JP2018012234A - Gas barrier film and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film capable of maintaining high gas barrier property for a predetermined period.SOLUTION: A gas barrier film 1 of the present invention includes a gas barrier unit 3 on a substrate 2. The gas barrier unit 3 includes, successively from the substrate 2 side, a first gas barrier region 31, a first reactive region 32 essentially comprising a metal compound, a second gas barrier region 33, a second reactive region 34 essentially comprising a metal compound including a metal element that is an element of a different group in the periodical table from the metal element of the metal compound included as the main component in the first reactive region 32, and a third gas barrier region 35.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier film and an electronic device. In particular, the present invention relates to a gas barrier film capable of maintaining a high gas barrier property for a predetermined period and an electronic device using the same.

Conventionally, as an organic electroluminescence (hereinafter also referred to as “organic EL”) device, a device having a characteristic of using a gas barrier film for a substrate or sealing and being light, unbreakable and bent is being studied. It has been. It is said that a gas barrier film used for an organic EL device needs a water vapor barrier property at a glass level, such as a water vapor permeability of 1 × 10 ⁻⁶ g / (m ² · 24 h).

  In recent years, application of these organic EL devices to highly decorative lighting such as illumination and mobile display devices such as smartphones and smart watches is also under consideration. Since these electronic devices are viewed from a very close position, if there is a dark spot in the organic EL device, it is easily viewed even if it is a minute size. Therefore, a higher gas barrier property is required for the gas barrier film used in the organic EL device.

  On the other hand, these various electronic devices are unlikely to be used for a long period of time. For example, mobile display devices are often replaced by purchases in two to three years. For this reason, the durability required for the gas barrier film may be applicable even if it is not so high.

  For such applications, the durability of the gas barrier property is a short period, but if it is within that short period, the gas barrier film can maintain a very high gas barrier property. A gas barrier film having a property (hygroscopic) layer has been studied.

  For example, Patent Document 1 discloses that a barrier film having a laminated structure of a base material / a planarization layer / a first barrier layer / a reactive layer / a second barrier layer has a chemical reaction with moisture and oxygen in the reactive layer. It is disclosed that aluminum oxide nanoparticles and titanium oxide nanoparticles are contained. The barrier film is considered to have a configuration in which the reactive layer is sandwiched between two barrier layers to suppress a rapid reaction (moisture absorption) of the reactive layer and maintain the reactivity for a certain period. Also disclosed is a multi-layered structure in which alternating layers of reactive layers / barrier layers are further repeated.

  However, the various nanoparticles used in the above-described prior art and CaO, which is generally used as a hygroscopic material, have a very high reactivity with moisture. For this reason, if there is a defect in the barrier layer sandwiching the reactive layer, or if the barrier property is insufficient, the reactive layer will draw in moisture, resulting in quick deterioration of performance after the barrier film is manufactured. If the environment is not strictly controlled, there is a problem that the period during which the initial high barrier property can be maintained is short. In addition, even when an organic EL device is manufactured using a barrier film in which the storage environment is strictly controlled as described above, the number of dark spots immediately after manufacturing is small, but the period until dark spots start to occur is short. The performance was insufficient.

JP 2010-511267 Gazette

  The present invention has been made in view of the above problems and situations, and a solution to the problem is to provide a gas barrier film capable of maintaining high gas barrier properties for a predetermined period of time and an electronic device using the same. It is.

As a result of investigating the cause of the above-mentioned problem in order to solve the above-mentioned problems related to the present invention, the gas barrier unit provided on the base material contains the first gas barrier region, the metal compound as the main component. The metal element of the metal compound contained as a main component in the reactive region, the second gas barrier region, and the first reactive region is a metal element containing a metal compound containing a metal element that is a different element in the periodic table as a main component. It has been found that by having two reactive regions and a third gas barrier region, it is possible to provide a gas barrier film capable of maintaining a high gas barrier property for a predetermined period.
That is, the subject concerning this invention is solved by the following means.

1. A gas barrier film comprising a gas barrier unit on a substrate,
The gas barrier unit is in order from the substrate side,
A first gas barrier region;
A first reactive region containing a metal compound as a main component;
A second gas barrier property region;
A metal element of the metal compound contained as a main component in the first reactive region is a second reactive region containing as a main component a metal compound containing a metal element that is a heterogeneous element in the periodic table;
A gas barrier film comprising a third gas barrier region.

2. The first reactive region contains an alkaline earth metal;
2. The gas barrier film according to item 1, wherein the second reactive region has a composition represented by SiO _x N _y (0 ≦ x <2, 0 <y).

3. The first reactive region has a composition represented by SiO _x N _y (0 ≦ x <2, 0 <y);
The gas barrier film according to item 1, wherein the second reactive region contains an alkaline earth metal.

  4). The ratio of the speed of reaction with moisture in the first reactive region and the speed of reaction with moisture in the second reactive region is in the range of 5 to 20 times. The gas barrier film according to any one of items 1 to 3 above.

  5. The gas barrier according to any one of claims 1 to 4, wherein the first reactive region is faster in reaction with moisture than the second reactive region. Sex film.

6). Region having a composition represented by _{SiO x N y (0 ≦ x} <2,0 <y) of the gas barrier unit, from the second term, which is a vapor-deposited layer to a fifth term The gas barrier film according to any one of the above.

7). The region having a composition represented by SiO _x N _y (0 ≦ x <2, 0 <y) in the gas barrier unit is a polysilazane layer. The gas barrier film according to any one of the above.

  8). An electronic device comprising the gas barrier film according to any one of items 1 to 7.

ADVANTAGE OF THE INVENTION According to this invention, the gas barrier property film which can maintain high gas barrier property for a predetermined period, and an electronic device using the same can be provided.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
Since the first reactive region and the second reactive region are different in the group in the periodic table of the metal element of the metal compound contained as the main component, the speed of the reaction between the water and oxygen is different. Since the reactivity of the first reactive region and the second reactive region is different, the base material of the gas barrier film is more than the case where the first reactive region and the second reactive region are made of the same material. It is possible to lengthen the time until water vapor or the like that permeates from the side passes through the third gas barrier region. Thereby, a high gas barrier property can be maintained for a predetermined period.
When the gas barrier film is stored in a specific environment with both surfaces exposed, the first reactive region faces the external environment through the substrate and the first gas barrier region, while the second reactive region The reactive region faces the external environment only through the third gas barrier region. In the case where the first gas barrier region and the third gas barrier region have the same gas barrier property, the second reactive region is more than the amount of water vapor permeated to the first reactive region due to the presence of the base material. The amount of water vapor permeated to the water increases. Therefore, the first reactive region and the second reactive region at the time of storage can be obtained by configuring the first reactive region to have a higher speed of reaction with moisture than the second reactive region. The difference in the degree of moisture absorption is reduced, and it is possible to maintain a higher gas barrier property for a predetermined period.

Schematic sectional view showing an example of the gas barrier film of the present embodiment Schematic configuration diagram showing an example of a vacuum plasma CVD apparatus that can be used to form a gas barrier region or a reactive region Schematic configuration diagram showing an example of a vacuum ultraviolet irradiation apparatus that can be used to form a gas barrier region or a reactive region

The gas barrier film of the present invention is a gas barrier film provided with a gas barrier unit on a substrate, and the gas barrier unit includes a first gas barrier region and a metal in order from the substrate side. The first reactive region containing the compound as the main component, the second gas barrier region, and the metal element of the metal compound contained as the main component in the first reactive region are metals that are different elements in the periodic table It has the 2nd reactive area | region which contains the metal compound containing an element as a main component, and a 3rd gas-barrier area | region. This feature is a technical feature common to or corresponding to each claim.
In the present invention, the first reactive region contains an alkaline earth metal, and the second reactive region has a composition represented by SiO _x N _y (0 ≦ x <2, 0 <y). It is preferable to have. The first reactive region has a composition represented by SiO _x N _y (0 ≦ x <2, 0 <y), and the second reactive region contains an alkaline earth metal. Is also preferable. Thereby, the effect of extending the time which gives a reaction rate difference between the 1st reactive region and the 2nd reactive region, and can maintain favorable gas barrier property is acquired. The effect can be obtained regardless of whether the reaction rate of the first reactive region or the second reactive region is high.
Moreover, in this invention, from the viewpoint of expression of the effect of this invention, the ratio of the reaction speed with the water | moisture content of the said 1st reactive region and the speed of the reaction with the water | moisture content of the said 2nd reactive region is 5-5. It is preferably within a range of 20 times.
Moreover, in this invention, it is preferable from the viewpoint of expression of the effect of this invention that the speed of the reaction with moisture is faster in the first reactive region than in the second reactive region.
Further, in the present invention, a region having a composition represented by _{SiO x N y (0 ≦ x} <2,0 <y) of the gas barrier unit is preferably a vapor-deposited layer. By the vapor deposition layer, it is possible to slow down the reaction rate of the region having a composition represented by SiO _x N _y, it is possible to adjust the time which can maintain good gas barrier properties.
Further, in the present invention, a region having a composition represented by _{SiO x N y (0 ≦ x} <2,0 <y) of the gas barrier unit is preferably a polysilazane layer. With polysilazane layer, it is possible to slightly slow down the reaction rate of the region having a composition represented by SiO _x N _y, it is possible to adjust the time which can maintain good gas barrier properties.

  The electronic device of the present invention comprises the above gas barrier film. Thereby, the function of an electronic device can be maintained more reliably for a predetermined period.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<Outline of gas barrier film>
The gas barrier film of the present invention is a gas barrier film comprising a gas barrier unit on a substrate, and the gas barrier unit comprises a first gas barrier region and a metal compound in order from the substrate side. The first reactive region contained as the main component, the second gas barrier region, and the metal element of the metal compound contained as the main component in the first reactive region include a metal element that is a different element in the periodic table. It has the 2nd reactive area | region which contains a metal compound as a main component, and a 3rd gas barrier property area | region, It is characterized by the above-mentioned.

  FIG. 1 is a schematic cross-sectional view showing a configuration of a gas barrier film 1 according to an embodiment of the present invention. The gas barrier film 1 includes a gas barrier unit 3 on a substrate 2. The gas barrier unit 3 includes a first gas barrier region 31, a first reactive region 32, a second gas barrier region 33, a second reactive region 34, and a third gas barrier region in order from the substrate 2 side. 35. When the gas barrier film 1 is mounted on an electronic device, the base material 2 is disposed outside and the third gas barrier region 35 is disposed inside.

  Below, the base material, gas barrier unit, etc. which comprise the gas barrier film of this invention are demonstrated in detail. In the following description, when it is not necessary to distinguish between the first to third gas barrier regions, they are simply referred to as “gas barrier regions”, and the first reactive region and the second reactive region are described. When it is not necessary to distinguish the description from the region, it will be simply referred to as “reactive region”.

"Base material"
The substrate according to the present invention is not particularly limited as long as it can hold the gas barrier unit. As the substrate, a resin substrate (plastic film or sheet) is usually used, and a film or sheet made of a colorless and transparent resin is preferably used as the substrate. The resin substrate used is not particularly limited in material, thickness, and the like, and can be appropriately selected according to the purpose of use.

  Examples of the resin base material include poly (meth) acrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene ( PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyethersulfone, polyimide, polyetherimide, cycloolefin polymer, cycloolefin copolymer, and other resins Film, heat-resistant transparent film (product name Sila-DEC, manufactured by Chisso Corp.) having silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton, and a resin obtained by laminating two or more layers of the above-mentioned resin And the like can be given Irumu.

  The thickness of the substrate is not particularly limited, but is preferably in the range of 5 to 300 μm, and more preferably in the range of 10 to 100 μm.

  The base material may have functional layers such as a transparent conductive layer, a primer layer, and a clear hard coat layer. As the functional layer, those described in paragraphs 0036 to 0038 of JP-A-2006-289627 can be preferably employed.

  Moreover, it is preferable that the base material which concerns on this invention is transparent. Since the base material is transparent and the layer formed on the base material is also transparent, a transparent gas barrier film can be obtained. For example, it can be a transparent substrate such as an organic EL element. It becomes.

  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 gas barrier unit is provided, may be polished to improve smoothness.

  At least on the side of the substrate where the gas barrier unit is provided, various known processes for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, smooth layer lamination, etc., are performed. It is preferable to combine the above treatments as necessary.

《Gas barrier unit》
The gas barrier unit includes, in order from the substrate side, a first gas barrier region, a first reactive region containing a metal compound as a main component, a second gas barrier region, and a first reactive region. The metal element of the metal compound contained as a component has a second reactive region containing a metal compound containing a metal element that is a heterogeneous element in the periodic table as a main component, and a third gas barrier property region.

  In the present invention, the “region” is a plane that is substantially perpendicular to the thickness direction of the gas barrier unit (that is, a plane parallel to the outermost surface of the gas barrier unit). This refers to a three-dimensional range (region) between two opposing surfaces formed when divided by thickness. Even if the composition of components in the region is constant in the thickness direction, it is gradually increased. It may change to.

In the present invention, the “gas barrier region” and the “reactive region” are the XPS when the region formed on the substrate is left to stand in an environment of 20 ° C. and 50% RH for 1000 hours. A distinction is made by confirming composition changes in the analysis. The XPS analysis can be performed under the same conditions as in the case of measuring the speed of reaction with moisture in the reactive region described later.
That is, the change in oxygen atom ratio after standing for 1000 hours (oxygen atom ratio after standing for 1000 hours (at%) / initial oxygen atom ratio (at %)) Is 1.03 or less, it is regarded as a “gas barrier region”, and when it exceeds 1.03, it is regarded as a “reactive region”. As the gas barrier region, the change in the oxygen atom ratio is preferably 1.02 or less, more preferably 1.01 or less, and substantially no change (does not react with moisture). Is more preferable.

<Gas barrier properties>
The gas barrier region is not particularly limited as long as it has gas barrier properties, and may have any configuration. Further, the gas barrier region may be formed by any known method. For example, a vapor-deposited layer having a gas barrier property formed by a vapor deposition method, a polysilazane modified layer having a gas barrier property formed by irradiating vacuum ultraviolet light to a coating film applied with a liquid containing polysilazane and dried Can be used.

Examples of the method for forming the vapor deposition layer include physical vapor deposition and chemical vapor deposition.
The physical vapor deposition method (PVD (Physical Vapor Deposition) method) is a method of depositing a thin film of a target substance (for example, a carbon film) on a substrate surface by a physical method in a gas phase. Examples of the method include a vapor deposition method (resistance heating method, electron beam vapor deposition method, molecular beam epitaxy method), an ion plating method, a sputtering method, and the like.
On the other hand, chemical vapor deposition (chemical vapor deposition, CVD (Chemical Vapor Deposition)) is a method in which a source gas containing a target thin film component is mixed with an excited discharge gas on the surface of a substrate in a gas phase. This is a method of depositing a thin film on a substrate by supplying and chemical reaction in the gas phase or in the gas phase. In particular, there is a method of generating plasma etc. for the purpose of activating a 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. Etc.

  The layer thickness of the gas barrier region varies depending on the composition, formation method, and the like, but is preferably in the range of 0.01 to 1 μm, more preferably in the range of 10 to 600 nm, for example, 100 Particularly preferably, it is in the range of ˜400 nm.

  Further, the first to third gas barrier regions according to the present invention may all have the same configuration / formation method, or at least one of these may be a different configuration / formation method.

(Plasma CVD method)
As a method for forming a vapor deposition layer (vapor deposition film) as a gas barrier region, a vacuum or atmospheric pressure plasma CVD method is preferable from the viewpoint of film formation speed and processing area.
The excited gas as used in the present invention means that at least part of the molecules in the gas move from the existing state to a higher energy state by obtaining energy, and the excited gas molecules, radicalized gas This includes molecules and gas containing ionized gas molecules.

As a method for forming a gas barrier region that is a vapor deposition layer containing metal oxide, metal nitride, or metal oxynitride, a metal element such as silicon is contained in a discharge space in which a high-frequency electric field is generated. A plasma CVD method is preferred in which a source gas is mixed with an excited discharge gas to form a secondary excitation gas, and the substrate is exposed to the secondary excitation gas to form an inorganic film (ceramic film) on the substrate. . That is, a discharge gas is introduced between the counter electrodes (discharge space), a high-frequency voltage is applied between the counter electrodes to bring the discharge gas into a plasma state, and then the discharge gas and the raw material gas that are in the plasma state are moved outside the discharge space Then, the substrate is exposed to this mixed gas (secondary excitation gas) to form a vapor deposition layer on the substrate.
Note that the vapor deposition layer containing metal oxide, metal nitride, and metal oxynitride formed by the plasma CVD method in the present invention includes at least one of metal oxide, metal nitride, and metal oxynitride. The deposited film may be a composite compound such as a metal oxide, metal nitride, metal oxynitride, or metal carbide.

  The plasma CVD method appropriately sets conditions such as raw materials such as organic or inorganic metal compounds, decomposition gas, decomposition temperature, input power, etc., so that a metal oxide ceramic film, metal oxide and metal carbide, metal nitride It is preferable because a ceramic film of a mixture of metal sulfides can be formed separately. For example, if a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, a silicon oxide ceramic film is formed. Further, if a zinc compound is used as a raw material compound and carbon disulfide is used as a decomposition gas, a zinc sulfide ceramic film is formed. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  As a raw material for such an inorganic film (ceramic film), as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use by a solvent and can use organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence on the film formation can be almost ignored.

In addition, as a decomposition gas for decomposing a raw material gas containing a metal element to obtain an inorganic compound, for example, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, suboxide Examples thereof include nitrogen gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.
A ceramic film of a mixture of a metal oxide, a metal oxide and a metal carbide, a metal nitride, a metal oxynitride, a metal halide, a metal sulfide, etc., by appropriately selecting a source gas containing a metal element and a decomposition gas Can be obtained.

When forming the vapor deposition layer, a discharge gas that is likely to be in a plasma state can be mixed with the reactive gas of the raw material gas and the decomposition gas, and the mixed gas can be sent to the plasma discharge processing apparatus.
As such a discharge gas, nitrogen gas and / or Group 18 atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  A vapor deposition layer is formed by supplying a mixed gas obtained by mixing a discharge gas and a reactive gas to a plasma discharge treatment apparatus. Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, it is preferable to supply the reactive gas with the ratio of the discharge gas being 50% by volume or more with respect to the entire mixed gas.

In the ceramic film used as the gas barrier region, the inorganic compound contained in the ceramic film is SiO _x , SiO _x C _y (x = 1.5 to 2.0, y = 0 to 0.5), or SiO _x. N _y (x = 0.1-2, y = 0.1-1.3) is preferred, and particularly from the viewpoint of gas barrier properties, moisture permeability, and light transmittance, SiO _x or SiO _x N _y is preferred.

  As described above, various inorganic films (ceramic films) can be formed by using the source gas (reactive gas) as described above together with the discharge gas. The vapor deposition layer of the present invention may be composed of a plurality of layers in which these conditions are changed, and the ratio of the discharge gas to the reactive gas and the discharge conditions are continuously changed. It may be composed of a homogeneous film.

The CVD method is such that a volatilized / sublimated organometallic compound adheres to the surface of a high-temperature support and undergoes a decomposition reaction due to heat, thereby producing a thermally stable inorganic thin film. Such a normal CVD method (also referred to as a thermal CVD method) normally requires a substrate temperature of 500 ° C. or higher, and thus is difficult to use for film formation on a resin base material.
On the other hand, in the plasma CVD method, an electric field is applied to the space in the vicinity of the support to generate a space (plasma space) where a gas in a plasma state exists, and the volatilized / sublimated organometallic compound is introduced into the plasma space. By spraying on the support after the decomposition reaction occurs, an inorganic thin film is formed. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the gas temperature is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions or radicals, the organometallic compound as the raw material of the inorganic film can be decomposed even at a low temperature. Therefore, it is a film forming method that can lower the temperature of the support on which the inorganic material is formed, and can sufficiently form a film on a resin base material. According to this plasma CVD method, when a ceramic film is formed on a resin substrate, the film density is dense and a thin film having stable performance can be obtained. In addition, the residual stress is compressive stress, and a ceramic film within a range of 0.01 to 20 MPa can be stably obtained.

  For example, the gas barrier region can be formed using the vacuum plasma CVD apparatus shown in FIG. FIG. 2 is a schematic diagram showing an example of a vacuum plasma CVD apparatus.

  In FIG. 2, the vacuum plasma CVD apparatus 100 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom side inside the vacuum chamber 102. 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. In this way, the heat medium circulates between the susceptor 105 and the heating / cooling device 160, and the susceptor 105 is heated or cooled by the supplied heat 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 100, the inside of the vacuum chamber 102 is evacuated in advance and the heat medium is heated to start from room temperature. The temperature is raised to the 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 and placed on the susceptor 105 while maintaining the vacuum atmosphere in the vacuum chamber 102.

  A 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 high-frequency power source 109 is activated while supplying a CVD gas from the gas introduction system 108 into the vacuum chamber 102 and supplying a heat medium having a constant temperature from the heating / cooling device 160 to the susceptor 105, and applying a high-frequency voltage 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 gas barrier region which is a thin film grows on the surface of the substrate 110. At this time, 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 30 to 300 sccm, and the flow rate of the decomposition gas is 100 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 the 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 minimum temperature and maximum temperature vary depending on the material of the thin film to be formed and the material of the thin film that has already been formed, but the minimum temperature is 50 ° C. or higher in order to ensure a film quality with high gas barrier properties. It is preferable that it is below the heat-resistant temperature of a material.

  The correlation between the film quality and deposition temperature of the thin film formed by the vacuum plasma CVD method and the correlation between the damage to the deposition object (substrate 110) and the deposition 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 during the vacuum plasma CVD process is preferably 50 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, a 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. Here, for example, a gas barrier made of silicon nitride (SiN) is supplied by supplying a mixed gas of silane gas, ammonia gas, and nitrogen gas as a CVD gas and maintaining the substrate 110 at a temperature condition not lower than the lower limit temperature and not higher than the upper limit temperature. Sex regions are formed.

  Immediately after startup of the vacuum plasma CVD apparatus 100, 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 startup, 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 the plurality of substrates 110, the susceptor 105 is heated by heat flowing from the plasma. In this case, since the heat medium refluxed 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 the heat medium having the set temperature is transferred to 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 105, 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.

(Sputtering method)
As another method for forming a vapor deposition layer (vapor deposition film) as a gas barrier region, there is a sputtering method which is one of vacuum film formation methods.
Sputtering is a method in which an inert gas such as argon gas is ionized (plasmaized) using an electric field or magnetic field, and the target atoms are knocked out by the kinetic energy obtained by accelerating the ionized ions. It is a physical process for depositing on a substrate to form a target film. In the sputtering method, a sputtering gas such as argon is ionized (plasmaized) using an electric field or a magnetic field and accelerated to collide with the target surface. Then, target atoms are ejected from the target with which the plasma particles collide, and the ejected atoms are deposited on the object to be processed to form a sputtered film.

  As a sputtering target, silicon dioxide, silicon nitride, silicon oxynitride, or the like can be used. Examples of the atmosphere in which the target and the substrate on which the sputtered film is formed include a nitrogen-containing gas atmosphere or an atmosphere in which a nitrogen-containing gas is added to an inert gas, and particularly nitrogen, dinitrogen monoxide, and ammonia. An atmosphere containing a nitrogen-containing gas such as nitrogen trifluoride is preferable, and a transparent gas barrier region can be formed without impairing the gas barrier property. Gas barrier properties include other components such as aluminum, zinc, antimony, indium, cerium, calcium, cadmium, silver, gold, chromium, silicon, cobalt, zirconium, tin, titanium, iron, copper, nickel, platinum, palladium -By containing a metal such as bismuth, magnesium, manganese, molybdenum, vanadium, barium, or an inorganic material of these oxides or nitrides, high gas barrier properties can be maintained or improved.

Note that when the flow rate of the nitrogen-containing gas into the sputtering atmosphere is too small, the transparency of the gas barrier region of the silicon nitride oxide film is undesirably lowered. On the other hand, if the flow rate of the nitrogen-containing gas is too large, ionization (plasmaization) of the inert gas is difficult to occur, which is not preferable. For example, in a magnetron sputtering apparatus, silicon nitride is used as a target, argon (Ar) gas and nitrogen (N ₂ ) gas at a flow rate of 30 sccm are introduced, and high frequency power (input power 1.2 kW) with a frequency of 13.56 MHz is applied. When the gas barrier region of the silicon nitride oxide film is formed at a film forming pressure of 0.25 Pa and a film thickness of 120 to 150 nm, the flow rate of nitrogen gas is preferably about 5 to 15 sccm. Thereby, the gas barrier property area | region which has favorable gas barrier property can be formed, without impairing transparency.

  The laminated body in which the silicon nitride oxide film having each of the above-described characteristics is formed with a thin thickness of 5 to 300 nm is difficult to crack in the silicon nitride oxide film, so that it exhibits excellent gas barrier properties. It can be used as a region. When the silicon nitride oxide film has a thickness of 5 nm or more, the silicon nitride oxide film can more reliably cover the entire surface of the substrate, and gas barrier properties can be improved. On the other hand, when the thickness of the silicon oxynitride film is 300 nm or less, cracks are less likely to occur, transparency and appearance are improved, curling of the resin base material is suppressed, and production is easier to produce. Advantages such as improved performance and reduced cost are easily obtained.

(Polysilazane modified layer)
As another method for forming the gas barrier region, there is a method for forming a polysilazane modified layer. In this method, a polysilazane layer-containing coating liquid containing polysilazane is applied and dried to form a precursor layer, and then the precursor layer is subjected to a modification treatment with vacuum ultraviolet light to form a gas barrier layer. It is.

  In the formation of the gas barrier region, any appropriate wet coating method can be applied as a coating method for applying a gas barrier region forming coating solution containing a polysilazane compound. Examples thereof include a roller 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 thickness of the coating film can be set according to the purpose of use of the gas barrier film and is not particularly limited. For example, the thickness of the coating film is preferably 0.01 to as the thickness after drying. It is in the range of 1 μm, more preferably in the range of 20 to 600 nm, and most preferably in the range of 40 to 400 nm.

In a preferred use "polysilazane compound" present invention, the silicon in the structure - a polymer with a nitrogen bonds, Si-N, Si-H , SiO 2 consisting of N-H or the like, _Si 3 _{N 4} and both the intermediate It is a ceramic precursor inorganic polymer such as solid solution SiO _x N _y .

As such a polysilazane compound, those having the following structure are preferably used.
—Si (R ₁ ) (R ₂ ) —N (R ₃ ) —
In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

In the present invention, from the viewpoint of the denseness of the resulting gas barrier layer as a film, perhydropolysilazane (abbreviation: PHPS) in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms is particularly preferable.

  As an organic solvent for preparing a coating solution containing a polysilazane compound, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane. Examples of the organic solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbon solvents, or ethers such as aliphatic ethers or alicyclic ethers. Can be used.

  The concentration of the polysilazane compound in the polysilazane compound-containing coating solution is about 0.2 to 35% by mass, although it depends on the thickness of the target gas barrier region and the pot life of the coating solution.

  An amine or a metal catalyst may be added to the coating solution in order to promote modification to the silicon oxide compound. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. The addition amount of these catalysts is preferably adjusted to 2% by mass or less with respect to the polysilazane compound in order to avoid excessive silanol formation by the catalyst, decrease in film density, increase in film defects, and the like.

  In addition to the polysilazane compound, the coating liquid containing the polysilazane compound can contain an inorganic precursor compound. The inorganic precursor compound other than the polysilazane compound is not particularly limited as long as the coating liquid can be prepared. For example, paragraphs 0140 to 0142 of International Publication No. 2012/090644, paragraphs of International Publication No. 2013/002026 Examples thereof include silicon-containing compounds and polysilsesquioxanes described in 0112 to 0114 and paragraphs 0072 to 0074 of JP-A-2015-33764.

  The modification treatment of polysilazane in the present invention refers to a reaction in which a part or all of the polysilazane compound is converted into silicon oxide or silicon oxynitride.

  For this modification treatment, a known method based on the conversion reaction of polysilazane can be selected. Formation of a silicon oxide film or a silicon oxynitride film by a substitution reaction of a polysilazane compound requires a high temperature of 450 ° C. or more, and is difficult to adapt to a flexible substrate using a resin film as a base material. Therefore, in the case of using a resin base material, a method using ultraviolet light that can be converted at a lower temperature is preferable. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures. It is.

  For the vacuum ultraviolet light irradiation treatment in the present invention, a commonly used ultraviolet ray generator can be used. In addition, the ultraviolet light as used in the field of this invention means the ultraviolet light containing the electromagnetic wave which has a wavelength of 10-200 nm generally called vacuum ultraviolet light.

  For irradiation with vacuum ultraviolet light, set the irradiation intensity and irradiation time within the range where the substrate carrying the pre-modified polysilazane layer and other areas constituting the gas barrier unit are not damaged. It is preferable to do.

  Examples of such ultraviolet ray generating means include, but are not limited to, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, an excimer lamp, and a UV light laser. In addition, when the polysilazane layer before modification is irradiated with the generated ultraviolet light, the polysilazane before modification is reflected after reflecting the ultraviolet light from the generation source with a reflector from the viewpoint of improving efficiency and uniform irradiation. It is desirable to hit the layer.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. When the substrate having the polysilazane modified layer is in the form of a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. Can do. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although depending on the base material used and the composition and concentration of the polysilazane modified layer.

Moreover, it is preferable that oxygen concentration at the time of irradiating vacuum ultraviolet light (VUV) is 300-10000 volume ppm (1 volume%), More preferably, it is 500-5000 volume ppm. By adjusting to such an oxygen concentration range, it is possible to prevent the generation of a gas-barrier region with excessive oxygen and to prevent the deterioration of the gas barrier property.
A dry inert gas is preferably used as a gas other than oxygen at the time of vacuum ultraviolet light (VUV) irradiation, and dry nitrogen gas is particularly preferable from the viewpoint of cost.

  In addition, the gas barrier region can be formed by a wet method using a vacuum ultraviolet irradiation apparatus 200 shown in FIG.

In FIG. 3, an apparatus chamber 201 supplies nitrogen and oxygen in appropriate amounts from a gas supply port (not shown), and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber. Can be maintained at a predetermined concentration. In the apparatus chamber 201, an Xe excimer lamp (excimer lamp light intensity: 130 mW / cm ² ) 202 having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, an excimer lamp holder 203 also serving as an external electrode, a sample stage 204, and A light shielding plate 206 and the like are provided. The sample stage 204 is configured to be movable horizontally (at a V direction in FIG. 3) at a predetermined speed in the apparatus chamber 201 by a moving means (not shown), and can return to the original position again. The sample stage 204 can be maintained at a predetermined temperature by a heating means (not shown). A sample 205 on which a polysilazane compound coating layer is formed is placed on the sample stage 204. When the sample stage 204 moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the coating layer surface of the sample 205 and the excimer lamp tube surface is 3 mm. The light shielding plate 206 prevents the application layer of the sample 205 from being irradiated with vacuum ultraviolet rays while the Xe excimer lamp 202 is aged.

  The amount of irradiation energy irradiated to the coating layer surface of the sample 205 by the vacuum ultraviolet irradiation apparatus 200 is measured using a 172 nm sensor head using an ultraviolet integrated light meter (C8026 / H8025 UV POWER METER) manufactured by Hamamatsu Photonics Co., Ltd. can do. In the measurement, the sensor head is installed in the center of the sample stage 204 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 201 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen are supplied so that the oxygen concentration is the same as the time, and the sample stage 204 is moved at a speed of 0.5 m / min to perform measurement. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 202, an aging time of 10 minutes is provided after the Xe excimer lamp is turned on, and then the sample stage is moved to start the measurement. Based on the irradiation energy obtained by this measurement, the amount of irradiation energy can be adjusted by adjusting the moving speed of the sample stage.

(Mixed region of non-transition metal and transition metal)
Here, it is preferable that a mixed region of a non-transition metal and a transition metal is provided as the gas barrier region according to the present invention, because a high gas barrier property can be obtained. The gas barrier region may be composed only of the mixed region, or may partially include the mixed region.

  The mixed region according to the present invention includes a non-transition metal (M1) selected from metals of Group 12 to Group 14 of the long-period periodic table and a transition metal selected from metals of Group 11 to Group 3 elements. A region where (M2) is contained and the value (M2 / M1) of the atomic ratio of the transition metal M2 to the non-transition metal M1 is in the range of 0.02 to 49, It is a region having 5 nm or more continuously in the direction.

  Further, the mixed region may be formed as a plurality of regions having different chemical compositions of the constituent components, or may be formed as a region in which the chemical compositions of the constituent components are continuously changed.

In the present invention, it is preferable that a part of the composition contained in the mixed region according to the present invention has a non-stoichiometric composition (oxygen deficient composition) in which oxygen is deficient.
In the present invention, the oxygen deficient composition is defined by the following relational expression (2) when at least a part of the composition of the mixed region is expressed by the following chemical composition formula (1). It is defined as satisfying the condition. In addition, as the oxygen deficiency index indicating the degree of oxygen deficiency in the mixed region, the minimum value obtained by calculating (2y + 3z) / (a + bx) in the certain mixed region is used. Details will be described later.
Chemical composition formula (1): (M1) (M2) _x O _y N _z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
In the above formulas, M1 represents a non-transition metal, M2 represents a transition metal, O represents oxygen, N represents nitrogen, and x, y, and z represent stoichiometric coefficients, respectively. a represents the maximum valence of M1, and b represents the maximum valence of M2.

As described above, the composition of the mixed region of the non-transition metal (M1) and the transition metal (M2) according to the present invention is represented by (M1) (M2) _x O _y N _z which is the formula (1). As is clear from this composition, the composition of the mixed region may partially include a nitride structure, and it is more preferable to include a nitride structure from the viewpoint of gas barrier properties.

  Here, the maximum valence of the non-transition metal (M1) is a, the maximum valence of the transition metal (M2) is b, the valence of O is 2, and the valence of N is 3. When the composition of the mixed region (including a part of the nitride) is a stoichiometric composition, (2y + 3z) / (a + bx) = 1.0. This formula means that the total number of bonds of non-transition metal (M1) and transition metal (M2) is equal to the total number of bonds of O and N. In this case, non-transition metal (M1) And the transition metal (M2) are bonded to either O or N. In the present invention, when two or more kinds are used together as the non-transition metal (M1), or when two or more kinds are used together as the transition metal (M2), the maximum valence of each element is set to The composite valence calculated by performing the weighted average according to the existence ratio is adopted as the values of a and b of each “maximum valence”.

  On the other hand, in the mixed region according to the present invention, when (2y + 3z) / (a + bx) <1.0 shown by the relational expression (2), a bond between the non-transition metal (M1) and the transition metal (M2) This means that the total number of O and N bonds is insufficient with respect to the total, and such a state is the above-mentioned “oxygen deficiency”.

  In the oxygen deficient state, the remaining bonds of the non-transition metal (M1) and the transition metal (M2) have the possibility of bonding to each other, and the metals of the non-transition metal (M1) and the transition metal (M2) When they are directly bonded, it is considered that a denser and higher-density structure is formed than when bonded between metals via O or N, and as a result, gas barrier properties are improved.

  In the present invention, the mixed region is a region where the value of x satisfies 0.02 ≦ x ≦ 49 (0 <y, 0 ≦ z). This is defined as a region where the value of the number ratio of transition metal (M2) / non-transition metal (M1) is in the range of 0.02 to 49 and the thickness is 5 nm or more. It is the same definition as that.

  In this region, since both the non-transition metal (M1) and the transition metal (M2) are involved in the direct bonding between the metals, a mixed region that satisfies this condition exists in a thickness of a predetermined value or more (5 nm). Therefore, it is thought that it contributes to the improvement of gas barrier properties. In addition, since it is considered that the closer the abundance ratio of the non-transition metal (M1) and the transition metal (M2), the more the gas barrier property can be improved, the mixed region is a region satisfying 0.1 ≦ x ≦ 10. It is preferable to include a thickness of 5 nm or more, more preferably include a region satisfying 0.2 ≦ x ≦ 5 at a thickness of 5 nm or more, and a region satisfying 0.3 ≦ x ≦ 4 to a thickness of 5 nm or more. It is further preferable to contain.

  Here, as described above, if there is a region satisfying the relationship of (2y + 3z) / (a + bx) <1.0 represented by the relational expression (2) within the range of the mixed region, the effect of improving the gas barrier property is obtained. Although it was confirmed that the mixed region exhibits at least a part of the composition, (2y + 3z) / (a + bx) ≦ 0.9, and (2y + 3z) / (a + bx) ≦ 0.85 in the mixed region. It is more preferable to satisfy | fill, and it is still more preferable to satisfy | fill (2y + 3z) / (a + bx) <= 0.8. Here, the smaller the value of (2y + 3z) / (a + bx) in the mixed region, the higher the gas barrier property, but the greater the absorption in visible light. Therefore, in the case of a gas barrier layer used for applications where transparency is desired, 0.2 ≦ (2y + 3z) / (a + bx) is preferable, and 0.3 ≦ (2y + 3z) / (a + bx). Is more preferable, and 0.4 ≦ (2y + 3z) / (a + bx) is still more preferable.

In the present invention, the thickness of the mixed region where good gas barrier properties can be obtained is 5 nm or more as the sputtering thickness in terms of SiO ₂ in the XPS analysis method described later, and this thickness is 8 nm or more. Is preferably 10 nm or more, more preferably 20 nm or more. The thickness of the mixed region is not particularly limited from the viewpoint of gas barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less from the viewpoint of optical characteristics. preferable.

  A gas barrier layer having a mixed region having a specific configuration as described above exhibits a very high gas barrier property that can be used as a gas barrier layer for an electronic device such as an organic EL element.

(Method for forming mixed region)
As a method for forming the mixed region, a region (non-transition metal-containing region) containing a non-transition metal (M1) selected from Group 12 to Group 14 metals of the long-period periodic table, and a Group 3 element When forming a region containing a transition metal (M2) selected from Group 11 to metal (transition metal-containing region) adjacent to each other, the respective formation conditions are adjusted as appropriate so that no transition occurs. A method of forming a mixed region between the metal-containing region and the transition metal-containing region is preferable.

  When the non-transition metal-containing region is formed by the vapor phase growth method, for example, the ratio of the non-transition metal (M1) and oxygen in the film forming raw material, the ratio of the inert gas and the reactive gas during film formation, Mixing by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation Regions can be formed.

  When the non-transition metal-containing region is formed by the above-described coating method, for example, a film-forming raw material type (polysilazane type or the like) containing a non-transition metal (M1), a catalyst type, a catalyst content, a coating film thickness, a drying temperature, The mixed region can be formed by adjusting one or more conditions selected from the group consisting of time, reforming method, and reforming conditions.

  When the transition metal-containing region is formed by the vapor phase growth method, for example, the ratio of the transition metal (M2) and oxygen in the film forming raw material, the ratio of the inert gas and the reactive gas during film formation, and the film formation Adjusting the mixing region by adjusting one or more conditions selected from the group consisting of the amount of gas supplied, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation Can be formed.

In addition to this, a method of directly forming a mixed region of a non-transition metal and a transition metal is also preferable.
As a method for directly forming the mixed region, it is preferable to use a known co-evaporation method. As such a co-evaporation method, a co-sputtering method is preferable. The co-sputtering method employed in the present invention is, for example, a composite target made of an alloy containing both a non-transition metal (M1) and a transition metal (M2), or a composite of a non-transition metal (M1) and a transition metal (M2). One-way sputtering using a composite target made of an oxide as a sputtering target may be used.

  In addition, the co-sputtering method in the present invention is multi-source simultaneous sputtering using a plurality of sputtering targets including a single non-transition metal (M1) or its oxide and a single transition metal (M2) or its oxide. May be. Regarding the method for producing these sputtering targets and the method for producing a thin film made of a complex oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP The description of 2013-043761 gazette etc. can be referred suitably.

  The film forming conditions for performing the co-evaporation method include the ratio of transition metal (M2) and oxygen in the film forming raw material, the ratio of inert gas to reactive gas during film formation, Examples include one or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation, and these film formation conditions (preferably oxygen partial pressure) ) Can be adjusted to form a thin film made of a complex oxide having an oxygen-deficient composition. That is, by forming the gas barrier region using the co-evaporation method as described above, most of the region in the thickness direction of the formed gas barrier region can be a mixed region. For this reason, according to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region. In addition, what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method in order to control the thickness of a mixing area | region, for example.

《Reactive area》
The reactive region is configured to contain a material that reacts with moisture, oxygen, and the like entering from either side of the gas barrier film and absorbs them. The gas barrier property is improved because the gas barrier unit has a reactive region.

  In the gas barrier film of the present invention, the first and second reactive regions may have any configuration / formation method as long as the metal elements of the metal compound contained as main components are different from each other in the periodic table. May be. In the present invention, the “main component” refers to a metal compound having a maximum content as an atomic composition ratio. When one of the first and second reactive regions contains two or more main components, each of the metal elements of the two or more metal compounds and the other of the first and second reactive regions is the main. What is necessary is just to be a different group in the periodic table from the metal element of the metal compound contained as a component.

The first and second reactive regions may have any configuration as long as they have reactivity, and are not particularly limited. For example, the reactive region may contain an alkaline earth metal to be described later, or may have a composition represented by SiO _x N _y . When the first reactive region contains an alkaline earth metal, the metal elements of the metal compound contained as the main component are different from each other in the periodic table as described above, so that the first reactive region contains an alkaline earth metal. The second reactive region preferably has a composition represented by SiO _x N _y . On the other hand, when the first reactive region has a composition represented by SiO _x N _y , the second reactive region preferably contains an alkaline earth metal.

  Moreover, it is preferable that the ratio of the reaction speed with the moisture in the first reactive region and the reaction speed with the moisture in the second reactive region is in the range of 5 to 20 times. Thereby, higher gas barrier property can be maintained for a predetermined period.

Here, in the present invention, the speed of reaction with moisture can be measured by the following method, as in Examples described later.
That is, a laminate having a three-layer structure in which a target reactive region is first formed on a substrate and a gas barrier region is further formed is used as a measurement sample. In addition, a measurement sample having the same configuration including a reactive region to be compared is prepared. Each measurement sample is transferred to an environment of 20 ° C. and 50% RH. From each sample, a small sample is cut out every 6 hours until the first 24 hours and every 24 hours thereafter, and XPS of the following conditions is promptly extracted. The composition distribution profile in the thickness direction of the reactive region is measured by analysis.

・ Device: Quantera SXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement was repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).
Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. For data processing, MultiPak manufactured by ULVAC-PHI was used. The analyzed elements are Si, Ca, Mg, Fe, Nb, O, N, and C.

From the obtained data, the average composition of the reactive region can be obtained, and the time during which the reactive region has completely reacted with moisture can be obtained from the composition as the speed of reaction with moisture.
For example, if the composition of the reactive region is CaO, it will be Ca (OH) ₂ when completely reacted with moisture, and _x of CaO _x will be 2 in XPS analysis. In the present invention, the time when _x of CaO _x becomes 1.9 or more (20 ° C., 50% RH storage time) is determined as the time when the reactive region has completely reacted with moisture. MgO and SrO are the same as CaO. In addition, when the reactive region has a mixed composition of at least two of CaO _x , MgO _x and SrO _x , the time when x of the main component becomes 1.9, In some cases, when the total atomic composition ratio of each element is 1, x is 1.9.
For example, if the composition of the reactive region is SiO _x N _y , x ≧ 2 and y = 0 when completely reacted with moisture. In the present invention, when the _x of SiO _x N _y becomes 1.9 or more (20 ° C., 50% RH storage time), the reactive region is completely reacted with moisture, Ask. When the surface layer of the reactive region is modified to make the modified layer a gas barrier region, the gas barrier region and the reactive region are determined from the change in the oxygen atomic ratio based on the XPS analysis result in the SiO _x N _y composition. The value of x in the reactive region is calculated. Further, when an NbO _x layer is formed on a polysilazane layer or a polysilazane modified layer as a reactive region and the Si—Nb mixed region is used as a gas barrier region, the Nb / Si ratio is 0.02 or more. The gas barrier region is defined, the boundary with the reactive region is clarified, and the value of x is calculated.

  In addition, it is preferable that the first reactive region is faster in reaction with moisture than the second reactive region. Thereby, higher gas barrier property can be maintained for a predetermined period. The rate of reaction with moisture is faster in the first reactive region than in the second reactive region. The time required for the reactive region to completely react with moisture is determined as described above. It means that the first reactive region is shorter than the two reactive regions.

  The thickness of the reactive region is not particularly limited and varies depending on the material, but is preferably in the range of 0.01 to 3 μm, more preferably in the range of 10 to 600 nm, for example, 100 A range of ˜400 nm is particularly preferred.

(Alkaline earth metal)
Examples of the reactive region containing an alkaline earth metal include those configured to contain an alkaline earth metal such as CaO, MgO, and SrO.

  The reactive region configured to contain these materials can be formed by a PVD method using a target containing at least one of CaO, MgO, and SrO. In order to form a reactive region from these targets by PVD, one or more oxide powders selected from MgO, CaO, and SrO are sintered to form a sintered body. The PVD method may be performed using as a starting material. The target is preferably added with a transition metal oxide such as Cu, Fe, Cr or the like, or a rare earth oxide such as La as a stabilizer, and the content thereof is, for example, in the range of 10 to 10000 mass ppm. It is preferable to be within. By containing these stabilizers, the reactivity of the formed reactive region can be further improved.

  Although it does not specifically limit as said PVD method, Vacuum deposition methods, such as an electron beam heating method and an ion plating method, a sputtering method, etc. can be employ | adopted suitably. The film forming conditions can also be appropriately set according to the starting material, the film thickness of the reactive region to be formed, and the like.

  The film thickness of the reactive region is set to, for example, 200 to 3000 nm, and the film density is set to, for example, 50 to 98%. However, as the film thickness increases and the film density decreases, the moisture absorption performance is Since it becomes high, it can set suitably in relation to a film | membrane density so that a desired moisture absorption performance can be exhibited. If the film density in the reactive region is too low, cracks may occur, and if the film thickness in the reactive region is too thick, the film formation cost increases or the reactive region peels off. There is a risk. For this reason, when applying to an organic EL device, it is preferable that the film thickness and film density of the reactive region are set in the above ranges.

  The target containing at least one of CaO, MgO, and SrO can be manufactured as follows.

Here, as a method for obtaining a polycrystalline body, a method obtained by sintering is shown, but it is not particularly limited. In the step of forming the polycrystalline body, first, at least one oxide powder or composite oxide powder of MgO, CaO, SrO having a purity of 90 to 99.99%, and transition metal oxidation as a stabilizer A predetermined amount of a composite oxide or rare earth oxide composite oxide powder is prepared.
The average particle size of the prepared powder is preferably in the range of 0.01 to 100 μm. If the average particle size of the powder is less than 0.01 μm, the powder is too fine and agglomerates, so that the handling of the powder becomes worse and it is difficult to prepare a high-concentration slurry. This is because it is difficult to control and a dense polycrystal cannot be obtained. Moreover, if the average particle diameter of powders, such as MgO, is limited to the said range, a desired polycrystal can be obtained without using a sintering aid.

Next, any one of those powders, a binder, and an organic solvent are mixed to prepare a slurry. The concentration of the slurry at this time is preferably 40 to 70% by mass, and when it is 70% by mass or less, stable granulation is facilitated, and when it is 40% by mass or more, a dense polycrystal having a uniform structure is obtained. It is because it is easy to get a body.
That is, when the slurry concentration is limited to the above range, the viscosity of the slurry becomes 200 cps or less, and for example, powder granulation by a spray dryer can be performed stably. Crystals can be manufactured.

The wet mixing of the powder, the binder, and the organic solvent, particularly the wet mixing of the powder and the organic solvent that is the dispersion medium is performed by a wet ball mill or a stirring mill. In the wet ball mill, when ZrO ₂ balls are used, wet mixing is performed for 8 to 24 hours, preferably 20 to 24 hours, using a large number of ZrO ₂ balls having a diameter of 5 to 10 mm.
When the diameter of the ZrO ₂ ball is 5 mm or more, mixing is sufficiently performed, and when it is 10 mm or less, impurities can be reduced. The reason why the mixing time is as long as 24 hours is that the generation of impurities is small even if the mixing is continued for a long time. On the other hand, in a wet ball mill, when using a resin ball with an iron core, it is preferable to use a ball having a diameter of 10 to 15 mm.

In the stirring mill, wet mixing is performed for 0.5 to 1 hour using a ZrO ₂ ball having a diameter of 1 to 3 mm. When the diameter of the ZrO ₂ ball is 1 mm or more, mixing is sufficiently performed, and when it is 3 mm or less, impurities can be reduced.
Also, the mixing time is as short as 1 hour at the longest, because when it exceeds 1 hour, not only the mixing of raw materials but also the work of pulverization causes the generation of impurities. It is.

Next, the slurry is spray-dried to obtain a granulated powder having an average particle diameter of 50 to 300 μm, preferably 50 to 200 μm, and the granulated powder is put into a predetermined mold and molded at a predetermined pressure. If the average particle size of the granulated powder is 50 μm or more, the moldability is good, and if it is 300 μm or less, the density of the compact can be increased and the strength can be increased.
The spray drying is preferably performed using a spray dryer. Moreover, it is preferable to perform the shaping | molding of a pellet using the die press method in any one of a mechanical press method, a tablet machine method, or a briquette machine method. Thereby, a pellet-shaped molded body is obtained.

  Furthermore, the obtained pellet-shaped molded body is sintered at a predetermined temperature. It is preferable to degrease the molded body at a temperature of 350 to 620 ° C. before sintering. This degreasing treatment is performed in order to prevent color unevenness after sintering of the molded body, and it is preferable that the degreasing treatment is sufficiently performed over time. Sintering is preferably performed at a temperature of 1500 to 1700 ° C. When the sintering temperature is 1500 ° C. or higher, a dense sintered body can be obtained, and when it is 1700 ° C. or lower, the rate of grain growth can be suppressed and the characteristics can be improved. Moreover, when sintering a molded object in inert gas atmosphere, it is preferable to use argon gas as inert gas. In this way, a dense polycrystal having a density of 90 to 99.9% can be obtained as a target.

(Composition represented by SiO _x N _y )
When SiO _x N _y completely reacts with moisture, x ≧ 2 and y = 0. For this reason, when the reactive region has a composition represented by SiO _x N _y , it is preferable that 0 ≦ x <2 and 0 <y.

The reactive region having a composition represented by SiO _x N _y can be formed by the same method as the gas barrier region described above.

For example, in the case of a plasma CVD method, a vapor deposition layer having a composition represented by SiO _x N _y can be formed by using a silicon-containing gas, nitrogen gas, oxygen gas, or the like. By using silicon oxynitride as a target, a vapor-deposited layer having a SiO _x N _y composition can be formed.

For example, when using a coating solution containing a polysilazane compound, the polysilazane layer formed by applying and drying a coating solution containing a polysilazane compound is not subjected to a modification treatment with vacuum ultraviolet light or the like. , A polysilazane layer having a composition represented by SiO _x N _y can be formed.

  In addition, when both the reactive region and the gas barrier region disposed on the reactive region are formed using a polysilazane compound, a coating liquid containing the polysilazane compound is applied and dried to form a polysilazane layer. These can be simultaneously formed by irradiation with vacuum ultraviolet light. That is, only the surface of the polysilazane layer is modified by irradiation with vacuum ultraviolet light, and the polysilazane compound in the polysilazane layer is left partially or completely unreacted, thereby making the inner region of the polysilazane layer a reactive region. The reactive region and the gas barrier region can be formed by a single coating process so that the gas barrier region which is a modified layer is formed on the reactive region.

  In order to realize such a configuration, the oxygen concentration in the atmosphere at the time of irradiation with vacuum ultraviolet light is set to a relatively high concentration of 0.5 to 5.0% by volume, and the irradiation time is performed in a short time. To do. By doing so, the vicinity of the surface of the polysilazane layer is preferentially oxidized and modified to form a gas barrier region. On the other hand, in the region inside the surface of the polysilazane layer, the supply of oxygen is blocked, and the reactive region is formed by the unreacted substance remaining without the oxidation reforming reaction proceeding.

《Electronic device》
The gas barrier film of the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, the gas barrier film of the present invention can be applied to an electronic device provided with an electronic device body.

  Examples of the electronic device body used in the electronic device provided with the gas barrier film of the present invention include, for example, an organic electroluminescence element (organic EL element), a QD film having a quantum dot (QD) -containing resin layer, and a liquid crystal display An element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like can be given. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

  The gas barrier film of the present invention can be applied to an organic EL element. For the outline of the organic EL element applicable to the present invention, for example, JP2013-157634A and JP2013-168552A. JP, 2013-177361, JP 2013-187221, JP 2013-191644, JP 2013-191804, JP 2013-225678, JP 2013-235994, JP 2013-243234, JP 2013-243236, JP 2013-242366, JP 2013-243371, JP 2013-245179, JP 2014-003249, JP 2014 JP-A-003299, JP-A-2014-013910 JP 2014-017493 JP include a configuration described in JP-2014-017494 Publication.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

[Example 1]
<Reactivity evaluation in the reactive region>
First, in the gas barrier films 1 to 17 to be described later, samples A to G are prepared as follows in order to evaluate the reactivity of each reactive region of each composition provided as the first or second reactive region. did.

(Preparation of base material)
As a base material, a polyethylene terephthalate film (Lumilar (registered trademark) (U48), manufactured by Toray Industries, Inc.) having a thickness of 100 μm and subjected to easy adhesion treatment on both surfaces was used. A clear hard coat layer having an anti-block function having a thickness of 0.5 μm was formed on the surface of the resin substrate opposite to the surface on which the gas barrier unit was formed, as follows. Specifically, a UV curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied on a substrate so that the dry layer thickness was 0.5 μm, dried at 80 ° C., and then high-pressure mercury in air. Curing was performed using a lamp under the condition of an irradiation energy amount of 0.5 J / cm ² .

Next, a clear hard coat layer having a thickness of 2 μm was formed as follows on the surface of the resin base on the side where the gas barrier unit is to be formed. UV curable resin OPSTAR (registered trademark) Z7527 (manufactured by JSR Corporation) was applied to the substrate so that the dry layer thickness was 2 μm, and then dried at 80 ° C., and then using a high-pressure mercury lamp in the air. Then, curing was performed under the condition of an irradiation energy amount of 0.5 J / cm ² . In this way, a resin substrate with a clear hard coat layer was obtained. Henceforth, in a present Example and a comparative example, this resin substrate with a clear hard-coat layer is only used as a base material for convenience.

(Preparation of sample A (CaO layer))
The substrate was fully dried in the glove box.
The dried substrate is moved from the glove box to an electron beam (EB) deposition apparatus without exposure to the atmosphere, and the surface of the substrate on the side where the gas barrier unit is formed is reacted by EB deposition. A CaO layer having a thickness of 200 nm was formed as the active region.

A commercially available EB vapor deposition apparatus was used for forming the CaO layer. A commercially available CaO pellet (purity: 99.9%) was used as the vapor deposition material, and was formed under the conditions of oxygen partial pressure: 2.0 × 10 ⁻² Pa, substrate temperature: 80 ° C. or lower, and deposition rate: 5 nm / sec. .

Next, the base material on which the CaO layer had been formed was moved to the sputtering apparatus without exposure to the atmosphere through the glove box, and a SiO ₂ layer having a thickness of 100 nm was formed as a gas barrier region on the CaO layer. .

For the formation of the SiO ₂ layer, a magnetron sputtering apparatus (manufactured by Canon Anelva Co., Ltd .: Model EB1100) was used. A commercially available silicon target was used as a target, Ar and O ₂ were used as process gases, an oxygen partial pressure was set to 20%, and film formation was performed by DC sputtering. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. Regarding the layer thickness, after taking the layer thickness change data with respect to the deposition time in the range of 100 to 300 nm, calculating the layer thickness to be deposited per unit time, and then setting the deposition time to be the set layer thickness Thus, the layer thickness was adjusted.

This gave a sample A consisting of substrate / CaO layer / SiO ₂ layer. Sample A was stored in the glove box (the same applies to the following samples).

(Preparation of sample B (MgO layer))
In the preparation of Sample A, the base material / MgO layer was manufactured in the same manner except that a commercially available MgO pellet (purity: 99.9%) was used as the vapor deposition material, and the MgO layer was formed as the reactive region with a thickness of 200 nm. / Sample ₂ consisting of SiO ₂ layer was produced.

(Preparation of sample C (CaO / MgO mixed layer))
In the preparation of Sample A, CaO and MgO were mixed so as to contain a mass ratio of 1: 1 as a vapor deposition material, and CaO / MgO mixed pellets (purity 98.1%) obtained by sintering were used. A sample C composed of a base material / CaO / MgO mixed layer / SiO ₂ layer was produced in the same manner except that a CaO / MgO mixed layer having a thickness of 200 nm was formed as a reactive region.

(Preparation of sample D (Fe-containing MgO layer))
In preparation of the sample A, an Fe-containing MgO layer was formed as a reactive region using Fe-containing MgO pellets (purity 98.4%) obtained by sintering so as to contain 15000 mass ppm of Fe as an evaporation material. A sample D composed of a base material / Fe-containing MgO layer / SiO ₂ layer was produced in the same manner except that it was formed with a thickness of 200 nm.

(Production of sample E (silicon nitride layer formed by CVD method))
After the prepared base material is set in the vacuum plasma CVD apparatus 100 shown in FIG. 2 and evacuated, a silicon nitride layer (hereinafter referred to as a reactive region) is formed on the surface of the base material on the side where the gas barrier unit is formed. , A CVD silicon nitride layer) was formed. The high frequency power source used at this time was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm. The source gas was introduced into the vacuum chamber at a silane gas flow rate of 60 sccm, an ammonia gas flow rate of 60 sccm, and a nitrogen gas flow rate of 1200 sccm. Furthermore, the substrate temperature was set to 80 ° C. at the start of film formation, and a CVD silicon nitride layer was formed with a layer thickness of 200 nm.
Next, in the same manner as in the preparation of Sample A, a SiO ₂ layer was formed with a thickness of 100 nm, and Sample E consisting of a base material / CVD silicon nitride layer / SiO ₂ layer was prepared.

(Preparation of sample F (polysilazane layer))
The substrate was conditioned for 24 hours in an environment of 20 ° C. and 50% RH.
The following coating solution was applied to the surface of the conditioned substrate on the side where the gas barrier unit was formed in an environment of 20 ° C. and 50% RH by a spin coat method so that the dry layer thickness was 200 nm. Dry at 80 ° C. for 2 minutes. Thereby, a polysilazane layer was formed as a reactive region.

  The coating solution was a dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6- Dihydrohexane (TMDAH))-containing perhydropolysilazane 20 mass% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) is mixed at a ratio of 4: 1 (mass ratio), and further dibutyl ether And diluted to a solid content concentration of 6% by mass. The coating solution was prepared in a glove box.

Next, in the same manner as in the preparation of Sample A, a SiO ₂ layer was formed with a thickness of 100 nm, and Sample F consisting of base material / polysilazane layer / SiO ₂ layer was prepared.

(Preparation of sample G (polysilazane modified layer))
In the same manner as in the preparation of Sample E, a polysilazane layer was formed on the substrate. Next, vacuum ultraviolet irradiation treatment was performed on the dried coating film using the vacuum ultraviolet irradiation apparatus of FIG. 3 having an Xe excimer lamp with a wavelength of 172 nm under the condition that the irradiation energy amount was 6.0 J / cm ² . At this time, the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. The stage temperature for installing the sample was set to 80 ° C. In this way, a polysilazane modified layer was obtained as a reactive region.
Here, the modified polysilazane layer has a gas barrier property that does not substantially absorb moisture (no reactivity or composition change) in an environment where the surface layer side of 40 nm is 20 ° C. and 50% RH within a thickness of 200 nm. A region was formed, and the substrate side 160 nm was a reactive region.

Next, in the same manner as Sample A, an SiO ₂ layer was formed to a thickness of 100 nm, and Sample G consisting of base material / polysilazane modified layer / SiO ₂ layer was produced.

(Measurement of reaction speed of samples A to G with moisture)
The obtained samples A to G were quickly transferred from the glove box to an environment of 20 ° C. and 50% RH. From each sample, a small sample was cut out every 6 hours until the first 24 hours and every 24 hours thereafter, and the composition distribution profile in the thickness direction of the reactive region was measured by XPS analysis immediately. The XPS analysis conditions are as follows.

<XPS analysis conditions>
・ Device: Quantera SXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement was repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).
Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. For data processing, MultiPak manufactured by ULVAC-PHI was used. The analyzed elements are Si, Ca, Mg, Fe, Nb, O, N, and C.

The average composition of the reactive region was determined from the obtained data, and the time during which the reactive region completely reacted with moisture was determined from the composition, and this was defined as the rate of reaction with moisture.
For example, if the composition of the reactive region is CaO, it will be Ca (OH) ₂ when completely reacted with moisture, and _x of CaO _x will be 2 in XPS analysis. In the present invention, the time when the CaO _x x was 1.9 or more (20 ° C., 50% RH storage time) was determined as the time when the reactive region completely reacted with moisture. . About MgO, it is the same as that of CaO. Therefore, this index was used for samples A to D, and for sample C, when the sum of the atomic composition ratios of Ca and Mg was set to 1, x was 1.9.

For example, if the composition of the reactive region is SiO _x N _y , x ≧ 2 and y = 0 when completely reacted with moisture. In the present invention, when the _x of SiO _x N _y becomes 1.9 or more (20 ° C., 50% RH storage time), the reactive region is completely reacted with moisture, Asked. Therefore, this index was used for samples EG. For sample G, when the modified layer composition of the surface layer is represented by SiO _x N _y , the boundary between the gas barrier region and the reactive region is clarified from the change in the oxygen atom ratio based on the XPS analysis result, The value of x in the reactive region was calculated.
The results are shown in Table 1.

<< Production of Gas Barrier Films 1-17 >>
On the base material in the reactivity evaluation of the reactive region, the first gas barrier region, the first reactive region, the second gas barrier region, the second reactive region, and the third layer in the laminated configuration shown in Table 2. A gas barrier unit composed of a gas barrier region was formed, and gas barrier films 1 to 17 were produced. The first and second reactive regions of the gas barrier films 1 to 17 were formed in the same manner as the reactive regions of the samples A to G. Further, the first to third gas barrier regions of each gas barrier film 1 to 17 were formed as follows.

(Gas barrier property region: formation of SiO ₂ layer)
Using a magnetron sputtering apparatus (manufactured by Canon Anelva Co., Ltd .: model EB1100), an SiO ₂ layer was formed under the following conditions. The layer thickness was 100 nm.
A commercially available silicon target was used as a target, Ar and O ₂ were used as process gases, an oxygen partial pressure was set to 20%, and film formation was performed by DC sputtering. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. Regarding the layer thickness, after taking the layer thickness change data with respect to the deposition time in the range of 100 to 300 nm, calculating the layer thickness to be deposited per unit time, and then setting the deposition time to be the set layer thickness Thus, the layer thickness was adjusted.

(Gas barrier property region: formation of Si-Nb mixed region)
A niobium oxide layer was formed using a magnetron sputtering apparatus (manufactured by Canon Anelva Co., Ltd .: model EB1100) under the following conditions. The layer thickness was 8 nm.
A commercially available oxygen-deficient niobium oxide target was used. The composition was Nb ₁₂ O ₂₉ . Films were formed by DC sputtering using Ar and O _{2 as} process gases and an oxygen partial pressure of 12%. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. In addition, regarding the layer thickness, after taking the data of the change in the layer thickness with respect to the film formation time in the range of 50 to 200 nm and calculating the layer thickness formed per unit time, the film formation time is set to the set layer thickness. The layer thickness was adjusted by setting.

  By forming the niobium oxide layer on the polysilazane layer or the polysilazane modified layer as the reactive region as described above, Si and Nb are interdiffused, and a Si—Nb mixed region of about 30 nm is formed. This Si—Nb mixed region has a very high barrier property.

In addition, when the gas barrier region is a Si—Nb mixed region, the reaction speed with water in the underlying reactive region is a gas barrier region where the Nb / Si ratio is 0.02 or more. The boundary with the reactive region was clarified, and the value of x of SiO _x N _y of the reactive region was calculated in the same manner as the reactivity evaluation of the reactive region.

<Evaluation of gas barrier film>
The following evaluation was performed about each produced gas barrier property film. The evaluation results are shown in Table 2.

(Ratio of the rate of reaction with moisture in the first and second reactive regions)
For each gas barrier film produced, the ratio of the rate of reaction with moisture in the first and second reactive regions was calculated based on the rate of reaction with moisture described in Table 1. That is, a value calculated by dividing a large value among the reaction speeds with moisture in the first and second reactive regions by a small value was defined as a ratio of the reaction speed with moisture.

(Comparison of reaction speed with moisture in the first and second reactive regions)
About each produced gas barrier property film, based on the reaction speed with the water | moisture content of Table 1, the magnitude relationship of the reaction speed with the water | moisture content of a 1st and 2nd reactive region was confirmed. In Table 2, when the value of the rate of reaction with moisture is smaller in the first reactive region than in the second reactive region, “◯”, in the first reactive region than in the second reactive region When the direction is larger, “x” is given.

(Gas barrier property evaluation)
About each produced gas-barrier film, it stored at 20 degreeC and the environment of 50% RH (it shows as "no storage" in Table 2), and 60 degreeC and 90% RH environment of humidity, respectively. Four types of samples stored for 100 hr, 200 hr, and 300 hr were prepared.

  After the surface of the gas barrier unit of the gas barrier film was UV-cleaned, a thermosetting sheet adhesive (epoxy resin) was bonded to the surface of the gas barrier unit as a sealing resin layer with a thickness of 20 μm. This was punched out to a size of 50 mm × 50 mm, then placed in a glove box and dried for 24 hours.

  Next, one side of a 50 mm × 50 mm non-alkali glass plate (thickness 0.7 mm) was UV cleaned. Using a vacuum vapor deposition apparatus manufactured by ALS Technology, Inc., Ca was vapor-deposited in the center of the glass plate with a size of 20 mm × 20 mm through a mask. The thickness of Ca was 80 nm.

  The glass plate on which Ca has been deposited is taken out into the glove box, placed so that the sealing resin layer surface of the gas barrier film to which the sealing resin layer is bonded and the Ca deposition surface of the glass plate are in contact with each other, and adhered by vacuum lamination. . At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the glass plate facing down, and cured for 30 minutes to produce an evaluation cell.

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film was used as a comparative sample. It was stored at a high temperature and high humidity of 90 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 500 hours.

  The Ca vapor deposition area of the evaluation cell was photographed under transmission conditions to obtain a high-resolution digital image. Next, the evaluation cell was stored in an environment of 85 ° C. and 85% RH for 100 hours, and the Ca vapor deposition area was similarly photographed under transmission conditions to obtain a high-resolution digital image. Comparing the images before and after storage, the area where a 50% decrease in concentration was observed with respect to the initial concentration of the Ca deposition area was determined as the corrosion area, the area ratio (%) of the corrosion area was obtained, and the gas barrier property index did.

From the results shown in Table 2, it can be seen that the gas barrier film of the present invention can maintain high gas barrier properties for a predetermined period of time as compared with the gas barrier film of the comparative example.
In addition, when the ratio of the reaction rate with the moisture in the first reactive region and the reaction rate with the moisture in the second reactive region is within a range of 5 to 20 times, a higher gas barrier for a predetermined period. It can be seen that the sex can be maintained. Also, it can be seen that even when the first reactive region is faster than the second reactive region, the higher gas barrier property can be maintained for a predetermined period. .

[Example 2]
<< Production of organic EL devices >>
Using a non-alkali glass plate (thickness 0.7 mm) as a base material and using the gas barrier films 8 to 16 produced in Example 1 as a sealing member, the area of the light emitting region is as shown below. The bottom emission type organic EL devices 8 to 16 were respectively prepared so that the thickness of the organic EL devices was 5 cm × 5 cm. The materials used for manufacturing the organic EL device are shown below.

  A sufficiently washed alkali-free glass plate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, the compound 118 is placed in a resistance heating boat made of tungsten, and the substrate holder and the resistance heating boat are connected to the vacuum deposition apparatus. Installed in the first vacuum chamber. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

Next, after depressurizing the first vacuum tank of the vacuum deposition apparatus to 4 × 10 ⁻⁴ Pa, the heating boat containing the compound 118 was energized and heated, and the first deposition rate was 0.1 to 0.2 nm / second. A base layer of one electrode was provided with a thickness of 10 nm.

Next, the base material formed up to the underlayer was transferred to the second vacuum chamber while being vacuumed, and the second vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing silver was energized and heated. As a result, a first electrode made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 to 0.2 nm / second.

Subsequently, the pressure was reduced to a vacuum degree of 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, and then the compound HT-1 was deposited at a deposition rate of 0.1 nm / second while moving the base material. A hole transport layer (HTL) was provided.

  Next, the deposition rate of the compound A-3 (blue light emitting dopant) and the compound H-1 (host compound) depending on the location so that the compound A-3 is linearly 35% to 5% by weight with respect to the layer thickness. The vapor deposition rate was changed depending on the location so that the compound H-1 was 65% by mass to 95% by mass, and the light emitting layer was formed by co-evaporation to a thickness of 70 nm.

  Thereafter, the compound ET-1 was vapor deposited to a layer thickness of 30 nm to form an electron transport layer, and potassium fluoride (KF) was further formed to a thickness of 2 nm. Furthermore, aluminum 110nm was vapor-deposited and the 2nd electrode was formed.

  Next, a sealing member was prepared by bonding a thermosetting sheet-like adhesive (epoxy resin) with a thickness of 20 μm as a sealing resin layer to the gas barrier unit surface of each gas barrier film. . This sealing member was overlaid on the sample formed up to the second electrode. At this time, the adhesive forming surface of the sealing member and the organic functional layer surface of the element were continuously overlapped so that the end portions of the extraction electrodes of the first electrode and the second electrode were exposed.

Next, the laminated body was placed in a decompression device, and the laminated base material and the sealing member were pressed and held for 5 minutes under a reduced pressure condition of 90 MPa at 0.1 MPa. Subsequently, the sample was returned to the atmospheric pressure environment and further heated at 120 ° C. for 30 minutes to cure the adhesive.
The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a water content of 1 mass ppm or less, in accordance with JIS B 9920: 2002. The measured cleanliness is class 100, the dew point temperature is −80 ° C. or less, and the oxygen concentration It was performed at an atmospheric pressure of 0.8 ppm or less. In addition, the description regarding formation of the lead-out wiring from an anode and a cathode is abbreviate | omitted.

  In this way, an organic EL device having a light emitting region area of 5 cm × 5 cm was manufactured.

<< Dark spot evaluation of organic EL devices >>
The organic EL device produced above was stored in an environment of 85 ° C. and 85% RH for up to 500 hours, and light was emitted every 50 hours to confirm whether or not dark spots with a circular equivalent diameter of 50 μm or more were generated. . The storage time when dark spot generation of 50 μm or more was confirmed was used as an evaluation index. In addition, it can be said that there is an ultra-high barrier property for a short time in 300 hours or more. The evaluation results are shown in Table 3.

  From the results shown in Table 3, the organic EL device provided with the gas barrier film of the present invention was suppressed from generating dark spots for a predetermined period compared to the organic EL device provided with the gas barrier film of the comparative example. I understand that.

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2 Base material 3 Gas barrier unit 31 1st gas barrier area | region 32 1st reactive area 33 2nd gas barrier area | region 34 2nd reactive area 35 3rd gas barrier area | region

Claims (8)

A gas barrier film comprising a gas barrier unit on a substrate,
The gas barrier unit is in order from the substrate side,
A first gas barrier region;
A first reactive region containing a metal compound as a main component;
A second gas barrier property region;
A metal element of the metal compound contained as a main component in the first reactive region is a second reactive region containing as a main component a metal compound containing a metal element that is a heterogeneous element in the periodic table;
A gas barrier film comprising a third gas barrier region. The first reactive region contains an alkaline earth metal;
2. The gas barrier film according to claim 1, wherein the second reactive region has a composition represented by SiO _x N _y (0 ≦ x <2, 0 <y). The first reactive region has a composition represented by SiO _x N _y (0 ≦ x <2, 0 <y);
The gas barrier film according to claim 1, wherein the second reactive region contains an alkaline earth metal.   The ratio of the speed of reaction with moisture in the first reactive region and the speed of reaction with moisture in the second reactive region is in the range of 5 to 20 times. The gas barrier film according to any one of claims 1 to 3.   The gas barrier according to any one of claims 1 to 4, wherein the first reactive region is faster in reaction with moisture than the second reactive region. Sex film. The region having a composition represented by SiO _x N _y (0 ≦ x <2, 0 <y) in the gas barrier unit is a vapor deposition layer. The gas barrier film according to any one of the above. The region having a composition represented by SiO _x N _y (0 ≦ x <2, 0 <y) in the gas barrier unit is a polysilazane layer. The gas barrier film according to any one of the above.   An electronic device comprising the gas barrier film according to any one of claims 1 to 7.

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