JP6504284B2 - Gas barrier film, method for producing the same, and electronic device using the same - Google Patents

Description

  The present invention relates to a gas barrier film, a method for producing the same, and an electronic device using the same.

  Conventionally, gas barrier films in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide or silicon oxide is formed on the surface of a plastic substrate or film are used to package articles in the field of food, medicines, etc. Used in By using a gas barrier film, it is possible to prevent deterioration of the article due to a gas such as water vapor or oxygen.

  In recent years, there has been a demand for the development of electronic devices such as organic electroluminescent (EL) elements and liquid crystal display (LCD) elements for gas barrier films that prevent such permeation of water vapor, oxygen, etc., and many studies have been made. . These electronic devices are required to have high gas barrier properties, for example, gas barrier properties comparable to glass substrates. However, at present the gas barrier film having such high barrier properties has not been obtained yet.

  As a method for producing a gas barrier film, a method using an inorganic film forming method by a vapor phase method is known. As the inorganic film forming method by the vapor phase method, metal (tetraethoxysilane (TEOS) is exemplified by plasma CVD method (Chemical Vapor Deposition: chemical vapor deposition method) on a substrate such as a film. Method to form an inorganic film (gas barrier layer) by oxidizing an organic silicon compound or the like while oxidizing with oxygen plasma, and evaporating a metal using a semiconductor laser etc. to deposit on a substrate in the presence of oxygen Examples of the method include a method of forming an inorganic film (gas barrier layer) by a vacuum evaporation method or a sputtering method.

  These inorganic film-forming methods by the vapor phase method have been used for the production of gas barrier films used for packaging articles in the fields of food, medicine and the like. And in recent years, in order to apply the gas barrier film manufactured by the said inorganic film-forming method to an electronic device, examination for obtaining still higher gas-barrier property is performed.

  As such examination, for example, a gas barrier film of a laminate in which an oxide layer obtained by modifying a coating solution containing polysilazane on a metal oxide layer formed by a vapor deposition method is formed is disclosed. (See, for example, JP-A-8-281861 and JP-A-2012-106421).

  However, in the conventional gas barrier film described in the above-mentioned JP-A-8-281861 or JP-A-2012-106421, although the gas barrier performance is high, when the film is bent, the gas barrier performance may be deteriorated. The In particular, when the film is disposed under high temperature and high humidity conditions, the deterioration of the gas barrier performance of the film becomes remarkable, and the required gas barrier performance is not satisfied.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a gas barrier film which exhibits sufficient gas barrier performance even under high temperature and high humidity conditions.

  The present inventors diligently studied to solve the above problems. As a result, the substrate, the first layer, the second layer, and the third layer are included in this order, and the first layer is at least one oxidation selected from the group consisting of silicon, aluminum and titanium. , Nitride, oxynitride or at least one of oxycarbides, and formed by a chemical vapor deposition method, the second layer contains an inorganic oxide, and is formed by atomic layer deposition; The layer of No. 3 is a gas barrier film obtained by applying a solution containing a silicon compound to form a gas barrier film, which is obtained by modifying the coating film. I found that I could get it.

It is a schematic diagram which shows an example of the vacuum plasma CVD apparatus used for formation of the 1st layer which concerns on this invention. It is a schematic diagram which shows an example of the other manufacturing apparatus used for formation of the 1st layer based on this invention. It is an example of each element profile of the thickness direction of the layer by the XPS depth profile of the gas barrier layer which does not have an extreme value etc. It is a figure which shows the film thickness composition of the 1st layer in the gas barrier film 2 which is an Example. It is an example of the organic electroluminescent panel which is an electronic device which used the gas barrier film which concerns on this invention as a sealing film.

  The present invention comprises a substrate, a first layer, a second layer, and a third layer in this order, the first layer comprising at least one oxidation selected from the group consisting of silicon, aluminum and titanium. A nitride layer, an oxynitride or an oxide carbide, and formed by a chemical vapor deposition method, the second layer includes an inorganic oxide, and is formed by an atomic layer deposition method; The layer relates to a gas barrier film obtained by modifying a coating film formed by applying a solution containing a silicon compound. The gas barrier film of the present invention has excellent gas barrier properties and exhibits sufficient gas barrier performance even under bending or under high temperature and high humidity conditions.

  By forming the gas barrier layer by a chemical vapor deposition method (hereinafter, also simply referred to as a CVD method), a film having a high gas barrier performance can be obtained, and the CVD method has a high film forming speed and high productivity. It has been practiced to form a gas barrier layer by the method. However, when the film surface is formed by the CVD method, defects occur on the film surface, and the CVD method is easy to etch the film surface, and the smoothness of the film surface is poor.

  In order to compensate for the defects of the gas barrier layer by such a CVD method, for example, a layer formed by the CVD method as described in the above-mentioned JP-A-8-281861 and JP-A-2012-106421 (hereinafter also referred to as a CVD layer) A gas barrier film obtained by laminating a layer obtained by modifying a silicon compound (hereinafter also referred to as a silicon compound modified layer) has been proposed. Such a gas barrier film has a barrier layer formed by different mechanisms, and the passage of gas in the two layers is different. Therefore, when the two layers are laminated, the gas barrier performance is improved. Furthermore, it is considered that the defect is repaired and the gas barrier performance is improved by impregnating the film surface defect of the CVD layer with the coating liquid used when forming the silicon compound modified layer.

  However, the present inventors have found that such a gas barrier film lowers the gas barrier performance at the time of bending and does not satisfy the required gas barrier performance. And as a result of earnestly examining the factor which causes such a phenomenon, when applying the coating liquid used when forming a silicon compound modified layer, minute defects such as pinholes present in the CVD layer which is a coated surface However, it was considered that some coating solutions were not sufficiently repaired. It is presumed that this is because the coating solution can enter into large defects but can not enter into minute defects.

  The following mechanism can be considered as a cause of the deterioration of the gas barrier performance due to the presence of the above-mentioned minute defects. As the film is densified when the silicon compound is reformed by vacuum ultraviolet light or plasma, the film thickness of the silicon compound layer decreases and stress remains in the film. If micro defects such as pinholes are present on the application surface of the coating solution used when forming the silicon compound modified layer, the remaining stress is concentrated on the pinholes, resulting in micro cracks, resulting in barrier performance. Is considered to deteriorate. Therefore, even with the coating solution used in forming the silicon compound modified layer, microdefects still exist on the coated surface, and stress concentration at the time of modification to such microdefects is particularly observed in the gas barrier layer at bending. It was considered to be the main factor that impedes improvement.

  In view of the above problems, the inventors of the present invention improve the film performance at the time of bending as a result of using the second layer of the inorganic oxide formed by the ALD method in the upper layer of the CVD layer when repairing the minute defects. I was able to. It is considered that this is because the inorganic oxide formed by the ALD method has a relatively small molecular weight, can fill micro defects, and can repair micro defects.

  In addition, when the silicon compound modified layer is formed on the inorganic oxide layer formed by the ALD method, the deterioration of the gas barrier performance at high temperature and high humidity is surprisingly suppressed, and sufficient gas barrier properties are secured. I found that.

  The following mechanism can be considered as a reason which can suppress the fall of the gas barrier performance at the time of high temperature and high humidity.

  The contact area between the silicon compound modified layer and the second layer is increased as compared with the case where the CVD layer becomes the lower layer of the silicon compound modified layer by the repair of micro defects, and the silicon compound modified layer and the second layer Adhesion is improved. The silicon compound modified layer has the property of expanding under high temperature and high humidity conditions. By improving the adhesion between the silicon compound modified layer and the second layer, it is considered that the force that counteracts such expansion is increased, and the decrease in the gas barrier property can be suppressed. In addition, by forming an oxide with a film deposited by ALD, the entire surface can be made into an OH group, and the silicon compound closely adheres to the atomic layer deposition film in atomic units, and the silicon compound is reformed. Since the layer itself becomes dense, it is considered that the gas barrier performance is improved.

  The above mechanism is presumed, and the effect of the present invention is not limited to these mechanisms.

  Therefore, in the gas barrier film of the present invention, a preferred embodiment includes a substrate, a first layer, a second layer formed on the first layer, and a third layer. In this order. Furthermore, a preferred embodiment includes a substrate, a first layer, a second layer formed on the first layer, and a third layer formed on the second layer. , In this order.

  Also, a gas barrier unit having a first layer, a second layer, and a third layer may be formed on one surface of the substrate, and is formed on both surfaces of the substrate May be Moreover, the gas barrier unit may include a layer not necessarily having the gas barrier property.

In addition, the gas barrier film of the present invention preferably has a water permeation amount measured by the method described in the below-mentioned Examples of less than 1 × 10 ⁻³ g / (m ² · 24 h), 1 × 10 ⁻ More preferably, it is less than ⁴ g / (m ² · 24 h).

  Hereinafter, preferred embodiments of the present invention will be described in detail, but the present invention is not limited thereto.

[First layer (CVD layer)]
The thickness per one layer of the first layer is not particularly limited, but is usually in the range of 30 to 500 nm, preferably 50 to 300 nm, from the viewpoint of the gas barrier performance and the possibility of defects. The first layer may be a laminated structure consisting of a plurality of sublayers, each layer being formed by a CVD method. In this case, the number of sublayers is preferably 2 to 10. Also, each sublayer may have the same composition or different compositions.

The first layer comprises at least one of at least one oxide, nitride, oxynitride or oxycarbide selected from the group consisting of silicon, aluminum and titanium. As at least one oxide, nitride, oxynitride or oxycarbide selected from the group consisting of silicon, aluminum and titanium, specifically, silicon oxide (SiO ₂ ), silicon nitride, silicon oxynitride ( SiON), silicon oxycarbide (SiOC), aluminum oxide, titanium oxide, and their complexes such as aluminum silicate. These may contain other elements as secondary components.

The first layer has a gas barrier property by having the above-described compound. Here, when the gas barrier properties of the first layer are calculated using the laminate in which the first layer is formed on the base material, the amount of moisture transmission measured by the method described in the examples described later is 0. is preferably 1g ^/ (m 2 · 24h) or less, and more preferably 0.01g ^/ (m 2 · 24h) or less.

  The first layer is formed by a chemical vapor deposition method (CVD method). Chemical vapor deposition (Chemical Vapor Deposition) is a method in which a source gas containing the components of a target thin film is supplied onto a substrate, and the film is deposited by a chemical reaction on the substrate surface or in the gas phase. It is. In addition, there is a method of generating plasma etc. for the purpose of activating chemical reaction, and known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method System etc. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of the film forming speed and the processing area. Forming the first layer by chemical vapor deposition is advantageous in terms of gas barrier properties.

  The gas barrier layer obtained by vacuum plasma CVD method or plasma CVD method under atmospheric pressure or pressure near atmospheric pressure selects conditions such as metal compounds which are raw materials (also referred to as raw materials), decomposition gas, decomposition temperature, input electric power, etc. It is preferable because the desired compound can be produced.

  For example, if a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, a silicon oxide is formed. This is because, in the plasma space, highly active charged particles and active radicals exist at a high density, so multistep chemical reactions are promoted at high speed in the plasma space, and the elements present in the plasma space are thermodynamics. It is converted to a very stable compound in a very short time.

  As a raw material compound, a silicon compound, a titanium compound, and an aluminum compound are used.

  Among these, as a silicon compound, silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, di Ethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane , Tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, Pargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethyl Cyclotetrasiloxane, hexamethyl cyclotetrasiloxane, M silicate 51, etc. are mentioned. Moreover, the silicon compound which is a raw material compound used in the case of formation of the layer which satisfy | fills the requirements of (i)-(ii) which is the below-mentioned suitable form is mentioned.

  Examples of titanium compounds include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium tetraisopropoxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium Diisopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, butyl titanate dimer and the like can be mentioned.

  As the aluminum compound, aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, triethyldialuminum tri-s-butoxide, etc. It can be mentioned.

  In addition, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide, etc. can be used as the decomposition gas for decomposing source gases containing these metals to obtain inorganic compounds. Gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor and the like can be mentioned. In addition, the decomposition gas may be mixed with an inert gas such as argon gas or helium gas.

  A desired barrier layer can be obtained by appropriately selecting the source gas containing the source compound and the decomposition gas. The first layer formed by chemical vapor deposition is an oxide, a nitride, an oxynitride or an oxycarbide.

  Hereinafter, among the CVD methods, the plasma CVD method which is a preferable embodiment will be specifically described.

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

  In FIG. 1, a vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom side inside the vacuum chamber 102. Further, on the ceiling side inside the vacuum chamber 102, a cathode electrode 103 is disposed at a position facing the susceptor 105. A heat medium circulation system 106, a vacuum evacuation 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 and cooling device 160 having a storage device is provided.

  The heating and 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 to heat or cool the susceptor 105 and return 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 it to the susceptor 105. Thus, the cooling medium circulates between the susceptor and the heating and cooling device 160, and the susceptor 105 is heated or cooled by the supplied heating medium of the set temperature.

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

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

  A large number of nozzles (holes) are formed on the surface of the cathode electrode 103 facing the susceptor 105.

  The cathode electrode 103 is connected to a gas introduction system 108. When 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 the ground potential.

  When the CVD gas is supplied from the gas introduction system 108 into the vacuum chamber 102 and the heating medium with a constant temperature is supplied from the heating and cooling device 160 to the susceptor 105, the high frequency power supply 109 is started and a high frequency voltage is applied to the cathode electrode 103, A plasma of the introduced CVD gas is formed. When the CVD gas activated in the plasma reaches the surface of the substrate 110 on the susceptor 105, a first layer which is a thin film is grown on the surface of the substrate 110.

  The distance between the susceptor 105 and the cathode electrode 103 at this time is appropriately set.

  Further, the flow rates of the source gas and the decomposition gas are appropriately set in consideration of the source gas, the type of the decomposition gas, 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 10 to 1000 sccm.

  During thin film growth, a heating medium at a constant temperature is supplied from the heating and 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 in a state of being maintained at a constant temperature. In general, the lower limit temperature of the growth temperature in forming the thin film is determined by the film quality of the thin film, and the upper limit temperature is determined by the allowable range of damage to the thin film already formed on the substrate 110. The lower limit temperature and the upper limit temperature vary depending on the material of the thin film to be formed, the material of the thin film already formed, etc., but the lower limit temperature is 50 ° C. or higher to secure the film quality with high gas barrier properties. It is preferable that it is below the heat-resistant temperature of.

  The correlation between the film quality of the thin film formed by the vacuum plasma CVD method and the film forming temperature, and the correlation between the damage to the film forming object (substrate 110) and the film forming temperature is determined in advance, and the lower limit temperature and the upper limit temperature are determined. Be done. For example, the temperature of the substrate 110 during the vacuum plasma CVD process is preferably 50-250.degree.

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

  For example, the lower limit temperature (here, 50 ° C.) is stored, and a heat medium 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 returned from the susceptor 105 is heated or cooled, and the heat medium having the set temperature of 50 ° C. is supplied to the susceptor 105. For example, a mixed gas of silane gas, ammonia gas, and nitrogen gas is supplied as a CVD gas, and a SiN film is formed in a state where the temperature condition of the substrate 110 is equal to or higher than the lower limit temperature and equal to or lower than the upper limit temperature.

  Immediately after startup of the vacuum plasma CVD apparatus 101, the susceptor 105 is at room temperature, and the temperature of the heat medium returned from the susceptor 105 to the heating and cooling device 160 is lower than the set temperature. Therefore, immediately after the start-up, the heating and cooling device 160 heats the heated heat medium to be heated to the set temperature, and supplies the heat medium 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 the range of the lower limit temperature or more and the upper limit temperature or less.

  When thin films are continuously formed on a plurality of substrates 110, the susceptor 105 is heated by the heat flowing from the plasma. In this case, the heating medium returned from the susceptor 105 to the heating and cooling device 160 has a temperature higher than the lower limit temperature (50 ° C.). Therefore, the heating and cooling device 160 cools the heating medium and Supply to 105. Thereby, the thin film can be formed while maintaining the substrate 110 in the range of the lower limit temperature or more and the upper limit temperature or less.

  As described above, the heating and cooling device 160 heats the heat medium when the temperature of the heat medium returned is lower than the set temperature, and cools the heat medium when the temperature is higher than the set temperature. Also, the heat medium of the set temperature is supplied to the susceptor, and as a result, the substrate 110 maintains the temperature range of the lower limit temperature or more and the upper limit temperature or less.

  When the thin film is formed to a predetermined film thickness, the substrate 110 is carried out of the vacuum chamber 102, the substrate 110 without film formation is carried into the vacuum chamber 102, and the heat medium of the set temperature is supplied as described above. Form a thin film.

(Preferred form of the first layer)
Moreover, as a preferred embodiment of the first layer of the present invention, the first layer preferably contains carbon, silicon and oxygen as constituent elements. A more preferable form is a layer satisfying the following requirements (i) to (ii).

(I) Ratio of the amount of silicon atoms to the total amount of the distance (L) from the surface of the first layer in the film thickness direction of the first layer and the amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of silicon) A silicon distribution curve showing a relationship with the oxygen distribution curve, a oxygen distribution curve showing a relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen) The carbon distribution curve has at least two extreme values in a carbon distribution curve that shows the relationship between the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of carbon)
(Ii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.

  Having such a composition is preferable from the viewpoint of achieving both gas barrier properties and flexibility at the same time.

  Furthermore, in the region of 90% or more of the total layer thickness of the first layer, the average atomic ratio of each atom to the total amount (100 at%) of silicon atoms, oxygen atoms and carbon atoms is represented by the following formula (A) or (B It is preferable to have the magnitude relation of the order represented by).

Formula (A) (carbon average atomic ratio) <(silicon average atomic ratio) <(oxygen average atomic ratio)
If the formula (B) (oxygen average atomic ratio) <(silicon average atomic ratio) <(carbon average atomic ratio), the bending resistance is further improved, which is more preferable.

  The above preferred embodiment will be described below.

  (I) Ratio of the amount of silicon atoms to the total amount of the distance (L) from the surface of the first layer in the film thickness direction of the first layer and the amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of silicon) Distribution curve showing the relationship with L, oxygen distribution curve showing the relationship between L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), and L and silicon atoms Preferably, the carbon distribution curve has at least two extreme values in a carbon distribution curve showing a relationship with the ratio of the amount of carbon atoms to the total amount of oxygen atoms and carbon atoms (atomic ratio of carbon). The first layer preferably has a carbon distribution curve having at least three extreme values, more preferably at least four extreme values, but may have five or more. When the carbon distribution curve has at least two extreme values, the carbon atom ratio changes continuously with a concentration gradient, and the gas barrier performance at the time of bending is enhanced. The upper limit of the number of extreme values can not be generally defined because it is also due to the film thickness of the barrier layer.

  Here, in the case of having at least three extreme values, one extreme value of the carbon distribution curve and the surface of the first layer in the film thickness direction of the first layer at the extreme value adjacent to the extreme value The absolute value of the difference in distance (L) (hereinafter, also simply referred to as “distance between extreme values”) is preferably 200 nm or less in any case, more preferably 100 nm or less, and preferably 75 nm or less Particularly preferred. With such a distance between the extremes, the first layer is provided with a suitable flexibility because a portion (maximum value) having a large carbon atom ratio is present in a proper cycle in the first layer, It is possible to more effectively suppress or prevent the occurrence of cracks at the time of bending of the gas barrier film. In the present specification, the extreme value means the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the first layer in the film thickness direction of the first layer. In the present specification, the maximum value is a point at which the value of the atomic ratio of an element (oxygen, silicon or carbon) changes from an increase to a decrease when the distance from the surface of the first layer is changed. And the value of the atomic ratio of the element at a position at which the distance from the surface of the first layer in the film thickness direction of the first layer is further changed by 4 to 20 nm than the atomic ratio of the element at that point. Refers to the point at which 3at% or more decreases. That is, when changing in the range of 4 to 20 nm, the value of the atomic ratio of the elements may be reduced by 3 at% or more in any range. This varies with the thickness of the first layer. For example, when the first layer has a thickness of 300 nm, the atomic ratio of elements at positions at which the distance from the surface of the first layer in the thickness direction of the first layer is changed by 20 nm decreases by 3 at% or more A point is preferred. Furthermore, in the present specification, the minimum value is a point at which the value of the atomic ratio of the element (oxygen, silicon or carbon) changes from a decrease to an increase when the distance from the surface of the first layer is changed, and The value of the atomic ratio of the element at a position where the distance from the surface of the first layer in the film thickness direction of the first layer is further changed by 4 to 20 nm is more than the atomic ratio of the element at that point. It refers to a point that increases by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the value of the atomic ratio of the elements may be increased by 3 at% or more in any range. Here, in the case of having at least three extreme values, the lower limit of the distance between the extreme values is particularly high because the smaller the distance between the extreme values, the higher the effect of suppressing crack prevention / prevention at the time of bending of the gas barrier film. It is not restricted.

  Furthermore, in the first layer, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the (ii) carbon distribution curve is preferably 3 at% or more, more preferably 5 at% or more More preferably, it is 7 at% or more. When the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more, the gas barrier performance at the time of bending is enhanced. In the present specification, the “maximum value” is the atomic ratio of each element which becomes the largest in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in the present specification, the “minimum value” is an atomic ratio of each element which is minimum in the distribution curve of each element, and is the lowest value among the minimum values.

  Also, in the region of 90% or more (upper limit: 100%) of the film thickness of the first layer, (atomic ratio of oxygen), (atomic ratio of silicon), (atomic ratio of carbon) increase in order of (atomic ratio Is preferably O> Si> C). Here, at least 90% or more of the film thickness of the first layer may not be continuous in the barrier layer, and the above-described relationship may be satisfied only at 90% or more. Under such conditions, the gas barrier properties and flexibility of the obtained gas barrier film become sufficient. In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the first layer, If satisfied, the atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the layer is preferably 25 to 45 at%, and more preferably 30 to 40 at%. preferable. The atomic ratio of the content of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the first layer is preferably 33 to 67 at%, and more preferably 45 to 67 at%. preferable. Furthermore, the atomic ratio of the content of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the first layer is preferably 3 to 33 at%, more preferably 3 to 25 at%. preferable.

  The oxygen distribution curve of the first layer preferably has at least one extremum, more preferably at least two extrema, and even more preferably at least three extrema. When the oxygen distribution curve has at least one extreme value, the gas barrier property in the case where the obtained gas barrier film is bent is further improved. Even at the upper limit of the number of extreme values of the oxygen distribution curve, there is a portion due to the film thickness of the barrier layer, and it can not be specified in a definite manner. In addition, in the case of having at least three extreme values, one extreme value of the oxygen distribution curve and the extreme value adjacent to the extreme value from the surface of the first layer in the film thickness direction of the first layer The absolute value of the difference in distance is preferably 200 nm or less, and more preferably 100 nm or less. With such a distance between extreme values, the occurrence of cracks at the time of bending of the gas barrier film can be more effectively suppressed / prevented.

In addition, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the first layer (hereinafter, also simply referred to as “O _max −O _min difference”) is 3 at% or more The content is preferably 5 at% or more, more preferably 6 at% or more, and still more preferably 7 at% or more. If the said absolute value is 3 at% or more, the gas barrier property in the case where the film of the gas barrier film obtained is bent will improve more.

Furthermore, it is preferable that the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of the first layer (hereinafter, also simply referred to as “Si _max −Si _min difference”) is less than 5 at% It is more preferably less than 4 at%, and even more preferably less than 3 at%. When the said absolute value is less than 5 at%, the gas barrier property and mechanical strength of the gas barrier film obtained will improve more. The _lower limit of Si max _{-Si min difference,} since Si max improvement of cracking suppressing / preventing flexion enough gas barrier film _{-Si min} difference is small is high, not particularly limited.

The total amount of carbon and oxygen atoms in the film thickness direction of the first layer is preferably substantially constant. Thereby, the first layer exhibits appropriate flexibility, and the crack generation at the time of bending of the gas barrier film can be more effectively suppressed / prevented. More specifically, the sum of oxygen atoms and carbon atoms relative to the total amount of the distance (L) from the surface of the first layer in the thickness direction of the first layer and silicon atoms, oxygen atoms, and carbon atoms In the oxygen carbon distribution curve showing the relationship with the ratio of amounts (atomic ratio of oxygen and carbon), the absolute value of the difference between the maximum value and the minimum value of the sum of the atomic ratio of oxygen and carbon in the oxygen carbon distribution curve preferably also referred to as _"OC max _{-OC min} difference") is less than 5at%, more preferably less than 4at%, more preferably less than 3at%. If the absolute value is less than 5 at%, the gas barrier properties of the obtained gas barrier film will be further improved.

  The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. The surface composition analysis can be sequentially performed while exposing the so-called XPS depth profile measurement. The distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the distribution curve of the element in which the horizontal axis represents the etching time, the etching time generally correlates with the distance (L) from the surface of the first layer in the thickness direction of the first layer, As “the distance from the surface of the first layer in the thickness direction of the first layer”, from the surface of the first layer calculated from the relationship between the etching rate and the etching time employed in the measurement of the XPS depth profile Distance can be adopted. In the present invention, a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve were created under the following measurement conditions.

(Measurement condition)
Etching ion species: argon (Ar ⁺ );
Etching rate (SiO ₂ thermal oxide film conversion value): 0.05 nm / sec;
Etching interval (SiO ₂ conversion value): 10 nm;
X-ray photoelectron spectrometer: manufactured by Thermo Fisher Scientific, model name "VG Theta Probe";
Irradiated X-ray: Single crystal spectroscopy AlKα
X-ray spots and their sizes: 800 × 400 μm ovals.

  From the viewpoint of forming a first layer having uniform and excellent gas barrier properties over the entire film surface, the first layer is substantially uniform in the film surface direction (direction parallel to the surface of the first layer) Is preferred. Here, that the first layer is substantially uniform in the film surface direction means that the oxygen distribution curve, the carbon distribution curve and the oxygen are measured at any two measuring points on the film surface of the first layer by XPS depth profile measurement. When creating a carbon distribution curve, the number of extremums possessed by the carbon distribution curve obtained at any two measurement points is the same, and the maximum value and the minimum value of the atomic ratio of carbon in each carbon distribution curve The absolute values of the differences between the two are the same or within 5 at%.

  Furthermore, the carbon distribution curve is preferably substantially continuous. Here, that the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously, and specifically, it is calculated from the etching rate and the etching time. The distance (x, unit: nm) from the surface of the first layer in the film thickness direction of at least one of the first layers to be measured and the atomic ratio of carbon (C, unit: at%) In the relationship, it means that the condition represented by the following formula (1) is satisfied.

  Further, in the carbon distribution curve, the carbon atom ratio of the first layer is preferably in the range of 8 to 20 at% as an average value of the whole layer, and more preferably in the range of 10 to 20 at%. By setting it in the said range, the gas 1st layer which fully satisfy | fills gas-barrier property and flexibility can be formed.

  When the first layer has sublayers, a plurality of sublayers satisfying all the conditions (i) to (ii) may be stacked to form the first layer. When two or more sublayers are provided, the materials of the plurality of sublayers may be the same or different.

  The layer satisfying the requirements of (i) to (ii), which is a preferred embodiment of the first layer, is preferably a layer formed by plasma CVD (PECVD) method, and a substrate is further formed into a film It is more preferable to form by a plasma CVD method which is disposed on a roller and discharged between the pair of film forming rollers to generate plasma. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

  When plasma is generated in the plasma CVD method, it is preferable to generate plasma discharge in the space between a plurality of film forming rollers, and a pair of film forming rollers is used, and the above-mentioned base is formed on each of the pair of film forming rollers. It is more preferable to arrange a material and discharge between a pair of film forming rollers to generate plasma. In this manner, the substrate is disposed on the pair of film forming rollers using the pair of film forming rollers, and discharge is performed between the pair of film forming rollers, thereby forming one of the film forming rollers on at the time of film formation. In addition to the film formation on the surface of the substrate present on the surface of the substrate, the film formation on the surface of the substrate present on the other film formation roller can be simultaneously formed, enabling efficient production of a thin film. The film deposition rate can be doubled as compared with the plasma CVD method that does not use a roller, and since a film having substantially the same structure can be deposited, it is possible to at least double the extreme value in the carbon distribution curve. It becomes possible to form a layer satisfying all the above conditions (i) to (ii).

  Moreover, when discharging between a pair of film-forming rollers in this way, it is preferable to reverse the polarity of the pair of film-forming rollers alternately. Furthermore, as a film forming gas used in such a plasma CVD method, one containing an organic silicon compound and oxygen is preferable, and the content of oxygen in the film forming gas is the total amount of the organosilicon compound in the film forming gas. Is preferably less than the theoretical amount of oxygen required to completely oxidize. Moreover, in the gas barrier film of the present invention, the first layer is preferably a layer formed by a continuous film forming process.

  Moreover, it is preferable to form a 1st layer on the surface of a base material by a roll-to-roll system from a viewpoint of productivity. Further, an apparatus that can be used when manufacturing the first layer by such plasma CVD method is not particularly limited, but it comprises at least a pair of film forming rollers and a plasma power source, and a pair of components The apparatus is preferably configured to be capable of discharging between film rollers. For example, in the case of using the manufacturing apparatus shown in FIG. 2, the roll-to-roll system is used while using the plasma CVD method. It will also be possible.

  Hereinafter, the method of forming the first layer will be described in more detail with reference to FIG. In addition, FIG. 2 is a schematic diagram which shows an example of the manufacturing apparatus which can be suitably utilized in order to manufacture a 1st layer (CVD layer). Further, in the following description and the drawings, the same or corresponding elements will be denoted by the same reference symbols, without redundant description.

  The manufacturing apparatus 31 shown in FIG. 2 includes a delivery roller 32, transport rollers 33, 34, 35, 36, film forming rollers 39, 40, a gas supply pipe 41, a power source 42 for plasma generation, a film forming roller 39. And 40, and a take-up roller 45. As shown in FIG. Further, in such a manufacturing apparatus, at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power supply 42, and the magnetic field generating devices 43 and 44 are disposed in a vacuum chamber (not shown). ing. Furthermore, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  In such a manufacturing apparatus, each film forming roller is a power source for plasma generation so that the pair of film forming rollers (film forming roller 39 and film forming roller 40) can function as a pair of opposing electrodes. Connected to 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge the space between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power supply 42, and this makes it possible. Plasma can be generated in the space between the film roller 39 and the film forming roller 40. When the film forming roller 39 and the film forming roller 40 are also used as an electrode as described above, the material and design of the film forming roller 39 and the film forming roller 40 may be appropriately changed so that the film can be used as an electrode. Further, in such a manufacturing apparatus, it is preferable that the pair of film forming rollers (film forming rollers 39 and 40) be disposed such that the central axes thereof are substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 39 and 40), the film forming rate can be doubled, and since a film having the same structure can be formed, extreme values in the carbon distribution curve can be obtained. It is possible to at least double. And according to such a manufacturing apparatus, it is possible to form the first layer 3 on the surface of the substrate 2 by the CVD method, and the first layer 3 is formed on the surface of the substrate 2 on the film forming roller 39. Since the first layer component can also be deposited on the surface of the substrate 2 on the film forming roller 40 while depositing the layer components of the first layer, the first layer can be efficiently deposited on the surface of the substrate 2 It can be formed.

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

  The magnetic field generators 43 and 44 respectively provided on the film forming roller 39 and the film forming roller 40 are the magnetic field generator 43 provided on one of the film forming rollers 39 and the magnetic field generator provided on the other film forming roller 40 It is preferable to arrange the magnetic poles so as to form a magnetic circuit in which magnetic field lines do not extend between the magnetic field generator 44 and each magnetic field generator 43, 44. By providing such magnetic field generating devices 43, 44, formation of a magnetic field in which magnetic lines of force expand near the opposing surface of each film forming roller 39, 40 can be promoted, and the plasma converges on the expanded portions. Since it becomes easy, it is excellent at the point which can improve film-forming efficiency.

  Further, the magnetic field generating devices 43 and 44 respectively provided on the film forming roller 39 and the film forming roller 40 have racetrack-shaped magnetic poles long in the roller axis direction, and one magnetic field generating device 43 and the other magnetic field generating device It is preferable to arrange the magnetic poles such that the opposite magnetic poles 44 have the same polarity. By providing such magnetic field generating devices 43 and 44, the magnetic field generating devices 43 and 44 do not cross the magnetic field generating devices on the roller side where the magnetic field lines oppose, and the facing space along the length direction of the roller axis Since a racetrack magnetic field can be easily formed near the roller surface facing the (discharge area), and the plasma can be converged to the magnetic field, a wide base wound along the roller width direction It is excellent in the point which can form the 1st layer 3 which is a vapor deposition film | membrane efficiently using the material 2. FIG.

  As the film forming roller 39 and the film forming roller 40, appropriately known rollers can be used. As such film forming rollers 39 and 40, it is preferable to use those having the same diameter from the viewpoint of forming a thin film more efficiently. Further, the diameter of such film forming rollers 39 and 40 is preferably in the range of 300 to 1000 mm in diameter, particularly in the range of 300 to 700 mm in diameter, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space does not become small, and there is no deterioration in productivity, and it is possible to avoid that the total heat of plasma discharge is applied to the substrate 2 in a short time. The damage to the material 2 can be reduced, which is preferable. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, practicability can be maintained including the uniformity of the plasma discharge space and the like, which is preferable.

  In such a manufacturing apparatus 31, the base material 2 is arrange | positioned on a pair of film-forming roller (the film-forming roller 39 and the film-forming roller 40) so that the surface of the base material 2 may each oppose. By arranging the base material 2 in this manner, when discharge is generated in the opposing space between the film forming roller 39 and the film forming roller 40 to generate plasma, a group existing between the pair of film forming rollers It becomes possible to simultaneously deposit the respective surfaces of the material 2. That is, according to such a manufacturing apparatus, the first layer component is deposited on the surface of the substrate 2 on the film forming roller 39 by plasma CVD, and the first layer component is further formed on the film forming roller 40. Since the layer components can be deposited, it is possible to efficiently form the first layer on the surface of the substrate 2.

  Well-known rollers can be appropriately used as the delivery roller 32 and the transport rollers 33, 34, 35, 36 used in such a manufacturing apparatus. The winding roller 45 is not particularly limited as long as it can wind the gas barrier film 1 in which the first layer 3 is formed on the substrate 2, and a known roller is appropriately used. be able to.

  As the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging a source gas or the like at a predetermined speed can be appropriately used.

  Further, the gas supply pipe 41, which is a gas supply means, is preferably provided in one of the facing spaces (discharge area; film formation zone) between the film forming roller 39 and the film forming roller 40. It is preferable to provide a pump (not shown) in the other of the said opposing space. Thus, by arranging the gas supply pipe 41 which is a gas supply means and the vacuum pump which is a vacuum evacuation means, the film forming gas is efficiently supplied to the opposing space between the film forming roller 39 and the film forming roller 40 It is excellent at the point which can improve the film-forming efficiency.

  Furthermore, as the power supply 42 for plasma generation, the power supply of a well-known plasma generator can be used suitably. Such a power supply 42 for plasma generation supplies electric power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use them as an opposing electrode for discharge. As such a power supply 42 for plasma generation, since it becomes possible to carry out plasma CVD more efficiently, it is possible to alternately reverse the polarity of a pair of film forming rollers (AC power supply etc.) It is preferred to use. Moreover, since it becomes possible to carry out plasma CVD more efficiently as such a power supply 42 for plasma generation, the applied power can be set to 100 W to 10 kW, and the frequency of alternating current is set to 50 Hz to 500 kHz. More preferably, it is possible to In addition, as the magnetic field generation devices 43 and 44, known magnetic field generation devices can be appropriately used.

  By using the manufacturing apparatus 31 shown in FIG. 2, for example, the type of raw material gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the film transport speed are appropriately adjusted. By doing this, the first layer formed by the CVD method can be manufactured. That is, discharge is generated between a pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (source gas etc.) into the vacuum chamber using the manufacturing apparatus 31 shown in FIG. , The film forming gas (raw material gas etc.) is decomposed by plasma, and the first layer 3 is plasma on the surface of the substrate 2 on the film forming roller 39 and on the surface of the substrate 2 on the film forming roller 40 It is formed by the CVD method. At this time, a racetrack magnetic field is formed in the vicinity of the roller surface facing the opposing space (discharge area) along the length direction of the roller axes of the film forming rollers 39 and 40 to converge the plasma to the magnetic field. For this reason, when the base material 2 passes A of the film-forming roller 39 in FIG. 2 and B point of the film-forming roller 40, the maximum value of the carbon distribution curve is formed in the first layer. On the other hand, when the base material 2 passes the points C1 and C2 of the film forming roller 39 in FIG. 2 and the points C3 and C4 of the film forming roller 40, the minimum of the carbon distribution curve in the first layer A value is formed. Therefore, five extreme values are usually generated for two film forming rollers. In addition, the distance between the extremes of the barrier layer (one extreme of the carbon distribution curve and the difference of the distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer at the extreme adjacent to the extreme) The absolute value can be adjusted by the rotational speed of the film forming rollers 39 and 40 (the transfer speed of the substrate). In addition, in the case of such film formation, the substrate 2 is conveyed by the delivery roller 32, the film formation roller 39, and the like, respectively, so that the surface of the substrate 2 is continuously formed by the roll-to-roll method. The first layer 3 is formed.

  As film-forming gas (raw material gas etc.) supplied from the gas supply pipe 41 to the opposing space, a raw material gas containing a raw material compound, a reaction gas, a carrier gas and a discharge gas may be used singly or in combination of two or more it can. The source gas in the film forming gas used for forming the first layer 3 can be appropriately selected and used according to the material of the first layer 3 to be formed.

  In order to form a layer satisfying the above requirements (i) to (ii), it is preferable to use an organosilicon compound as a raw material compound. As such an organosilicon compound, for example, hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxysilane Silane and octamethylcyclotetrasiloxane can be mentioned. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoint of the handleability of the compound and the properties such as the gas barrier property of the first layer to be obtained. These organosilicon compounds can be used alone or in combination of two or more.

  In addition to the source gas, a reaction gas may be used as the film formation gas. As such a reaction gas, a gas which reacts with the source gas and becomes an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, oxygen or ozone can be used, for example. Further, as a reaction gas for forming a nitride, for example, nitrogen or ammonia can be used. These reactive gases may be used alone or in combination of two or more, and for example, in the case of forming oxynitride, for forming reactive gas and nitride for forming an oxide. It can be used in combination with the reaction gas.

  As a film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Furthermore, as a film-forming gas, a discharge gas may be used as necessary to generate plasma discharge. As such a carrier gas and a discharge gas, known ones can be appropriately used. For example, rare gases such as helium, argon, neon, xenon and the like; hydrogen can be used.

  When such a film forming gas contains a source gas and a reaction gas, the ratio of the source gas to the reaction gas is that of the reaction gas that is theoretically required to completely react the source gas and the reaction gas. It is preferred that the proportion of the reaction gas not be excessive, rather than the proportion of the quantity. By not making the ratio of reaction gas too much, it is excellent at the point which can acquire the outstanding barrier property and bending resistance by the 1st layer 3 formed. When the film forming gas contains an organosilicon compound and oxygen, it is preferable that the theoretical oxygen amount is equal to or less than the theoretical oxygen amount necessary to completely oxidize the total amount of the organosilicon compound in the film forming gas.

Hereinafter, hexamethyldisiloxane (organic silicon compound, HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and one containing oxygen (O ₂ ) as a reaction gas are used as a film forming gas, A preferred ratio of the source gas to the reaction gas in the film-forming gas will be described in more detail, taking the case of producing a silicon-oxygen thin film as an example.

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

  In such a reaction, the amount of oxygen required to completely oxidize one mole of hexamethyldisiloxane is 12 moles. Therefore, when 12 mol or more of oxygen is contained in the film forming gas with respect to 1 mol of hexamethyldisiloxane and completely reacted, a uniform silicon dioxide film is formed. ) (Ii) can not be formed. Therefore, in the present invention, when the first layer is formed, 1 mole of hexamethyldisiloxane (flow rate of hexamethyldisiloxane) so that the reaction of the above reaction formula (1) does not proceed completely. Preferably, the amount of oxygen (flow rate of oxygen) is less than 12 moles (flow rate ratio 12 times) of the stoichiometric ratio. In the actual reaction in the plasma CVD chamber, the hexamethyldisiloxane of the raw material and the oxygen of the reaction gas are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen of the reaction gas Even if (flow rate) is 12 times the molar amount (flow rate) of the molar amount (flow rate) of the raw material hexamethyldisiloxane, in reality the reaction can not be completely advanced, and the oxygen content The reaction is considered to be completed only by supplying a large excess relative to the stoichiometric ratio (for example, in order to obtain complete oxidation by CVD to obtain silicon oxide, the molar amount (flow rate) of oxygen is used as the raw material hexamethyl di- It may be about 20 times or more the molar amount (flow rate) of siloxane). Therefore, it is preferable that the molar amount (flow rate) of oxygen to the molar amount (flow rate) of hexamethyldisiloxane as the raw material is 12 times or less (more preferably, 10 times or less) as the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane not completely oxidized are taken into the first layer, and the above conditions (i) to (i) It becomes possible to form the first layer satisfying (ii), and it is possible to exhibit excellent gas barrier properties and flex resistance in the obtained gas barrier film. From the viewpoint of application to a flexible substrate for devices requiring transparency such as organic EL elements and solar cells, the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas The lower limit of (flow rate) is preferably 0.1 times or more of the molar amount (flow rate) of hexamethyldisiloxane, and more preferably 0.5 times or more.

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

  Further, in such a plasma CVD method, an electrode drum connected to the power supply 42 for plasma generation in order to discharge between the film forming roller 39 and the film forming roller 40 (in the present embodiment, the film forming roller 39 And 40) can be properly adjusted according to the type of raw material gas, the pressure in the vacuum chamber, etc. It is preferable to set it as a range. If such applied power is 100 W or more, generation of particles can be sufficiently suppressed, and if 10 kW or less, the amount of heat generated at the time of film formation can be suppressed, and the substrate at the time of film formation It is possible to suppress the temperature rise on the surface. Therefore, it is excellent at the point which can prevent that a wrinkles generate | occur | produces at the time of film-forming, without heat loss of a base material.

  The transfer speed (line speed) of the substrate 2 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is in the range of 0.5 to 20 m / min. When the line speed is 0.25 m / min or more, generation of wrinkles due to heat on the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient thickness as a 1st layer, without impairing productivity.

  As described above, as a more preferable mode of the present embodiment, the first layer is formed by the plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the opposing roll electrode shown in FIG. This is excellent in flexibility (flexibility) and mechanical strength, particularly in the case of roll-to-roll conveyance, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having opposing roll electrodes. This is because it is possible to efficiently manufacture the first layer in which both the and the barrier performance are compatible. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce a gas barrier film which is required to have durability against temperature change, which is used for solar cells, electronic parts and the like.

  FIG. 3: is an example of each element profile of the thickness direction of the layer by the XPS depth profile of the gas barrier layer which does not have an extreme value etc. The gas barrier layer is formed by a CVD method using a flat electrode (horizontal transport) type plasma discharge, and it can be seen that a continuous change in concentration gradient of carbon atomic components does not occur. In FIG. 3, symbols A to D respectively indicate A: carbon distribution curve, B: silicon distribution curve, C: oxygen distribution curve, and D: oxygen carbon distribution curve.

[Second layer (inorganic oxide layer)]
The second layer is an inorganic oxide layer formed by atomic layer deposition (ALD).

The inorganic oxide is not particularly limited, and examples thereof include oxides such as aluminum, titanium, silicon, zirconium, hafnium, and lanthanum, and composite oxides. The inorganic oxide is selected from the group consisting of Al ₂ O ₃ , TiO ₂ , SiO ₂ and ZrO ₂ from the viewpoint of obtaining a high quality film at a temperature of 50 ° C. to 120 ° C. in consideration of forming a film on a resin substrate. It is preferable to include at least one of Since minute defects can be impregnated with the material, it is further considered that the inorganic oxide contains Al ₂ O ₃ and TiO ₂ which can use TMA (trimethylaluminum) or TiCl (titanium chloride) in consideration of the molecular weight of the material. Preferably, in consideration of the gas barrier performance and the gas barrier performance under high temperature and high humidity conditions, the inorganic oxide particularly preferably contains Al ₂ O ₃ , and the second layer is most preferably an Al ₂ O ₃ layer.

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

  The ALD method is a method in which an atomic layer is deposited layer by layer by alternately introducing two or more kinds of gases (a first gas and a second gas) onto a substrate. More specifically, first, a first gas is introduced onto a substrate to form a gas molecular layer (monoatomic layer). The first gas is then purged (removed) by introducing an inert gas. Note that the formed gas molecular layer of the first gas is not purged even if the inert gas is introduced by chemical adsorption. Next, the gas molecular layer formed by introducing the second gas is oxidized to form an inorganic film. Finally, introducing the inert gas purges the second gas and completes one cycle of the ALD method. By repeating the above cycle, atomic layers can be deposited one by one to form a first gas barrier layer having a predetermined film thickness. In the ALD method, the inorganic film can be formed including the shaded portion regardless of the unevenness of the surface of the substrate.

  Activation of the substrate surface is necessary for adsorption of gas molecules to the substrate. Therefore, the film forming temperature is preferably high to a certain extent, and may be appropriately adjusted in a range not exceeding the glass transition temperature or the decomposition start temperature of the plastic substrate of the base material. When using a plastic base material, the temperature in a reactor is about 50-200 degreeC normally. The deposition rate per cycle is usually 0.01 to 0.3 nm, and the film deposition cycle is repeated to obtain a desired film thickness.

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

  The aluminum compound is not particularly limited as long as it contains aluminum and can be vaporized. Specific examples of aluminum compounds include trimethylaluminum (TMA), triethylaluminum (TEA), and trichloroaluminum.

In addition, the source gas may be appropriately selected depending on the inorganic oxide film to be formed. Ritala: Appl. Surf. Sci. 112, 223 (1997) can be used. Specifically, when the inorganic oxide of the second layer is silicon oxide, the first gas is a gas obtained by vaporizing a silicon compound. Such silicon compounds include monochlorosilane (SiH ₃ Cl, MCS), hexachlorodisilane (Si ₂ Cl ₆ , HCD), tetrachlorosilane (SiCl ₄ , STC), trichlorosilane (SiHCl ₃ , TCS) and the like. Inorganic materials such as chlorosilanes, trisilanes (Si ₃ H ₈ , TS), disilanes (Si ₂ H ₆ , DS), monosilanes (SiH ₄ , MS), and aminosilanes, tetrakis dimethylaminosilane (Si [N (CH ₃₎ ) ₂ ] 4, 4 DMAS), trisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₃ H, 3DMASi), bisdiethylaminosilane (Si [N (C ₂ H ₅ ) ₂ ] ₂ H ₂ , 2DEAS), Bister tert-butylamino silane _{(SiH 2 [NH (C 4} H 9)] 2, B BAS) and the like.

When the inorganic oxide in the second layer is titanium oxide, the first gas is a gas obtained by vaporizing a titanium compound. As such a titanium compound, titanium tetrachloride (TiCl ₄₎ , titanium (IV) isopropoxide (Ti [(OCH) (CH ₃ ) ₂ ] ₄ ), tetrakis dimethylamino titanium ([(CH ₃ ) ₂ N] ₄ Ti, TDMATi), tetrakisdiethylaminotitanium (Ti [N (CH ₂ CH ₃ ) ₂ ] ₄ , TDEATi, etc. may be mentioned.

When the inorganic oxide of the second layer is zirconium oxide, the first gas is a gas obtained by vaporizing a zirconium compound. As such a zirconium compound, tetrakis dimethylamino zirconium (IV); [(CH ₃ ) ₂ N] ₄ Zr and the like can be mentioned.

The oxidizing gas is not particularly limited as long as it can oxidize the gas molecular layer. For example, ozone (O ₃ ), water (H ₂ O), hydrogen peroxide (H ₂ O ₂ ), methanol (CH ₃ ) OH), ethanol (C ₂ H ₅ OH) and the like can be used. It is also possible to use oxygen radicals. In the case of using a radical, it is possible to generate a high density of oxygen radicals by exciting the gas using a high frequency power supply (for example, a power supply with a frequency of 13.56 MHz) to further promote the oxidation and nitridation reaction. be able to. In consideration of upsizing of the device and practicability, discharge in ICP (Inductively Coupled Plasma) mode using a 13.56 MHz power supply is desirable.

  In addition, when it is desired to use nitride and nitrogen oxide, nitrogen radical can be used. Nitrogen radicals can be generated in the same manner as the aforementioned oxygen radical generation.

  Further, it is preferable to use ozone and oxygen radicals as the oxidizing gas from the viewpoint of the size of the apparatus and shortening of one cycle time. Further, from the viewpoint of forming a dense film at a low temperature, it is preferable to use an oxygen radical.

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

  The introduction time of the first gas is preferably 0.05 to 10 seconds, more preferably 0.1 to 3 seconds, and still more preferably 0.5 to 2 seconds. It is preferable that the introduction time of the first gas is 0.05 seconds or more because the time for forming the gas molecular layer can be sufficiently secured. On the other hand, the introduction time of the first gas is preferably 10 seconds or less because the time required for one cycle can be reduced.

  Further, the introduction time of the inert gas for purging the first gas is preferably 0.05 to 10 seconds, more preferably 0.5 to 6 seconds, and 1 to 4 seconds. Is more preferred. The introduction time of the inert gas is preferably 0.05 seconds or more because the first gas can be sufficiently purged. On the other hand, when the introduction time of the inert gas is 10 seconds or less, the time required for one cycle can be reduced, and the influence on the formed gas molecule layer is reduced, which is preferable.

  Furthermore, the introduction time of the second gas is preferably 0.05 to 10 seconds, and more preferably 0.1 to 3 seconds. It is preferable that the introduction time of the second gas is 0.05 seconds or more, since the time for which the gas molecular layer can be oxidized can be sufficiently secured. On the other hand, when the second gas introduction time is 10 seconds or less, the time required for one cycle can be reduced, and side reactions can be prevented, which is preferable.

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

  The thickness of the inorganic oxide layer is preferably 1 to 100 nm, and more preferably 10 to 50 nm. When the film thickness of the inorganic oxide layer is 1 nm or more, the effect of the ALD layer such as repair of fine defects can be appropriately obtained, and in consideration of the film formation rate of ALD, the thickness is preferably 100 nm or less.

  Further, in the relation between the film thickness of the first layer and the film thickness of the second layer, the film thickness of the first layer is preferably less than 30 times the film thickness of the second layer, and 2 to 10 times It is more preferable that The gas barrier performance is improved by setting the film thicknesses of the two in such ranges. It is considered that this is because the micro defect repair effect of the second layer is appropriately obtained.

  Since the inorganic oxide layer is formed by the ALD method, defect repair in the lower layer is easily performed. As a result, the film surface of the inorganic oxide layer formed by the ALD method has high smoothness. Therefore, it is preferable to use the center line average surface roughness (Ra) of the surface in contact with the upper layer (preferably, the silicon compound modified layer) of the inorganic oxide layer as an index that can indicate the degree of defect repair of the lower layer. it is conceivable that. Here, the center line average surface roughness (Ra) of the surface in contact with the upper layer of the inorganic oxide layer is preferably 0.8 to 100 nm, and more preferably 1.0 to 10 nm. Within such a range, it can be judged that repair of defects by the ALD layer is suitably performed, and the gas barrier performance of the entire film is improved. In addition, centerline average surface roughness (Ra) can be measured by the method as described in an Example.

Although the second layer has gas barrier performance, the gas barrier performance of the second layer alone may not be high because the gas barrier properties of the first layer and the third layer are high. Therefore, the gas barrier performance of the second layer is determined by the method described in the below-mentioned example in the laminate in which the second layer is formed on the substrate, and the amount of moisture transmission is 0.5 g / (m ² ··· 24 h) or less is preferable, and 0.1 g / (m ² · 24 h) or less is more preferable.

[Third layer (silicon compound modified layer)]
The third layer is formed by modifying a coating film formed by applying a solution containing a silicon compound.

(Silicon compound)
The silicon compound is not particularly limited as long as preparation of a coating solution containing the silicon compound is possible.

  Specifically, for example, perhydropolysilazane, organopolysilazane, silsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, Tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldivinylsilane, dimethyl Ethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-trifluoro Propyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane , Aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxysilane, diaryldimethoxysilane, butyldimethoxyvinylsilane , Trimethyl-3-vinylthiopropylsilane, phenyltrimethylsilane Dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3-glycidoxypropyl Trimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethylphenyl phenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacrylic acid Roxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, dib Toxydimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane, Acetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycidoxypropylmethylsilane , Octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylphenylsilane, diphenylmethyl Nylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1,3-divinyl-1,1,3,3- Tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) tetramethyldi Siloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane Siloxane, octamethylcyclotetrasiloxane, 1, 3, 5 7-tetraethoxy-1,3,5,7-tetramethyl cyclotetrasiloxane, may be mentioned decamethylcyclopentasiloxane like.

  Examples of the above silsesquioxanes include Octakis (tetramethylammonium) pentacycloammonium-octasiloxane (octa) hydrate (Oloxylate) hydrate; Octa (tetramethylammonium) silsesquioxane, Octakis (dimethylsiloxy) octasilsequioxane, Octaris (dimethylamoxy) Octa sylcosquioxane, Octalys [(3--3-a] Ethyl-3-oxetanyl) methoxy] propyl] dimethylsiloxy] octasilsesquioxane; Octaallyloxetane silsesquioxane, Octa [(3-Propylglycidylethe ) Dimethylsiloxy] silsesquioxane; Octakis [[3- (2,3-epoxypropoxy) propyl] dimethylsiloxy] octasilsesquioxane, Octakis [[2- (3,4-epoxycyclohexyl) ethyl] dimethylsilyl] octasilsesquioxane, Octakis [2- (vinyl) dimethylsilyl] silsesquioxane; Octakis (dimethylvinylsiloxy) octasilsesquioxane, Octakis [(3-hydroxypropyl) dimethylsilyloxy] octasilsesquioxane, Octa [(m Ethacryloylpropyl) dimethylsilyloxy] silsesquioxane, Octakis [(3-methacryloxypropyl) dimethylsilyloxy] octasilsesquioxane, hydrogenated silsesquioxane not containing an organic group and the like can be mentioned.

  Among them, polysilazanes such as perhydropolysilazane and organopolysilazane; polysiloxanes such as silsesquioxane and the like are preferable in view of film forming property, less defects such as cracks, and less residual organic substances; Polysilazane is more preferable because the barrier performance is maintained even under bending and under high temperature and high humidity conditions.

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

  Specifically, polysilazane preferably has the following structure.

In the above general formula (I), R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group . At this time, R ₁ , R ₂ and R ₃ may be the same or different. Here, as an alkyl group, a C1-C8 linear, branched or cyclic alkyl group is mentioned. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. Moreover, a C6-C30 aryl group is mentioned as an aryl group. More specifically, non-fused hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group, etc .; pentalenyl group, indenyl group, naphthyl group, azulenyl group, heptalenyl group, biphenylenyl group, fluorenyl group, acenaphthyrenyl group, prey adenyl group And fused polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc. It can be mentioned. As a (trialkoxy silyl) alkyl group, the C1-C8 alkyl group which has a silyl group substituted by the C1-C8 alkoxy group is mentioned. More specifically, 3- (triethoxysilyl) propyl group, 3- (trimethoxysilyl) propyl group and the like can be mentioned. The substituent optionally present in R _{1 to} R ₃ is not particularly limited, and examples thereof include an alkyl group, a halogen atom, a hydroxyl group (-OH), a mercapto group (-SH) and a cyano group (-CN), sulfo group _(-SO 3 H), carboxyl group (-COOH), a is nitro group (-NO _2). In addition, the substituent which exists depending on the case will not be the same as R < ₁ > -R < ₃ > to substitute. For example, when R _{1 to} R ₃ are alkyl groups, they are not further substituted by alkyl groups. Among these, preferably, R ₁ , R ₂ and R _{3 each} are a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, phenyl group, vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.

  Further, in the above general formula (I), n is an integer, and it is determined that a polysilazane having a structure represented by the general formula (I) has a number average molecular weight of 150 to 150,000 g / mol. preferable.

In the compound having a structure represented by the above general formula (I), one of the preferable embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

  Alternatively, polysilazane has a structure represented by the following general formula (II).

In the above general formula (II), R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, It is an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. At this time, R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} may be the same or different. The substituted or unsubstituted alkyl group, the aryl group, the vinyl group or the (trialkoxysilyl) alkyl group in the above is the same as the definition of the above general formula (I), and thus the description is omitted.

  Further, in the above general formula (II), n ′ and p are integers, and it is determined that polysilazane having a structure represented by the general formula (II) has a number average molecular weight of 150 to 150,000 g / mol. Being preferred. Note that n 'and p may be the same or different.

Among the polysilazanes of the above general formula (II), compounds wherein R _{1 ′} , R _{3 ′} and R _{6 ′} each represent a hydrogen atom, and R _{2 ′} , R _{4 ′} and R _{5 ′} each represent a methyl group; R _{1 ',} R _3' and R _{6 'are} each a hydrogen atom, R _2', R _{4 'are} each a methyl group, R _5' compound represents a vinyl _{group; R 1 ', R 3'} , R 4 Compounds in which _' and R _6' each represent a hydrogen atom, and R _{2 '} and R _5' each represent a methyl group are preferred.

  Alternatively, polysilazane has a structure represented by the following general formula (III).

In the above general formula (III), R _{1 ′ ′} , R _{2 ′ ′} , R _{3 ′ ′} , R _{4 ′ ′} , R _{5 ′ ′} , R _{6 ′ ′} , R _{7 ′ ′} , R _{8 ′ ′} and R _{9 ′ ′} are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group, wherein R _{1 ′ ′} , R _{2 ′ ′} , R _{3 ′ ′} , R _{4 ′ ′} , R _{5 ′ ′} , R _{6 ′ ′} , R _{7 ′ ′} , R _{8 ′ ′} and R _{9 ′ ′} may be the same or different. The substituted or unsubstituted alkyl group, the aryl group, the vinyl group or the (trialkoxysilyl) alkyl group in the above is the same as the definition of the above general formula (I), and thus the description is omitted.

  In the above general formula (III), n ′ ′, p ′ ′ and q are integers, and polysilazane having a structure represented by general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferred that the Note that n ′ ′, p ′ ′ and q may be the same or different.

Among polysilazanes of the above general formula (III), R _{1 ′ ′} , R _{3 ′ ′} and R _{6 ′} ′ each represent a hydrogen atom, and R _{2 ′ ′} , R _{4 ′ ′} , R _{5 ′ ′} and R _{8 ′} ′ each represent a methyl group. And R _{9 ′ ′} represents a (triethoxysilyl) propyl group, and a compound in which R _{7 ′ ′} represents an alkyl group or a hydrogen atom is preferred.

  On the other hand, the organopolysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like improves the adhesion to the substrate as the base by having an alkyl group such as a methyl group, and is hard There is an advantage that the ceramic film made of brittle polysilazane can have toughness, and generation of cracks can be suppressed even when the (average) film thickness is increased. Therefore, these perhydropolysilazanes and organopolysilazanes may be appropriately selected depending on the application, and may be used as a mixture.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centering on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (in terms of polystyrene) in number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.

  Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercial product can be used as it is as a coating solution for forming a polysilazane layer. As commercial products of polysilazane solution, Aquamica (registered trademark) NN 120-10, NN 120-20, NAX 120-20, NN 110, NN 320, NL 110 A, NL 120 A, NL 120 A, NL 120 A, NL 150 A, NP110 manufactured by AZ Electronic Materials, Inc. , NP 140, SP 140, and the like.

  Other examples of the polysilazane which can be used in the present invention include, but are not limited to, for example, silicon alkoxide-added polysilazane obtained by reacting silicon alkoxide with the above polysilazane (JP-A-5-238827) and glycidol. Glycidol-added polysilazane (JP-A-6-122852) obtained by reaction, alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), metal carboxylate obtained by reacting a metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonato complex-added polysilazane obtained by reacting metal-containing acetylacetonate complex (JP-A-6-306329), metal obtained by adding metal fine particles Fine particle added polysila Emissions, such as (JP-A-7-196986), and a polysilazane ceramic at low temperatures.

  The content of polysilazane in the third layer according to the present invention may be 100% by weight, when the total weight of the third layer is 100% by weight. When the third layer contains a material other than polysilazane, the content of polysilazane in the layer is preferably 10% by weight to 99% by weight, and is 40% by weight to 95% by weight. Is more preferably 70% by weight to 95% by weight.

  The method for forming the third layer is not particularly limited, and known methods can be applied. However, known wet coating methods for forming a silicon compound modifying layer containing a silicon compound and, if necessary, a catalyst in an organic solvent Preferred is a method of coating by a method, evaporating and removing the solvent, and then performing a reforming treatment.

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

  The concentration of the silicon compound in the coating liquid for forming a silicon compound modified layer is not particularly limited, and varies depending on the film thickness of the layer and the pot life of the coating liquid, but is preferably 1 to 80% by weight, more preferably 5 to 50. % By weight, particularly preferably 10 to 40% by weight.

  The coating liquid for forming a silicon compound reformed layer preferably contains a catalyst in order to promote reforming. As a catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N Amine catalysts such as N ', N'-tetramethyl-1,3-diaminopropane, N, N, N', N'-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propionone Examples include Pd compounds such as acid Pd, metal catalysts such as Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Among these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10 mol%, more preferably 0.5 to 7 mol%, based on the silicon compound. By setting the amount of catalyst added in this range, excessive silanol formation due to rapid progress of the reaction, decrease in film density, increase in film defects and the like can be avoided.

  The following additives can be used as needed in the coating liquid for forming a silicon compound modified layer. For example, cellulose ethers, cellulose esters; eg, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate etc., natural resins; eg, rubber, rosin resins etc., synthetic resins; eg, polymer resins etc., condensation resins; Aminoplasts, in particular urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes etc.

  Moreover, a sol gel process can be used for formation of a silicon compound modified layer like Unexamined-Japanese-Patent No. 2005-231039. The coating solution used when forming the modified layer by the sol-gel method preferably contains at least one of a silicon compound and a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer. Furthermore, the coating solution preferably contains a sol-gel method catalyst, an acid, water, and an organic solvent. In the sol-gel method, a modified layer is obtained by performing polycondensation using such a coating solution.

As the silicon compound used in the sol-gel method, it is preferable to use an alkoxide represented by the general formula R ^A _O Si (OR ^B ) _p . Here, R ^A and R ^B each independently represent an alkyl group having 1 to 20 carbon atoms, O represents an integer of 0 or more, and p represents an integer of 1 or more. Specific examples of the above alkoxysilane include, for example, tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (0 C ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) ₄ , others, etc. can be used. As such a silicon compound, a commercial item may be used, and ethyl silicate 40 (made by Colcoat Co., Ltd.) etc. may be used.

  When a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination in the coating solution, the blending ratio of each is polyvinyl alcohol-based resin: ethylene / vinyl alcohol The copolymer is preferably 10: 0.05 to 10: 6. Further, the content of the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer in the coating solution is in the range of 5 to 500 parts by weight with respect to 100 parts by weight of the total amount of the silicon compounds. Preferably, the compounding ratio is about 20 to 200 parts by weight. Generally as a polyvinyl alcohol-type resin, what is obtained by saponifying polyvinyl acetate can be used. As said polyvinyl alcohol-type resin, partially saponified polyvinyl alcohol-type resin in which several dozens of acetic acid groups remain, even completely saponified polyvinyl alcohol in which acetic acid groups do not remain, or modified polyvinyl alcohol in which OH groups were modified Any of resin based resins may be used. As a specific example of a polyvinyl alcohol-type resin, Kuraray's Kuraray Poval, Goshenol made by Nippon Synthetic Chemical Industry Co., Ltd., etc. can be used. In the present invention, as the ethylene / vinyl alcohol copolymer, a saponified copolymer of ethylene and vinyl acetate, that is, one obtained by saponifying an ethylene-vinyl acetate random copolymer is used. Can. Specifically, a partially saponified product in which several tens mol% of acetic acid groups remain, and a completely saponified product in which only a few mol% of acetic acid groups remain or no acetic acid groups remain, are particularly limited. Although not preferred, it is preferable to use one having a degree of saponification of 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. In addition, the content of repeating units derived from ethylene in the above ethylene-vinyl alcohol copolymer (hereinafter also referred to as "ethylene content") is usually 0 to 50 mol%, preferably 20 to 45 mol% It is preferred to use one. As a specific example of said ethylene-vinyl alcohol copolymer, Kuraray Co., Ltd. make, Eval EP-F101 (ethylene content; 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd. make, soarol D2908 (ethylene content; 29 mol%) Etc. can be used. As a sol-gel method catalyst, mainly a polycondensation catalyst, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent is used. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. Moreover, as an acid, it is used as a catalyst for the said sol-gel method, a catalyst for hydrolysis of an alkoxide, a silane coupling agent, etc. mainly. As the above-mentioned acid, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid, and the like can be used. Furthermore, the coating solution preferably contains water in a proportion of 0.1 to 100 moles, preferably 0.8 to 2 moles, per mole of the total molar amount of the above-mentioned alkoxide.

  As an organic solvent used for the coating liquid by a sol gel method, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used, for example. Further, as the ethylene / vinyl alcohol copolymer solubilized in the solvent, for example, one commercially available as Soarnol (trade name) can be used. Furthermore, for example, a silane coupling agent can be added to the coating solution by the sol-gel method.

(Improvement of paintability)
Next, the coating solution for forming a silicon compound modified layer is applied to the lower layer (preferably ALD layer), but before coating, the coating property improvement treatment described in JP 2011-143577 and the treatment are carried out. Heating (heat treatment) may be performed.

  Specific methods of the coating property improvement treatment include light irradiation treatment (excimer irradiation, UV ozone oxidation, etc.) in an oxidizing gas atmosphere, or plasma irradiation treatment (vacuum oxygen plasma, atmospheric pressure oxygen plasma, etc.) In addition to dry treatment, corona discharge treatment can be applied. Alternatively, a wet treatment such as washing with pure water after treatment of the laminate in a heated alkaline solution is also applicable. The dry treatment is more preferable in that the step of removing unnecessary moisture and the like is not required separately.

  Further, among the dry processing, light irradiation processing under an oxidizing gas atmosphere which is capable of an atmospheric process and can be shortened and cost-reduced is most preferable. The oxidizing gas represents oxygen, ozone and atomic oxygen. The oxygen concentration at the time of coating property improvement treatment is preferably in the range of 0.05% to 21% (the actually detected oxygen concentration includes the range of ± 10%), preferably 0.1% to 20%. More preferably, it is in the range of 1%.

As a light irradiation process applied to a coating property improvement process, it is more preferable that the light in the light irradiation process in oxidizing gas atmosphere is ultraviolet light. By irradiation with ultraviolet light, active oxygen and ozone are generated, and generation of reactive groups such as OH group or COOH group on the treated surface progresses more. Furthermore, the shortage of reactive ozone may be generated from oxygen by a known method such as a discharge method at a portion different from the light irradiation portion and introduced into the ultraviolet light irradiation portion. The wavelength of the ultraviolet light irradiated at this time is not particularly limited, but the wavelength of the ultraviolet light is preferably 100 nm to 450 nm, and more preferably irradiated with vacuum ultraviolet light of about 150 nm to 300 nm. As a light source, a low pressure mercury lamp, a deuterium lamp, a xenon excimer lamp, a metal halide lamp, an excimer laser or the like can be used. As the output of the lamp 400W～30kW, more preferably preferably ^{10mJ / cm 2 ~5000mJ / cm 2} , 100mJ / cm 2 ~2000mJ / cm 2 as ^{100mW / cm 2 ~100kW / cm 2} , irradiation energy as illuminance . Further, the illuminance at the time of ultraviolet irradiation ^1mW / cm ^{2 ~10W} / cm 2 is preferred. Among the above, as the wavelength, vacuum ultraviolet light of 100 nm to 200 nm is most preferable, and it becomes possible to advance the oxidation reaction at a lower temperature and in a short time. Further, as a light source, a rare gas excimer lamp such as a xenon excimer lamp is most preferably used. In addition to continuous irradiation, irradiation may be performed a plurality of times, and so-called pulse irradiation may be used in which irradiation is performed for a short time.

  The time required for the coating property improvement processing varies depending on the light source lamp to be selected, the illuminance, or the processing conditions, but it is preferable that the time is approximately 0.1 seconds to about 15 minutes. Further, in consideration of damage to the resin base material and the coated surface, it is preferable that the time is shorter, and about 0.1 second to 5 minutes is more preferable.

Corona discharge treatment is carried out under generally used treatment conditions, for example, under the condition of a distance of 0.2 to 5 mm between the electrode tip and the substrate to be treated, and the treatment amount thereof is preferably 10 W · min or more per 1 m ^2. It is in the range of 10 to 200 W · min, more preferably in the range of 20 to 180 W · min.

  Plasma irradiation treatment may be performed using a single gas such as argon, helium, krypton, neon, xenon, hydrogen, nitrogen, oxygen, ozone, carbon monoxide, carbon dioxide, sulfur dioxide or a mixed gas thereof, for example, an oxygen concentration of 5 to 15 volumes It can be implemented by supplying a mixed gas of oxygen and nitrogen containing% between the counter electrodes and applying a voltage to generate plasma discharge. As the plasma treatment conditions, for example, the distance between the electrodes through which the plastic substrate to be treated passes is appropriately determined in accordance with the thickness of the substrate, the magnitude of the applied voltage, the flow rate of the mixed gas, etc. The voltage applied is preferably in the range of 1 to 20 mm, preferably 0.2 to 10 mm, and the voltage applied between the electrodes is preferably 1 to 40 kV / cm when the voltage is applied. The frequency of the power supply is in the range of 1 to 100 kHz, preferably 1 to 100 kHz.

  Furthermore, it is preferable to perform a heat treatment before performing the coating property improvement processing, simultaneously with the coating property improvement processing, or after performing the coating property improvement processing. Specifically, when heating is performed before or after the coating property improvement treatment, for example, a method of heating the laminate on a hot plate or in an oven, or heating with an infrared heater can be applied. In addition, when heating the substrate at the time of coating property improvement treatment, when performing excimer irradiation treatment, UV ozone oxidation treatment, etc., the base on which the substrate is placed is heated or treated in a heating atmosphere. The method is applicable. It is more preferable to heat a laminated body at the time of a coating property improvement process from a coating property including a variation, and an adhesive viewpoint. The heating temperature is preferably 30 ° C. to 150 ° C., more preferably 50 ° C. to 100 ° C. If it is lower than 30 ° C., the heating effect as described above can not be obtained, and if it is higher than 150 ° C., there is a concern that the substrate and other components may be damaged. The temperature of the heat treatment is controlled by the set temperature when the temperature of the table or roll on which the base material is installed is detectable, and when the device can not detect the temperature, separately before or after the treatment, It was detected and confirmed by a thermometer (in the case of a solution) such as mercury or alcohol, a surface thermometer using a thermocouple, a radiation thermometer, a fiber thermometer, a thermo label or the like.

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

  The application thickness may be appropriately set depending on the purpose. For example, the thickness of the coating after drying is preferably about 10 nm to 10 μm, more preferably 15 nm to 1 μm, and still more preferably 20 to 500 nm. If the film thickness is 10 nm or more, sufficient barrier properties can be obtained, and if 10 μm or less, stable coatability can be obtained at the time of layer formation, and high light transmittance can be realized.

  After applying the coating solution, it is preferable to dry the coating. By drying the coating, the organic solvent contained in the coating can be removed. At this time, the organic solvent contained in the coating film may be all dried, but may be partially left. Even when a part of the organic solvent is left, a suitable gas barrier layer can be obtained. The remaining solvent can be removed later.

  Although the drying temperature of a coating film changes also with the base materials to apply, it is preferable that it is 50-200 degreeC. For example, when using a polyethylene terephthalate base material having a glass transition temperature (Tg) of 70 ° C. as the base material, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the base material due to heat and the like. The temperature may be set by using a hot plate, an oven, a furnace or the like. It is preferable to set the drying time to a short time, for example, when the drying temperature is 150 ° C., it is preferable to set it within 30 minutes. Further, the drying atmosphere may be any conditions such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, and a reduced pressure atmosphere in which the oxygen concentration is controlled.

  The coating film (hereinafter, simply referred to as a silicon compound coating film) obtained by applying the coating liquid for forming a silicon compound modifying layer includes a step of removing water before or during the modifying treatment. It is also good. As a method of removing water, the form which maintains a low humidity environment and dehumidifies is preferable. Since the humidity in a low humidity environment changes with temperature, the relationship between temperature and humidity is preferably indicated by the definition of dew point temperature. The preferable dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), more preferable dew point temperature is −5 ° C. (temperature 25 ° C./humidity 10%) or less, and the maintained time is the film of the third layer It is preferable to set suitably by thickness. Under the conditions where the film thickness of the third layer is 1.0 μm or less, it is preferable that the dew point temperature be −5 ° C. or less and the maintained time be 1 minute or more. Although the lower limit of the dew point temperature is not particularly limited, it is usually −50 ° C. or higher, and preferably −40 ° C. or higher. It is a preferable form from the viewpoint of promoting the dehydration reaction of the third layer converted to silanol by removing water before or during the modification treatment.

(Modification treatment of the third layer)
The modification treatment in the present invention refers to a conversion reaction of a silicon compound to silicon oxide or silicon oxynitride, and specifically, the gas barrier film of the present invention has a gas barrier property (water vapor permeability: 1 × 10 ⁻ as a whole). A treatment that forms an inorganic thin film at a level that can contribute to the expression of ³ g / (m ² · 24 h) or less. Therefore, the third layer is also a gas barrier layer having gas barrier properties.

  The conversion reaction of the silicon compound into silicon oxide or silicon oxynitride can be selected from known methods based on the conversion reaction of the third layer. Specific examples of the modification treatment include plasma treatment, ultraviolet radiation treatment, and heat treatment. However, in the case of modification by heat treatment, the formation of a silicon oxide film or a silicon oxynitride layer by a substitution reaction of a silicon compound requires a high temperature of 450 ° C. or more, so adaptation is difficult in flexible substrates such as plastics. Therefore, the heat treatment is preferably performed in combination with other modification treatments.

  Therefore, when producing the gas barrier film of the present invention, from the viewpoint of application to a plastic substrate, a conversion reaction by plasma treatment or an ultraviolet irradiation treatment capable of a conversion reaction at a lower temperature is preferable.

(Plasma treatment)
In the present invention, as the plasma treatment that can be used as the reforming treatment, known methods can be used, but preferably atmospheric pressure plasma treatment and the like can be mentioned. Atmospheric pressure plasma CVD method that performs plasma CVD process near atmospheric pressure does not need to be decompressed compared to plasma CVD method under vacuum, it is not only necessary to have high productivity, but also because plasma density is high density. At high pressure conditions, such as high film speed and further high pressure conditions such as atmospheric pressure, as compared with the conditions of the normal CVD method, a very homogeneous film can be obtained because the mean free path of gas is very short.

  In the case of atmospheric pressure plasma treatment, nitrogen gas or a group 18 atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc., are used as the discharge gas. Among these, nitrogen, helium and argon are preferably used, and nitrogen is particularly preferable because of its low cost.

  As plasma processing, low pressure plasma processing may be performed. Low pressure plasma treatment is performed by introducing a gas into the apparatus after reducing the pressure to an atmosphere substantially free of oxygen or water vapor. The low pressure plasma treatment utilizes vacuum ultraviolet light emission when atoms or molecules excited by plasma under low pressure fall to the ground state or lower level. The wavelength of vacuum ultraviolet light generated by the low pressure plasma depends on the type of gas that generates the plasma. The range of 50 to 125 nm is preferable as the wavelength of light used in low pressure plasma treatment.

  Vacuum ultraviolet light emitted from an atom in an excited state formed by plasma is absorbed by another ground state atom, which has an effect of self-absorption used to excite the atom. Therefore, if the pressure is too high, the generated vacuum ultraviolet light may be absorbed by atoms and molecules of the atmosphere gas, and the vapor deposition film may not be efficiently irradiated. Therefore, the pressure is preferably 100 Pa or less. On the other hand, if the pressure is too low, generation of plasma may be difficult. Therefore, the lower limit of the pressure is different depending on the type of plasma generation, but is preferably about 0.1 Pa or more.

  As the low-pressure plasma gas species, at least one noble gas selected from helium (He), neon (Ne), and argon (Ar) is used. The major vacuum ultraviolet light wavelengths emitted by these excited rare gas atoms are 58.4 nm for helium (He), 73.6 nm and 74.4 nm for neon (Ne), and argon (Ar). In some cases it is known to be 104.8 nm and 106.7 nm.

  The frequency of the power source required to generate a low pressure plasma is preferably 1 MHz to 100 GHz. Within this range, it is possible to efficiently give energy to the electrons directly contributing to the plasma generation reaction, and the electron density, that is, the plasma density becomes high. Along with this, the intensity of vacuum ultraviolet light generated by plasma also becomes strong. In addition, the energy transfer efficiency is improved. The frequency of the power supply is more preferably 4 MHz to 10 GHz.

  A publicly known method can be used as a generation method of plasma which emits light with a wavelength of 150 nm or less. Preferably, a method capable of coping with the processing of a vapor deposition film formed on a wide base material is preferable, for example, capacitively coupled plasma (CCP), inductively coupled plasma (ICP), surface wave plasma, electron cyclotron resonance (ECR) plasma, helicon Wave plasma and the like.

  The input power density normalized by the area occupied by the plasma source reflecting the size of the plasma is defined as an index of the size of the input power to the plasma facing the deposition film. This is a parameter correlating to the irradiation intensity of vacuum ultraviolet light irradiated to the vapor deposition film per unit area. In particular, in the case of an electroded plasma such as capacitively coupled plasma, the electrode area on the side to which a high frequency is applied substantially defines the size of the plasma, which is the area occupied by the plasma source.

The input power density is preferably 0.1 to 20 W / cm ² , more preferably 0.3 to 10 W / cm ² . Within this range, irradiation with sufficient intensity can be performed, and thermal deformation due to temperature rise of the substrate, non-uniformization of plasma, damage to members constituting a plasma source such as an electrode and the like can be prevented.

(Heat treatment)
The heat treatment can be performed efficiently by combining the coating film containing the silicon compound with another modification treatment, preferably with an excimer irradiation treatment described later, and the like.

  In the case of forming a layer using a sol-gel method, it is preferable to use heat treatment. As the heating conditions, condensation is carried out by heating and drying at a temperature of 50 to 300 ° C., preferably 70 to 200 ° C., for 0.005 to 60 minutes, preferably 0.01 to 10 minutes. , Layer can be formed.

  As the heat treatment, for example, a method of heating the coating film by heat conduction by bringing the substrate into contact with a heating element such as a heat block, a method of heating the atmosphere by an external heater such as a resistance wire, an infrared heater such as an IR heater Although the method using light etc. may be mentioned, there is no particular limitation. Moreover, you may select the method of maintaining the smoothness of the coating film containing a silicon compound suitably.

  The temperature of the coating film at the time of heat treatment is preferably adjusted to a range of 50 to 250 ° C., more preferably 50 to 120 ° C.

  Moreover, as heating time, the range of 1 second-10 hours is preferable, More preferably, the range of 10 seconds-1 hour is preferable.

In the present invention, the layer (third layer) formed of the coating preferably having a silicon compound preferably has gas barrier properties (preferably, a water vapor transmission rate of 1 × 10 ⁻³ g / (m ² · 24 h) The following excimer light processing is particularly preferable as a modification means for obtaining such a third layer.

(UV irradiation treatment)
As one of the methods of modification treatment, treatment by ultraviolet irradiation is also preferable. Ozone and active oxygen atoms generated by ultraviolet light (equivalent to ultraviolet light) have high oxidation ability, and can form a silicon oxide film or silicon oxynitride film having high density and insulation at low temperature It is.

By this ultraviolet irradiation, the substrate is heated, and O ₂ and H ₂ O contributing to ceramization (silica conversion), the ultraviolet absorber, and the polysilazane itself are excited and activated, so that the polysilazane is excited and polysilazane The formation of a ceramic is promoted, and the obtained ceramic film becomes more compact. It is effective to carry out the ultraviolet irradiation at any time after the film formation.

  In the ultraviolet irradiation treatment, it is also possible to use any of the commonly used ultraviolet light generators.

  In addition, although the ultraviolet rays said by this invention generally mean electromagnetic waves which have a wavelength of 10-400 nm, in the case of ultraviolet irradiation processing other than the vacuum ultraviolet (10-200 nm) process mentioned later, preferably 210-375 nm Use ultraviolet light.

  It is preferable to set the irradiation intensity and the irradiation time within the range in which the base material carrying the third layer to be irradiated is not damaged by the irradiation of the ultraviolet light.

In the case of using a plastic film as a substrate, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the substrate surface has a strength of 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the substrate and the ultraviolet irradiation lamp can be set to be ² and irradiation can be performed for 0.1 seconds to 10 minutes.

  In general, when the substrate temperature at the time of ultraviolet irradiation treatment reaches 150 ° C. or more, in the case of a plastic film or the like, the characteristics of the substrate are impaired, such as deformation of the substrate and deterioration of its strength. Become. However, in the case of a highly heat-resistant film such as polyimide or a substrate such as metal, reforming at a higher temperature is possible. Therefore, there is no general upper limit as a substrate temperature at the time of this ultraviolet irradiation, and those skilled in the art can appropriately set it depending on the type of the substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, It may carry out in air.

  As means for generating such ultraviolet light, for example, metal halide lamp, high pressure mercury lamp, low pressure mercury lamp, xenon arc lamp, carbon arc lamp, excimer lamp (172 nm, 222 nm, 308 nm single wavelength, for example, Ushio Electric Co., Ltd. ), UV light laser, etc., but it is not particularly limited. In addition, when the generated ultraviolet light is irradiated to the third layer, the ultraviolet light from the generation source is reflected by the reflection plate and then applied to the third layer from the viewpoint of achieving the efficiency improvement and uniform irradiation. Is desirable.

  The ultraviolet irradiation is compatible with both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used. For example, in the case of batch processing, the laminate having the third layer on the surface can be treated in an ultraviolet calciner equipped with an ultraviolet light source as described above. The ultraviolet baking furnace itself is generally known, and for example, an ultraviolet baking furnace manufactured by Eye Graphics Co., Ltd. can be used. When the laminate having the third layer on the surface is in the form of a long film, it is continuously irradiated with ultraviolet light in a drying zone equipped with an ultraviolet light source as described above while being transported. It can be made into ceramic. The time required for the ultraviolet irradiation depends on the composition and concentration of the used base material and the third layer, but is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes.

(Vacuum UV radiation treatment: excimer radiation treatment)
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by vacuum ultraviolet radiation uses light energy of 100 to 200 nm, which is larger than the interatomic bonding force in the polysilazane compound, preferably using light energy of 100 to 180 nm wavelength, and uses only light photons whose atomic bonds are called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or less) by advancing an oxidation reaction with active oxygen and ozone while directly cutting by action. In addition, when performing excimer irradiation processing, it is preferable to use heat processing together as mentioned above, and the detail of the heat processing conditions in that case is as having mentioned above.

  The radiation source in the present invention may be any as long as it generates light with a wavelength of 100 to 180 nm, preferably an excimer radiator (for example, a Xe excimer lamp) having a maximum emission at about 172 nm and a bright line at about 185 nm. Low pressure mercury vapor lamps, and medium and high pressure mercury vapor lamps with wavelength components below 230 nm, and excimer lamps with maximum emission at about 222 nm.

  Among them, the Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light of 172 nm having a short wavelength at a single wavelength. Since this light has a large absorption coefficient of oxygen, it can generate radical oxygen atom species and ozone at high concentration with a small amount of oxygen.

  In addition, it is known that the energy of 172 nm light having a short wavelength has a high ability to dissociate the binding of an organic substance. The high energy possessed by the active oxygen and ozone and the ultraviolet radiation can realize the modification of the polysilazane layer in a short time.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power input. In addition, since light having a long wavelength causing temperature rise due to light is not emitted, energy is irradiated in the ultraviolet region, that is, at a short wavelength, so that the rise of the surface temperature of the object to be deciphered is suppressed. Therefore, it is suitable for flexible film materials such as PET which are considered to be susceptible to heat.

  Oxygen is required for the reaction at the time of ultraviolet irradiation, but vacuum ultraviolet rays are absorbed by oxygen and the efficiency in the ultraviolet irradiation process is likely to be reduced. It is preferable to carry out in the state where water vapor concentration is low. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 10 to 210,000 volume ppm, more preferably 50 to 10,000 volume ppm. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

  It is preferable to set it as dry inert gas as gas which satisfy | fills irradiation atmosphere used at the time of vacuum ultraviolet irradiation, and it is preferable to set it as dry nitrogen gas especially from a viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation storage and changing the flow ratio.

In vacuum ultraviolet irradiation step, the illuminance of the vacuum ultraviolet rays in the coated surface of the coating film is subjected is preferably from 30~200mW / cm ^2, more preferably 50~160mW / cm ^2. If it is less than 30 mW / cm ^2, there is a concern that the modification efficiency may be greatly reduced, and if it exceeds 200 mW / cm ² , there is a concern that the coating may be ablated or the substrate may be damaged.

Irradiation energy amount of the VUV in the coated surface is preferably 200~5000mJ / cm ^2, more preferably 500~3000mJ / cm ^2. Is less than 200 mJ / cm ^2, there is a fear that the reforming becomes insufficient, 5000 mJ / cm ² than the cracking or due to excessive modification concerns the thermal deformation of the substrate emerges.

In addition, vacuum ultraviolet light used for reforming may be generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . Furthermore, although a gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as a carbon-containing gas) may use a carbon-containing gas alone, carbon containing noble gas or H ₂ as a main gas It is preferable to add a small amount of contained gas. Examples of plasma generation methods include capacitively coupled plasma.

  Next, when the silicon compound which is a preferable form is perhydropolysilazane, the reaction mechanism presumed to produce silicon oxynitride and further silicon oxide from perhydropolysilazane in the vacuum ultraviolet irradiation step will be described below. .

(I) Dehydrogenation and associated formation of Si-N bond Si-H bond and N-H bond in perhydropolysilazane are relatively easily cleaved by excitation with vacuum ultraviolet radiation, etc., and under inert atmosphere, Si-- It is considered that they recombine as N (Si dangling bonds may be formed in some cases). That is, it cures as a SiN _y composition without oxidation. In this case no cleavage of the polymer backbone occurs. Cleavage of Si-H bond and N-H bond is promoted by the presence of a catalyst and heating. The cleaved H is released out of the membrane as H ₂ .

(II) Formation of Si-O-Si Bond by Hydrolysis and Dehydration Condensation Si-N bond in perhydropolysilazane is hydrolyzed by water and the polymer main chain is cleaved to form Si-OH. The two Si-OHs are dehydrated and condensed to form Si-O-Si bonds and cure. This is a reaction that occurs in the atmosphere, but during vacuum ultraviolet irradiation under an inert atmosphere, it is considered that water vapor generated as an outgas from the substrate by the heat of irradiation becomes the main moisture source. When the water content is excessive, Si-OH which can not be dehydrated and condensed remains, and a cured film having low gas barrier properties represented by the composition of SiO _2.1 to SiO _2.3 is obtained.

(III) Direct oxidation by singlet oxygen, formation of Si-O-Si bond During vacuum ultraviolet irradiation, when an appropriate amount of oxygen is present in the atmosphere, singlet oxygen having a very strong oxidizing power is formed. H and N in perhydropolysilazane replace O to form a Si-O-Si bond and cure. It is believed that cleavage of the polymer backbone may result in recombination of bonds.

(IV) Oxidation accompanied by cleavage of Si-N bond by vacuum ultraviolet irradiation / excitation The energy of vacuum ultraviolet ray is higher than the bonding energy of Si-N in perhydropolysilazane, so the Si-N bond is broken and oxygen, In the presence of an oxygen source such as ozone and water, it is considered that oxidation occurs to form Si-O-Si bond and Si-O-N bond. It is believed that cleavage of the polymer backbone may result in recombination of bonds.

  The composition of silicon oxynitride in the layer obtained by vacuum ultraviolet irradiation of a layer containing polysilazane can be adjusted by controlling the oxidation state by appropriately combining the above-mentioned oxidation mechanisms (I) to (IV). .

  Here, in the case of polysilazane suitable as a silicon compound, in the silica conversion (reforming treatment), cleavage of Si-H, N-H bond and formation of Si-O bond occur, and conversion to ceramics such as silica occurs. The degree of this conversion can be evaluated semiquantitatively by the SiO / SiN ratio by IR measurement, by equation (1) defined below.

Here, the SiO absorbance is calculated by about 1160 cm ⁻¹ , and the SiN absorbance is calculated by absorption (absorbance) at about 840 cm ⁻¹ . The larger the SiO / SiN ratio, the more the conversion to ceramics closer to the silica composition is shown.

Here, the SiO / SiN ratio, which is an index of the degree of conversion to ceramics, is preferably 0.3 or more, preferably 0.5 or more. If it is less than 0.3, the expected gas barrier properties may not be obtained. Moreover, as a measuring method of a silica conversion rate ( _x in SiOx), it can measure, for example using XPS method.

  The film composition of the third layer can be measured by measuring the atomic composition ratio using an XPS surface analyzer. It is also possible to measure the atomic composition ratio by cutting the barrier layer and measuring the cut surface with an XPS surface analyzer.

Also, the film density of the third layer can be appropriately set depending on the purpose. For example, the film density of the third layer is preferably in the range of 1.5 to 2.6 g / cm ³ . If the thickness is out of this range, the density of the film may be reduced, and the barrier property may be deteriorated, or the film may be oxidized and deteriorated due to humidity.

  The thickness of the third layer can be set appropriately depending on the purpose. For example, the thickness of the third layer is preferably about 10 nm to 10 μm, more preferably 15 nm to 1 μm, and still more preferably 20 to 500 nm. If the film thickness is 10 nm or more, sufficient barrier properties can be obtained, and if 10 μm or less, stable coatability can be obtained at the time of layer formation, and high light transmittance can be realized.

  In addition, the film thickness of the third layer is preferably three or more times the film thickness of the second layer. Under high temperature and high humidity conditions, the substrate or the first layer expands. Then, stress may act on the second layer to affect the layer. However, in the present invention, since the third layer is present, the stress acting on the second layer is relaxed. And since the effect of the said stress relaxation under high temperature, high humidity conditions is further improved by being in the range of the said film thickness, gas barrier property is maintained. The thickness of the third layer is preferably 3 to 15 times, and more preferably 3 to 5 times the thickness of the second layer.

  The refractive index of the third layer is not particularly limited, but is preferably 1.7 to 2.1, more preferably 1.8 to 2, and 1.9 to 2.0. Particularly preferred. The barrier layer having such a refractive index has high visible light transmittance and high gas barrier ability can be stably obtained.

〔Base material〕
The gas barrier film of the present invention usually uses a plastic film as a substrate. The plastic film to be used is not particularly limited in material, thickness and the like as long as the film can hold the barrier laminate, and can be appropriately selected according to the purpose of use and the like. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluorine resin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide Resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin resin, fluorene ring modified polycarbonate resin, alicyclic resin Thermoplastic resins such as modified polycarbonate resin, fluorene ring modified polyester resin, acryloyl compound and the like can be mentioned.

  When the gas barrier film of the present invention is used as a substrate of a device such as an organic EL element, the substrate is preferably made of a material having heat resistance. Specifically, a fat base having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a Tg of 100 ° C. or more and 300 ° C. or less is used. The substrate satisfies the requirements as an electronic component application and a laminated film for a display. That is, when using the gas-barrier film of this invention for these uses, a gas-barrier film may be exposed to the process 150 degreeC or more. In this case, when the linear expansion coefficient of the substrate in the gas barrier film exceeds 100 ppm / K, the substrate dimensions are not stable when flowing the gas barrier film in the process of the temperature as described above, and along with thermal expansion and contraction, It is apt to cause a problem that the barrier performance degrades or a problem that the heat process can not withstand. If it is less than 15 ppm / K, the film may be broken like glass and the flexibility may be deteriorated.

  The Tg and linear expansion coefficient of the substrate can be adjusted by additives and the like. More preferable specific examples of the thermoplastic resin that can be used as a substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic Polyolefin (for example, Zeon Corporation, Zeonoa (registered trademark) 1600: 160 ° C), polyarylate (PAr: 210 ° C), polyethersulfone (PES: 220 ° C), polysulfone (PSF: 190 ° C), cycloolefin copolymer (COC: compound described in JP-A-2001-150584: 162 ° C.), polyimide (eg, Neoprim (registered trademark): 260 ° C. manufactured by Mitsubishi Gas Chemical Co., Ltd.), fluorene ring modified polycarbonate (BCF-PC: JP-A In the publication 2000-227603 Compound: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound described in JP-A 2000-227603: 205 ° C.), acryloyl compound (compound described in JP-A 2002-80616): 300 ° C. And the like) and the like (the parenthesis indicates Tg). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  When the gas barrier film of the present invention is used in combination with a polarizing plate, it is preferable that the barrier laminate of the gas barrier film be directed to the inside of the cell and disposed at the innermost (adjacent to the element). At this time, since the gas barrier film is disposed on the inner side of the cell from the polarizing plate, the retardation value of the gas barrier film becomes important. The mode of use of the gas barrier film in such an embodiment is a gas barrier film using a base film having a retardation value of 10 nm or less and a circularly polarizing plate (1/4 wavelength plate + (1/2 wavelength plate) + straight line It is preferable to use a linear polarizing plate in combination with a gas barrier film using a base film having a retardation value of 100 nm to 180 nm, which can be used by laminating the polarizing plate or as a quarter wavelength plate. .

  As a base film having a retardation of 10 nm or less, for example, cellulose triacetate (manufactured by Fuji Film Co., Ltd .: Fujitac (registered trademark)), polycarbonate (manufactured by Teijin Chemicals Ltd .: Pure Ace (registered trademark), Kaneka Corporation: Elmec (registered trademark), cycloolefin polymer (manufactured by JSR Corporation: Arton (registered trademark), manufactured by Nippon Zeon Corporation: Zeonor (registered trademark)), cycloolefin copolymer (manufactured by Mitsui Chemicals, Inc .: Apel (registered trademark) (Pellets) Polyplastics Co., Ltd .: Topas (registered trademark) (pellets)) Polyarylate (manufactured by Unitika, Inc .: U100 (pellets)), transparent polyimide (manufactured by Mitsubishi Gas Chemical Co., Ltd .: Neoprim (registered trademark)) Etc. can be mentioned.

  Moreover, the film adjusted to the desired retardation value can be used by extending | stretching said film suitably as a quarter wavelength plate.

  Since the gas barrier film of the present invention is used as a device such as an organic EL element, the plastic film is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K 7105: 1981, that is, an integrating sphere type light transmittance measurement apparatus, and subtracting the diffuse transmittance from the total light transmittance. can do.

  However, even when the gas barrier film of the present invention is used for display applications, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can also be used as the plastic film. As an opaque material, a polyimide, polyacrylonitrile, a well-known liquid crystal polymer etc. are mentioned, for example.

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

  The substrate preferably has high surface smoothness. As surface smoothness, that whose average surface roughness (Ra) is 2 nm or less is preferable. There is no particular lower limit, but in practice it is at least 0.01 nm. If necessary, both sides of the substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.

  Moreover, the base material using resin etc. which were mentioned above may be an unstretched film, and a stretched film may be sufficient.

  The substrate used in the present invention can be produced by a commonly known conventional method. For example, a resin as a material is melted by an extruder, and extruded and quenched by an annular die or a T-die, whereby a substantially amorphous unoriented non-oriented substrate can be produced. In addition, the base material flow (vertical axis) direction, or the unstretched substrate by a known method such as uniaxial stretching, tenter type successive biaxial stretching, tenter type simultaneous biaxial stretching, tubular type simultaneous biaxial stretching, or A stretched substrate can be produced by stretching in a direction (horizontal axis) perpendicular to the flow direction of the substrate. Although the draw ratio in this case can be suitably selected according to resin used as the raw material of a base material, 2 to 10 times are preferable in a vertical axis direction and a horizontal axis direction, respectively.

  On both sides of the substrate, at least on the side where the barrier layer (curable resin layer) according to the present invention is provided, various known treatments for improving adhesion, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, or The lamination of the smooth layer can be performed in combination as needed.

[Intermediate layer]
In the range which does not impair the effect of this invention, you may provide an intermediate | middle layer separately to the above-mentioned base material, 1st layer, 2nd layer, and 3rd layer or surface.

(Curable resin layer)
The gas barrier film according to the present invention preferably has a curable resin layer formed by curing a curable resin on a substrate. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material or the like with an active energy ray such as ultraviolet rays and curing it is heated. And thermosetting resins obtained by curing. The curable resins may be used alone or in combination of two or more.

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

  As the active energy ray-curable material, for example, a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene The composition etc. which contain polyfunctional acrylate monomers, such as glycol acrylate and a glycerol methacrylate, are mentioned. Specifically, a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series (a compound obtained by binding an organic compound having a polymerizable unsaturated group to silica fine particles) manufactured by JSR Corporation may be used. it can. Also, it is possible to use any mixture of the compositions as described above, and an active energy ray curable material containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule. There is no particular limitation as long as

  As reactive monomers having one or more photopolymerizable unsaturated bonds in the molecule, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxy ethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glyci Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobonyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-metric ethyl acrylate, methoxy ethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2, 2-dimethylol propane diacrylate, glycerol diacrylate, tripropyle Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyl trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propion Oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyl trimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Lymethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and the above acrylates replaced with methacrylates, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone etc. are mentioned. The above-mentioned reactive monomers can be used as a mixture of one or more, or as a mixture with other compounds.

  The composition containing the active energy ray curable material preferably contains a photopolymerization initiator.

  As the photopolymerization initiator, for example, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4, 4-bis (diethylamine) benzophenone, α-amino acetophenone, 4, 4-dichloro Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-Butyl dichloroacetophenone, thioxanthone, 2-methyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, diethyl thioxanthone, benzyl dimethyl ketal, benzyl methoxyethyl acetal, benzoi Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butyl anthraquinone, 2-amyl anthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methylene anthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azide Benzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxy , Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monophorino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monophorinophenyl) -butanone-1, naphthalenesulfonyl chloride , Quinoline sulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, peroxidated benzoin And combinations of photoreducible dyes such as eosin and methylene blue with reducing agents such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more. .

  As the thermosetting material, specifically, Tutoprom series (organic polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat Co., Ltd., nano hybrid silicone manufactured by Adeka, Uni manufactured by DIC Corporation Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (super high heat resistant epoxy resin), silicone resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nitto Boseki Co., Ltd. Inorganic / organic nanocomposite material SSG coat, thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohydrin resin And the like.

  The method for forming the curable resin layer is not particularly limited, but a coating liquid containing a curable material may be applied by spin coating, spraying, blade coating, dip coating, wet coating such as gravure printing, vapor deposition, etc. The above coating is applied by the dry coating method to form a coating film, and then the coating is performed by irradiation and / or heating of active energy rays such as visible light, infrared rays, ultraviolet rays, X rays, α rays, β rays, γ rays, and electron beams. The method of curing and forming a film is preferred. As a method of irradiating active energy rays, for example, ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc, metal halide lamps etc. are preferably used to irradiate ultraviolet light in a wavelength range of 100 to 400 nm, more preferably 200 to 400 nm. Another example is a method of irradiating an electron beam in a wavelength range of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

  As a solvent to be used when forming a curable resin layer using a coating liquid in which a curable material is dissolved or dispersed in a solvent, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, etc. Alcohols, terpenes such as α- or β-terpineol, etc., acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, ketones such as 2-heptanone, 4-heptanone, toluene, xylene, tetramethyl Aromatic hydrocarbons such as benzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbi Acetate esters such as tall acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, etc. , Diethylene glycol dialkyl ether, dip Propylene glycol dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

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

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

  As for the smoothness of the curable resin layer, the center line average surface roughness (Ra) is preferably 0.3 to 2.0 nm, and more preferably 0.3 to 1.0 nm. Within such a range, one purpose of the curable resin layer to make the substrate surface smooth can be achieved. In addition, centerline average surface roughness (Ra) can be measured by the method as described in an Example.

  The elastic modulus of the curable resin layer is preferably 2.0 to 20.0 Pa. Within such a range, the hard coatability of the film surface is improved, and one purpose of the curable resin layer that the stress due to the upper layer lamination can be relaxed can be achieved. The elastic modulus can be determined by a conventionally known elastic modulus measurement method, for example, a method of measuring under a condition that a constant strain is applied at a constant frequency (Hz) using Vibron DDV-2 manufactured by Orientec Co., Ltd. After forming a curable resin layer on a substrate using RSA-II (manufactured by Rheometrics) as a measuring device, a method of obtaining a measurement value obtained when the applied strain is changed at a constant frequency, or nano It can be measured by a nano indenter to which the indentation method is applied, for example, a nano indenter (Nano IndenterTMXP / DCM) manufactured by MTS System, Inc.

(Primer layer (smooth layer))
The gas barrier film of the present invention may have a primer layer (smooth layer) on the surface of the substrate having the barrier layer. The primer layer is provided to flatten the rough surface of the substrate on which protrusions and the like are present. Such a primer layer is basically formed by curing an active energy ray curable material or a thermosetting material or the like. The primer layer may basically have the same configuration as the above curable resin layer as long as it has the above-described function.

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

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

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

(Anchor coat layer)
An anchor coat layer may be formed as an easy adhesion layer on the surface of the substrate according to the present invention for the purpose of improving the adhesion (adhesion) with the barrier layer. As an anchor coat agent used for this anchor coat layer, polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, alkyl titanate, etc. , 1 or 2 or more types can be used in combination. The anchor coating agent may be a commercially available product. Specifically, a siloxane-based UV-curable polymer solution (Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) can be used.

A conventionally known additive can also be added to these anchor coating agents. Then, the above-mentioned anchor coating agent is coated on the substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc. and coated by drying and removing the solvent, diluent and the like. Can. As a coating amount of said anchor coating agent, about 0.1-5 g / m < ² > (dry state) grade is preferable. In addition, you may use a commercially available base material with an easily bonding layer.

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

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

(Bleed out prevention layer)
In the gas barrier film of the present invention, a bleed out preventing layer can be provided. The bleed-out preventing layer is intended to suppress the phenomenon that unreacted oligomers and the like migrate from the film substrate to the surface and contaminate the contacting surface when the film having the curable resin layer / smooth layer is heated. Is provided on the opposite side of the substrate having the curable resin layer / smooth layer. The bleed-out preventing layer may basically have the same configuration as the curable resin layer / smooth layer as long as it has this function.

  As a hard coating agent that can be included in the bleed-out prevention layer, a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or one polymerizable unsaturated compound in the molecule The unitary unsaturated organic compound etc. which have group can be mentioned.

  Here, as polyunsaturated organic compounds, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meth) acrylate ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, ditrimethylolpropane Tiger (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Moreover, as a unitary unsaturated organic compound, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (2-hydroxypropyl (meth) acrylate Meta) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethene) 2-Siethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2- Methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and the like .

  A matting agent may be contained as another additive. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.

  As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent comprising inorganic particles is 2 parts by weight or more, preferably 4 parts by weight or more, more preferably 6 parts by weight to 20 parts by weight, preferably 100 parts by weight of the solid content of the hard coating agent. It is desirable that they are mixed in a proportion of 18 parts by weight or less, more preferably 16 parts by weight or less.

  In addition, the bleed out preventing layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coating agent and the matting agent.

  As such a thermoplastic resin, cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose and the like, vinyl acetate and its copolymer, vinyl chloride and its copolymer, vinylidene chloride and its copolymer Etc., acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Resin etc. are mentioned.

  Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acryl polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, unsaturated polyester resin, a silicone resin etc. are mentioned.

  In addition, as the ionizing radiation curable resin, an ionizing radiation curing paint obtained by mixing one or more kinds of photopolymerizable prepolymers or photopolymerizable monomers is irradiated with ionizing radiation (ultraviolet ray or electron beam). Those that cure can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer which has two or more acryloyl groups in one molecule and forms a three-dimensional network structure by crosslinking and curing is particularly preferably used. As the acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above and the like can be used.

  Further, as a photopolymerization initiator, acetophenone, benzophenone, Michler's ketone, benzoin, benzyl methyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) And 1) propane, α-acyloxime esters, thioxanthones and the like.

  The above bleed out preventing layer is prepared as a coating solution by blending a hard coating agent and, if necessary, other components as appropriate, with a dilution solvent used as needed, and the coating solution is applied to the substrate film surface. After apply | coating by the conventionally well-known application method, it can form by irradiating and hardening ionizing radiation. In addition, as a method of irradiating ionizing radiation, ultraviolet light in a wavelength range of preferably 100 to 400 nm, more preferably 200 to 400 nm emitted from an ultrahigh pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, metal halide lamp etc. Or it can carry out by irradiating the electron beam of a 100 nm or less wavelength range emitted from a scanning type or curtain type electron beam accelerator.

  The thickness of the bleed out preventing layer in the present invention is desirably 1 to 10 μm, preferably 2 to 7 μm. By setting the thickness to 1 μm or more, the heat resistance as a film can be easily made sufficient, and by setting the thickness to 10 μm or less, the balance of the optical characteristics of the smooth film can be easily adjusted, and the curable resin layer / smooth layer is transparent. When provided on one surface of the polymer film, the curl of the gas barrier film can be easily suppressed.

  The gas barrier film of the present invention may be provided with other functional layers such as an organic layer, a protective layer, a moisture absorption layer, an antistatic layer and the like, if necessary.

[Method of producing gas barrier film]
A preferred embodiment of the method for producing a gas barrier film of the present invention is selected from the group consisting of oxides, nitrides, oxynitrides and oxycarbides containing at least one of Si, Al and Ti by chemical vapor deposition. A step of forming a first layer containing at least one kind, a step of forming a second layer containing an inorganic oxide by atomic layer deposition, and applying a solution containing a silicon compound And b) forming a third layer obtained by the modification treatment. The details of each step are as described above in each layer. A further preferred embodiment is the first layer comprising at least one selected from the group consisting of oxides, nitrides, oxynitrides and oxycarbides comprising at least one of Si, Al and Ti by chemical vapor deposition. Forming a second layer containing an inorganic oxide by atomic layer deposition on the first layer, and applying a solution containing a silicon compound on the second layer. And forming a third layer obtained by subjecting the obtained coating film to a modification treatment.

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

(Electronic device body)
The electronic element main body is a main body of the electronic device, and is disposed on the gas barrier film side according to the present invention. As the electronic element body, a known electronic device body to which sealing with a gas barrier film can be applied can be used. For example, an organic EL element, a solar cell (PV), a liquid crystal display element (LCD), an electronic paper, a thin film transistor, a touch panel and the like can be mentioned. From the viewpoint of obtaining the effects of the present invention more efficiently, the electronic element body is preferably an organic EL element or a solar cell. The configuration of these electronic device bodies is also not particularly limited, and may have a conventionally known configuration.

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

(Organic EL element)
The organic EL element 5 sealed by the gas barrier film 10 in the organic EL panel 9 will be described.

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

(Organic EL element)
The organic EL element 5 sealed with the gas barrier film 10 in the organic EL panel 9 will be described.

  Although the preferable specific example of the laminated constitution of the organic EL element 5 is shown below below, this invention is not limited to these.

(1) Anode / light emitting layer / cathode (2) anode / hole transport layer / light emitting layer / cathode (3) anode / light emitting layer / electron transport layer / cathode (4) anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) Anode / anode buffer layer (hole injection layer) / hole transport layer / emission layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode (anode)
As the anode (transparent electrode 4) in the organic EL element 5, one having a metal having a large work function (4 eV or more), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is preferably used. Specific examples of such an electrode material include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. It may also be used IDIXO _{(In 2} O 3 -ZnO) spruce amorphous in can prepare a transparent conductive film material.

  The anode may be formed as a thin film of these electrode materials by a method such as vapor deposition or sputtering, and the thin film may be formed into a pattern of a desired shape by a photolithography method, or in cases where pattern accuracy is not much required ( The pattern may be formed through a mask having a desired shape at the time of deposition or sputtering of the electrode material, for example, about 100 μm or more).

  In the case of taking out light emission from this anode, it is desirable to make the transmittance larger than 10%. The sheet resistance as the anode is preferably several hundreds Ω / sq or less. Moreover, although the film thickness of an anode is based also on material, it is 10-1000 nm normally, Preferably it is chosen in 10-200 nm.

(cathode)
As a cathode in the organic EL element 5, one having a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O) ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals etc. may be mentioned. Among them, a mixture of an electron injectable metal and a second metal which is a stable metal having a large work function value from the viewpoint of electron injectability and oxidation resistance, eg, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum etc. are suitable as the cathode.

  The cathode can be produced by forming a thin film of such an electrode material by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundreds Ω / sq or less. The film thickness of the cathode is usually 10 nm to 5 μm, preferably 50 to 200 nm. In addition, if either the anode or the cathode of the organic EL element 5 is transparent or semitransparent in order to transmit the emitted light, it is advantageous because the light emission luminance is improved.

  Moreover, after producing the said metal mentioned by description of the cathode by film thickness of 1-20 nm, a transparent or semi-transparent cathode is produced by producing the electroconductive transparent material mentioned by description of the anode on it. By applying this, it is possible to produce a device in which both the anode and the cathode are transparent.

(Injection layer: electron injection layer, hole injection layer)
The injection layer has an electron injection layer and a hole injection layer, and is provided with an electron injection layer and a hole injection layer as needed, and between the anode and the light emitting layer or the hole transport layer, and the cathode and the light emitting layer or the electron transport It exists between the layers.

  The injection layer is a layer provided between the electrode and the organic layer to lower the driving voltage and improve the light emission luminance. “The organic EL device and its industrial frontier (November 30, 1998 issued by NTS Co., Ltd.) 2), “Electrode materials” (pages 123 to 166), and there are a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, etc. As a specific example, copper A phthalocyanine buffer layer represented by phthalocyanine, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) and polythiophene, and the like can be mentioned.

  The details of the cathode buffer layer (electron injection layer) are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, etc. Specifically, strontium And metal buffer layers represented by aluminum, alkali metal compound buffer layers represented by lithium fluoride, alkaline earth metal compound buffer layers represented by magnesium fluoride, oxide buffer layers represented by aluminum oxide, etc. Can be mentioned. The buffer layer (injection layer) is preferably a very thin film, and although depending on the material, the film thickness is preferably in the range of 0.1 nm to 5 μm.

(Emitting layer)
The light emitting layer in the organic EL element 5 is a layer which emits light by recombining electrons and holes injected from the electrode (cathode, anode) or electron transporting layer, hole transporting layer, and the light emitting portion is the light emitting layer Or the interface between the light emitting layer and the adjacent layer.

  The light emitting layer of the organic EL element 5 preferably contains the following dopant compound (light emitting dopant) and host compound (light emitting host). Thereby, the light emission efficiency can be further enhanced.

(Emitting dopant)
There are two types of light emitting dopants: fluorescent dopants that emit fluorescence and phosphorescent dopants that emit phosphorescent light.

  Representative examples of fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrilium dyes, perylene dyes And stilbene dyes, polythiophene dyes, or rare earth complex phosphors.

  Representative examples of phosphorescent dopants are preferably complex compounds containing metals of Groups 8, 9 and 10 in the periodic table of the elements, more preferably iridium compounds and osmium compounds, and the most preferable among them Is an iridium compound. The light emitting dopant may be used as a mixture of a plurality of compounds.

(Light emitting host)
The light emitting host (simply referred to as a host) means the compound having the largest mixing ratio (mass) in the light emitting layer composed of two or more compounds, and the “dopant compound ( It is simply referred to as a dopant). For example, when the light emitting layer is composed of two compounds, compound A and compound B, and the mixing ratio is A: B = 10: 90, compound A is a dopant compound and compound B is a host compound. Furthermore, when the light emitting layer is composed of three types of compound A, compound B and compound C, and the mixing ratio is A: B: C = 5: 10: 85, compound A and compound B are dopant compounds, the compounds C is a host compound.

  The light emitting host is not particularly limited structurally, but typically, a basic skeleton such as carbazole derivative, triarylamine derivative, aromatic borane derivative, nitrogen-containing heterocyclic compound, thiophene derivative, furan derivative, oligoarylene compound, etc. Or a derivative of a carboline derivative or a diazacarbazole derivative (wherein the diazacarbazole derivative is a derivative of a carboline derivative in which at least one carbon atom of a hydrocarbon ring constituting the carboline ring is substituted with a nitrogen atom) And the like. Among them, carboline derivatives, diazacarbazole derivatives and the like are preferably used.

  The light emitting layer can be formed by forming the above-described compound by a known thin film formation method such as vacuum evaporation, spin coating, casting, LB method, and inkjet method. Although the film thickness as a light emitting layer is not particularly limited, it is usually selected in the range of 5 nm to 5 μm, preferably 5 to 200 nm. The light emitting layer may have a single layer structure comprising one or more dopant compounds or host compounds, or may have a multilayer structure comprising a plurality of layers of the same composition or different compositions.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material is one having either hole injection or transport or electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, in particular thiophene oligomers. As the hole transport material, those described above can be used, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound. Furthermore, it is also possible to use a polymer material in which these materials are introduced into a polymer chain or in which these materials are used as a polymer main chain. Inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  The hole transport layer may be formed by thinning the above hole transport material by a known method such as vacuum evaporation, spin coating, casting, printing including inkjet, LB, etc. it can. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The hole transport layer may be a single layer structure composed of one or more of the above materials.

(Electron transport layer)
The electron transport layer is made of an electron transport material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.

The electron transport material may have any function of transferring electrons injected from the cathode to the light emitting layer, and any material can be selected and used from conventionally known compounds as the material, For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like can be mentioned. Furthermore, in the above-mentioned oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted by a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as the electron transport material. Furthermore, it is also possible to use a polymer material in which these materials are introduced into a polymer chain, or in which these materials are used as a polymer main chain. Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) Aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and central metals of these metal complexes are In, Mg Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material. In addition, metal free or metal phthalocyanine, or those whose terminal is substituted with an alkyl group, a sulfonic acid group or the like can also be preferably used as the electron transport material. Further, as with the hole injection layer and the hole transport layer, inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the electron-transporting material.

  The electron transporting layer can be formed by thinning the electron transporting material by a known method such as a vacuum evaporation method, a spin coating method, a casting method, a printing method including an inkjet method, an LB method and the like. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may be a single layer structure comprising one or more of the above materials.

(Method of manufacturing organic EL element)
The manufacturing method of the organic EL element 5 is demonstrated.

  Here, as an example of the organic EL element 5, a method of manufacturing an organic EL element including an anode / a hole injection layer / a hole transport layer / a light emitting layer / an electron transport layer / an electron injection layer / a cathode will be described.

  First, a desired electrode substance, for example, a thin film made of a substance for an anode, is formed on the gas barrier film 10 to a film thickness of 1 μm or less, preferably 10 to 200 nm by a method such as evaporation, sputtering or plasma CVD. Then, form an anode.

Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, which is an organic EL element material, is formed thereon. The organic compound thin film can be formed by vapor deposition, wet process (spin coating, casting, inkjet, printing), etc., but it is easy to obtain a homogeneous film and it is difficult to generate pinholes. From the viewpoint of the like, a vacuum evaporation method, a spin coating method, an ink jet method and a printing method are particularly preferable. Furthermore, different film formation methods may be applied to each layer. When a deposition method is employed for film formation, the deposition conditions vary depending on the type of compound used, etc., but generally the boat heating temperature is 50 to 450 ° C., the vacuum degree is 10 ^-6 to 10 ^-2 Pa, the deposition rate is 0.01 It is desirable to select appropriately in the range of 50 nm / second, substrate temperature −50 to 300 ° C., film thickness 0.1 nm to 5 μm, preferably 5 to 200 nm.

  After forming these layers, a thin film made of a cathode material is formed thereon by a method such as evaporation or sputtering so as to have a thickness of 1 μm or less, preferably 50 to 200 nm, and a cathode is provided. Thereby, a desired organic EL element can be obtained.

  It is preferable to fabricate this organic EL element 5 consistently from the anode and the hole injection layer to the cathode by one evacuation, but it is also possible to take out in the middle and apply different film forming methods. At this time, it is necessary to take into consideration that the operation is performed in a dry inert gas atmosphere. In addition, it is also possible to reverse the order of preparation and to prepare in order of a cathode, an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer and an anode.

  When a DC voltage is applied to a multicolor display device (organic EL panel 9) including the organic EL element 5 obtained in this manner, the anode is positive and the negative polarity is about 2 to 40 V The light emission can be observed by applying Alternatively, an alternating voltage may be applied. In addition, the waveform of the alternating current to apply may be arbitrary.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples.

Example 1: Preparation of gas barrier film <Preparation of sample>
(Base material)
A 125 μm thick polyester film (manufactured by Teijin DuPont Film Co., Ltd., extremely low heat recovery PET Q83) which is a thermoplastic resin and subjected to easy adhesion processing on both sides was used as a base material.

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

(Formation of a curable resin layer (smooth layer))
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation is applied to the opposite side of the above base material, and it is coated with a die coater so that the film thickness after drying becomes 4 μm. After drying at 80 ° C. for 3 minutes, curing was performed under an air atmosphere, using a high pressure mercury lamp, curing conditions: 1.0 J / cm ² to form a curable resin layer. At this time, Ra of the surface of the curable resin layer was 0.8 nm.

[Preparation of gas barrier film 1]
(Formation of CVD layer)
An SiOC film was formed on a film provided with a curable resin layer using the vacuum plasma CVD apparatus shown in FIG. 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. As a source gas, a tetraethoxysilane (TEOS) gas flow rate of 7.5 sccm and an oxygen gas flow rate of 30 sccm were introduced into the vacuum chamber. At this time, the film substrate temperature was set to 100 ° C. at the start of film formation, and the gas pressure at the time of film formation was set to 30 Pa to form a 50 nm SiOC film.

Subsequently, using the same apparatus as described above, a SiO ₂ film was formed on SiOC. At this time, the high frequency power source used was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm. As a source gas, a silane gas flow rate of 7.5 sccm and an oxygen gas flow rate of 30 sccm were introduced into the vacuum chamber. At this time, the film substrate temperature was set to 100 ° C. at the start of film formation, and the gas pressure at the time of film formation was set to 30 Pa to form a 50 nm SiO ₂ film. At this time, Ra on the surface of the CVD layer was 7.4 nm.

(Formation of ALD layer)
Subsequently, a thin film of alumina Al ₂ O ₃ was deposited on SiO ₂ with SUNALE (registered trademark) R-200 ALD manufactured by Picosun Oy. Trimethylaluminum (TMA) was used as an aluminum source, and water was used as an oxygen source.

The ALD film is mounted in a reactor, the reactor is evacuated with a vacuum pump, then nitrogen gas is purged to adjust the pressure in the reactor to about 800-1100 Pa, and then the substrate temperature is 100 ° C. Adjusted to Then, the raw material was introduced into the reactor in a pulsed manner in the following cycle. The pulse cycle was performed by TMA: 0.1 second, nitrogen purge: 4.0 seconds, water: 0.1 second, nitrogen purge: 4.0 seconds. At this time, the deposition rate of Al ₂ O ₃ from TMA and water was 0.1 nm / cycle. Here, 100 cycles were carried out to form a 10.0 nm Al ₂ O ₃ thin film. At this time, Ra on the surface of the ALD layer was 6.1 nm.

(Formation of polysilazane layer)
Subsequently, a polysilazane coating was formed on the ALD layer. 10% by mass dibutyl ether solution of perhydropolysilazane (AQUAMICA NN 120-10, manufactured by AZ Electronic Materials Co., Ltd.) and N, N of an amine catalyst (AQUAMICA LExp. NAXCAT-10DB, manufactured by AZ Electronic Materials (Coated)) Using a wireless bar, a liquid prepared by mixing a 10 mass% dibutyl ether solution of N, N ', N'-tetramethyl-1,6-diaminohexane in a ratio of 99: 1 has an (average) film thickness after drying, It applied so that it might be set to 150 nm, and it dried with dry air of temperature 25 degreeC and dew point-5 degreeC for 1 minute, and obtained the application sample. The obtained coated sample was treated for 2 minutes in an atmosphere at a temperature of 85 ° C. and a humidity of 55% RH.

[Modification treatment of polysilazane coating film]
The above sample after drying the polysilazane coating film was subjected to an excimer modification treatment under the following apparatus and conditions to form a polysilazane modified layer. The dew point temperature at the time of the reforming treatment was performed at -20 ° C. The film thickness after modification was 120 nm.
・ Reforming apparatus Excimer irradiation apparatus MODEL: MECL-M-1-200 manufactured by M.D.
Wavelength: 172 nm
Lamp filling gas: Xe
Modification conditions Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2 mm
Stage heating temperature: 80 ° C
Oxygen concentration in the irradiation device: 0.3% by volume
Stage conveyance speed at the time of excimer light irradiation: 10 mm / second Stage conveyance number at the time of excimer light irradiation: 3 reciprocations In this way, the gas barrier film 1 was produced.

[Preparation of gas barrier film 2]
A gas barrier film 2 was produced in the same manner as the gas barrier film 1 except that the CVD layer was formed as follows.

(Formation of CVD layer)
Using the vacuum plasma CVD apparatus shown in FIG. 2, a CVD layer was formed to 100 nm under the following film forming conditions. At this time, the surface roughness Ra of the CVD layer surface was 8.6 nm. The film thickness composition of this CVD layer was as shown in FIG.

  Here, in FIG. 4, symbols A to D respectively indicate A: carbon distribution curve, B: silicon distribution curve, C: oxygen distribution curve, and D: oxygen carbon distribution curve. There are nine extreme values in the carbon distribution curve of FIG. Further, in the carbon distribution curve of FIG. 4, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is 10 at% or more.

Plasma deposition conditions
・ Supply amount of source gas (HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
-Degree of vacuum in the vacuum chamber: 3 Pa
-Applied power from plasma power supply: 0.8 kW
・ Frequency of power supply for plasma generation: 80kHz
・ Conveying speed of film; 1.5 m / min
[Preparation of gas barrier film 3]
A gas barrier film 3 was produced in the same manner as the gas barrier film 1 except that the modification of the polysilazane film was as follows.

[Modification treatment of polysilazane coating film]
Low pressure plasma treatment was performed on the produced polysilazane coating film under the following conditions.

Plasma processing apparatus: Low pressure capacitively coupled plasma processing apparatus (manufactured by U-Tech Corporation)
Gas: Ar + CO (CO is 1 vol%)
Pressure: 10 Pa Substrate heating temperature: room temperature (25 ° C)
Input power density: 1.3 W / cm ²
Frequency: 13.56 MHz
Processing time: 3 seconds [Preparation of gas barrier film 4]
A gas barrier film 4 was produced in the same manner as the gas barrier film 1 except that the formation of the ALD layer was formed as follows.

(Formation of ALD layer)
A thin film of SiO ₂ was deposited by SUNALE (registered trademark) R-200 ALD manufactured by Picosun Oy. Tris dimethylaminosilane (3DMASi) was used as a Si source, and ozone was used as an oxygen source.

The film is mounted in a reactor, the reactor is evacuated with a vacuum pump, then nitrogen gas is purged to adjust the pressure in the reactor to about 800-1100 Pa, and then the substrate temperature is 100 ° C. It was adjusted. Then, the raw material was introduced into the reactor in a pulsed manner in the following cycle. The pulse cycle is 3DMASi: 0.1 seconds, nitrogen purge: 8.0 seconds, ozone: 0.1 seconds, nitrogen purge: 8.0 seconds. At this time, the deposition rate of SiO ₂ from 3DMASi and ozone was 0.0625 nm / cycle. Here, 160 cycles were performed to form a 10.0 nm SiO ₂ thin film. Ra at this time was 6.0 nm.

[Preparation of gas barrier film 5]
A gas barrier film 5 was produced in the same manner as the gas barrier film 1 except that the formation of the ALD layer was formed as follows.

(Formation of ALD layer)
A thin film of TiO ₂ was deposited with SUNALE® R-200 ALD manufactured by Picosun Oy. Tetrakis dimethylamino titanium (TDMATi) was used as a Ti source, and ozone was used as an oxygen source.

The film is mounted in a reactor, the reactor is evacuated with a vacuum pump, then nitrogen gas is purged to adjust the pressure in the reactor to about 800-1100 Pa, and then the substrate temperature is 100 ° C. It was adjusted. Then, the raw material was introduced into the reactor in a pulsed manner in the following cycle. The pulse cycle is TDMA Ti: 0.1 seconds, nitrogen purge: 4.0 seconds, ozone: 0.1 seconds, nitrogen purge: 4.0 seconds. At this time, the deposition rate of TiO ₂ from TDMA Ti and ozone was 0.06 nm / cycle. Here, a cycle of 167 cycles was performed to form a 10.0 nm TiO ₂ thin film. Ra at this time was 6.0 nm.

[Preparation of gas barrier film 6]
A gas barrier film 6 was produced in the same manner as the gas barrier film 1 except that the formation of the ALD layer and the formation of the CVD layer were formed as follows.

(Formation of CVD layer)
An SiOC film was formed on a film provided with a curable resin layer using the vacuum plasma CVD apparatus shown in FIG. 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. As a source gas, a tetraethoxysilane (TEOS) gas flow rate of 7.5 sccm and an oxygen gas flow rate of 30 sccm were introduced into the vacuum chamber. At this time, the film substrate temperature was set to 100 ° C. at the start of film formation, and the gas pressure at the time of film formation was set to 30 Pa to form a SiOC film of 100 nm.

Subsequently, using the same apparatus as described above, a SiO ₂ film was formed on SiOC. At this time, the high frequency power source used was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm. As a source gas, a silane gas flow rate of 7.5 sccm and an oxygen gas flow rate of 30 sccm were introduced into the vacuum chamber. At this time, the film substrate temperature was set to 100 ° C. at the start of film formation, and the gas pressure at the time of film formation was set to 30 Pa to form a SiO ₂ film 100 nm. At this time, Ra on the surface of the CVD layer was 9.8 nm.

(Formation of ALD layer)
Subsequently, a thin film of alumina Al ₂ O ₃ was deposited on the SiO ₂ film by SUNALE (registered trademark) R-200 ALD manufactured by Picosun Oy. Trimethylaluminum (TMA) was used as an aluminum source, and water was used as an oxygen source.

The ALD film is mounted in a reactor, the reactor is evacuated with a vacuum pump, then nitrogen gas is purged to adjust the pressure in the reactor to about 800-1100 Pa, and then the substrate temperature is 100 ° C. Adjusted to Then, the raw material was introduced into the reactor in a pulsed manner in the following cycle. The pulse cycle was performed by TMA: 0.1 second, nitrogen purge: 4.0 seconds, water: 0.1 second, nitrogen purge: 4.0 seconds. At this time, the deposition rate of Al ₂ O ₃ from TMA and water was 0.1 nm / cycle. Here, 200 cycles were performed to form a 20.0 nm Al ₂ O ₃ thin film. At this time, Ra on the ALD layer surface was 7.1 nm.

[Preparation of gas barrier film 7]
A gas barrier film 7 was produced in the same manner as the gas barrier film 1 except that the formation of the ALD layer was formed as follows.

(Formation of ALD layer)
Subsequently, a thin film of alumina Al ₂ O ₃ was deposited on SiO ₂ with SUNALE (registered trademark) R-200 ALD manufactured by Picosun Oy. Trimethylaluminum (TMA) was used as an aluminum source, and water was used as an oxygen source.

The ALD film is mounted in a reactor, the reactor is evacuated with a vacuum pump, then nitrogen gas is purged to adjust the pressure in the reactor to about 800-1100 Pa, and then the substrate temperature is 100 ° C. Adjusted to Then, the raw material was introduced into the reactor in a pulsed manner in the following cycle. The pulse cycle was performed by TMA: 0.1 second, nitrogen purge: 4.0 seconds, water: 0.1 second, nitrogen purge: 4.0 seconds. At this time, the deposition rate of Al ₂ O ₃ from TMA and water was 0.1 nm / cycle. Here, 300 cycles were performed to form a 30.0 nm Al ₂ O ₃ thin film. At this time, Ra on the surface of the ALD layer was 5.3 nm.

[Preparation of gas barrier film 8]
A gas barrier film 8 was produced in the same manner as the gas barrier film 1 except that the formation of the ALD layer was formed as follows.

(Formation of ALD layer)
Subsequently, a thin film of alumina Al ₂ O ₃ was deposited on SiO ₂ with SUNALE (registered trademark) R-200 ALD manufactured by Picosun Oy. Trimethylaluminum (TMA) was used as an aluminum source, and water was used as an oxygen source.

The ALD film is mounted in a reactor, the reactor is evacuated with a vacuum pump, then nitrogen gas is purged to adjust the pressure in the reactor to about 800-1100 Pa, and then the substrate temperature is 100 ° C. Adjusted to Then, the raw material was introduced into the reactor in a pulsed manner in the following cycle. The pulse cycle was performed by TMA: 0.1 second, nitrogen purge: 4.0 seconds, water: 0.1 second, nitrogen purge: 4.0 seconds. At this time, the deposition rate of Al ₂ O ₃ from TMA and water was 0.1 nm / cycle. Here, 400 cycles were performed to form a 40.0 nm Al ₂ O ₃ thin film. At this time, Ra on the surface of the ALD layer was 4.3 nm.

[Preparation of gas barrier film 9]
A gas barrier film 9 was produced in the same manner as the gas barrier film 1 except that the solid content concentration was adjusted so that the coating thickness of the polysilazane layer would be 45 nm.

[Preparation of gas barrier film 10]
A gas barrier film 10 was produced in the same manner as the gas barrier film 1 except that the formation of the ALD layer and the formation of the polysilazane layer were formed as follows.

(Formation of ALD layer)
Subsequently, a thin film of alumina Al ₂ O ₃ was deposited on the SiO ₂ film by SUNALE (registered trademark) R-200 ALD manufactured by Picosun Oy. Trimethylaluminum (TMA) was used as an aluminum source, and water was used as an oxygen source.

The ALD film is mounted in a reactor, the reactor is evacuated with a vacuum pump, then nitrogen gas is purged to adjust the pressure in the reactor to about 800-1100 Pa, and then the substrate temperature is 100 ° C. Adjusted to Then, the raw material was introduced into the reactor in a pulsed manner in the following cycle. The pulse cycle was performed by TMA: 0.1 second, nitrogen purge: 4.0 seconds, water: 0.1 second, nitrogen purge: 4.0 seconds. At this time, the deposition rate of Al ₂ O ₃ from TMA and water was 0.1 nm / cycle. Here, 200 cycles were performed to form a 20.0 nm Al ₂ O ₃ thin film. At this time, Ra on the surface of the ALD layer was 5.0 nm.

(Formation of polysilazane layer)
The solid content concentration was adjusted so that the coating thickness of the polysilazane layer would be 55 nm.

[Preparation of gas barrier film 11]
A gas barrier film 11 was produced in the same manner as the gas barrier film 1 except that the formation of the ALD layer and the formation of the polysilazane layer were performed as follows.

(Formation of ALD layer)
Subsequently, a thin film of alumina Al ₂ O ₃ was deposited on SiO ₂ with SUNALE (registered trademark) R-200 ALD manufactured by Picosun Oy. Trimethylaluminum (TMA) was used as an aluminum source, and water was used as an oxygen source.

The ALD film is mounted in a reactor, the reactor is evacuated with a vacuum pump, then nitrogen gas is purged to adjust the pressure in the reactor to about 800-1100 Pa, and then the substrate temperature is 100 ° C. Adjusted to Then, the raw material was introduced into the reactor in a pulsed manner in the following cycle. The pulse cycle was performed by TMA: 0.1 second, nitrogen purge: 4.0 seconds, water: 0.1 second, nitrogen purge: 4.0 seconds. At this time, the deposition rate of Al ₂ O ₃ from TMA and water was 0.1 nm / cycle. Here, 300 cycles were performed to form a 30.0 nm Al ₂ O ₃ thin film. At this time, Ra on the ALD layer surface was 4.7 nm.

(Formation of polysilazane layer)
The solid content concentration was adjusted so that the coating film thickness of the polysilazane layer would be 30 nm.

[Preparation of gas barrier film 12]
A gas barrier film 12 was produced in the same manner as the gas barrier film 1 except that a silicon compound modified layer was formed as follows instead of the polysilazane layer.

(Formation of silicon compound modified layer)
According to the compositions shown in Table 1 below, compositions A.1. Composition B. EVOH solution prepared by dissolving EVOH (ethylene copolymerization ratio 29%, Soanol D2908 manufactured by Japan Synthetic Chemical Industry Co., Ltd.) in a mixed solvent of isopropyl alcohol and ion-exchanged water. A hydrolyzate consisting of ethyl silicate 40, isopropyl alcohol, aluminum acetylacetone and ion-exchanged water is added and stirred, and a composition C. A mixed solution of polyvinyl alcohol (manufactured by Kuraray, PVA 110), a silane coupling agent (epoxy silica SH 6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent gas barrier composition.

Using the coating solution prepared above, this is coated by gravure roll coating, and then heat treated at 100 ° C. for 30 seconds to a thickness of 0.4 g / m ² (0.2 μm) State) silicon compound modified layer was formed.

[Preparation of gas barrier film 13]
In the formation of the gas barrier film 1, the gas barrier film 13 was produced except for the formation of the ALD layer.

[Preparation of gas barrier film 14]
In the formation of the gas barrier film 2, the gas barrier film 14 was produced except for the formation of the ALD layer.

[Preparation of gas barrier film 15]
In the formation of the gas barrier film 1, the formation of the CVD layer was changed as follows, and the gas barrier film 15 was produced except for the formation of the ALD layer.

(Formation of CVD layer)
A film formed to a smooth layer was set in a vacuum chamber of a commercially available sputtering apparatus, vacuumed to ^10-4 Pa level, and 0.5 Pa of argon and oxygen as partial pressure was introduced as a discharge gas. When the atmospheric pressure stabilized, discharge was started to generate plasma on the Si target, and the sputtering process was started. When the process was stabilized, the shutter was opened to start formation of a silicon oxide layer on the film, and when a 100 nm film was deposited, the shutter was closed to complete film formation.

[Preparation of gas barrier film 16]
In the formation of the gas barrier film 1, the formation of the CVD layer was changed as follows, and the gas barrier film 16 was produced except for the formation of the ALD layer.

(Formation of CVD layer)
It formed using the vacuum evaporation system of a commercially available electron beam heating system. In the vapor deposition material, a powder having a diameter of 50 μm or less is 95% or more in metallic silicon, a powder containing 95% of a crystal structure in silicon dioxide, and a powder having a diameter of 50 μm or less is 95% or more A mixed vapor deposition material was prepared, which was prepared by mixing metal silicon and silicon dioxide mixed such that the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) was 1.50. The mixed deposition material was put into a crucible and press-molded so that the bulk density was 1.0 g / cm ³ .

This material was evaporated by irradiating the mixed deposition material with the electron beam emitted from the electron gun in a vacuum deposition apparatus of an electron beam heating system, to form a SiO ₂ film of 100 nm.

[Evaluation method]
Each characteristic value of the gas barrier film is measured according to the following method.

[Center line average surface roughness (Ra)]
A scanning probe microscope SPI3700, manufactured by Seiko Instruments Inc., is used as an atomic force microscope (AFM), and the surface of the sample is measured in a dynamic force mode, measuring area 10 × 10 μm square, scanning speed 1 Hz, xy direction 512 × The AFM topography image measured under the conditions of 256 divisions and cantilever SI-DF-20 (Si, f = 126 kHz, c = 16 N / m) is subjected to tilt automatic correction processing, and then centerline average in three-dimensional roughness analysis The surface roughness Ra (nm) was determined. Under the present circumstances, the cantilever used for the measurement used the thing of a state without abrasion or stain | pollution | contamination.

[Evaluation of water vapor barrier property (WVTR)]
The water permeation amount of each gas barrier film was measured according to the following measurement method, and the water vapor barrier property was evaluated according to the following criteria.

(apparatus)
Vapor deposition apparatus: manufactured by JEOL Ltd., vacuum deposition apparatus JEE-400
Constant temperature and humidity oven: Yamato Humidic ChamberIG47M
Metals that react with moisture and corrode: Calcium (granular)
Water vapor impermeable metal: Aluminum (φ3 to 5 mm, granular)
(Fabrication of water vapor barrier property evaluation cell)
A portion (9 12 mm × 12 mm) to be deposited on the gas barrier film sample before the transparent conductive film is attached using a vacuum deposition apparatus (vacuum deposition apparatus JEE-400 manufactured by Nippon Denshi Co., Ltd.) on the barrier layer surface of the sample The other was masked and metallic calcium was deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited from another metal vapor deposition source on the entire surface of one side of the sheet. After aluminum sealing, release the vacuum state, and immediately face the aluminum sealing side via a sealing ultraviolet curing resin (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere. The cell for evaluation was produced by irradiating with ultraviolet rays.

  Based on the method described in JP-A-2005-283561, the amount of moisture transmitted through the inside of the cell was calculated from the amount of corrosion of metallic calcium based on the method of sealing a sample obtained by sealing both sides.

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample in which metallic calcium is deposited using a quartz glass plate with a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample. Storage under high temperature and high humidity conditions of 60 ° C. and 90% RH, and it was confirmed that metallic calcium corrosion did not occur even after 1000 hours.

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

(Rank rating)
5: 1 × 10 ⁻⁵ g / m ² / day or less 4: 1 × 10 ⁻⁵ g / m ² / day or more, 5 × 10 ⁻⁵ g / m ² / day or less 3: 5 × 10 ⁻⁵ g / day m ² / day or more, 1 × 10 ⁻⁴ g / m ² / day or less 2: 1 × 10 ⁻⁴ g / m ² / day or more, 1 × 10 ⁻³ g / m ² / day or less 1: 1 × 10 ^-3 g / m ² / day or more (Evaluation of bending resistance (flexibility))
For the gas barrier film, the water vapor transmission rate of the gas barrier film which has been repeatedly processed 100 times of bending at an angle of 180 degrees so as to obtain a curvature of radius 10 mm in order to confirm changes in the gas barrier property before and after bending The WVTR) was measured and a similar rank rating was performed.

[Evaluation of high temperature and high humidity tolerance]
The obtained gas barrier film is continuously stored for 100 hours in a high temperature and high humidity tank (temperature and humidity oven: Yamato Humidic Chamber IG 47 M) adjusted to 60 ° C. and 90% RH without bending, and thereafter, the above bending resistance Evaluation was performed, the water vapor transmission rate was similarly measured, and the same rank evaluation was performed.

  The results are shown in Table 2 below. In Table 2 below, the PHPS layer refers to a layer obtained by modifying perhydropolysilazane (PHPS).

  As described in the results of Table 2 above, for film No. It can be seen that the films 1 to 12 have high bending resistance, particularly high bending resistance even under high temperature and high humidity conditions, and the gas barrier performance is maintained.

Example 2: Production of Organic EL Element A transparent conductive film was produced on the gas barrier layer of the produced samples 1 to 16 by the following method.

-Formation of Transparent Conductive Film As a plasma discharge device, a parallel plate type electrode was used, a gas barrier film of each sample was placed between the electrodes, and a mixed gas was introduced to form a thin film. As a ground (ground) electrode, a 200 mm × 200 mm × 2 mm stainless steel plate is coated with a high density, high adhesion alumina sprayed film, and then a solution of tetramethoxysilane diluted with ethyl acetate is applied and dried. It hardened by ultraviolet irradiation and sealed treatment was carried out, the dielectric surface covered in this way was ground, smoothed, and the electrode processed so that Rmax might be set to 5 micrometers was used. Further, as the application electrode, an electrode coated with a dielectric under the same conditions as the ground electrode was used for a hollow square pure titanium pipe. A plurality of application electrodes were prepared and provided facing the earth electrode to form a discharge space. Further, as a power source used for plasma generation, a power of 5 W / cm ² was supplied at a frequency of 13.56 MHz using a high frequency power source CF-5000-13M manufactured by Pearl Industrial Co., Ltd. A mixed gas of the following composition is then flowed between the electrodes to form a plasma state, the gas barrier film described above is subjected to atmospheric pressure plasma treatment, and a tin-doped indium oxide (ITO) film 100 nm thick on the gas barrier layer (ceramic film). It formed into a film by this, and obtained the samples 1-16 with a transparent conductive film.

Discharge gas: Helium 98.5% by volume
Reactive gas 1: oxygen 0.25% by volume
Reactive gas 2: Indium acetylacetonate 1.2% by volume
Reactive gas 3: dibutyltin diacetate 0.05% by volume
-Preparation of organic EL element After 100 mm x 100 mm of the obtained samples 1 to 16 with a transparent conductive film was used as a substrate and patterning was performed thereon, the gas barrier film substrate provided with this ITO transparent electrode was ultrasonicated with isopropyl alcohol Wash and dry with dry nitrogen gas. The transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of α-NPD (equation (2) below) is put in a molybdenum resistance heating boat, and a host compound is put in another molybdenum resistance heating boat Put 200 mg of CBP (formula (3) below) as another, put 200 mg of vasocuproin (formula (4) below) in another molybdenum resistance heating boat, and put Ir-1 (in another molybdenum resistance heating boat 100 mg of the following formula (5) was added, and 200 mg of Alq ₃ (the following formula (6)) was further put in another molybdenum resistance heating boat, and attached to a vacuum evaporation apparatus.

Next, the vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing α-NPD is energized and heated to deposit on a transparent support substrate at a deposition rate of 0.1 nm / sec. A layer was provided. Further, the heating boat containing CBP and Ir-1 was energized by heating and coevaporated on the hole transport layer at an evaporation speed of 0.2 nm / sec and 0.012 nm / sec, respectively, to provide a light emitting layer. . In addition, the substrate temperature at the time of vapor deposition was room temperature. Further, the heating boat containing BCP was energized to be heated, and vapor deposited on the light emitting layer at a vapor deposition rate of 0.1 nm / sec to provide a hole blocking layer with a film thickness of 10 nm. Furthermore, the heating boat containing Alq ₃ is energized by heating and is deposited on the hole blocking layer at a deposition rate of 0.1 nm / sec to provide an electron transport layer with a film thickness of 40 nm. The In addition, the substrate temperature at the time of vapor deposition was room temperature. Then, 0.5 nm of lithium fluoride and aluminum 110 nm were vapor-deposited, the cathode was formed, and the organic electroluminescent element samples 1-16 using the samples 1-16 with a transparent conductive film were produced, respectively.

Sealing of organic EL element sample Under an environment purged with nitrogen gas (inert gas), the aluminum deposition surface of the organic EL element samples 1 to 16 is made to face the aluminum foil of 100 μm in thickness. It sealed by making it adhere using a Chemtex company make epoxy system adhesive agent.

[Evaluation of organic EL device sample (dark spot)]
The sealed organic EL element samples 1 to 16 were energized under an environment of 60 ° C. and 90% RH, and a change in light emission unevenness such as occurrence of dark spots from 0 to 120 days was observed.

  The light emission unevenness of each sample thus observed was classified into the following five levels and evaluated.

  No dark spots and uneven brightness were observed on day 5: 0, and after 120 days, the non-emitting area was 0.1% or less of the total light emitting area, and all generated dark spots were not easily observed visually ( The diameter was 0.1 mm or less).

  The dark spots generated on day 4: 0 are all of a size (0.1 mm or less) which can not be easily observed visually, no unevenness in luminance is observed, and after 120 days, the non-emission area has a total emission area of 0 The dark spot generated maintained the size (0.1 mm or less) which can not be easily visually observed by more than 1% and 0.2% or less.

  All dark spots generated on day 3: 0 were of a size (0.1 mm or less) which could not be easily observed visually, and after 120 days, the non-emission area exceeded 2% of the total emission area.

  A dark spot visually distinguishable on day 2 and day 0 and uneven brightness were observed, and after 120 days, the non-light emitting area exceeded 2% of the total light emitting area and was 10% or less.

  A dark spot visually distinguishable on day 1: 0 and a non-emission area of uneven brightness were observed exceeding 1% of the total emission area, and within 120 days the non-emission area exceeded 10% of the total emission area .

  The above evaluation results (five-step evaluation) are shown in Table 3.

[Evaluation of organic EL element sample (dark spot after bending)]
In order to confirm the change of dark spots before and after bending, the dark spots of the sealed organic EL element samples 1 to 16 are repeatedly bent 100 times at an angle of 180 degrees so as to have a radius of 10 mm in advance. After the treatment, the same rank evaluation was performed under the above-mentioned dark spot evaluation conditions. The above evaluation results are shown in Table 3.

  The organic EL device samples 1 to 12 of the present invention showed good results in the dark spot evaluation for the high temperature and high humidity environment and the bending resistance. On the other hand, in the case of the organic EL element samples 13 to 16, occurrence of remarkable dark spots was observed in a high temperature and high humidity environment and bending resistance.

  This application is based on Japanese Patent Application No. 2012-273806 filed on Dec. 14, 2012 and Japanese Patent Application No. 2013-023840 filed on February 8, 2013, the disclosure content of which is incorporated herein by reference. , Referenced and incorporated as a whole.

1, 10 gas barrier film,
2 base materials,
3 first layer,
4 transparent electrodes,
5 Organic EL elements,
6 adhesive layer,
7 Opposite film,
9 Organic EL panels,
31 manufacturing equipment,
32 delivery rollers,
33, 34, 35, 36 transport rollers,
39, 40 deposition rollers,
41 gas supply pipe,
42 Power supply for plasma generation,
43, 44 Magnetic field generator,
45 winding rollers,
101 Plasma CVD equipment,
102 vacuum chamber,
103 cathode electrode,
105 susceptors,
106 heat medium circulation system,
107 evacuation system,
108 gas introduction system,
109 high frequency power supply,
110 substrates,
160 heating and cooling system.

Claims (10)

A substrate, a first layer, a second layer, and a third layer in this order,
The first layer is a chemical vapor deposition layer containing at least one of at least one oxide, nitride, oxynitride or oxycarbide selected from the group consisting of silicon, aluminum and titanium,
The second layer is an atomic layer deposition layer containing an inorganic oxide,
The third layer, Ri silicon compound heating layer der,
The silicon compound is Ru polysilazane der, gas-barrier film. The gas barrier film according to claim 1, wherein the film thickness of the third layer is three or more times the film thickness of the second layer. A substrate, a first layer, a second layer, and a third layer in this order,
The first layer is a chemical vapor deposition layer containing at least one of at least one oxide, nitride, oxynitride or oxycarbide selected from the group consisting of silicon, aluminum and titanium,
The second layer is an atomic layer deposition layer containing an inorganic oxide,
The third layer is a silicon compound heat treatment layer,
A gas barrier film, wherein the film thickness of the third layer is at least three times the film thickness of the second layer.   The gas barrier film according to any one of claims 1 to 3, having a curable resin layer formed by curing a curable resin on the substrate.   The gas barrier film according to any one of claims 1 to 4, wherein the film thickness of the first layer is less than 30 times the film thickness of the second layer.   The gas barrier film according to any one of claims 1 to 5, wherein the second layer is a heat treatment layer.   The electronic device using the gas-barrier film of any one of Claims 1-6. Forming a first layer comprising at least one selected from the group consisting of an oxide comprising at least one of silicon, aluminum and titanium, a nitride, an oxynitride and an oxycarbide by chemical vapor deposition;
Forming a second layer containing an inorganic oxide by atomic layer deposition;
Applying a solution containing a silicon compound, and modifying the resulting coating to form a third layer obtained.
It said Ri reforming process is heat treatment der,
The silicon compound is Ru polysilazane der method for producing a gas barrier film. The manufacturing method of the gas barrier film of Claim 8 whose film thickness of the said 3rd layer is 3 times or more of the film thickness of the said 2nd layer. Forming a first layer comprising at least one selected from the group consisting of an oxide comprising at least one of silicon, aluminum and titanium, a nitride, an oxynitride and an oxycarbide by chemical vapor deposition;
Forming a second layer containing an inorganic oxide by atomic layer deposition;
Applying a solution containing a silicon compound, and modifying the resulting coating to form a third layer obtained.
It said Ri reforming process is heat treatment der,
Wherein the thickness of the third layer is Ru der least three times the thickness of the second layer, the manufacturing method of the gas barrier film.