WO2014203892A1

WO2014203892A1 - Gas barrier film and method for producing same

Info

Publication number: WO2014203892A1
Application number: PCT/JP2014/066030
Authority: WO
Inventors: 廣瀬　達也; 河村　朋紀
Original assignee: コニカミノルタ株式会社
Priority date: 2013-06-20
Filing date: 2014-06-17
Publication date: 2014-12-24
Also published as: JPWO2014203892A1

Abstract

[Problem] To provide a gas barrier film which exhibits sufficient gas barrier performance even under high temperature high humidity conditions. [Solution] A gas barrier film which comprises, in the following order, a base, a first layer that has barrier properties and a second layer that is formed by an atomic layer deposition method, and which is characterized in that: the second layer contains a region, in which the carbon concentration is from 0.3 at% to 3.0 at% (inclusive) relative to the total amount of aluminum, titanium, silicon, zirconium, oxygen and carbon, so that the region makes up 30% or more of the thickness of the second layer; and the carbon concentration relative to the total amount of aluminum, titanium, silicon, zirconium, oxygen and carbon in the second layer is 3.0 at% or less.

Description

Gas barrier film and method for producing the same

The present invention relates to a gas barrier film and a method for producing the same.

Conventionally, a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging articles in the fields of food, medicine, etc. It is used for. By using the gas barrier film, it is possible to prevent alteration of the article due to gas such as water vapor or oxygen.

In recent years, with regard to such a gas barrier film that prevents permeation of water vapor, oxygen, and the like, development for electronic devices such as an organic electroluminescence (EL) element and a liquid crystal display (LCD) element has been requested, and many studies have been made. . In these electronic devices, a high gas barrier property, for example, a gas barrier property comparable to a glass substrate is required.

As a method for producing a gas barrier film, a method using an inorganic film forming method by vapor deposition is known. As an inorganic film-forming method by the said vapor deposition method, CVD method (Chemical Vapor Deposition: Chemical vapor deposition method, chemical vapor deposition method) and PVD method (PVD: Physical Vapor Deposition: physical vapor deposition method, physical vapor deposition method) are used. It is used.

However, when the PVD method is used, in the thin film growth process, columnar growth or island-like growth is generally performed. Therefore, grain boundaries are generated in the film, and high barrier properties are exhibited. Have difficulty. In addition, the film formation by the CVD method has less grain boundary than the film formation by the PVD method, but it is not sufficient, and it generates particles compared to the PVD method, and barrier performance such as pinholes. Defects that degrade. When grain boundaries and defects are present in the film, the gas barrier performance is saturated even if the film thickness is increased.

For the purpose of supplementing the insufficient gas barrier performance of the metal oxide layer formed by the PVD method or the CVD method, JP 2011-241421A further describes a layer formed by the PVD method / CVD method on A manufacturing method in which a gas barrier layer is laminated using an atomic layer deposition method is disclosed. By performing film formation by the atomic layer deposition method, defects such as pinholes and grain boundaries generated by the PVD method / CVD method can be covered or filled.

However, when the gas barrier film in which the metal oxide film formed by the atomic layer deposition method is laminated on the gas barrier layer formed by the PVD method / CVD method is disposed under a high temperature and high humidity condition In particular, especially during bending, the gas barrier performance was remarkably lowered, and the required gas barrier performance was not achieved.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a gas barrier film that has excellent gas barrier performance and maintains sufficient gas barrier performance even when stored under high temperature and high humidity conditions. It is to be.

The gas barrier film of the present invention includes a base material, a first layer having barrier performance, and a second layer formed by atomic layer deposition in this order, and the second layer is made of aluminum, titanium, silicon. Including a region having a carbon concentration of 0.3 at% or more and 3.0 at% or less with respect to the total amount of zirconium, nitrogen, oxygen and carbon with respect to the film thickness of the second layer, and the second It is characterized in that the carbon concentration with respect to the total amount of aluminum, titanium, silicon, zirconium, nitrogen, oxygen and carbon in the layer is 3.0 at% or less.

It is a schematic diagram which shows an example of the vacuum plasma CVD apparatus used for formation of the 1st layer concerning this invention. 101 is a plasma CVD apparatus, 102 is a vacuum chamber, 103 is a cathode electrode, 105 is a susceptor, 106 is a heat medium circulation system, 107 is a vacuum exhaust system, 108 is a gas introduction system, 109 is a high-frequency power supply, 110 is a substrate, 160 is A heating / cooling apparatus is shown. It is a schematic diagram which shows an example of the manufacturing apparatus used for formation of the 1st layer concerning this invention. 11 is a gas barrier film, 12 is a base material, 13 is a manufacturing apparatus, 14 is a delivery roller, 15, 16, 17, and 18 are transport rollers, 19 and 20 are film forming rollers, 21 is a gas supply pipe, and 22 is a plasma

generator Power source

23, 24 and 24 are magnetic field generators, 25 is a winding roller, and 26 is a first layer. It is a schematic diagram which shows an example of the manufacturing apparatus used for formation of the 2nd layer concerning this invention. Reference numeral 80 denotes a feed roller, 81 denotes a take-up roller, and 82 denotes a substrate. It is a schematic diagram which shows another example of the manufacturing apparatus used for formation of the 2nd layer concerning this invention. 83 is a delivery roller, 84 is a substrate, 85 and 88 are guide rolls, 86 is MR, 87 is a coating head, 89 is a winding roller, and 90 is a temperature adjusting means. FIG. 5 is a schematic diagram illustrating an example of a coating head for ALD film formation used in the apparatus illustrated in FIGS. 3 and 4. Reference numeral 70 denotes a coating head, 71 denotes a source gas supply device, 72 denotes an inert gas supply device, 73 denotes a second gas supply device, 74 denotes a gas introduction pipe, 75 denotes an exhaust pipe, and 76 denotes a substrate. It is an example of the organic electroluminescent panel which is an electronic device using the gas barrier film which concerns on this invention as a sealing film. 4 is a transparent electrode, 5 is an organic EL element, 6 is an adhesive layer, 7 is a counter film, 9 is an organic EL panel, and 10 is a gas barrier film. It is the schematic for demonstrating the interface of a 1st layer and a 2nd layer in case a 1st layer and a 2nd layer have a different metal as a main component. It is the schematic for demonstrating the interface of a 1st layer and a 2nd layer in case a 1st layer and a 2nd layer have the same kind metal as a main component.

One embodiment of the present invention includes a substrate, a first layer having a barrier performance, and a second layer formed by an atomic layer deposition method in this order, and the second layer has a carbon concentration of 0.3 at. The total amount of aluminum, titanium, silicon, zirconium, nitrogen, oxygen, and carbon in the second layer is 30% or more with respect to the film thickness of the second layer. It is a gas barrier film characterized by having a carbon concentration of 3.0 at% or less. The gas barrier film of the present invention has excellent gas barrier properties and exhibits sufficient gas barrier performance even under high temperature and high humidity conditions.

The present invention is characterized in that it has a second layer formed by an atomic layer deposition method on a first layer having gas barrier performance and in which a region where carbon exists is present in a certain amount or more. With such a configuration, not only the initial gas barrier performance is excellent, but the gas barrier performance (particularly flex resistance) is maintained even when the gas barrier film is stored under high temperature and high humidity conditions.

Although the detailed mechanism is unknown, it is presumed that the mechanism that achieves the above-mentioned effect by the configuration of the present invention is as follows.

Since the second layer is formed by the atomic layer deposition method, it has a repair effect of covering or filling defects such as pinholes and grain boundaries of the first layer generated by the PVD method / CVD method. The inorganic oxide formed by the atomic layer deposition method has a relatively small molecular weight, can fill in the minute defects present in the first layer, and can repair the minute defects.

Furthermore, since a certain concentration of carbon atoms is present in a certain region or more in the second layer, a flexible portion is generated in the film as compared with a film formed only from an inorganic oxide such as silicon oxide, It is considered that the occurrence of cracks is also suppressed when the film is bent. Further, in a humid heat environment, a change in shape (expansion / shrinkage) of the base material due to changes in temperature and humidity occurs. Such a shape change of the substrate is larger than that of the gas barrier layer. On the other hand, since the carbon atoms are present in the second layer, the film is more flexible than a film formed only from an inorganic oxide such as silicon oxide. The layers are also easily expanded, and the upper and lower sides (base material and second layer) of the first gas barrier layer are similarly expanded in the lateral direction, so that the external force applied to the first layer is reduced, and the first Since the layer is protected, it is considered that the gas barrier performance does not deteriorate even when stored under high temperature and high humidity conditions.

However, if the carbon concentration in the second layer is high, it tends to react with H ₂ O in the air, and the film composition tends to change over time. For this reason, the carbon concentration in the second layer needs to be 3.0 at% or less.

In addition, the said mechanism is estimation and the effect of this invention is not bound to these mechanisms.

Therefore, in the gas barrier film of the present invention, a preferred embodiment is that the base material, the first layer, and the second layer formed (directly) on the first layer are arranged in this order. It is a form to have.

In addition, the gas barrier unit having the first layer and the second layer may be formed on one surface of the base material, or may be formed on both surfaces of the base material. The gas barrier unit may include a layer that does not necessarily have a gas barrier property.

In addition, the gas barrier film of the present invention preferably has a permeated water amount measured by the method described in Examples below, of less than 1 × 10 ⁻³ g / (m ² · 24 h).

Hereinafter, preferred modes for carrying out the present invention will be described in detail, but the present invention is not limited thereto. 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%.

[First layer]
The thickness of the first layer is not particularly limited, but is usually in the range of 20 to 1000 nm, preferably 50 to 300 nm in order to improve the gas barrier performance while making it difficult to cause defects. The film thickness referred to here is the total of each sub-layer when it is composed of a plurality of sub-layers. Here, the thickness of the first layer employs a film thickness measurement method by observation with a transmission microscope (TEM) described later. The first layer may have a stacked structure including a plurality of sublayers. In this case, the number of sublayers is preferably 2 to 30. Moreover, each sublayer may have the same composition or a different composition.

The first layer has gas barrier performance. Here, having gas barrier performance means that only the first layer is laminated on the base material, and the permeated water amount measured by the method described in Examples below is 0.1 g / (m ² · 24 h) or less. It is more preferable that it is 0.01 g / (m ² · 24h) or less.

The first layer preferably contains at least one oxide, nitride, oxynitride, or oxycarbide selected from the group consisting of silicon, aluminum, and titanium. Specific examples of the at least one oxide, nitride, oxynitride, or oxycarbide selected from the group consisting of silicon, aluminum, and titanium include silicon oxide (SiO ₂ ), silicon nitride, silicon oxynitride ( These composites include SiON), silicon oxycarbide (SiOC), silicon carbide, aluminum oxide, titanium oxide, and aluminum silicate. These may contain other elements as secondary components.

The first layer can be formed by physical vapor deposition or chemical vapor deposition. The physical vapor deposition method is a method in which a thin film of a target substance is deposited on the surface of the substance by a physical method in a gas phase, and these methods include vapor deposition (resistance heating method, electron beam evaporation, molecular beam). Epitaxy), ion plating, sputtering, and the like. On the other hand, in the chemical vapor deposition method (chemical vapor deposition method), a raw material gas containing a target thin film component is supplied onto a base material, and a film is deposited by a chemical reaction on the substrate surface or in the gas phase. It is a method to do. In addition, there is a method of generating plasma etc. for the purpose of activating chemical reaction, and known CVD methods such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, plasma CVD method, atmospheric pressure plasma CVD method, etc. In the present invention, any of them can be advantageously used.

Hereinafter, the plasma CVD method which is a preferable form among the CVD methods will be described in detail.

FIG. 1 is a schematic view showing an example of a vacuum plasma CVD apparatus used for forming the first layer according to the present invention.

In FIG. 1, the vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface side inside the vacuum chamber 102. Further, a cathode electrode 103 is disposed on the ceiling side inside the vacuum chamber 102 at a position facing the susceptor 105. A heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are disposed outside the vacuum chamber 102. A heat medium is disposed in the heat medium circulation system 106. The heat medium circulation system 106 stores a pump for moving the heat medium, a heating device for heating the heat medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heat medium, and a set temperature of the heat medium. A heating / cooling device 160 having a storage device is provided.

The heating / cooling device 160 is configured to measure the temperature of the heat medium, heat or cool the heat medium to a stored set temperature, and supply the heat medium to the susceptor 105. The supplied heat medium flows inside the susceptor 105, heats or cools the susceptor 105, and returns to the heating / cooling device 160. At this time, the temperature of the heat medium is higher or lower than the set temperature, and the heating and cooling device 160 heats or cools the heat medium to the set temperature and supplies the heat medium to the susceptor 105. Thus, the cooling medium circulates between the susceptor and the heating / cooling device 160, and the susceptor 105 is heated or cooled by the supplied heating medium having the set temperature.

The vacuum chamber 102 is connected to an evacuation system 107, and before the film formation process is started by the vacuum plasma CVD apparatus 101, the inside of the vacuum chamber 102 is evacuated in advance and the heat medium is heated from room temperature. The temperature is raised to a set temperature, and a heat medium having the set temperature is supplied to the susceptor 105. The susceptor 105 is at room temperature at the start of use, and when a heat medium having a set temperature is supplied, the susceptor 105 is heated.

After circulating the heat medium at a set temperature for a certain time, the substrate 110 to be deposited is carried into the vacuum chamber 102 while maintaining the vacuum atmosphere in the vacuum chamber 102 and placed on the susceptor 105.

A large number of nozzles (holes) are formed on the surface of the cathode electrode 103 facing the susceptor 105. The cathode electrode 103 is connected to a gas introduction system 108. When a CVD gas is introduced from the gas introduction system 108 to the cathode electrode 103, the CVD gas is ejected from the nozzle of the cathode electrode 103 into the vacuum chamber 102 in a vacuum atmosphere.

The cathode electrode 103 is connected to a high frequency power source 109, and the susceptor 105 and the vacuum chamber 102 are connected to a ground potential.

When a CVD gas is supplied from the gas introduction system 108 into the vacuum chamber 102, a high-frequency power source 109 is activated while a heating medium having a constant temperature is supplied from the heating / cooling device 160 to the susceptor 105, and a high-frequency voltage is applied to the cathode electrode 103, Plasma of the introduced CVD gas is formed.

When the CVD gas activated in the plasma reaches the surface of the substrate 110 on the susceptor 105, a first layer which is a thin film grows on the surface of the substrate 110.

In this case, the distance between the susceptor 105 and the cathode electrode 103 is set as appropriate.

Further, the flow rates of the raw material gas and the cracked gas are appropriately set in consideration of the raw material gas, the cracked gas type and the like. In one embodiment, the flow rate of the source gas is 5 to 300 sccm, and the flow rate of the decomposition gas is 10 to 1000 sccm.

During the growth of the thin film, a heating medium having a constant temperature is supplied from the heating / cooling device 160 to the susceptor 105, and the susceptor 105 is heated or cooled by the heating medium, and a thin film is formed while being maintained at a constant temperature.

Generally, the lower limit temperature of the growth temperature when forming a thin film is determined by the film quality of the thin film, and the upper limit temperature is determined by the allowable range of damage to the thin film already formed on the substrate 110.

The lower limit temperature and upper limit temperature vary depending on the material of the thin film to be formed, the material of the thin film already formed, etc., but the lower limit temperature is 50 ° C. or more in order to ensure the film quality with high gas barrier properties, It is preferable that it is below the heat-resistant temperature.

The correlation between the film quality of the thin film formed by the vacuum plasma CVD method and the film formation temperature and the correlation between the damage to the film formation target (substrate 110) and the film formation temperature are obtained in advance, and the lower limit temperature and the upper limit temperature are determined. Is done. For example, the temperature of the substrate 110 (at the start of film formation) during the vacuum plasma CVD process is preferably 20 to 250 ° C.

Furthermore, the relationship between the temperature of the heat medium supplied to the susceptor 105 and the temperature of the substrate 110 when plasma is formed by applying a high frequency voltage of 13.56 MHz or more to the cathode electrode 103 is measured in advance, and vacuum plasma CVD is performed. In order to maintain the temperature of the substrate 110 between the lower limit temperature and the upper limit temperature during the process, the temperature of the heat medium supplied to the susceptor 105 is required.

For example, the lower limit temperature (here, 50 ° C.) is stored, and a heat medium whose temperature is controlled to a temperature equal to or higher than the lower limit temperature is set to be supplied to the susceptor 105. The heat medium refluxed from the susceptor 105 is heated or cooled, and a heat medium having a set temperature of 50 ° C. is supplied to the susceptor 105. For example, as a CVD gas, a mixed gas of silane gas, ammonia gas, and nitrogen gas is supplied, and the SiN film is formed in a state where the substrate 110 is maintained at a temperature condition not lower than the lower limit temperature and not higher than the upper limit temperature.

Immediately after the startup of the vacuum plasma CVD apparatus 101, the susceptor 105 is at room temperature, and the temperature of the heat medium returned from the susceptor 105 to the heating / cooling apparatus 160 is lower than the set temperature. Therefore, immediately after the activation, the heating / cooling device 160 heats the refluxed heat medium to raise the temperature to the set temperature, and supplies it to the susceptor 105. In this case, the susceptor 105 and the substrate 110 are heated and heated by the heat medium, and the substrate 110 is maintained in a range between the lower limit temperature and the upper limit temperature.

When a thin film is continuously formed on a plurality of substrates 110, the susceptor 105 is heated by heat flowing from the plasma. In this case, since the heat medium recirculated from the susceptor 105 to the heating / cooling device 160 is higher than the lower limit temperature (50 ° C.), the heating / cooling device 160 cools the heat medium and converts the heat medium at the set temperature into the susceptor. It supplies to 105. Thereby, it is possible to form a thin film while maintaining the substrate 110 in a range between the lower limit temperature and the upper limit temperature.

Thus, the heating / cooling device 160 heats the heating medium when the temperature of the refluxed heating medium is lower than the set temperature, and cools the heating medium when the temperature is higher than the set temperature. In addition, a heat medium having a set temperature is supplied to the susceptor, and as a result, the substrate 110 is maintained in a temperature range between the lower limit temperature and the upper limit temperature.

Once the thin film has been formed to a predetermined thickness, the substrate 110 is unloaded from the vacuum chamber 102, the undeposited substrate 110 is loaded into the vacuum chamber 102, and a heating medium having a set temperature is supplied as described above. A thin film is formed.

The above operation may be repeated if necessary.

(Suitable form of the first layer)
The first layer has a condition (i) a distance (L) from the surface of the first layer in the thickness direction of the first layer, and the amount of silicon atoms relative to the total amount of silicon atoms, oxygen atoms, and carbon atoms. Silicon distribution curve showing the relationship with the ratio (atomic ratio of silicon), oxygen distribution showing the relationship between 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) 80% of the thickness of the first layer in the curve and the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of L and silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio) In the above region (upper limit: 100%), the following formula (A): formula (A) (carbon atomic ratio) <(silicon atomic ratio) <(oxygen atomic ratio) or the following formula (B): B) (average atomic ratio of oxygen) <(atomic ratio of silicon) <(atomic ratio of carbon) It is preferable to have a magnitude relation represented by ordered in.

Since the first layer has the above relationship, carbon atoms exist in addition to silicon atoms and oxygen atoms. Among these, the presence of silicon atoms and oxygen atoms is preferable because gas barrier properties can be imparted, and the presence of carbon atoms can impart flexibility to the barrier layer, which improves moisture and heat resistance. Here, at least 80% or more of the film thickness of the first layer does not need to be continuous in the barrier layer, and simply needs to satisfy the above-described relationship at a portion of 80% or more.

In the above distribution curve, the relationship between 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. It is more preferable to satisfy | fill, and it is more preferable to satisfy | fill in the area | region of 93% or more (upper limit: 100%). Preferably, in the region of 80% or more (upper limit: 100%) of the film thickness of the first layer, (oxygen atomic ratio), (silicon atomic ratio), (carbon atomic ratio) increase in this order. (Atomic ratio is O> Si> C, order magnitude relationship represented by formula (A)). By satisfying such conditions, the resulting gas barrier film has sufficient gas barrier properties and flexibility.

Here, the film thickness of the first layer in the “region of 80% or more of the film thickness of the first layer” in the condition (i) is calculated from the distribution curve obtained by “XPS depth profile measurement” described below. The film thickness of the first layer.

In the case where the adjacent layer is a base material (particularly a resin base material) or an organic layer (such as a curable resin layer, a smooth layer, and an easy adhesion layer), in the silicon distribution curve (at%) and the carbon distribution curve (at%), When plotting XPS depth profile data in the depth direction, a point P where the silicon atomic ratio changes by −0.5 at% / nm or more and the carbon atomic ratio changes by +1.0 at% or more is defined as the first layer. And the interface between adjacent layers.

This is because at the interface between the first layer and an adjacent layer (an organic layer such as an intermediate layer formed on the base material) due to the nature of the measurement when performing composition analysis with an XPS depth profile. This is because there is always a transition region in which both compositions are mixed.

XPS can obtain information on the elemental composition and chemical state of the surface by irradiating the sample surface with X-rays under vacuum and observing the kinetic energy of photoelectrons emitted from the surface into the vacuum by the photoelectric effect. Although it is possible, near the interface at the time of the X-ray irradiation, X-rays reach not only the film but also the base material, and there is a transition region that is mixed in composition due to the influence thereof, It is difficult to specify a clear position as an interface. Therefore, the “film thickness of the first layer calculated from the distribution curve obtained by XPS depth profile measurement” in the present invention refers to the first layer from the interface between the first layer and the second layer. It is defined as the distance to the point P that is the transition point in the transition region where both the component and the component of the base material or the organic layer are detected.

Furthermore, the interface between the first layer and the second layer is determined as follows.

i) When the first layer and the second layer are mainly composed of dissimilar metals (for example, when the first layer is a layer made of SiOC and the second layer is a layer made of AlOC) in the depth direction When XPS depth profile data is plotted, the intersection of two different metals is taken as the interface (see FIG. 7A). Here, the main component refers to a metal or silicon atom having the highest content ratio among all metals and silicon atoms, and preferably refers to a metal that is 80 at% or more in all metals and silicon atoms.

ii) When the first layer and the second layer are mainly composed of the same kind of metal (for example, when the first layer is a layer made of SiOC and the second layer is a layer made of SiOC), the depth from the surface When the XPS depth profile data is plotted in the direction, the change amount a of the C amount in the second layer is a = δC (at%) / δ sputter depth (nm) ≧ 2, and the second A point where the carbon value from the surface of the layer to the above point satisfies both the average value within ± 2 at% of the interval is A, and when the carbon content is observed in a direction where the sputter depth is deeper than the point A, The change amount a of the C amount of the two layers is a = δC (at%) / δ sputter depth (nm) <2, and the value of the carbon amount in the direction from the point toward the deeper sputter depth is The point where the carbon amount is within ± 5 at% for 5 nm or more, and the carbon concentration difference Δ from the point A is 3 at% or more. And B, and it defines the midpoint of the points A and B and the interface.

In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve, in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 80% or more of the film thickness of the first layer, the formula ( When the condition of A) is satisfied, the atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer is preferably 25 to 45 at%, preferably 30 to 40 at%. % Is more preferable. The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the first layer is preferably 33 to 67 at%, and preferably 45 to 67 at%. More preferred. Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the layer is preferably 3 to 33 at%, and more preferably 3 to 25 at%.

The first layer of the present invention is a carbon / oxygen distribution curve showing the relationship between the distance (L) from the surface of the first layer in the film thickness direction of the first layer and the ratio of the amount of carbon atoms to oxygen atoms. It is preferable that the carbon / oxygen distribution curve has at least two extreme values. The existence of such an extreme value indicates that the carbon and oxygen abundance ratio in the film is a non-uniform layer, and the presence of a part having a large number of carbon atoms results in the entire layer being It becomes a flexible structure and the flexibility is improved. The first layer preferably has a carbon / oxygen distribution curve having at least 3 extreme values, more preferably at least 5 extreme values. In addition, in the apparatus shown in FIG. 2 described later, when the number of opposed rolls (the number of TRs, the number of two opposite roll sets) is n (n is an integer of 1 or more), the theoretical number of extreme values is Approximately (5 + 4 × (n−1)). However, the actual number of extreme values is not always the theoretical number of extreme values depending on the conveyance speed of the substrate, and may increase or decrease. When the extreme value of the carbon / oxygen distribution curve is two or more, the gas barrier property when the obtained gas barrier film is bent is sufficient. The upper limit of the extreme value of the carbon / oxygen 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.

A silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and a carbon / oxygen distribution curve can be obtained by combining X-ray photoelectron spectroscopy (XPS) measurement with rare gas ion sputtering such as argon. It can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of each element and the horizontal axis as the etching time (sputtering time). In this way, in the element distribution curve with the horizontal axis as the etching time, the etching time is the distance (L) from the surface of the first layer in the film thickness direction of the first layer in the film thickness direction. Since there is a general correlation, the “distance from the surface of the first layer in the film thickness direction of the first layer” is calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. The distance from the surface of one layer (that is, SiO ₂ equivalent film thickness (nm) = (etching time (sec) × etching rate (nm / sec)) can be employed.

In the present invention, the silicon distribution curve, oxygen distribution curve, carbon distribution curve and carbon / oxygen distribution curve were prepared under the following measurement conditions.

[Measurement condition]
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): SiO ₂ equivalent film thickness of the barrier film ÷ 20 nm
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval.

Also, when plotting a film produced by a plasma CVD apparatus having a counter roll electrode, the plot position is defined by the number of counter rolls that pass (etching interval below).

[Measurement condition]
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value) (data plot interval): SiO ₂ equivalent film thickness of the barrier film ÷ 10 ÷ TR number (number of opposing rolls) (nm)
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopic AlKα X-ray spot and size: 800 × 400 μm ellipse.

In addition, the more rapid the change in the carbon / oxygen composition distribution in the film thickness direction, the more remarkable is the effect of maintaining gas barrier performance under high-temperature and high-humidity conditions (improving wet heat resistance) by laminating the second layer. It becomes. From this point of view, the effect of the present invention is remarkably obtained when the interval between at least one set of adjacent extreme values is 1 to 10 nm in the carbon / oxygen distribution curve. The effect is more remarkable when the distance between at least one set of adjacent extreme values is 1 to 7 nm. As described above, the film having the first layer having a small interval between adjacent extreme values, that is, a rapid change in the composition of the film, has a remarkable decrease in gas barrier performance under high temperature and high humidity conditions. Even if it is a simple film, the fall of the gas barrier performance at the time of high temperature and high humidity is suppressed by providing a 2nd layer. Surprisingly, a film comprising a first layer (the second layer is a layer having an extreme interval larger than the extreme interval in the first layer of the film of the present invention) Gas barrier performance at high temperature and high humidity is good. The interval between at least one pair of adjacent extreme values is a value proportional to the conveyance speed of the base material when the apparatus shown in FIG. Specifically, when the conveyance speed of the base material is increased, the interval between adjacent extreme values tends to be shortened. In consideration of a realistic conveyance speed, the interval between at least one set of adjacent extreme values is 1 nm or more. Here, in the carbon / oxygen distribution curve, the first layer in which the distance between at least one pair of adjacent extreme values is 10 nm or less is particularly when the substrate conveying speed is 1 m / min or more in the apparatus of FIG. It can be formed easily. Furthermore, if it is 3 m / min or more, it will be easier. That is, in a preferred embodiment of the present invention, the first layer is a layer formed by a plasma CVD method using a plasma CVD apparatus having a counter roll electrode. In the carbon / oxygen distribution curve, It is a form that satisfies the requirement that the interval between at least one set of adjacent extreme values is 1 to 10 nm (more preferably 1 to 7 nm).

The interval between the extreme values in the carbon / oxygen distribution curve is obtained from the carbon / oxygen distribution curve, and is calculated from the SiO ₂ equivalent film thickness (nm) from the surface of the first layer of each extreme value. Note that the interval between adjacent extreme values refers to the distance from the surface of the first layer in the thickness direction of the first layer at one extreme value of the carbon / oxygen distribution curve and the extreme value adjacent to the extreme value. The absolute value of the difference in distance (L) (hereinafter also simply referred to as “distance between extreme values”). In addition, the “extreme value” in the carbon / oxygen distribution curve refers to a maximum value or a minimum value of C / O (carbon atom / oxygen atom) in the carbon / oxygen distribution curve. The maximum value in the carbon / oxygen distribution curve is a point where the value of the atomic ratio of carbon atoms to oxygen atoms (C / O) changes from increasing to decreasing when the distance from the surface of the first layer is changed. That means. Further, the minimum value in the carbon / oxygen distribution curve is that the value of the atomic ratio (C / O) of the carbon to oxygen element changes from decreasing to increasing when the distance from the surface of the first layer is changed. I mean.

Alternatively, in the first layer, the film thickness (nm) measured by the film thickness measurement method by observation with a transmission electron microscope (TEM) described in the examples described later is divided by the number of extreme values of the carbon / oxygen distribution curve. The measured value (hereinafter referred to as “film thickness (nm) by TEM / number of extreme values”) is preferably 20 (nm / number) or less. This value indicates the relationship between the film thickness and the extreme value. For example, when the film thickness is the same and the number of extreme values on one side is larger, the first layer having the larger number of extreme values is more The extreme value interval is smaller than that of the other first layer. Therefore, it can be said that the composition in the film thickness direction changes as the film thickness (nm) by TEM / the number of extreme values decreases. In this invention, even if it is a film which has a 1st layer which has such a rapid in-film composition change, the fall of the gas barrier performance at the time of high temperature and high humidity is suppressed. The lower limit of the film thickness (nm) / extreme number by TEM is not particularly limited, but is usually 3.5 (nm / number) or more. When the film thickness (nm) / extremum number by TEM is 15 (nm / number) or less, since the effect is particularly great, it is more preferable. Here, the first layer whose film thickness (nm) / extreme number by TEM is 20 (nm / number) or less is the substrate conveyance speed in the apparatus of FIG. 2 (that is, when TR number = 1). Can be formed easily, particularly when the conveyance speed is 1.5 m / min or more. Further, in the oxygen / carbon distribution curve, the effect is large when at least one set of adjacent extreme value intervals is 1 to 10 nm, and more than two sets. That is, in a preferred embodiment of the present invention, the first layer is a layer formed by a plasma CVD method using a plasma CVD apparatus having a counter roll electrode, and is a transmission electron microscope (TEM). In this embodiment, the value obtained by dividing the film thickness (nm) measured by the film thickness measurement method by observation by the number of extreme values of the carbon / oxygen distribution curve is 20 (nm / number) or less.

Also, the carbon distribution curve preferably has at least two extreme values, preferably has at least three extreme values, and more preferably has at least five extreme values. When the carbon distribution curve has at least two extreme values, the carbon atom ratio continuously changes with a concentration gradient, and the gas barrier performance during bending is enhanced. Here, the “extreme value” in the carbon distribution curve means the distance (L) from the surface of the first layer in the film thickness direction of the first layer and the maximum or minimum value of carbon atoms in the carbon distribution curve. That means. In addition, the maximum value in the carbon distribution curve means that when the distance from the surface of the first layer is changed, the value of the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms decreases from an increase. This is a change. Furthermore, the minimum value in the carbon distribution curve means that when the distance from the surface of the first layer is changed, the value of the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms increases from a decrease. It refers to a changing point.

The oxygen distribution curve of the first layer preferably has at least one extreme value, more preferably at least two extreme values, more preferably at least three extreme values, and at least five extreme values. It is particularly preferred to have 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. Here, the “extreme value” in the oxygen distribution curve is the distance (L) from the surface of the first layer in the film thickness direction of the first layer, and the maximum or minimum value of oxygen atoms in the oxygen distribution curve. That means. Further, the maximum value in the oxygen distribution curve means that when the distance from the surface of the first layer is changed, the value of the oxygen atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms decreases from an increase. A point that changes. Furthermore, the minimum value in the oxygen distribution curve means that when the distance from the surface of the first layer is changed, the value of the oxygen atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms increases from a decrease. A point that changes.

Moreover, it is preferable that the total amount of carbon and oxygen atoms in the film thickness direction of the first layer is substantially constant. Thereby, the 1st layer exhibits moderate flexibility, and the crack generation at the time of bending of a gas barrier film can be controlled and prevented more effectively. More specifically, the total amount of oxygen atoms and carbon atoms with respect to the distance (L) from the surface of the barrier layer in the film thickness direction of the first layer and the total amount of silicon atoms, oxygen atoms, and carbon atoms. In the distribution curve showing the relationship with the ratio (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 distribution curve (hereinafter simply referred to as “OC _max −OC”). preferably also referred _min difference ") is less than 5at%, more preferably less than 4at%, more preferably less than 3at%. 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%.

From the viewpoint of forming the first layer having a uniform and excellent gas barrier property over the entire film surface, the first layer is substantially uniform in the film surface direction (direction parallel to the surface of the first layer). It is preferable that Here, the fact that the first layer is substantially uniform in the film surface direction means that the oxygen distribution curve and the carbon distribution curve are measured at any two measurement points on the film surface of the first layer by XPS depth profile measurement. When the oxygen carbon 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 value of the atomic ratio of carbon in each carbon distribution curve And the absolute value of the difference between the minimum values is the same as each other or within 5 at%.

Furthermore, 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. Satisfying the condition expressed by the following formula (1) in the relationship between the distance from the surface in the film thickness direction (x, unit: nm) and the atomic ratio of carbon (C, unit: at%). Say.

The formation method of the first layer is not particularly limited, and can be applied in the same manner as the conventional method or appropriately modified. The first layer is preferably a chemical vapor deposition (CVD) method, particularly a plasma chemical vapor deposition method (plasma CVD, plasma-enhanced chemical vapor deposition (PECVD), hereinafter also simply referred to as “plasma CVD method”). It is preferably formed by.

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

Although it does not specifically limit as a plasma CVD method, The plasma CVD method using the plasma CVD method of the atmospheric pressure or the atmospheric pressure described in the international publication 2006/033233, and the plasma CVD apparatus with a counter roll electrode is mentioned. . In particular, since the productivity is high, it is preferable to form the first layer by a plasma CVD method using a plasma CVD apparatus having a counter roll electrode. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

Hereinafter, a method for forming the first layer by plasma CVD using a plasma CVD apparatus having a counter roll electrode will be described.

When generating plasma in the plasma CVD method, it is preferable to generate a plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and a substrate is provided for each of the pair of film forming rollers. (Here, the base material includes a form in which the base material has been processed or has an intermediate layer on the base material) and discharge between a pair of film forming rollers to generate plasma. Is more preferable. 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 to form a film on the surface part of the base material existing on the other film, and simultaneously form the film on the surface part of the base material present on the other film forming roller, so that a thin film can be produced efficiently. In addition, the film formation rate can be doubled compared to the normal plasma CVD method that does not use a roller, and a film with substantially the same structure can be formed, so it is possible to at least double the extreme value in the carbon distribution curve. Thus, it is possible to efficiently form a layer that satisfies the above conditions (i) and (ii).

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 addition, the first layer is preferably a layer formed by a continuous film formation process.

Moreover, it is preferable that the gas barrier film according to the present invention forms the first 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. 2 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 the first layer will be described in more detail with reference to FIG. FIG. 2 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the first layer. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

The production apparatus 13 shown in FIG. 2 includes a delivery roller 14,

transport rollers

15, 16, 17, 18,

film formation rollers

19, 20, a gas supply pipe 21, a plasma generation power source 22, and a film formation roller 19. And 20 are provided with

magnetic field generators

23 and 24 and winding rollers 25. Further, in such a manufacturing apparatus, at least the

film forming rollers

19 and 20, the gas supply pipe 21, the plasma generating power source 22, and the magnetic

field generating apparatuses

23 and 24 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 13, 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 generating plasma so that the pair of film-forming rollers (film-forming roller 19 and film-forming roller 20) can function as a pair of counter electrodes. 22 is connected. Therefore, in such a manufacturing apparatus 13, it is possible to discharge to the space between the film forming roller 19 and the film forming roller 20 by supplying electric power from the plasma generating power source 22, thereby Plasma can be generated in the space between the film roller 19 and the film formation roller 20. In addition, when using the film-forming roller 19 and the film-forming roller 20 as electrodes as described above, the material and design may be changed as appropriate so that the film-forming roller 19 and the film-forming roller 20 can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable that the pair of film forming rollers (film forming rollers 19 and 20) be arranged so that their central axes are substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 19 and 20), the film forming rate can be doubled as compared with a normal plasma CVD method that does not use a roller, and the structure is the same. Since the film can be formed, the extreme value in the carbon distribution curve can be at least doubled. And according to such a manufacturing apparatus, on the surface of the base material 12 (here, the base material includes a form in which the base material is processed or has an intermediate layer on the base material) by the CVD method. The first layer 26 can be formed on the film forming roller 19 while the first layer component is deposited on the surface of the base material 12 on the film forming roller 19 and also on the film forming roller 20. Since the first layer component can also be deposited on the surface, the barrier layer can be efficiently formed on the surface of the substrate 12.

In the film forming roller 19 and the film forming roller 20,

magnetic field generators

23 and 24 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

The

magnetic field generators

23 and 24 provided on the film forming roller 19 and the film forming roller 20 respectively are a magnetic field generator 23 provided on one film forming roller 19 and a magnetic field generator provided on the other film forming roller 20. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between the magnetic field generators 24 and the

magnetic field generators

23 and 24 form a substantially closed magnetic circuit. By providing such

magnetic field generators

23 and 24, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell in the vicinity of the opposing surface of each of the

film forming rollers

19 and 20, 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

23 and 24 provided on the film forming roller 19 and the film forming roller 20 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generating device 23 and the other magnetic field generating device. It is preferable to arrange the magnetic poles so that the magnetic poles facing 24 have the same polarity. By providing such

magnetic field generators

23 and 24, 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

23 and 24 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 focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. The material 12 is excellent in that the first layer 26 which is a vapor deposition film can be efficiently formed.

As the film forming roller 19 and the film forming roller 20, known rollers can be appropriately used. As such

film forming rollers

19 and 20, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently. The diameters of the

film forming rollers

19 and 20 are 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 is not deteriorated, and it is possible to avoid applying the total amount of plasma discharge to the substrate 12 in a short time. It is preferable because damage to the material 12 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 13, the base material 12 is disposed on a pair of film forming rollers (the film forming roller 19 and the film forming roller 20) so that the surfaces of the base material 12 face each other. By disposing the base material 12 in this way, when the plasma is generated by performing discharge in the facing space between the film forming roller 19 and the film forming roller 20, the base existing between the pair of film forming rollers is present. Each surface of the material 12 can be formed simultaneously. That is, according to such a manufacturing apparatus, the barrier layer component is deposited on the surface of the substrate 12 on the film forming roller 19 by the plasma CVD method, and the barrier layer component is further deposited on the film forming roller 20. Therefore, the barrier layer can be efficiently formed on the surface of the substrate 12.

As the feed roller 14 and the

transport rollers

15, 16, 17, 18 used in such a manufacturing apparatus, known rollers can be used as appropriate. Further, the winding roller 25 is not particularly limited as long as the gas barrier film 11 having the first layer 26 formed on the substrate 12 can be wound, and a known roller is appropriately used. be able to.

Further, as the gas supply pipe 21 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 21 serving as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 19 and the film formation roller 20 and is a vacuum serving as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. In this way, by providing the gas supply pipe 21 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 19 and the film formation roller 20. It is excellent in that the film formation efficiency can be improved.

Furthermore, as the plasma generating power source 22, a known power source for a plasma generating apparatus can be used as appropriate. Such a power source 22 for generating plasma supplies power to the film forming roller 19 and the film forming roller 20 connected thereto, and makes it possible to use them as a counter electrode for discharging. Such a plasma generation power source 22 can perform plasma CVD more efficiently, so that the polarity of the pair of film forming rollers can be alternately reversed (AC power source or the like). Is preferably used. In addition, since the plasma generating power source 22 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

23 and 24, known magnetic field generators can be used as appropriate. Furthermore, as the base material 12, in addition to the base material used in the present invention, a material in which the first layer 26 is formed in advance can be used. As described above, by using the substrate 12 in which the first layer 26 is formed in advance, the thickness of the first layer 26 can be increased.

Using such a manufacturing apparatus 13 shown in FIG. 2, 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 first layer can be produced by appropriately adjusting the speed. That is, using the manufacturing apparatus 13 shown in FIG. 2, a discharge is generated between the pair of film forming rollers (film forming rollers 19 and 20) while supplying a film forming gas (raw material gas or the like) into the vacuum chamber. As a result, the film-forming gas (such as source gas) is decomposed by plasma, and the first layer 26 is formed on the surface of the base material 12 on the film-forming roller 19 and on the surface of the base material 12 on the film-forming roller 20. It is formed by the plasma CVD method. 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 axis of the

film forming rollers

19 and 20, and the plasma is converged on the magnetic field. Therefore, when the substrate 12 passes through the point A of the film forming roller 19 and the point B of the film forming roller 20 in FIG. 2, the maximum value of the carbon / oxygen distribution curve is formed in the first layer. . On the other hand, when the substrate 12 passes through the points C1 and C2 of the film forming roller 19 and the points C3 and C4 of the film forming roller 20 in FIG. 2, the carbon / oxygen distribution in the first barrier layer. A local minimum of the curve is formed. For this reason, five extreme values are usually generated for two film forming rollers.

The distance between the extreme values of the first layer (the surface of the first barrier layer in the film thickness direction of the first layer at one extreme value of the carbon / oxygen distribution curve and the extreme value adjacent to the extreme value) (The absolute value of the difference in distance (L) from) can be adjusted by the rotation speed of the film forming rollers 19 and 20 (the conveyance speed of the substrate). In such film formation, the substrate 12 is transported by the delivery roller 14 and the film formation roller 19, respectively, so that the surface of the substrate 12 is formed by a roll-to-roll continuous film formation process. First layer 26 is formed.

As the film forming gas (raw material gas or the like) supplied from the gas supply pipe 21 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 first layer 26 can be appropriately selected and used according to the material of the first layer 26 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 first layer 26.

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 and xenon; hydrogen; nitrogen 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 making the ratio of the reaction gas excessive, it is excellent in that excellent barrier properties and bending resistance can be obtained by the first layer 26 to be formed. 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, the first layer that satisfies the above conditions (i) and (ii) cannot be formed. Therefore, when forming the first layer, the oxygen amount is set to a stoichiometric ratio of 12 with respect to 1 mol of hexamethyldisiloxane so that the reaction of the reaction formula (1) does not proceed completely. It is preferable to make it less than a mole. 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 at 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) and (ii) It is possible to form a first layer that satisfies the above), and to exhibit excellent gas barrier properties and bending 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.

Further, in such a plasma CVD method, an electrode drum (in this embodiment, the film forming roller 19) connected to the plasma generating power source 22 for discharging between the film forming roller 19 and the film forming roller 20. The power to be 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 substrate 12 can be adjusted as appropriate 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 100 m / min.

In the plasma CVD apparatus having the counter roll electrode as shown in FIG. 2, the gas barrier performance is maintained even when the film is placed under high temperature and high humidity conditions when the substrate transport speed is increased for the purpose of increasing productivity. The For this reason, when the conveyance speed of a base material is quick, the effect of this invention becomes more remarkable. That is, a preferable manufacturing method of the present invention includes a step of forming a first layer containing silicon, oxygen, and carbon by conveying a substrate to a plasma CVD apparatus having a counter roll electrode at a conveyance speed of 1 m / min or more. And a step of forming a second layer containing an inorganic oxide by an atomic layer deposition method. In a more preferred form, the first layer containing silicon, oxygen and carbon is formed by transporting the substrate to a plasma CVD apparatus having a counter roll electrode at a transport speed of 5 m / min or more (more preferably 10 m / min or more). Including the steps of: The upper limit of the line speed is not particularly limited, and is preferably faster from the viewpoint of productivity. However, if it is 100 m / min or less, it is excellent in that a sufficient thickness can be secured as a barrier layer.

As described above, as a more preferable aspect of the present embodiment, the first layer is formed by a plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is characterized by. 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.

[Second layer]
The second layer is formed by an atomic layer deposition method (ALD method). Hereinafter, the second layer is also referred to as an ALD layer.

The second layer preferably contains an inorganic oxide, an inorganic nitride, or an inorganic oxynitride, and more preferably contains an inorganic oxide, from the viewpoint of gas barrier performance.

The inorganic oxide is not particularly limited, and examples thereof include oxides and composite oxides such as aluminum, titanium, silicon, zirconium, hafnium, and lanthanum. The inorganic oxide is selected from the group consisting of Al ₂ O ₃ , TiO ₂ , SiO ₂ and ZrO from the viewpoint of obtaining a good quality film at a temperature of 50 to 120 ° C. in consideration of forming a film on a resin substrate. It is preferable to contain at least one selected from the above. Since the material can be impregnated with minute defects, it is more preferable to include Al ₂ O ₃ and TiO ₂ in consideration of the molecular weight of the material.

The inorganic nitride is not particularly limited, and examples thereof include nitrides such as aluminum, titanium, silicon, zirconium, hafnium, lanthanum, and composite nitrides.

In addition, by adjusting the introduction time of each gas, the film formation temperature, and the pressure during film formation, intermediate oxides such as AlOx, TiOx, SiOx, ZrOx, nitrides, and the like are also possible. no problem.

The thickness of the second layer is preferably 1 to 100 nm, and more preferably 10 to 50 nm. When the film thickness of the second layer is 1 nm or more, the effect of the ALD layer such as repair of fine defects is appropriately obtained, and in view of the ALD film forming speed, it is preferably 100 nm or less from the viewpoint of productivity.

Although the second layer has gas barrier performance, the gas barrier performance of the second layer alone may not be high because the gas barrier performance of the first layer is high. Therefore, the gas barrier performance of the second layer is such that the amount of permeated moisture measured by the method described in Examples below in the laminate in which the second layer is formed on the substrate is 0.5 g / (m ² · 24 h) or less, and more preferably 0.1 g / (m ² · 24 h) or less.

In the present invention, in the second layer, the carbon concentration with respect to the total amount of aluminum, titanium, silicon, zirconium, nitrogen, oxygen and carbon is in a range of 0.3 at% to 3.0 at% (hereinafter simply referred to as carbon-containing). Is also 30% or more of the thickness of the second layer. When the region having a carbon concentration of 0.3 at% or more and 3.0 at% or less is 30% or more with respect to the film thickness of the second layer, wet heat resistance is improved. When a certain number of carbon atoms are present in the second layer, when a flexible part is generated in the film and the film is bent as compared with a film formed only from an inorganic oxide such as silicon oxide. It is thought that the occurrence of cracks is also suppressed. Further, in a humid heat environment, a change in shape (expansion / shrinkage) of the base material due to changes in temperature and humidity occurs. Such a shape change is larger than that of the gas barrier layer. On the other hand, since the carbon atoms are present in the second layer, the film is more flexible than a film formed only from an inorganic oxide such as silicon oxide. The layers are also easily expanded, and the upper and lower sides (base material and second layer) of the first gas barrier layer are similarly expanded in the lateral direction, so that the external force applied to the first layer is reduced, and the first Since the layer is protected, it is considered that the gas barrier performance does not deteriorate even when stored under high temperature and high humidity conditions.

In addition, the carbon-containing region may not be continuous in the second layer, may be discontinuous, and when the carbon-containing region is discontinuous, the total film thickness of the carbon-containing region is equal to that of the second layer. It becomes 30% or more with respect to the film thickness.

The upper limit of the ratio in the film thickness direction of the region where the carbon concentration is 0.3 at% or more is not particularly limited, and the carbon concentration is 0.1 in all regions (100% with respect to the film thickness of the second layer). It may be 3 at% or more and 3.0 at% or less. The carbon-containing region is preferably 40% or more, and more preferably 50% or more. The upper limit of the carbon-containing region is 100% (the carbon concentration in the layer is 0.3 to 3.0 at%). However, in order to ensure the initial gas barrier performance, the carbon concentration region is low (the carbon concentration is 0.00%). (Region of less than 3 at%) is preferably present, and the region of 0.3 at% or more and 3.0 at% or less is preferably 70% or less with respect to the film thickness of the second layer.

The carbon (atom) concentration in the second layer is 3.0 at% or less with respect to the total amount of aluminum, titanium, silicon, zirconium, nitrogen, oxygen and carbon. That is, the maximum value of the carbon concentration in the second layer is 3.0 at% or less. When the carbon concentration in the second layer is high, it tends to react with H ₂ O in the air, the film composition tends to change over time, and the resistance to moist heat is significantly reduced. For this reason, the carbon concentration in the second layer needs to be 3.0 at% or less. The carbon concentration in the second layer is preferably 2.5 at% or less. The carbon concentration in the second layer refers to the carbon concentration in the film thickness direction measured by the following XPS depth profile measurement. Further, when performing the XPS depth profile, the composition changes easily under the influence of the surface in the vicinity of the surface. For this reason, the interface between the surface and the second layer is defined as follows.

i) When the carbon concentration changes abruptly by 5 at% or more in the range of sputter depth of 0 to 3 nm and the metal component increases rapidly in contradiction. Carbon component slope Δ Carbon concentration (at%) / Δ Sputter depth The point where (nm) is less than 0.5 at% / nm is defined as the surface. Since the etching rate is 0.05 nm / sec, it can be said that the amount of change in carbon every 0.05 nm is less than 0.5 at% / nm.

Ii) Except i), the sputtering depth is from 3 nm to the outermost surface (interface between the surface and the second layer).

The region having a low carbon concentration (region having a carbon concentration of less than 0.3 at%) is preferably present on the surface side of the second layer opposite to the substrate. This is because when the carbon concentration is large in the surface layer, the carbon on the surface reacts with moisture in the atmosphere, the film composition changes, and as a result, internal stress is generated in the film and the initial gas barrier performance decreases. It is.

Therefore, in a preferred embodiment of the present invention, the region within at least 3 nm from the outermost surface of the second layer has an average carbon concentration of 0. 0 relative to the total amount of aluminum, titanium, silicon, zirconium, nitrogen, oxygen and carbon. It is less than 3 at%. When the average carbon concentration in the region within 3 nm from the outermost surface is less than 0.3 at%, the initial gas barrier performance is enhanced. Here, the “region within 3 nm from the outermost surface” means that the average carbon concentration of “region within 3 nm from the outermost surface” is essentially less than 0.3 at%, and the average carbon up to the region exceeding 3 nm. It means that the concentration may be less than 0.3 at%. Here, a region within at least 3 nm from the outermost surface indicates a region where “distance from the surface of the second layer in the film thickness direction of the second layer” is within 3 nm in the following XPS depth profile. In addition, the calculation method of “distance from the surface of the second layer in the film thickness direction of the second layer” in the XPS depth profile is the same as the method described in the first layer.

The carbon concentration in the film thickness direction in the second layer is sequentially measured while exposing the inside of the sample by using both X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon. It can be measured by so-called XPS depth profile measurement in which surface composition analysis is performed. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of carbon elements and the horizontal axis as the etching time (sputtering time).

In the present invention, it was created under the following measurement conditions.

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

Also, the average carbon concentration within 3 nm from the outermost surface is a value obtained by measuring the carbon composition in the film thickness direction, integrating the carbon content in the film thickness direction, and dividing by the integrated film thickness.

In the following examples, after the ALD film is formed, it is kept in the atmosphere at room temperature of 20 to 30 ° C. (humidity) for one week or longer, and then X-ray photoelectron spectroscopy is performed under the conditions described above. The carbon concentration in the film thickness direction was measured by (XPS: Xray Photoelectron Spectroscopy). Moreover, in the film after manufacture, when the ALD layer is the outermost layer, the surface is the outermost surface, and when another adjacent layer is laminated on the ALD layer, the adjacent layer and the ALD layer Is the outermost surface. As described above, there are some carbon atoms in the second layer. The carbon atoms in the second layer are preferably those in which carbon atoms contained in the source gas remain. Therefore, it is preferable to use a gas containing carbon atoms as the source gas.

The ALD method is a method of depositing atomic layers one by one by introducing two or more kinds of gases (first gas and second gas) alternately onto a substrate. A desired film thickness is obtained by repeating the film forming cycle.

In the ALD method, a first gas, which is a source gas, is first introduced onto a first layer to form a gas molecular layer, and then an inert gas (purge gas) is introduced to purge the first gas ( Remove. Note that the gas molecule layer of the formed first gas is not purged even when an inert gas is introduced by chemical adsorption. Next, an inorganic film is formed by oxidizing a gas molecular layer formed by introducing a second gas (for example, an oxidizing gas) which is a reactive gas. Finally, the second gas is purged by introducing an inert gas, and one cycle of the ALD method is completed. By repeating the cycle, atomic layers are deposited one by one, and a second layer having a predetermined thickness can be formed. Note that the ALD method can form an inorganic film including a shaded portion regardless of the unevenness of the surface of the lower layer.

The method for controlling the concentration of carbon atoms in the second layer includes (1) controlling the introduction time of the first gas so that the first gas is not completely purged, and / or inert gas. A method for controlling the introduction time (hereinafter referred to as the method (1)) may be mentioned.

When the source gas is adsorbed on the first layer, the source gas is adsorbed in layers. Here, in the normal ALD method, the source gas that is not adsorbed by the inert gas is purged, so that only the gas molecule layer of the first gas adsorbed in the lower layer remains as a single layer. Since this gas molecule layer is almost completely oxidized by the second gas, almost no carbon atoms remain in the gas molecule layer.

On the other hand, after the first gas is introduced onto the substrate to form the gas molecular layer, the introduction time of the source gas and / or the introduction time of the inert gas is controlled so that the source gas is not completely purged. By doing so, the gas molecule layers remain stacked (multiple gas molecule layers not adsorbed on the lower layer exist). When the second gas is introduced in this state, only the surface of the gas molecular layer is oxidized, so that the gas molecules in the lower layer other than the surface layer are not oxidized and remain as the source gas containing carbon atoms. Therefore, a layer having a carbon concentration gradient in the film thickness direction is formed in one cycle of the ALD method. Similarly, by repeating the cycle, a layer having a carbon concentration distribution in the film thickness direction is formed.

Therefore, a preferred embodiment of the present invention is a method for producing a gas barrier film comprising a substrate, a first layer having barrier performance, and a second layer formed by an atomic layer deposition method in this order. The atomic layer deposition method includes a step (1) of introducing a first gas, which is a source gas containing carbon, onto the first layer, and purging the first gas by introducing an inert gas. A step (2), a step (3) for introducing a second gas which is an oxidizing gas, and a step (4) for purging the second gas by introducing an inert gas in this order, A region having a carbon concentration of 0.3 at% or more and 3.0 at% or less is included at 30% or more with respect to the film thickness of the second layer, and the carbon concentration in the second layer is 3.0 at% or less. In addition, the introduction time of the first gas is controlled in the step (1). Controls the deployment time of the inert gas in the step (2) is a method for producing the gas barrier film.

In the method (1), the introduction time of the first gas is appropriately set in balance with the purge time of the gas, the film formation rate, and the like. The time is preferably from 05 to less than 0.3 seconds, and more preferably from 0.01 to 0.15 seconds. The suitable first gas introduction time may be satisfied in all cycles, or a part of the cycle may satisfy the suitable first gas introduction time. Preferably, the above-mentioned preferable range is preferably at least in the region of the second layer on the substrate side. Specifically, the second layer side of the entire film thickness (the first half cycle of ALD lamination) It is preferable that the cycle for forming a region exceeding 25% of the above is at least within the above range, preferably within the above preferable range at a region of 50% or more, and within the above preferable range in all cycles. preferable.

In the method (1), the first gas purge time (inert gas introduction time) is preferably 0.1 to less than 20 seconds in at least one cycle, and is preferably 0.1 to 4.0 seconds. More preferably. The suitable inert gas introduction time may be satisfied in all cycles, or a part of the cycle may satisfy the suitable inert gas introduction time. As described above, since the form in which carbon does not remain on the surface side of the second layer is suitable, the preferred range is applied in a cycle when forming the region on the substrate side. Specifically, the region on the substrate side in this case is a region having a film thickness of 30% or more, preferably 40% or more, more preferably 50% or more from the substrate side, and preferably 80% or more. % Or less. On the contrary, when forming a region within 3 nm from the outermost surface, the purge time is set longer than the region having a carbon concentration of 0.3 at% or more and 3.0 at% or less so that the average carbon concentration is less than 0.3 at%. It is preferable to make it longer.

Further, since the carbon concentration in the second layer can be easily adjusted appropriately, the purge time (second) of the first gas / second introduction time (second) of the first gas in the step (2) = 10 to 100 It is preferable to include a certain process, and it is more preferable to include a process in which the purge time of the first gas (seconds) / the introduction time of the first gas (seconds) = 10 to 50. The preferred ratio may be satisfied in all cycles, and a part of the cycle may satisfy the preferred ratio. However, as described above, the surface side of the second layer is made of carbon. Since the form which does not remain is suitable, it is preferable that the suitable range is applied in a cycle when forming the region on the substrate side. For example, in the first half cycle (base material side) of film formation, the ratio is within the above-mentioned preferable range, and in the second half cycle (surface layer side), the normal ratio (for example, more than 100 and 500 or less) is performed. Is mentioned.

As another method for controlling the concentration of carbon atoms in the second layer, in addition to the method (1), (2) the formation thickness of the first gas in one cycle in the atomic layer deposition method is controlled. A method, (3) a method of using water or ozone as a reactive gas used in the atomic layer deposition method, (4) a method of controlling the substrate temperature when forming the second layer by introducing an oxidizing gas, etc. Can be mentioned. These control methods may be performed in all cycles or only in some cycles. That is, in a preferred embodiment of the present invention, in addition to the method of (1), (2) the formation thickness of the first gas in one cycle in the atomic layer deposition method is 0.2 to 0.5 nm. (3) the reaction gas used in the atomic layer deposition method is water or ozone, and (4) the temperature of the substrate in the step (2) is 120 ° C. or less (2) A method for producing a gas barrier film satisfying at least one of (4) to (4).

In the case of the above method (2), it is preferable to control the formation film thickness of the first gas in one cycle to be relatively thick. The larger the film thickness formed in one cycle, the more a source gas molecular layer is formed by laminating a number of monomolecular layers. Of the source gas molecular layers in the oxidation step by introducing the oxidizing gas in the next step, The monomolecular layer close to the surface layer is oxidized, and the molecular layer close to the first layer remains without being oxidized. For this reason, since the carbon concentration of the molecular layer closer to the first layer becomes high, the carbon concentration distribution in the second layer becomes large (a region with a high carbon concentration tends to exist). For this reason, resistance to moist heat resistance is improved. From such a viewpoint, it is preferable that the formation thickness of the first gas in at least one cycle in the atomic layer deposition method is 0.2 nm / cycle or more. On the other hand, the film thickness formed in at least one cycle is preferably 0.5 nm / cycle or less. By setting the formed film thickness to 0.5 nm / cycle or less, a region having an excessively high carbon concentration does not exist, and the initial gas barrier performance is maintained, which is preferable. In addition, the said suitable cycle speed may be satisfy | filled in all the cycles, and a part in cycle may satisfy | fill the said suitable cycle speed. For example, in the first half cycle (substrate side) of the film formation, the cycle rate is within the above-mentioned preferable range, and in the second half cycle (surface side), the normal cycle speed (for example, 0.05 to 0.2 nm / cycle) For example, a mode in which gas is introduced. Here, the region on the substrate side is specifically a region having a film thickness of 30% or more, preferably 40% or more, more preferably 50% or more from the substrate side, and preferably 80%. % Or less.

In the case of the above method (3), if the oxidizing power of the oxidizing agent is strong, it becomes difficult to control the progress of oxidation of the raw material gas. For this reason, it is preferable to use water or ozone as the oxidant since the progress of the reaction is mild and the oxidation of the molecular layer of the source gas is easy to control.

In the case of the above method (4), if the substrate temperature at the time of forming the second layer is high, the reaction between the molecular layer of the source gas and the oxidizing gas easily proceeds, and the oxidation of the source gas easily proceeds. The carbon concentration in the second layer is reduced. Specifically, the substrate temperature during the second gas reaction is preferably 120 ° C. or less, and preferably 100 ° C. or less. The lower limit of the substrate temperature is not particularly limited, but the film formation temperature requires activation of the substrate surface for adsorption of gas molecules to the substrate, and the film formation temperature may be high to some extent. preferable. For this reason, when using a plastic base material, it is preferable that the base-material temperature at the time of reaction is 50 degreeC or more.

A plurality of (2) to (4) may be combined, or all may be combined.

Conventional materials known in the art can be used as the source gas, reaction gas, and inert gas used in the ALD method.

For example, when the inorganic oxide of the second layer is aluminum oxide, the first gas may be a gas obtained by vaporizing an aluminum compound, and the second gas may be an oxidizing gas. The inert gas is a gas that does not react with the first gas and / or the second gas.

The reaction gas is not particularly limited, and the source gas may be appropriately selected depending on the inorganic oxide film to be formed. Ritala: Appl. Surf. Sci. 112, 223 (1997) can be used.

As described above, the reaction gas used in the present invention preferably contains a gas obtained by vaporizing a compound containing carbon atoms.

Examples of the compound containing a carbon atom include aluminum compounds such as trimethylaluminum (TMA) and triethylaluminum (TEA); aminosilane-based tetrakisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₄ , 4DMAS), trisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₃ H, 3DMASi), bisdiethylaminosilane (Si [N (C ₂ H ₅ ) ₂ ] ₂ H ₂ , 2DEAS), Vistaly butylaminosilane (SiH ₂ [NH (C ₄ H ₉₎ )] ₂ , BTBAS) and the like; titanium (IV) isopropoxide (Ti [(OCH) (CH ₃ ) ₂ ] ₄ ), tetrakisdimethylaminotitanium ([(CH ₃ ) ₂ N] ₄ Ti, TDMAT ), Tetrakisdiethylaminotitanium (Ti [N (C _{_{_{_{2 CH 3) 2] 4,}}}} TDEATi), tetramethyl titanium (Ti _(CH _{3) 4,} tetrakis (ethylmethylamino) titanium _{_{_{_{(Ti [N (CH 2 C}}}} 2 H 5) 2] 4, TMEAT) titanium such as Compound: Examples include zirconium compounds such as tetrakisdimethylaminozirconium (IV) ([(CH ₃ ) ₂ N] ₄ Zr).

In addition, in addition to the compound containing the carbon atom, a gas obtained by vaporizing the other compound may be included. Other compounds include trichloroaluminum; monochlorosilane (SiH ₃ Cl, MCS), hexachlorodisilane (Si ₂ Cl ₆ , HCD), tetrachlorosilane (SiCl ₄ , STC), trichlorosilane (SiHCl ₃ , TCS), etc. Chlorosilanes, inorganic materials such as trisilane (Si ₃ H ₈ , TS), disilane (Si ₂ H ₆ , DS), monosilane (SiH ₄ , MS); titanium tetrachloride (TiCl ₄ ) and the like.

The first gas is preferably obtained by vaporizing a compound having a molecular weight of 240 or less because it is effective to repair minute defects in the first layer and the initial gas barrier performance is improved. Compounds having a molecular weight of 240 or less include trimethylaluminum (TMA, molecular weight 72.1), triethylaluminum (TEA, molecular weight 114.17), tetramethoxytitanium (Ti (CH ₃ ) ₄ , molecular weight 172), tetrakisdimethylamino And titanium ([(CH ₃ ) ₂ N] ₄ Ti, TDMAT, molecular weight 224.21).

The oxidizing gas is not particularly limited as long as it can oxidize the gas molecular layer. For example, ozone (O ₃ ), water (H ₂ O), hydrogen peroxide (H ₂ O ₂ ), methanol (CH ₃ ). OH), ethanol (C ₂ H ₅ OH) and the like can be used. It is also possible to use oxygen radicals. In the case of using radicals, it is possible to generate high-density oxygen radicals by exciting the gas using a high-frequency power source (for example, a power source having a frequency of 13.56 MHz), which further promotes oxidation and nitridation reactions. be able to. Considering the increase in size and practicality of the apparatus, it is desirable to discharge in ICP (Inductively Coupled Plasma) mode using a 13.56 MHz power source. Among them, it is preferable to use water or ozone as the oxidizing agent because the reaction progress is mild and the oxidation of the molecular layer of the source gas is easy to control (form of the above method (3)).

In addition, nitrogen radicals can be used when nitrides and nitride oxides are desired. Nitrogen radicals can be generated in the same manner as the oxygen radical generation described above.

As the inert gas (purge gas), a rare gas (helium, neon, argon, krypton, xenon), nitrogen gas, or the like can be used.

The introduction time of the second gas is preferably 10 seconds or less, and more preferably 5 seconds or less. It is preferable that the introduction time of the second gas is 5 seconds or less because the reaction of the second layer does not proceed completely and the carbon concentration in the second layer is easily controlled. The introduction time of the second gas is preferably 0.1 seconds or more, and more preferably 0.5 seconds or more. It is preferable that the introduction time of the second gas is 0.5 seconds or longer because an inorganic oxide or the like can be formed and the gas barrier performance can be improved.

The introduction time of the inert gas for purging the second gas is preferably 0.05 to 10 seconds. It is preferable that the introduction time of the inert gas is 0.05 seconds or longer because the second gas can be sufficiently purged. On the other hand, an inert gas introduction time of 10 seconds or less is preferable because the time required for one cycle can be reduced and the influence on the formed atomic layer is small.

The second layer may be formed using a roll-to-roll film forming apparatus. When the first layer is produced by the roll-to-roll method, the film can be continuously produced by the roll-to-roll method. Therefore, when the second layer is formed using a roll-to-roll film forming apparatus, productivity is improved. Improved and preferred. As an apparatus used when forming the second layer by the roll-to-roll method, apparatuses described in US Patent Application Publication No. 2007/0224348 and US Patent Application Publication No. 2008/0026162 can be used.

Furthermore, as the formation of the second layer by the roll-to-roll method, as described in JP-T 2010-541242, an apparatus as shown in FIGS. 3 and 4 can be used. In the roll-to-roll apparatus for ALD film formation in FIG. 3, the substrate 82 (on which the first layer and other layers are laminated if necessary) is unwound from the feed roller 80, and taken up by the take-up roller 81. It is done. While being conveyed from the feed roller 80 to the take-up roller 81, the second layer is formed by the gas supplied from the coating head. In the roll-to-roll apparatus for ALD film formation in FIG. 4, the base material 84 (with the first layer and other layers laminated if necessary) is unwound from the feed roller 83, and the base material is guided by the guide roll 85. Then, it is supplied onto the MR (main roll) 86. A coating head 87 is disposed on the MR, and the substrate 84 is exposed to a gas supplied from the coating head. The temperature of the substrate 84 is appropriately adjusted by the temperature adjusting means 90 before being supplied to the coating head. Next, the base material 84 on which the second layer is formed passes through the guide roll 88 and is taken up by the take-up roller-89. As the guide roll, a stepped roll as disclosed in JP-A-2009-256709 may be used so as to be in contact with the film formation surface (barrier surface) and the water vapor transmission rate is not deteriorated. Furthermore, in order to suppress scratches on the film-forming surface during winding, if an adhesive protective film is attached to the film-forming surface before winding with a winding roller or a protective layer is provided, damage during winding will occur. Is more preferable ("protective film winding" shown in FIGS. 3 and 4). In particular, by providing an adhesive protective film, it helps to protect the gas barrier film surface from damage, and is easy to install on an object to which the gas barrier film is applied. The adhesive protective film is not particularly limited as long as it can be applied to a gas barrier film, and conventionally known ones can be used. For example, acrylic resin, urethane resin, epoxy resin, polyester resin, melamine resin, phenol resin, polyamide, Those formed of a ketone resin, a vinyl resin, a hydrocarbon resin or the like can be used.

FIG. 5 is a schematic diagram showing an example of a coating head for ALD film formation used in the apparatus shown in FIGS. Referring to FIG. 5, the coating head 70 includes a source gas supply device 71 that supplies a source gas, an inert gas supply device 72 that supplies an inert gas, a second gas supply device that supplies a second gas, and a gas. An introduction pipe 74 and an exhaust pipe 75 are provided. The substrate 76 (laminated with the first layer and other layers if necessary) is conveyed in the A to B directions. First, the source gas is supplied from the first gas (source gas) supply device 71 through the gas introduction pipe 74 to the base material. The supplied gas is then exhausted through the exhaust pipe 75. Next, an inert gas is introduced into the base material 76 from the inert gas supply device 72 and the source gas is purged (removed). Next, the second gas is introduced from the second gas (for example, oxidizing gas) supply device 73 through the gas introduction pipe 74 to form an inorganic film. Finally, the inert gas is introduced from the inert gas supply device 72 to purge the second gas, and one cycle of the ALD method is completed. The inert gas and the second gas are exhausted through the exhaust pipe before the gas supply in the next step. The source gas and the second gas may be supplied after being mixed with an inert gas (carrier gas) (see FIGS. 3 and 4). In the coating head, it suffices to provide as many gas introduction pipes and exhaust pipes as the number of cycles necessary to achieve a desired film thickness, and a plurality of coating heads may be used to obtain the desired number of cycles. .

By using an ALD apparatus that can be manufactured by these roll-to-roll methods, an ALD film can be formed with high productivity.

〔Base material〕
The gas barrier film of the present invention usually uses a plastic film 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 the barrier laminate, and can be appropriately selected depending on the purpose of use and the like. 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.

Since the gas barrier film can be used as a 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.

The thickness of the plastic film used for the gas barrier film is appropriately selected depending on the application and is not particularly limited, 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 smooth 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 employed.

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.

Various known treatments for improving adhesion, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, or both sides of the substrate, at least on the side where the barrier layer (curable resin layer) according to the present invention is provided, or The smooth layers can be laminated and combined as necessary.

[Middle layer]
An intermediate layer may be separately provided on the substrate, the first layer, and the second interlayer or the surface as long as the effects of the present invention are not impaired.

It is preferable to have a layer or a curable resin layer obtained by modifying a coating film formed by applying a liquid containing a silicon compound on the second layer. By having such a layer, there is an effect of protecting the barrier layer from stress such as thermal expansion and bending of the substrate.

(A layer obtained by modifying a coating film formed by applying a liquid containing a silicon compound (hereinafter also simply referred to as a silicon compound modified layer))
(Silicon compound)
The silicon compound is not particularly limited as long as a coating solution containing the silicon compound can be prepared.

Specifically, for example, perhydropolysilazane, organopolysilazane, silsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, Tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldivinylsilane, dimethyl Ethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-trifluoro Ropropyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltriacetoxy Silane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxysilane, diaryldimethoxysilane, butyldimethoxy Vinylsilane, trimethyl-3-vinylthiopropylsilane, phenyltrimethylsila , Dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3-glycidoxy Propyltrimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethoxyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3- Methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, di Butoxydimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane, di Acetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycidoxypropylmethylsilane , Octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylphenylsilane, diphenylmethyl Vinylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1,3-divinyl-1,1,3,3- Tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) tetramethyldi Siloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotri Siloxane, octamethylcyclotetrasiloxane, 1,3, , It may be mentioned 7-tetraethoxy-1,3,5,7-tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.

Among them, polysilazane such as perhydropolysilazane and organopolysilazane; polysiloxane such as silsesquioxane, etc. are preferable in terms of film formation, fewer defects such as cracks, and less residual organic matter, and high gas barrier performance. Polysilazane is more preferable because the barrier performance is maintained even when bent and under high temperature and high humidity conditions.

Polysilazane is a polymer having a silicon-nitrogen bond, such as SiO ₂ , Si ₃ N ₄ having a bond such as Si—N, Si—H, or N—H, and ceramics such as both intermediate solid solutions SiO _x N _y. It is a precursor inorganic polymer.

Specific examples of polysilazanes include paragraphs “0103” to “0117” of International Publication No. 2012-077753 (US Patent Application No. 2013/236710) and paragraphs “0038” to “0056” of JP2013-226758A. And polysilazane described in the above.

The content of polysilazane in the silicon compound modified layer may be 100% by weight when the total weight of the silicon compound modified layer is 100% by weight. When the silicon compound-modified layer contains a material other than polysilazane, the content of polysilazane in the layer is preferably 10% by weight or more and 99% by weight or less, and 40% by weight or more and 95% by weight or less. More preferably, it is 70 wt% or more and 95 wt% or less.

The method for forming the silicon compound modified layer is not particularly limited, and a known method can be applied. However, a coating liquid for forming a silicon compound modified layer containing a silicon compound and, if necessary, a catalyst in an organic solvent is used in a known wet process. A method of applying by a coating method, evaporating and removing the solvent, and then performing a modification treatment is preferable.

(Coating liquid for forming silicon compound modified layer)
The solvent for preparing the coating solution for forming the silicon compound modified layer is not particularly limited as long as it can dissolve the silicon compound, but water and reactive groups (for example, hydroxyl group) that easily react with the silicon compound. An organic solvent that is inert to the silicon compound and more preferably an aprotic organic solvent. Specifically, the solvent includes an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and turben. Hydrogen solvents; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like. The solvent is selected according to the purpose such as the solubility of the silicon compound and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

The concentration of the silicon compound in the coating solution for forming a silicon compound-modified layer is not particularly limited and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by weight, more preferably 5 to 50. % By weight.

The coating solution for forming a silicon compound modified layer preferably contains a catalyst in order to promote the modification.

Further, as described in JP-A-2005-231039, a sol-gel method can be used for forming the silicon compound modified layer.

(Method of applying a coating solution for forming a silicon compound modified layer)
As a method for applying the silicon compound-modified layer forming coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

The coating thickness can be appropriately set according to the purpose. For example, the coating thickness is preferably about 10 nm to 10 μm after drying, more preferably 15 nm to 1 μm, and even more preferably 20 to 500 nm. If the film thickness is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 μm or less, stable coating properties can be obtained during layer formation, and high light transmittance can be realized.

After applying the coating solution, it is preferable to dry the coating film.

A coating film obtained by applying a coating solution for forming a silicon compound modified layer (hereinafter simply referred to as a silicon compound coating film) includes a step of removing moisture before or during the modification treatment. Also good.

(Modification treatment of silicon compound modified layer)
The modification treatment in the present invention refers to a conversion reaction of a silicon compound into silicon oxide or silicon oxynitride. Specifically, the gas barrier film of the present invention as a whole has a gas barrier property (water vapor permeability is 1 × 10 ^{−2). 3} g / (m ² · 24 h) or less) is a treatment for forming an inorganic thin film at a level that can contribute to the development. Therefore, the silicon compound modified layer is also a gas barrier layer having gas barrier properties.

As the conversion reaction of the silicon compound to silicon oxide or silicon oxynitride, a known method based on the conversion reaction of the silicon compound modified layer can be selected. Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment, and vacuum ultraviolet irradiation treatment is particularly preferable. The method and specific conditions for each treatment are described in paragraphs “0132” to “0162” of International Publication No. 2012-077753 (US Patent Application No. 2013/236710), paragraphs “0075” to “0095” of JP2013-232320A. Or the like can be appropriately used.

The thickness of the silicon compound modified layer can be appropriately set according to the purpose. For example, the thickness of the silicon compound modified layer is preferably about 10 nm to 10 μm, more preferably 15 nm to 1 μm, and further preferably 20 to 500 nm. If the film thickness is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 μm or less, stable coating properties can be obtained during layer formation, and high light transmittance can be realized.

(Curable resin layer)
The gas barrier film may have a curable resin layer formed by curing a curable resin on a substrate. 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 with an active energy ray such as ultraviolet ray to be cured is heated. The thermosetting resin etc. which are obtained by curing by the above method. These curable resins may be used alone or in combination of two or more.

Such a curable resin layer is at least one of (1) smoothing the surface of the substrate, (2) relieving the stress of the upper layer to be laminated, and (3) improving the adhesion between the substrate and the upper layer. Has one function. For this reason, the curable resin layer may also be used as a smooth layer and an anchor coat layer (easy adhesion layer) described later.

Examples of the active energy ray-curable material 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, polyester acrylate, polyether acrylate, polyethylene Examples thereof include compositions containing polyfunctional acrylate monomers such as 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 restriction in particular.

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

(Primer layer (smooth layer))
The gas barrier film may have a primer layer (smooth layer) on the surface of the substrate having 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 curable resin layer as long as it has the above-described 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 curable resin layer, and thus the description thereof is omitted here.

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

The smooth layer may be used as the following anchor coat layer.

(Anchor coat layer)
On the surface of the base material, an anchor coat layer may be formed as an easy adhesion layer for the purpose of improving the adhesion (adhesion) with the barrier layer. 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 or two or more 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.

(Bleed-out prevention layer)
In the gas barrier film, a bleed-out prevention layer can be provided. The purpose of the bleed-out prevention layer is to suppress the phenomenon in which unreacted oligomers migrate from the film base material to the surface when the film having the curable resin layer / smooth layer is heated and contaminate the contact surface. And provided on the opposite surface of the substrate having the curable resin layer / smooth layer. The bleed-out prevention layer may basically have the same configuration as the curable resin layer / smooth layer as long as it has this function. As the constituent material and forming method of the bleed-out preventing layer, the materials and methods disclosed in paragraphs “0249” to “0262” of JP2013-52561A are appropriately employed.

The thickness of the bleed-out preventing layer is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of optical properties of the smooth film, and the curable resin layer / smooth layer is transparent. When it is provided on one surface of the polymer film, curling of the gas barrier film can be easily suppressed.

The gas barrier film may be further provided with functionalized layers such as another organic layer, a protective layer, a hygroscopic layer, and an antistatic layer as necessary.

[Method for producing gas barrier film]
In a preferred embodiment of the method for producing a gas barrier film of the present invention, the substrate is transferred to a plasma CVD apparatus having a counter roll electrode at a transfer speed of 1 m / min or more and contains silicon, oxygen and carbon. A method for producing a gas barrier film, comprising: forming a layer; and forming a second layer containing an inorganic oxide by an atomic layer deposition method. In the atomic deposition method, it is more preferable to use at least water or ozone as the oxidizing agent. Since water or ozone rarely has a physical influence on the first layer, micro defects or the like are rarely generated in the lower layer. If the influence on the first layer is taken into consideration, if an inorganic oxide is formed by ALD using water or ozone as the oxidizing agent from the surface of the first layer to about 5 nm, further film formation is possible. Then, for example, an inorganic oxide may be formed by oxygen radicals using ICP or the like. Therefore, a preferred embodiment according to the manufacturing method of the present invention is a method of forming the second layer by an atomic layer deposition method using water or ozone as an oxidizing agent at least from the surface of the first layer to the stacking direction of 5 nm. . Details of each step are as described above for each layer.

[Electronic device]
The gas barrier film of the present invention as described above has excellent gas barrier properties, transparency, and flexibility. Therefore, the gas barrier film of the present invention is a gas barrier film used for electronic devices such as packages such as electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various purposes such as an electronic device using the same.

(Electronic element body)
The electronic element main body is the main body of the electronic device, and is disposed on the gas barrier film side according to the present invention. As the electronic element body, a known electronic device body to which sealing with a gas barrier film can be applied can be used. For example, an organic EL element, a solar cell (PV), a liquid crystal display element (LCD), electronic paper, a thin film transistor, a touch panel, 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. There is no restriction | limiting in particular also about the structure of these electronic element main bodies, It can have a conventionally well-known structure.

Hereinafter, an organic EL element and an organic EL panel using the same will be described as an example of a specific electronic element body.

FIG. 6 shows an example of an organic EL panel 9 which is an electronic device using the gas barrier film 10 according to the present invention as a sealing film. As shown in FIG. 6, the organic EL panel 9 is formed on the gas barrier film 10 through the gas barrier film 10, the transparent electrode 4 such as ITO formed on the gas barrier film 10, and the transparent electrode 4. The organic EL element 5 and a counter film 7 disposed via an adhesive layer 6 so as to cover the organic EL element 5 are provided. It can be said that the transparent electrode 4 forms part of the organic EL element 5. The transparent electrode 4 and the organic EL element 5 are formed on the surface of the gas barrier film 10 on which the gas barrier layer is formed. The counter film 7 may be a gas barrier film according to the present invention in addition to a metal film such as an aluminum foil. When a gas barrier film is used as the counter film 7, the surface on which the gas barrier layer is formed may be attached to the organic EL element 5 with the adhesive layer 6.

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.

(Example 1: Production of gas barrier film 1)
<Preparation of sample>
(Base material)
A 125 μm thick polyester film (manufactured by Teijin DuPont Films Ltd., extremely low heat yield PET Q83), which is a thermoplastic resin and is easily bonded on both sides, was used as a base material.

(Formation of bleed-out prevention layer)
A UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation was applied to one side of the substrate, and after applying with a die coater so that the film thickness after drying was 4 μm, drying conditions: 80 ° C., After drying for 3 minutes, curing was performed in air using a high-pressure mercury lamp, curing conditions: 1.0 J / cm ² to form a bleed-out prevention layer.

(Formation of curable resin layer (smooth layer))
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation is applied to the opposite surface of the base material, and is applied with a die coater so that the film thickness after drying is 4 μm, followed by drying conditions; After drying at 80 ° C. for 3 minutes, curing was performed in an air atmosphere using a high-pressure mercury lamp, curing conditions: 1.0 J / cm ² to form a curable resin layer.

(Preparation of gas barrier film 1)
(Formation of the first layer)
A first layer was formed on the curable resin layer using the vacuum plasma CVD apparatus shown in FIG.

(Deposition conditions by CVD method)
A 50 nm thick SiOC film was formed on the curable resin layer using a vacuum plasma CVD apparatus. As a power source for applying a voltage to the cathode electrode, a high frequency power source of 27.12 MHz was used, and the distance between the electrodes was set to 20 mm. Hexamethyldisiloxane (HMDSO) with a flow rate of 7.5 sccm was used as a source gas, and was introduced into the vacuum chamber together with an oxygen gas with a flow rate of 30 sccm. Further, the substrate temperature at the start of film formation was set to 100 ° C., and the internal pressure of the apparatus at the time of film formation was set to 30 Pa.

Subsequently, a SiO ₂ film having a thickness of 50 nm was formed on the SiOC film using the same vacuum plasma CVD apparatus. A 27.12 MHz high frequency power source was used as the power source, and the distance between the electrodes was 20 mm. Silane gas with a flow rate of 7.5 sccm was used as the source gas, and was introduced into the vacuum chamber together with oxygen gas with a flow rate of 30 sccm. The substrate temperature at the start of film formation was set to 100 ° C., and the internal pressure of the apparatus at the time of film formation was set to 30 Pa.

Subsequently, using the same vacuum plasma CVD apparatus, a SiOC film having a thickness of 50 nm was formed on the SiO ₂ film, and these films (a SiOC film having a thickness of 50 nm and a SiO ₂ film having a thickness of 50 nm and a thickness of 50 nm were formed). A gas barrier layer was formed from the SiOC film. A 27.12 MHz high frequency power source was used as the power source, and the distance between the electrodes was 20 mm. Hexamethyldisiloxane (HMDSO) with a flow rate of 7.5 sccm was used as a source gas, and was introduced into the vacuum chamber together with an oxygen gas with a flow rate of 30 sccm. Further, the substrate temperature at the start of film formation was set to 100 ° C., and the internal pressure of the apparatus at the time of film formation was set to 30 Pa.

(Formation of second layer)
An ALD film was formed using a Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas 2 and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 20.1 nm. The deposition rate was 0.3 nm / cycle (67 cycles). The film formation speed of the ALD film is determined by measuring the film thickness by cross-sectional observation using the transmission electron microscope described below, and the first gas, purge gas, second gas, and purge gas required to form the film thickness. The film formation rate was obtained by dividing the value by the number of cycles taken as one cycle.

<Measurement method of film thickness of each layer>
The film thickness of each layer was measured at 10 locations by cross-sectional observation with a transmission electron microscope (TEM), and the average value was taken as the film thickness.

(TEM image of cross section in film thickness direction)
As a cross-sectional TEM observation, the observation sample was made into a thin piece by the following FIB processing apparatus, and then subjected to TEM observation. (FIB processing)
Device: SII SMI2050
Processed ions: (Ga 30 kV)
Sample thickness: 100 nm to 200 nm (TEM observation)
Apparatus: JEOL JEM2000FX (acceleration voltage: 200 kV)
In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
· Purge gas N ₂ 1.5sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
(Example 2: Production of gas barrier film 2)
In the gas barrier film 1, a gas barrier film 2 was produced in the same manner as in the production of the gas barrier film 1 except that the first layer was formed as follows.

(Formation of the first layer)
A first layer was formed on the curable resin layer using the vacuum plasma CVD apparatus shown in FIG.

(Deposition conditions by CVD method)
A SiO ₂ film having a thickness of 50 nm was formed on the curable resin layer using a vacuum plasma CVD apparatus. A 27.12 MHz high frequency power source was used as the power source, and the distance between the electrodes was 20 mm. Silane gas with a flow rate of 7.5 sccm was used as the source gas, and was introduced into the vacuum chamber together with oxygen gas with a flow rate of 30 sccm. The substrate temperature at the start of film formation was set to 100 ° C., and the internal pressure of the apparatus at the time of film formation was set to 30 Pa.

(Example 3: Production of gas barrier film 3)
In the gas barrier film 1, a gas barrier film 3 was produced in the same manner except that the second layer was formed as follows.

(Formation of second layer)
An ALD film was formed using a Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. ₂ and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 15 nm. The film formation rate was 0.3 nm / cycle (50 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
· Purge gas N ₂ 1.5sec
・ Second gas H ₂ O 1.0 sec
· Purge gas N ₂ 10.0sec
Subsequently, an ALD film was further formed by using Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. ₂ and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 5 nm. The film formation rate was 0.1 nm / cycle (50 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
・ Purge gas N ₂ 15.0 sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
(Example 4: Production of gas barrier film 4)
In the gas barrier film 2, a gas barrier film 4 was produced in the same manner except that the second layer was formed as follows.

(Formation of second layer)
An ALD film was formed using a Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. ₂ and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 15 nm. The deposition rate was 0.3 nm / cycle (50 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
· Purge gas N ₂ 1.5sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
Subsequently, an ALD film was further formed by using Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. ₂ and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 5 nm. The deposition rate was 0.1 nm / cycle (50 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
・ Purge gas N ₂ 15.0 sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
(Example 5: Production of gas barrier film 5)
In the gas barrier film 3, a gas barrier film 5 was produced in the same manner except that the first layer was formed as follows.

(Formation of the first layer)
A first layer of 250 nm was formed on the curable resin layer using the vacuum plasma CVD apparatus shown in FIG. At this time, in the region of 80% or more of the film thickness of the first layer, (i) the following formula (A): formula (A) (atomic ratio of carbon) <(atomic ratio of silicon) <(atomic ratio of oxygen) (Ii) the distance (L) from the surface of the first layer in the film thickness direction of the first layer and the amount of carbon atoms relative to the amount of oxygen atoms. In the carbon / oxygen distribution curve showing the relationship with the ratio, the carbon / oxygen distribution curve had five extreme values.

[Plasma deposition conditions]
<Film forming conditions>
・ Supply amount of source 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: 1.2 kW
・ Power supply frequency for plasma generation: 80 kHz
-Film transport speed: 1 m / min
-Number of times TR passed; 2 times (Example 6: Production of gas barrier film 6)
In the gas barrier film 5, a gas barrier film 6 was produced in the same manner except that a silicon compound modified layer was further formed under the following conditions following the second layer.

(Formation of silicon compound modified layer)
(Preparation of polysilazane coating solution)
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20: manufactured by AZ Electronic Materials Co., Ltd.) and 5% by mass of amine catalyst (N, N, N ′, N′-tetramethyl- 1,6-diaminohexane) and a dibutyl ether solution containing 20% by mass of perhydropolysilazane (Aquamica NAX120-20: manufactured by AZ Electronic Materials Co., Ltd.) at a ratio (mass ratio) of 4: 1, Further, the coating solution was diluted with dibutyl ether so that the solid content of the coating solution was 10% by weight. A polysilazane coating solution was prepared. The obtained coating liquid was 1% by mass (solid content) of the amine catalyst.

(Application of polysilazane coating solution, drying)
The polysilazane coating solution prepared above was applied on the second layer in the atmosphere with an oxygen concentration of about 21% under the condition that the layer thickness after drying was 100 nm, and was applied at 100 ° C. in an atmosphere with an oxygen concentration of about 21%. The sample was provided with a polysilazane layer by drying for a minute. The application was performed at room temperature using a spin coater.

(Modification process)
After fixing the sample on which the polysilazane layer was formed on the operation stage of the following reforming treatment apparatus, the reforming treatment was performed under the following conditions to produce a gas barrier film 6. The “Pass number” in the modification treatment condition is the number of times that the sample passes through the excimer light (ultraviolet) irradiation region in modifying the polysilazane layer.

《Reforming treatment equipment》
Apparatus: Ex D-irradiator MODEL manufactured by M.D. Com: MECL-M-1-200
Wavelength: 172 nm
Lamp filled gas: Xe
<Reforming treatment conditions>
Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 0.1% by volume
Film transport speed: 0.6 m / min
Pass number: 1 time Excimer irradiation time: 5 seconds Energy irradiated to polysilazane coating film at 1 Pass: 3.0 J / cm ²
(Example 7: Production of gas barrier film 7)
In the gas barrier film 5, a gas barrier film 7 was produced in the same manner except that the second layer was formed as follows.

(Formation of the second layer)
An ALD film was formed using a Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TDMAT (tetrakis). Dimethylaminotitanium), H ₂ O as the _second gas, and nitrogen as the purge gas were used, and the cycle was repeated until the film thickness reached 15 nm. The deposition rate was 0.25 nm / cycle (60 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TDMAT 0.05sec
· Purge gas N ₂ 1.5sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
Subsequently, an ALD film was further formed by using Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. ₂ and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 5 nm. The deposition rate was 0.1 nm / cycle (50 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
・ Purge gas N ₂ 15.0 sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
(Example 8: Production of gas barrier film 8)
In the gas barrier film 5, a gas barrier film 8 was produced in the same manner except that the second layer was formed as follows.

(Formation of the second layer)
An ALD film was formed using a Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. 2 and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 15.2 nm. The deposition rate was 0.4 nm / cycle (38 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.10 sec
· Purge gas N ₂ 1.5sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
Subsequently, an ALD film was further formed by using Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. ₂ and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 5 nm. The deposition rate was 0.1 nm / cycle (50 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
・ Purge gas N ₂ 15.0 sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
(Example 9: Production of gas barrier film 9)
In the gas barrier film 3, a gas barrier film 9 was produced in the same manner except that the second layer was formed as follows.

(Formation of second layer)
An ALD film was formed using a Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is tetrakis (ethyl). Methylamido) titanium (IV) (TMEAT) molecular weight 280.28, H ₂ O as the _second gas, nitrogen as the purge gas, and the cycle was repeated until the film thickness reached 14.8 nm. The film formation rate was 0.2 nm / cycle (74 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMEAT 0.05sec
· Purge gas N ₂ 1.5sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
Subsequently, an ALD film was further formed by using Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. ₂ and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 5 nm. The deposition rate was 0.1 nm / cycle (50 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
・ Purge gas N ₂ 15.0 sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
(Example 10: Production of gas barrier film 10)
In the gas barrier film 5, a gas barrier film 10 was produced in the same manner except that the second layer was formed as follows.

An ALD film was formed using a Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. ₂ and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 7.2 nm. The film formation rate was 0.3 nm / cycle (24 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
· Purge gas N ₂ 1.5sec
・ Second gas H ₂ O 1.0 sec
· Purge gas N ₂ 10.0sec
Subsequently, an ALD film was further formed by using Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, The cycle was repeated until the film thickness reached 12.8 nm using H ₂ O as the gas ₂ and nitrogen as the purge gas. The film formation rate was 0.1 nm / cycle (128 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
・ Purge gas N ₂ 15.0 sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
(Comparative Example 1: Production of gas barrier film 11)
In the gas barrier film 1, a gas barrier film 11 was produced in the same manner except that the second layer was formed as follows.

(Formation of second layer)
An ALD film was formed using a Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. ₂ and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 20 nm. The deposition rate was 0.1 nm / cycle (200 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
・ Purge gas N ₂ 15.0 sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
(Comparative Example 2: Production of gas barrier film 12)
In the gas barrier film 1, a gas barrier film 12 was produced in the same manner except that the second layer was formed as follows.

(Formation of second layer)
An ALD film was formed using a Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. 2 and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 15.2 nm. The deposition rate was 0.4 nm / cycle (38 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.15sec
・ Purge gas N ₂ 1.0 sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
Subsequently, an ALD film was further formed by using Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. ₂ and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 5 nm. The deposition rate was 0.1 nm / cycle (50 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
・ Purge gas N ₂ 15.0 sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
(Comparative Example 3: Production of gas barrier film 13)
In the gas barrier film 9, a gas barrier film 13 was produced in the same manner except that the second layer was formed as follows.

An ALD film was formed using a Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used for gas No. 2 and nitrogen was used for purge gas, and the cycle was repeated until the film thickness reached 3.6 nm. The film formation rate was 0.3 nm / cycle (12 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
· Purge gas N ₂ 1.5sec
・ Second gas H ₂ O 1.0 sec
· Purge gas N ₂ 10.0sec
Subsequently, an ALD film was further formed by using Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. 2 and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 16.4 nm. The film formation rate was 0.1 nm / cycle (164 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 0.05sec
・ Purge gas N ₂ 15.0 sec
・ Second gas H ₂ O 1.0 sec
・ Purge gas N ₂ 10.0 sec
(Comparative Example 4: Production of gas barrier film 14)
In the gas barrier film 11, a gas barrier film 14 was produced in the same manner except that the second layer was formed as follows.

An ALD film was formed using a Savannah S200 manufactured by Cambridge NanoTech. Here, the temperature of the substrate is maintained at 100 ° C., the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), and the first gas is TMA, H ₂ O was used as the gas No. ₂ and nitrogen was used as the purge gas, and the cycle was repeated until the film thickness reached 20 nm. The film formation rate was 0.4 nm / cycle (100 cycles). In addition, the supply time of each gas of 1 cycle was as follows.

・ First gas TMA 2.0sec
・ Purge gas N ₂ 2.0 sec
・ Second gas H ₂ O 2.0 sec
・ Purge gas N ₂ 2.0 sec
<Evaluation method of water vapor transmission rate>
The permeated water amount of each gas barrier film was measured according to the following measurement method, and the water vapor barrier property was evaluated according to the following criteria (Table 2, below, initial WVTR).

(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)
Using a vacuum deposition device (manufactured by JEOL Ltd., vacuum deposition device JEE-400) on the surface of the barrier layer of the sample, the portion of the gas barrier film sample to be deposited before attaching the transparent conductive film (9 locations of 12 mm x 12 mm) The metal calcium (granular form) was vapor-deposited (deposition film thickness 80 nm). Thereafter, the mask was removed in a vacuum state, and metal aluminum (φ3 to 5 mm, granular), which is a water vapor impermeable metal, was deposited on the entire surface of one side of the sheet from another metal deposition source. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

Based on the method described in Japanese Patent Application Laid-Open No. 2005-283561, the amount of moisture permeated into the cell was calculated from the corrosion amount of metallic calcium.

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 high temperature and high humidity at 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 and ranked as follows. In addition, if it is rank 3 or more, there is no problem in actual use and it is a pass product.

(Rank evaluation)
Less than 5: 1 × 10 ⁻⁴ g / m ² / day 4: 1 × 10 ⁻⁴ g / m ² / day or more and less than 5 × 10 ⁻⁴ g / m ² / day 3: 5 × 10 ⁻⁴ g / day m ² / day or more, less than 1 × 10 ⁻³ g / m ² / day 2: 1 × 10 ⁻³ g / m ² / day or more, less than 1 × 10 ⁻² g / m ² / day 1: 1 × 10 ^-2 g / m ² / day or more [Evaluation of resistance to high temperature and high humidity]
The obtained gas barrier film was stored for 100 hours continuously in a high-temperature and high-humidity tank (constant temperature and humidity oven: Yamato Humidic Chamber IG47M) adjusted to 85 ° C. and 85% RH without being bent. The film was repeatedly bent 100 times at an angle of 180 degrees so as to have a curvature, and the water vapor transmission rate was measured in the same manner, and the same rank evaluation was performed. In addition, if it is rank 3 or more, there is no problem in actual use and it is a pass product.

Table 1 below shows the composition of each gas barrier film, and Table 2 below shows the evaluation results. In addition, all the 1st layers of the Example and the comparative example had barrier performance.

From the above results, film no. In the gas barrier films 1 to 10, the initial gas barrier performance met the required level, and the gas barrier performance met the required level even after storage at high temperature and high humidity. On the other hand, film No. Although the gas barrier films Nos. 11 to 14 were excellent in the initial gas barrier performance, the gas barrier performance was remarkably lowered by storage under high temperature and high humidity conditions, and the gas barrier performance did not satisfy the required level.

This application is based on Japanese Patent Application No. 2013-129963 filed on June 20, 2013, the disclosure of which is incorporated by reference in its entirety.

Claims

A substrate, a first layer having barrier performance, and a second layer formed by atomic layer deposition in this order;
The second layer has a region having a carbon concentration of 0.3 at% or more and 3.0 at% or less with respect to the total thickness of aluminum, titanium, silicon, zirconium, nitrogen, oxygen and carbon with respect to the thickness of the second layer. 30% or more, and a carbon barrier film having a carbon concentration of 3.0 at% or less with respect to the total amount of aluminum, titanium, silicon, zirconium, nitrogen, oxygen and carbon in the second layer .
The gas barrier according to claim 1, wherein an average carbon concentration with respect to a total amount of aluminum, titanium, silicon, zirconium, nitrogen, oxygen and carbon in a region within a range of at least 3 nm from the surface of the second layer is less than 0.3 at%. Sex film.
The first layer has the following conditions (i) and (ii):
(I) The distance (L) from the surface of the first layer in the film thickness direction of the first layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (silicon atoms Ratio), a silicon distribution curve showing 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 In the carbon distribution curve showing the relationship between L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon),
In the region of 80% or more of the film thickness of the first layer, the following formula (A): formula (A) (atomic ratio of carbon) <(atomic ratio of silicon) <(atomic ratio of oxygen) or the following formula ( B): having an order of magnitude represented by the formula (B) (atomic ratio of oxygen) <(atomic ratio of silicon) <(atomic ratio of carbon),
(Ii) In a carbon / oxygen distribution curve showing the relationship between the distance (L) from the surface of the first layer in the film thickness direction of the first layer and the ratio of the amount of carbon atoms to the amount of oxygen atoms, The gas barrier film according to claim 1 or 2, wherein the carbon / oxygen distribution curve satisfies at least two extreme values.
The layer according to any one of claims 1 to 3, further comprising a layer obtained by modifying a coating film formed by applying a liquid containing a silicon compound on the second layer, or a curable resin layer. The gas barrier film according to Item.
A method for producing a gas barrier film comprising, in this order, a base material, a first layer having barrier performance, and a second layer formed by an atomic layer deposition method, wherein the atomic layer deposition method is a raw material containing carbon A step (1) of introducing a first gas as a gas onto the first layer, a step (2) of purging the second gas by introducing an inert gas, and a second as an oxidizing gas. The step (3) of introducing a gas of (2) and the step (4) of purging the second gas by introducing an inert gas in this order include aluminum, titanium, silicon, zirconium, oxygen and carbon. A region having a carbon concentration of 0.3 at% or more and 3.0 at% or less with respect to the total amount includes 30% or more with respect to the thickness of the second layer, and aluminum, titanium, silicon in the second layer The combination of zirconium, oxygen and carbon The introduction time of the first gas is controlled in the step (1) or the introduction time of the inert gas is controlled in the step (2) so that the carbon concentration with respect to the amount is 3.0 at% or less. The method for producing a gas barrier film according to any one of claims 1 to 4.
The formation thickness of the first gas in at least one cycle in the atomic layer deposition method is 0.2 to 0.5 nm / cycle, the reaction gas used in the atomic layer deposition method is water or ozone, and The manufacturing method of the gas-barrier film of Claim 5 which satisfy | fills at least one of the temperature of the base material in a process (2) being 120 degrees C or less.
The method for producing a gas barrier film according to claim 5 or 6, wherein the first gas is a gas obtained by vaporizing a compound having a molecular weight of 240 or less.