxygen amount to 1 mol of hexamethyldisiloxane is set so that the reaction of the reaction formula (1) does not proceed completely. The amount is preferably less than 12 moles. In the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas Even if the (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane (flow rate), the reaction cannot actually proceed completely, and the oxygen content is reduced. It is considered that the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is changed to the hexamethyldioxide raw material. (It may be about 20 times or more the molar amount (flow rate) of siloxane). Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the barrier layer, and the above conditions (i) to (iv) It is possible to form a barrier layer satisfying all of the above) and to exhibit excellent gas barrier properties and flex resistance in the obtained gas barrier film. From the viewpoint of use as a flexible substrate for devices that require transparency, such as organic EL elements and solar cells, the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas The lower limit of (flow rate) is preferably greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably greater than 0.5 times.

Further, the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 50 Pa.

In such a plasma CVD method, in order to discharge between the film forming roller 39 and the film forming roller 40, an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used. The power applied to the power source can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed, and if it is 10 kW or less, the amount of heat generated during film formation can be suppressed, and the substrate during film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.

The conveyance speed (line speed) of the base material 2 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is in the range of 5 to 20 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient thickness as a barrier layer, without impairing productivity.

As described above, as a more preferable aspect of the present embodiment, the barrier layer according to the present invention is formed by plasma CVD using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is characterized by doing. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently produce a barrier layer having both the barrier performance and the barrier performance. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.

[Hard coat layer]
The gas barrier film according to the present invention has a hard coat layer provided on the surface of the substrate opposite to the surface having the barrier layer. By having the hard coat layer, the electronic device of the present invention is a device with high long-term reliability. The hard coat layer may have a function of preventing scratches on the surface of the electronic device.

The hard coat layer contains a curable resin. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material or the like with an active energy ray such as an ultraviolet ray to be cured is heated. And thermosetting resins obtained by curing. These curable resins may be used alone or in combination of two or more.

Examples of the active energy ray-curable material used for forming the hard coat layer include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include compositions containing polyfunctional acrylate monomers such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate. Specifically, it is possible to use a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series (compound formed by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) manufactured by JSR Corporation. it can. It is also possible to use any mixture of the above-mentioned compositions, and an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. If there is no particular limitation.

Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, grease Dil acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropyl Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, Propion oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2 , 4- Trimethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decane diol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

The active energy ray-curable material is a (meth) acrylate compound, which is a trifunctional to octafunctional (meth) acrylate compound, and more preferably a trifunctional to octafunctional compound composed of only carbon, oxygen and hydrogen atoms. It is an octafunctional (meth) acrylate compound. These (meth) acrylate compounds are preferably linear or branched. The number of functional groups is particularly preferably 4 to 8 functions.

Furthermore, the active energy ray-curable material preferably contains phosphoric acid (meth) acrylate. By adding phosphoric acid (meth) acrylate, the adhesion to the substrate tends to be further improved. Phosphoric acid (meth) acrylate is preferably added in a proportion of 1 to 15% by weight, preferably in a proportion of 2 to 10% by weight, based on the total amount of polymerizable compounds contained in the compound forming the hard coat layer. More preferably.

In particular, the hard coat layer according to the present invention is obtained by curing a polymerizable composition containing an active energy ray-curable material, and 85 wt% to 99 wt% of the polymerizable compound includes carbon atoms, oxygen atoms and hydrogen atoms. 4 to 8 functional (meth) acrylate consisting of 1 to 15% by weight of phosphoric acid (meth) acrylate, and the hard coat layer preferably has a pencil hardness of H or higher. . Thereby, it exists in the tendency which the effect of this invention improves more notably.

It is preferable that the composition containing the active energy ray-curable material contains a photopolymerization initiator.

Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichloro Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzo Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p- Azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2 -(O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxy , Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl Chloride, quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, peroxide Examples include combinations of photoreducing dyes such as benzoin, eosin, and methylene blue with reducing agents such as ascorbic acid and triethanolamine. These photopolymerization initiators may be used alone or in combination of two or more. it can.

Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, Unicom manufactured by DIC, Inc. Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nittobo Co., Ltd. Inorganic / organic nanocomposite material SSG coating, thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohydrin Butter, and the like can be mentioned.

The method for forming the hard coat layer is not particularly limited, but a coating solution containing a curable material is applied to a spin coating method, a spray method, a blade coating method, a dipping method, a wet coating method such as a gravure printing method or a vapor deposition method After coating by a dry coating method to form a coating film, the coating film is irradiated with active energy rays such as visible rays, infrared rays, ultraviolet rays, X rays, α rays, β rays, γ rays, and electron beams and / or heated. A method of forming by curing is preferred. As a method of irradiating active energy rays, for example, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like is preferably used to irradiate ultraviolet rays in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm. Alternatively, a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator can be used.

Solvents used when forming a hard coat layer using a coating solution in which a curable material is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol. , Terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, toluene, xylene, tetramethylbenzene Aromatic hydrocarbons such as, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoe Glycol ethers such as chill ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carb Acetic esters such as tall acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate , Diethylene glycol dialkyl ether, Propylene glycol dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

The hard coat layer can contain additives such as a thermoplastic resin, an antioxidant, an ultraviolet absorber, and a plasticizer, if necessary, in addition to the above-described materials. In addition, an appropriate resin or additive may be used for improving the film formability and preventing the occurrence of pinholes in the film. Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof and the like. Examples include resins, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, and polycarbonate resins.

The thickness of the hard coat layer according to the present invention is 5 μm or more. When the thickness is less than 5 μm, the long-term reliability of the electronic device is lowered. The thickness of the hard coat layer is preferably 5 to 20 μm, more preferably 5 to 10 μm. By setting it to 5 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by setting it to 10 μm or less, it becomes easier to adjust the balance of the optical properties of the base material, and further curling of the gas barrier film is further suppressed. Can be made easier.

The film thickness ratio between the barrier layer and the hard coat layer described above is preferably 1: 3 to 1:50 (film thickness of the barrier layer (nm): film thickness of the hard coat layer (nm)). 1: 5 to 1:20 is more preferable. When the film thickness ratio is within this range, the long-term reliability of the electronic device of the present invention is further improved.

The pencil hardness of the hard coat layer according to the present invention is HB or higher. The pencil hardness is 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H in order from the softest. When the pencil hardness is less than HB, the surface of the electronic device is not sufficiently prevented from being scratched. The pencil hardness is preferably F or more, more preferably H or more. The upper limit of the hard coat layer is not particularly limited, but is preferably 10H or less, and more preferably 8H or less. The pencil hardness can be measured by the method described in JIS K5600-5-4: 1999. When measuring pencil hardness of 10H, 7B, 8B, 9B, 10B, use 10H, 7B, 8B, 9B, 10B pencils made by Mitsubishi Pencil Co., Ltd. Measure.

The smoothness of the hard coat layer is a value expressed by the surface roughness specified by JIS B0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. Note that the lower limit of the maximum cross-sectional height Rt (p) is not particularly limited and is 0 nm, but it may normally be 0.5 nm or more.

In this specification, the surface roughness is calculated from an uneven sectional curve continuously measured with a detector having a stylus having a minimum tip radius with an AFM (atomic force microscope), and the surface roughness is measured with a minimum tip radius. This is obtained from the average roughness of the amplitude of the fine irregularities by measuring the inside of the section whose measuring direction is several tens of μm with a needle many times.

The hard coat layer may be provided with anti-glare performance for the purpose of preventing the visibility of transmitted light from being reduced due to reflection of external light on the surface of the electronic device. The antiglare performance can be imparted by imparting a fine concavo-convex structure to the surface of the hard coat layer to be formed. A typical example of a material that imparts such a fine concavo-convex structure is a transparent resin. Specific examples include an ultraviolet curable resin containing an acrylic resin such as isocyanuric acid triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate, and a urethane resin such as isophorone diisocyanate polyurethane. Further, the provision of a fine concavo-convex structure is also performed by roughening (for example, sand blasting or embossing), blending of fine particles, and the like. When fine particles are used, any appropriate fine particles can be adopted as the fine particles depending on the purpose. Preferably, it is a transparent fine particle. Specifically, the fine particles are inorganic fine particles (for example, silica, alumina, talc, clay, titania, zirconia, calcium carbonate, magnesium carbonate, barium sulfate, tin oxide, indium oxide, cadmium oxide, water, which may be conductive) Aluminum oxide, titanium dioxide, zirconium oxide, or antimony oxide fine particles) and organic fine particles (for example, crosslinked or uncrosslinked polymer fine particles).

[Primer layer (smooth layer)]
The gas barrier film of the present invention may have a primer layer (smooth layer) between the surface of the substrate having the barrier layer, preferably between the substrate and the barrier layer. The primer layer is provided for flattening the rough surface of the substrate on which protrusions and the like exist. Such a primer layer is basically formed by curing an active energy ray-curable material or a thermosetting material. The primer layer may basically have the same configuration as the hard coat layer as long as it has the above function.

The examples of the active energy ray-curable material and the thermosetting material, and the method for forming the primer layer are the same as those described in the column of the hard coat layer, and thus the description thereof is omitted here.

The smoothness of the primer layer is a value expressed by the surface roughness defined by JIS B0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. Note that the lower limit of the maximum cross-sectional height Rt (p) is not particularly limited and is 0 nm, but it may normally be 0.5 nm or more.

The thickness of the primer layer is not particularly limited, but is preferably in the range of 0.1 to 10 μm.

[Anchor coat layer]
On the surface of the substrate according to the present invention, an anchor coat layer may be formed as an easy-adhesion layer for the purpose of improving adhesion (adhesion). Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One type or two or more types can be used in combination. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-2400” 3% isopropyl alcohol solution) can be used.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). A commercially available base material with an easy-adhesion layer may be used.

Alternatively, the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.

The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

[Electronic element body]
The electronic element main body is the main body of the electronic device of the present invention, and is disposed on the barrier layer side of the gas barrier film according to the present invention. As the electronic element main body, an electronic device main body whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in air is preferably used. Organic EL elements, solar cells (PV), liquid crystal display elements (LCD), electronic paper, thin film transistors, touch panels, and the like can be given. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic element body is preferably an organic EL element or a solar battery.

The gas barrier film according to the present invention can also be used for device film sealing. That is, it is a method of providing the gas barrier film of the present invention on the surface of the device itself as a support. The device may be covered with a protective layer before providing the gas barrier film.

The gas barrier film according to the present invention can also be used as a device substrate or a film for sealing by a solid sealing method. The solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.

(Organic EL device)
Examples of organic EL elements using a gas barrier film are described in detail in JP-A-2007-30387.

(Liquid crystal display element)
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has a structure consisting of a film. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The type of the liquid crystal cell is not particularly limited, but more preferably, a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment Electric), an EC type, a Bt type OCB type (Optically Compensated Bend), IPS type (In-Plane Switching), and CPA type (Continuous Pinwheel Alignment) are preferable.

(Solar cell)
The gas barrier film of the present invention can also be used as a sealing film for solar cell elements. Here, the gas barrier film of the present invention is preferably sealed so that the barrier layer is closer to the solar cell element. The solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited. For example, it is a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure type. Amorphous silicon-based solar cell elements, III-V group compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI group compound semiconductor solar cell elements such as cadmium tellurium (CdTe), I-III- such as copper / indium / selenium system (so-called CIS system), copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur system (so-called CIGS system), etc. Group VI compound semiconductor solar cell element, dye-sensitized solar cell element, organic solar cell element, etc. And the like. In particular, in the present invention, the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur. A group I-III-VI compound semiconductor solar cell element such as a system (so-called CIGSS system) is preferable.

(Other)
As other application examples, the thin film transistor described in JP-T-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., and described in JP-A-2000-98326 Electronic paper and the like.

<Optical member>
The gas barrier film of the present invention can also be used as an optical member. Examples of the optical member include a circularly polarizing plate.

(Circularly polarizing plate)
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate using the gas barrier film in the present invention as a substrate. In this case, the lamination is performed so that the angle formed by the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate is 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-86554 can be suitably used. .

The effect of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Further, in the examples, the display of “part” or “%” is used, but “part by weight” or “% by weight” is expressed unless otherwise specified.

Each characteristic value of the gas barrier film was measured according to the following method.

<< Method for measuring characteristic values of gas barrier film >>
[Evaluation of water vapor barrier properties (WVTR)]
In accordance with the following measurement method, the permeated moisture amount of each gas barrier film was measured, and the water vapor barrier property was evaluated according to the following criteria.

(apparatus)
Vapor deposition device: JEOL Ltd., vacuum evaporation device JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation cell)
Use a vacuum deposition device (vacuum deposition device JEE-400, manufactured by JEOL Ltd.) on the barrier layer surface of the sample to mask the portions other than the portion (12 mm x 12 mm 9 locations) on which the gas barrier film sample is to be deposited. Was evaporated. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and the aluminum sealing side is quickly passed through a UV-curable resin (manufactured by Nagase ChemteX Corporation) to 0.2 mm thick quartz glass in a dry nitrogen gas atmosphere. And an evaluation cell was produced by irradiating with ultraviolet rays. The obtained sample with both sides sealed was stored at 60 ° C. and 90% RH under high temperature and high humidity, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount of water was calculated.

In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample Was stored under the same high temperature and high humidity conditions of 60 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

The permeated water amount (g / m ² · day; “WVTR” in the table) of each gas barrier film measured as described above was evaluated by the Ca method.

[Evaluation of curl]
The evaluation of the degree of curling was performed as follows. That is, the produced gas barrier film was cut into a 15 cm × 15 cm sheet, the cut sheet sample was placed on a stainless steel substrate, and the orthogonal distance L between the apex of the sheet sample and the stainless steel substrate was measured. did.

〔Pencil hardness〕
The pencil hardness of the hard coat layer was measured according to JIS K5600-5-4: 1999.

(Examples 1 to 13, Comparative Examples 1 to 10)
[Production of gas barrier film]
(Formation of hard coat layer)
A PEN film with a thickness of 100 μm (Q65FA, Tg: 155 ° C., coefficient of thermal expansion: 8 ppm), which is 100 μm thick, is used as the base material. Hybrid hard coat material Opstar (registered trademark) Z7501 was applied with a wire bar so that the thickness after drying was the thickness shown in Table 1 (3, 5, 7, 10, 15 μm). Then, after drying at 80 ° C. for 3 minutes, a hard coat layer was formed by curing at an irradiation dose of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere. The pencil hardness was set to a desired hardness by appropriately changing the irradiation amount.

(Formation of primer layer (smooth layer))
Opstar (registered trademark) Z7501, which is a UV curable organic / inorganic hybrid coating material manufactured by JSR Corporation, on the surface opposite to the surface on which the hard coat layer of the substrate is formed, has a film thickness after drying of 4 μm. It applied with a wire bar so that it might become. After coating, the film was dried at 80 ° C. for 3 minutes to form a coating film. Thereafter, the coating film was cured by irradiating the coating film with ultraviolet rays of 1.0 J / cm ² with a high-pressure mercury lamp in an air atmosphere to form a primer layer (smooth layer).

(Formation of barrier layer)
The base material on which the hard coat layer and the primer layer are formed is mounted on a plasma CVD roll coater W35 series apparatus manufactured by Kobe Steel, Ltd., and hexamethyldisiloxane (HMDSO) is used to form the following film formation conditions (plasma Under the CVD conditions, a barrier layer was formed with a thickness of 300 nm on the substrate. This was repeated to form a film having a barrier layer thickness of 900 nm, 1000 nm, 1200 nm, and 1500 nm to obtain a gas barrier film.

<Film forming conditions>
Supply amount of raw material gas (HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 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 conveyance speed: 0.5 m / min.

[Production of organic EL elements]
A conductive glass substrate (surface resistance 10Ω / □, 0.6 mm thickness) having an ITO film (anode) as a substrate was washed with 2-propanol, and then subjected to UV-ozone treatment for 10 minutes. Layers containing the following organic compounds were sequentially deposited on the substrate by vacuum deposition.

(First hole transport layer)
Copper phthalocyanine: film thickness 10nm
(Second hole transport layer)
N, N′-diphenyl-N, N′-dinaphthylbenzidine: film thickness 40 nm
(Light emitting layer and electron transport layer)
Tris (8-hydroxyquinolinato) aluminum: film thickness 60nm
Finally, lithium fluoride was sequentially deposited at a thickness of 1 nm and metal aluminum was deposited at a thickness of 100 nm to form a cathode, and a silicon nitride film having a thickness of 5 μm was formed thereon by a parallel plate CVD method to produce an organic EL device.

[Installation of gas barrier film]
The organic EL element was sealed using the gas barrier film produced above as a sealing film and using a thermosetting adhesive as a sealing agent. Specifically, a vacuum muraminator is applied in the nitrogen purge glove box by applying a thermosetting adhesive onto the element surface of the organic EL element and stacking the gas barrier film so that the barrier layer side is in contact with the organic EL element side. The organic EL element was sealed by heating at 100 ° C. for 1 hour.

Each organic EL element immediately after fabrication was made to emit light by applying a voltage of 7 V using a source measure unit (SMU2400 type, manufactured by Keithley). The light emitting surface was observed using a microscope and evaluated according to the following criteria. ◎ is a practical level.
A: Uniform light emission without dark spots ○: Dark spots are observed only slightly but uniform light emission Δ: Dark spots are observed only slightly and light emission is non-uniform ×: Many dark spots Recognized and non-uniform luminescence.

Next, each organic EL element was allowed to stand at 25 ° C. and a relative humidity of 90% RH for 10 days, and then the deterioration of light emission was evaluated according to the following criteria by observing the light emitting surface using a microscope. . ○ Above is the practical level.
A: Deterioration of light emission is not observed at all compared with that immediately after manufacture. ○: Deterioration of light emission is recognized as compared to immediately after manufacture, but is within an allowable range. Δ: Deterioration of light emission is recognized as compared with immediately after manufacture. Outside x: Does not emit light.

Evaluation results are shown in Table 1 below.

As is clear from Table 1 above, the organic EL element of the present invention, that is, the organic EL element using the gas barrier film having a barrier layer thickness of more than 900 nm and a hard coat layer thickness of 5 μm or more, It can be seen that even after standing for 10 days under the conditions of 25 ° C. and 90% RH, the light emission does not deteriorate and the long-term reliability of the gas barrier performance is high. However, when the film thickness of the hard coat layer exceeds 10 μm, the curl becomes slightly large, and the production efficiency of the organic EL element is slightly inferior. Therefore, the more preferable thickness of the hard coat layer is 5 to 10 μm.

This application is based on Japanese Patent Application No. 2012-276929 filed on December 19, 2012 and Japanese Patent Application No. 2013-26873 filed on February 14, 2013, The disclosure is incorporated by reference in its entirety.

Claims (3)

A base material, a barrier layer containing silicon, oxygen, and carbon formed on one surface of the base material, and a curable resin formed on the other surface of the base material and having a film thickness of 5 μm And a gas barrier film having a hard coat layer having a pencil hardness of HB or more,
An electronic element body disposed on the barrier layer side of the gas barrier film;
An electronic device comprising:
An electronic device in which the barrier layer satisfies the following conditions (i) to (iv):
(I) The distance (L) from the surface of the barrier layer in the thickness direction of the barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atom ratio of silicon) A silicon distribution curve showing a relationship, an oxygen distribution curve showing a relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), and the L and silicon atoms In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of oxygen atoms, and carbon atoms (the atomic ratio of carbon),
In the region of 90% or more of the film thickness of the barrier layer, (atomic ratio of oxygen), (atomic ratio of silicon), (atomic ratio of carbon) in this order,
(Ii) the carbon distribution curve has at least two extreme values;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.
(Iv) The film thickness exceeds 900 nm. The film thickness ratio between the barrier layer and the hard coat layer (barrier layer thickness (nm): hard coat layer thickness (nm)) is from 1: 5 to 1:20. Electronic devices. The electronic device according to claim 1 or 2, wherein the electronic element body is an organic EL element or a solar battery.

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