JPWO2015178069A6 - Gas barrier film - Google Patents

Abstract

The present invention provides a gas barrier film that is excellent in durability in a high-temperature and high-humidity environment and excellent in blue light transmittance around a wavelength of 450 nm.
The gas barrier film of the present invention has (A) a resin substrate, (B) a first gas barrier layer containing an inorganic compound, and (C) a coating film obtained by applying and drying a coating liquid containing polysilazane. A region formed by application and satisfying the composition range represented by SiOwNx (where 0.2 <w ≦ 0.55, 0.66 <x ≦ 0.75) and having a thickness of 50 to 1000 nm And (D) a layer containing a metal oxide whose oxidation-reduction potential is lower than that of silicon as a main component and having a refractive index of light having a wavelength of 450 nm of 2.0 or more in this order.

Description

  The present invention relates to a gas barrier film.

  Conventionally, a gas barrier film formed by laminating a plurality of layers including thin films of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide on the surface of a plastic substrate or film is used to block various gases such as water vapor and oxygen. For example, it is widely used for packaging of articles that require the use of, for example, packaging for preventing deterioration of foods, industrial products, pharmaceuticals, and the like.

  In addition to packaging applications, gas barrier films are required to be developed into flexible electronic devices such as flexible solar cell elements, organic electroluminescence (EL) elements, and liquid crystal display elements, and many studies have been made. However, these flexible electronic devices are required to have an extremely high gas barrier property at the glass substrate level. In particular, there is a demand for an organic EL device in which the generation of dark spots is suppressed even when stored for a long time in a high temperature and high humidity environment such as 85 ° C. and 85% RH. Further, in the bottom emission type organic EL element, from the viewpoint of improving the light emission efficiency, a characteristic of transmitting more blue light particularly in the vicinity of a wavelength of 450 nm is required.

  Here, Patent Document 1 discloses a molded body having a layer obtained by implanting hydrocarbon compound ions into a layer containing a polysilazane compound. Patent Document 2 discloses a laminate including a base material and a silicon-containing film having a high nitrogen concentration region formed on the base material.

International Publication No. 2011/122547 (corresponding to US2014 / 0374665A1) International Publication No. 2011/007543 (corresponding to US2012 / 0107607A1)

  However, the molded article or laminate described in Patent Documents 1 and 2 have a high gas barrier property that suppresses the occurrence of dark spots in organic EL elements in a high temperature and high humidity environment such as 85 ° C. and 85% RH. There was no problem. Further, the molded body or laminate described in Patent Documents 1 and 2 have a low transmittance of blue light in the vicinity of a wavelength of 450 nm, and the light emission efficiency of blue light of an electronic device using the molded body or the laminate is low. There was a problem.

  Accordingly, an object of the present invention is to provide a gas barrier film that is excellent in durability in a high-temperature and high-humidity environment and excellent in blue light transmittance around a wavelength of 450 nm.

  The present inventor has intensively studied to solve the above problems. As a result, energy is applied to the coating film obtained by applying and drying the coating liquid containing (B) the first gas barrier layer containing the inorganic compound and (C) the polysilazane on (A) the resin base material. A second gas barrier layer formed and having a region having a specific composition and thickness, and (D) a metal oxide having a lower redox potential than silicon as a main component, and having a refractive index of light having a wavelength of 450 nm It has been found that the above-mentioned problems can be solved by a gas barrier film containing layers of 2.0 or more in this order. Based on the above findings, the present invention has been completed.

That is, the present invention applies energy to a coating film obtained by applying and drying (A) a resin base material, (B) a first gas barrier layer containing an inorganic compound, and (C) a polysilazane. And satisfies the composition range represented by SiO _w N _x (where 0.2 <w ≦ 0.55, 0.66 <x ≦ 0.75) and has a thickness of 50 to 1000 nm. A second gas barrier layer having a region, and (D) a layer containing, as a main component, an oxide of a metal having a lower oxidation-reduction potential than silicon and having a refractive index of light having a wavelength of 450 nm of 2.0 or more in this order. A gas barrier film.

It is a schematic diagram which shows an example of the film-forming apparatus which can be utilized suitably in order to manufacture the 1st gas barrier layer concerning this invention. In FIG. 1, S is a film formation space; 1a is a base material; 1b and 1c are base materials on which a film is formed; 10 is a delivery roll; 11, 12, 13, and 14 are transport rolls; 1 is a film forming roll; 16 is a second film forming roll; 17 is a winding roll; 18 is a gas supply pipe; 19 is a power source for generating plasma; 20 and 21 are magnetic field generators; and 30 is a vacuum chamber 40 represents a vacuum pump; 41 represents a control unit. It is a schematic diagram which shows the other example of the film-forming apparatus which can be utilized suitably in order to manufacture the 1st gas barrier layer based on this invention. In FIG. 2, S and S ′ are film forming spaces; 1 a is a base material; 1 b, 1 c, 1 d and 1 e are base materials on which a film is formed; 10 is a feeding roll; 11, 12, 12 ′ and 13. , 13 ′, 14 are transport rolls; 15 is a first film forming roll; 16 is a second film forming roll; 15 ′ is a third film forming roll; 16 ′ is a fourth film forming roll; 18, 18 'are gas supply pipes; 19, 19' is a power source for generating plasma; 20, 20 ', 21, 21' is a magnetic field generator; 30 is a vacuum chamber; 40, 40 'Indicates a vacuum pump; 41 indicates a control unit.

The present invention is formed by applying energy to (A) a resin substrate, (B) a first gas barrier layer containing an inorganic compound, and (C) a coating liquid obtained by applying and drying a polysilazane coating liquid. A region satisfying a composition range represented by SiO _w N _x (where 0.2 <w ≦ 0.55, 0.66 <x ≦ 0.75) and having a thickness of 50 to 1000 nm. A second gas barrier layer having, and (D) a layer containing a metal oxide having a lower redox potential than silicon as a main component and having a refractive index of light having a wavelength of 450 nm of 2.0 or more in this order. It is a gas barrier film. The gas barrier film of the present invention having such a configuration is excellent in durability in a high-temperature and high-humidity environment, and excellent in blue light transmission around a wavelength of 450 nm.

  The details of the reason why the above-described effects can be obtained by the gas barrier film of the present invention are not clear, but the following mechanism is conceivable. The following mechanism is based on speculation, and the present invention is not limited to the following mechanism.

That is, the second gas barrier layer according to the present invention exhibits gas barrier properties by having a region satisfying the composition range represented by the SiO _w N _x (hereinafter also simply referred to as region (c)). Unlike the case where it is formed by a vapor phase film forming method, by applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane, particles such as It is possible to form a gas barrier layer with almost no foreign matter and very few defects. However, this region (c) is not completely stable against oxidation and may be gradually oxidized in a high-temperature and high-humidity environment to lower the gas barrier property. There is water vapor that leaks in a spot manner from the resin base material side, and the second gas barrier layer is spot-oxidized by this water vapor to form a portion having a lowered gas barrier property. For example, when an organic EL element is formed on a gas barrier film, it is considered that water vapor permeates from the portion where the gas barrier property is lowered to become a dark spot.

  (D) a layer containing a metal oxide having a lower oxidation-reduction potential than silicon as a main component according to the present invention and having a refractive index of light having a wavelength of 450 nm of 2.0 or more (hereinafter simply referred to as “(D) layer”) Gas barrier property is not so high, and it is considered that there is no gas barrier property that contributes to the reduction of dark spots of the organic EL element. However, the layer (D) contains a metal oxide having a low oxidation-reduction potential as a main component, and is oxidized prior to the second gas barrier layer having the region (c) in a high temperature and high humidity environment. become. Therefore, it is considered that the effect of suppressing the oxidation of the surface of the second gas barrier layer in a high temperature and high humidity environment is exhibited, and the spot-like gas barrier property is hardly reduced. Therefore, the gas barrier film of the present invention is excellent in durability in a high temperature and high humidity environment.

  Further, the (D) layer according to the present invention has a refractive index of light having a wavelength of 450 nm of 2.0 or more. The gas barrier film of the present invention comprising the (D) layer having such a refractive index is excellent in light transmittance (light extraction property) in the vicinity of a wavelength of 450 nm, and an electronic device using the gas barrier film emits blue light. It is excellent in luminous efficiency.

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

  In the present specification, unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

[(A) Resin base material]
Specifically, as the resin base material (A) according to the present invention, polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, 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 copolymer, fluorene Examples include substrates containing thermoplastic resins such as ring-modified polycarbonate resins, alicyclic modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds. These resin substrates can be used alone or in combination of two or more.

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

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

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

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

  The resin base material preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is preferably 0.01 nm or more for practical use. If necessary, the surface of the substrate may be polished to improve smoothness.

  Moreover, the unstretched film may be sufficient as the resin base material quoted above, and a stretched film may be sufficient as it. The resin substrate can be produced by a conventionally known general method. Regarding the manufacturing method of these base materials, the items described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 (corresponding to US2014 / 0106151A1) can be appropriately employed.

  The resin base material may have a hard coat layer. Examples of the material contained in the hard coat layer include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold. Such curable resins can be used singly or in combination of two or more.

  The active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray. A functional resin layer, that is, a hard coat layer is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable. A commercially available resin base material on which a hard coat layer is formed in advance may be used. Specific examples thereof include trade name KB film (trademark) 125G1SBF (manufactured by Kimoto Co., Ltd.).

  The surface of the resin substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatments may be combined as necessary. May go.

  The resin substrate may be a single layer or a laminated structure of two or more layers. When the resin base material has a laminated structure of two or more layers, the resin base materials may be the same type or different types.

  The thickness of the resin substrate according to the present invention (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 200 μm, and more preferably 20 to 150 μm.

[(B) First gas barrier layer]
The gas barrier film of the present invention has (B) a first gas barrier layer containing an inorganic compound on (A) a resin substrate. By providing the first gas barrier layer, water vapor entering from the resin substrate side can be blocked, and a gas barrier film with improved durability in a high temperature and high humidity environment is obtained.

  The first gas barrier layer according to the present invention contains an inorganic compound. Although it does not specifically limit as an inorganic compound contained in a 1st gas barrier layer, For example, the metal oxide, metal nitride, metal carbide, metal oxynitride, or metal oxycarbide whose oxidation-reduction potential is higher than silicon or silicon Is mentioned. Among these, oxides, nitrides, carbides, oxynitrides or oxycarbides containing one or more metals selected from Si, In, Sn, Zn, Cu, and Ce are preferably used in terms of gas barrier performance. Can do. Specific examples of suitable inorganic compounds include silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, and silicon oxycarbide. You may contain another element as a secondary component.

  The content of the inorganic compound contained in the first gas barrier layer is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more with respect to the total mass of the first gas barrier layer. The content is more preferably 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 100% by mass (that is, the first gas barrier layer is made of an inorganic compound).

  Examples of the method for forming the first gas barrier layer include a method in which energy is applied to a coating film obtained by applying and drying a coating liquid containing polysilazane and a gas phase film forming method. In particular, it is preferably formed by a vapor deposition method that is not easily oxidized by humidity and can stably exhibit gas barrier properties even in a high-temperature and high-humidity environment.

  In a method for applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane, which is one of the methods for forming the first gas barrier layer, formation conditions other than the conditions for applying energy ( The type of polysilazane used, the solvent used in the coating solution, the concentration of the coating solution, the type of catalyst, etc.) will be described in detail in the section of (C) the second gas barrier layer, which will be described later.

  As a method for applying energy, a conversion reaction by a plasma treatment capable of a conversion reaction or an ultraviolet irradiation treatment is preferable, and vacuum ultraviolet irradiation is more preferable.

A gas barrier layer formed by applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane so as to come into contact with a resin base material having no gas barrier property is transmitted from the resin base material side. It becomes a composition in which the resin base material side in the thickness direction is oxidized by the influence of water vapor and oxygen coming, that is, a composition such as SiO _{2.0 to 2.4} . On the other hand, the surface side of the layer to which energy is applied has a SiON composition in which N is about 0.6 or less and O is about 0.6 or more with respect to Si, and this region has a high gas barrier property. It has better oxidation resistance under high temperature and high humidity conditions than the region (c). The substrate-side composition and the surface-side composition have a clear interface, and the region (c) according to the present invention is not formed.

  Examples of the vapor deposition method that is a preferable method for forming the first gas barrier layer include a physical vapor deposition method (PVD method) and a chemical vapor deposition method (CVD method).

  Hereinafter, the vapor deposition method will be described.

<Gas deposition method>
The physical vapor deposition method (PVD method) is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. Examples thereof include a DC sputtering method, an RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method, a vacuum deposition method, and an ion plating method.

  The chemical vapor deposition (CVD) method is a method of depositing a film by a chemical reaction on the surface of the substrate or in the vapor phase by supplying a raw material gas containing a target thin film component onto the substrate. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. Although not particularly limited, it is preferable to apply a plasma CVD method such as a vacuum plasma CVD method or an atmospheric pressure plasma CVD method from the viewpoint of film forming speed and processing area.

  For example, if a silicon compound is used as a raw material compound and oxygen is used as the decomposition gas, silicon oxide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  In the following description, a case where the first gas barrier layer is manufactured by using a counter roll type roll-to-roll film forming apparatus that forms a thin film by a plasma CVD method will be described as an example of the film forming apparatus. To do.

  1 and 2 are schematic configuration diagrams illustrating an example of a film forming apparatus. The film forming apparatus 101 illustrated in FIG. 2 has a basic structure in which two film forming apparatuses 100 illustrated in FIG. 1 are joined in tandem. Here, the case where the first gas barrier layer is formed will be described using the film forming apparatus illustrated in FIG. 2 as an example. However, the description relating to the film forming apparatus illustrated in FIG. 2 relates to the film forming apparatus illustrated in FIG. The explanation is also taken into consideration as appropriate.

  As shown in FIG. 2, the film forming apparatus 101 includes a delivery roll 10, transport rolls 11 to 14, first, second, third, and fourth film forming rolls 15, 16, 15 ′, 16 ′, Take-off roll 17, gas supply pipes 18, 18 ', plasma generation power sources 19, 19', magnetic field generators 20, 21, 20 ', 21', vacuum chamber 30, vacuum pumps 40, 40 ' And a control unit 41.

  The delivery roll 10, the transport rolls 11 to 14, the first, second, third and fourth film forming rolls 15, 16, 15 ′, 16 ′ and the take-up roll 17 are accommodated in the vacuum chamber 30.

  The feed roll 10 feeds the base material 1 a installed in a state of being wound in advance toward the transport roll 11. The delivery roll 10 is a cylindrical roll extending in a direction perpendicular to the paper surface, and is wound around the delivery roll 10 by rotating counterclockwise (see an arrow in FIG. 2) by a drive motor (not shown). The base material 1a is sent out toward the transport roll 11.

  The transport rolls 11 to 14 are cylindrical rolls configured to be rotatable around a rotation axis substantially parallel to the delivery roll 10. The transport roll 11 is a roll for transporting the base material 1 a from the feed roll 10 to the first film forming roll 15 while applying an appropriate tension to the base material 1 a. The conveyance rolls 12 and 13 convey the base material 1b from the first film formation roll 15 to the second film formation roll 16 while applying an appropriate tension to the base material 1b formed by the first film formation roll 15. It is a roll for. The transport rolls 12 ′ and 13 ′ apply the appropriate tension to the base material 1e formed by the third film forming roll 15 ′, while the base material 1e is transferred from the third film forming roll 15 ′ to the fourth film forming roll. It is a roll for conveying to 16 '. Furthermore, the conveyance roll 14 conveys the base material 1c from the fourth film formation roll 16 ′ to the take-up roll 17 while applying an appropriate tension to the base material 1c formed by the fourth film formation roll 16 ′. It is a roll for.

  The first film-forming roll 15 and the second film-forming roll 16 are a pair of film-forming rolls that have a rotation axis substantially parallel to the delivery roll 10 and are opposed to each other by a predetermined distance. Similarly, the third film-forming roll 15 ′ and the fourth film-forming roll 16 ′ have a rotation axis that is substantially parallel to the delivery roll 10, and are formed by a pair of film-forming rolls that are opposed to each other by a predetermined distance. is there. The second film forming roll 16 forms the base material 1b and conveys the base material 1d to the third film forming roll 15 'while applying an appropriate tension to the formed base material 1d. The fourth film forming roll 16 ′ forms the base material 1 e and conveys the base material 1 c to the transport roll 14 while applying an appropriate tension to the formed base material 1 c.

  In the example shown in FIG. 2, the separation distance between the first film-forming roll 15 and the second film-forming roll 16 is a distance connecting the point A and the point B, and the third film-forming roll 15 ′ and the fourth film-forming roll. The separation distance from the roll 16 ′ is a distance connecting the point A ′ and the point B ′. The first to fourth film forming rolls 15, 16, 15 ′, 16 ′ are discharge electrodes formed of a conductive material, and the first film forming roll 15, the second film forming roll 16, and the third film forming roll. The 15 ′ and the fourth film forming roll 16 ′ are insulated from each other. The materials and configurations of the first to fourth film forming rolls 15, 16, 15 ′, 16 ′ can be appropriately selected so that a desired function can be achieved as an electrode.

  Further, the first to fourth film forming rolls 15, 16, 15 ', 16' may be independently temperature controlled. The temperature of the first to fourth film forming rolls 15, 16, 15 ′, 16 ′ is not particularly limited, but is, for example, −30 to 100 ° C., but exceeds the glass transition temperature of the base material 1a. If the temperature is set too high, the substrate may be deformed by heat.

  Magnetic field generators 20, 21, 20 'and 21' are installed in the first to fourth film forming rolls 15, 16, 15 'and 16', respectively. The first film forming roll 15 and the second film forming roll 16 are supplied with a plasma generating power source 19, and the third film forming roll 15 ′ and the fourth film forming roll 16 ′ are supplied with a plasma generating power supply 19 ′. A generating high frequency voltage is applied. Thereby, the film forming section S between the first film forming roll 15 and the second film forming roll 16 or the film forming section S ′ between the third film forming roll 15 ′ and the fourth film forming roll 16 ′. An electric field is formed in the film, and discharge plasma of the film forming gas supplied from the gas supply pipe 18 or 18 'is generated. The voltage applied by the plasma generating power supply 19 and the voltage applied by the plasma generating power supply 19 ′ may be the same or different. The power source frequency of the plasma generating power source 19 or 19 ′ can be arbitrarily set. However, the apparatus of this configuration is, for example, 60 to 100 kHz, and the applied power is, for example, 1 to 1 m with respect to the effective film forming width 1 m. 10 kW.

  The take-up roll 17 has a rotation axis substantially parallel to the feed roll 10 and takes up the base material 1c and accommodates it in a roll shape. The take-up roll 17 takes up the substrate 1c by rotating counterclockwise by a drive motor (not shown) (see the arrow in FIG. 2).

  The substrate 1a fed from the feed roll 10 is wound around the transport rolls 11 to 14 and the first to fourth film forming rolls 15, 16, 15 ′ and 16 ′ between the feed roll 10 and the take-up roll 17. It is conveyed by rotation of each of these rolls while maintaining an appropriate tension by being applied. In addition, the conveyance direction of the base materials 1a, 1b, 1c, 1d, and 1e (hereinafter, the base materials 1a, 1b, 1c, 1d, and 1e are also collectively referred to as “base materials 1a to 1e”) is indicated by arrows. . The conveyance speed (line speed) of the base materials 1a to 1e (for example, the conveyance speed at the point C or the point C ′ in FIG. The conveyance speed is adjusted by controlling the rotation speeds of the drive motors of the delivery roll 10 and the take-up roll 17 by the control unit 41. When the conveyance speed is decreased, the thickness of the formed region is increased.

  When this film forming apparatus is used, the transport direction of the base materials 1a to 1e is set to a direction (hereinafter referred to as a reverse direction) opposite to a direction indicated by an arrow in FIG. 2 (hereinafter referred to as a forward direction). A gas barrier film forming step can also be performed. Specifically, the control unit 41 rotates the rotation direction of the drive motors of the feed roll 10 and the take-up roll 17 in the direction opposite to that described above in a state where the substrate 1c is taken up by the take-up roll 17. Control to do. When controlled in this way, the base material 1c sent out from the take-up roll 17 is transported between the feed roll 10 and the take-up roll 17, and the transport rolls 11 to 14, the first to fourth film forming rolls 15 and 16, While being wound around 15 'and 16', appropriate tension is maintained, and the rolls are conveyed in the reverse direction by rotation of these rolls.

  When (B) the first gas barrier layer is formed using the film forming apparatus 101, the substrate 1a is conveyed in the forward direction and the reverse direction, and the film forming unit S or the film forming unit S ′ is reciprocated, (B) The first gas barrier layer formation (film formation) step can be repeated a plurality of times.

  The gas supply pipes 18 and 18 ′ supply a film forming gas such as a plasma CVD source gas into the vacuum chamber 30. The gas supply pipe 18 has a tubular shape extending in the same direction as the rotation axes of the first film forming roll 15 and the second film forming roll 16 above the film forming section S, and is provided at a plurality of locations. A film forming gas is supplied to the film forming part S from the opened opening. Similarly, the gas supply pipe 18 ′ has a tubular shape extending above the film forming section S ′ in the same direction as the rotation axes of the third film forming roll 15 ′ and the fourth film forming roll 16 ′. The film forming gas is supplied to the film forming part S ′ from the openings provided at a plurality of locations. The film forming gas supplied from the gas supply pipe 18 and the film forming gas supplied from the gas supply pipe 18 'may be the same or different. Further, the supply gas pressure supplied from these gas supply pipes may be the same or different.

  A silicon compound can be used as the source gas. Examples of the silicon compound include hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, Examples include propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyldisilazane, and the like. In addition to this, the compounds described in paragraph “0075” of JP2008-056967 A can also be used. Among these silicon compounds, it is preferable to use HMDSO in the formation of the first gas barrier layer from the viewpoint of easy handling of the compound and high gas barrier properties of the obtained gas barrier film. Two or more of these silicon compounds may be used in combination. The source gas may contain monosilane in addition to the silicon compound.

  As the film forming gas, a reactive gas may be used in addition to the source gas. As the reaction gas, a gas that reacts with the raw material gas to become a silicon compound such as oxide or nitride is selected. As a reactive gas for forming an oxide as a thin film, for example, oxygen gas or ozone gas can be used. In addition, you may use these reaction gas in combination of 2 or more type.

  As the film forming gas, a carrier gas may be further used to supply the source gas into the vacuum chamber 30. Further, as a film forming gas, a discharge gas may be further used to generate plasma. As the carrier gas and the discharge gas, for example, a rare gas such as argon, hydrogen, or nitrogen is used.

  The magnetic field generators 20 and 21 are members that form a magnetic field in the film forming unit S between the first film forming roll 15 and the second film forming roll 16, and the magnetic field generating apparatuses 20 ′ and 21 ′ are similarly configured. It is a member that forms a magnetic field in the film forming section S ′ between the third film forming roll 15 ′ and the fourth film forming roll 16 ′. These magnetic field generators 20, 20 ', 21, 21' do not follow the rotation of the first to fourth film forming rolls 15, 16, 15 ', 16', and are stored at predetermined positions.

  The vacuum chamber 30 maintains the decompressed state by sealing the delivery roll 10, the transport rolls 11 to 14, the first to fourth film forming rolls 15, 16, 15 ′, 16 ′, and the take-up roll 17. The pressure (degree of vacuum) in the vacuum chamber 30 can be adjusted as appropriate according to the type of source gas. The pressure of the film forming part S or S ′ is preferably 0.1 to 50 Pa.

  The vacuum pumps 40 and 40 ′ are communicably connected to the control unit 41 and appropriately adjust the pressure in the vacuum chamber 30 in accordance with a command from the control unit 41.

  The control unit 41 controls each component of the film forming apparatus 101. The control unit 41 is connected to the drive motors of the feed roll 10 and the take-up roll 17 and adjusts the conveyance speed of the substrate 1a by controlling the rotation speed of these drive motors. Moreover, the conveyance direction of the base material 1a is changed by controlling the rotation direction of the drive motor. The control unit 41 is connected to a film-forming gas supply mechanism (not shown) so as to be communicable, and controls the supply amount of each component gas of the film-forming gas. The control unit 41 is communicably connected to the plasma generation power sources 19 and 19 ′ and controls the output voltage and output frequency of the plasma generation power source 19. Further, the control unit 41 is communicably connected to the vacuum pumps 40 and 40 ′, and controls the vacuum pump 40 so as to maintain the inside of the vacuum chamber 30 in a predetermined reduced pressure atmosphere.

  The control unit 41 includes a CPU (Central Processing Unit), an HDD (Hard Disk Drive), a RAM (Random Access Memory), and a ROM (Read Only Memory). The HDD stores a software program describing a procedure for controlling each component of the film forming apparatus 101 and realizing a method for producing a gas barrier film. When the film forming apparatus 101 is turned on, the software program is loaded into the RAM and sequentially executed by the CPU. The ROM stores various data and parameters used when the CPU executes the software program.

  The first gas barrier layer may be a single layer or a laminated structure of two or more layers. When the first gas barrier layer has a laminated structure of two or more layers, the first gas barrier layers may have the same composition or different compositions.

  The thickness of the first gas barrier layer (the total thickness in the case of a laminated structure of two or more layers) is not particularly limited, but is preferably 5 to 1000 nm, and more preferably 20 to 500 nm. If it is this range, the advantage of coexistence of productivity and gas barrier property will be acquired. The thickness of the first gas barrier layer can be measured by TEM observation.

[(C) Second gas barrier layer]
The (C) second gas barrier layer according to the present invention is formed by applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane, and SiO _w N _x (where 0.2 < w ≦ 0.55, 0.66 <x ≦ 0.75), and a region (region (c)) having a thickness of 50 to 1000 nm is satisfied. By applying energy, the second gas barrier layer exhibits gas barrier properties. Further, unlike the case where the film is formed by the vapor deposition method, foreign substances such as particles are not mixed at the time of film formation, so that the gas barrier layer has very few defects.

  The region (c) has a gas barrier property, but also functions as a so-called desiccant that captures water vapor by reacting with water that has entered slowly.

  The thickness of the region (c) is 50 to 1000 nm. When the thickness of the region (c) is less than 50 nm, since the total amount of the compound that reacts with water vapor as a desiccant is reduced, the amount of water vapor that can be captured is limited, and the desiccant function is lost within the service life required for the device. There is a possibility that the gas barrier property is lowered. On the other hand, if the thickness exceeds 1000 nm, for example, when the region (c) is formed by the modification by application of energy, the modification may be insufficient and the gas barrier property may be lowered, and the cost may be increased. In addition, the occurrence of cracks in the second gas barrier layer is a concern, and productivity is also reduced.

  The thickness of the region (c) is preferably 100 to 300 nm. Within this range, the effect of maintaining good gas barrier properties and the effect of reducing costs are further improved during the service life required for the device.

  If the region (c) is present in the second gas barrier layer formed by applying energy to the coating film obtained by applying and drying the coating liquid containing polysilazane, it is regarded as one continuous region. The form which exists may be sufficient as the form which exists as two or more several area | regions. When there are two or more regions, the sum of the thicknesses of all the regions (total thickness) only needs to be in the above range.

  A person skilled in the art can adjust the composition ratio of silicon, oxygen, and nitrogen in the region (c) and the thickness of the region (c) by any method. For example, the thickness of the coating solution containing polysilazane, the degree of drying after coating, and the amount of energy to be applied (for example, when irradiating vacuum ultraviolet rays to apply energy, the illuminance, plasma density, irradiation time, etc. are adjusted) The atmosphere (particularly the oxygen concentration) at the time of energy application may be adjusted. In the case of the coating film forming method, if the amount of energy to be applied is reduced, oxygen can be reduced in the composition ratio of the region. Further, when the thickness of the coating liquid containing polysilazane is increased, the thickness of the region (c) is increased, so that those skilled in the art can adjust the thickness of the coating film in accordance with the target region thickness. Further, for example, the second gas barrier layer including the region (c) having the above composition and thickness may be formed by alternately performing coating film formation and energy application a plurality of times.

  The second gas barrier layer according to the present invention including the region (c) is formed by applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane. In the method for forming the first gas barrier layer by applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane, which is one of the methods for forming the first gas barrier layer, the formation conditions (of the polysilazane used) The type, the solvent used in the coating solution, the concentration of the coating solution, the type of catalyst, the energy application conditions, etc.) are the same as described below. However, for the above reason, the region (c) according to the present invention is not formed in the first gas barrier layer, even if the first gas barrier layer and the second gas barrier layer are formed under the same conditions. However, the first gas barrier layer and the second gas barrier layer are clearly different layers.

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

  Specifically, the polysilazane preferably has the following structure.

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (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 group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. Moreover, as an aryl group, a C6-C30 aryl group is mentioned. More specifically, non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc. Can be mentioned. Examples of the (trialkoxysilyl) alkyl group include an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. 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. For example, an alkyl group, a halogen atom, a hydroxyl group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxyl group (—COOH), a nitro group (—NO ₂ ), and the like. In addition, the substituent which exists depending on the case does not become 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 with an alkyl group. Of these, R ₁ , R ₂ and R ₃ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.

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

  In the compound having the structure represented by the general formula (I), one of preferable embodiments is R ₁, R₂And R₃Is perhydropolysilazane, all of which are hydrogen atoms.

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

In the general formula (II), R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, 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, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

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

Among the polysilazanes of the above general formula (II), 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 '} each represents a hydrogen atom, R _2' , R _{4 '} each represents a methyl group, and R _5' represents a vinyl group; R _{1 '} , R _3' , R ₄ A compound in which _' and R _6' each represent a hydrogen atom and R _{2 '} and R _5' each represents a methyl group is preferred.

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

In the 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, aryl group, vinyl group or (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, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

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

Of the 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. , R _{9 ″} represents a (triethoxysilyl) propyl group, and R _{7 ″} represents an alkyl group or a hydrogen atom.

  On the other hand, the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard. The ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. For this reason, these perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of 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 a solution in an organic solvent, and the commercially available product can be used as it is as the second gas barrier layer forming coating solution. Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. Is mentioned.

  Another example of the polysilazane that can be used in the present invention is not limited to the following. For example, a silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-238827) or glycidol is reacted. Glycidol-added polysilazane (Japanese Patent Laid-Open No. 6-122852) obtained by reaction, alcohol-added polysilazane obtained by reacting alcohol (Japanese Patent Laid-Open No. 6-240208), metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, 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.

  When polysilazane is used, the content of polysilazane in the second gas barrier layer before energy application can be 100% by mass when the total mass of the second gas barrier layer is 100% by mass. When the second gas barrier layer contains a material other than polysilazane, the content of polysilazane in the layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass or less. More preferably, it is 70 mass% or more and 95 mass% or less.

(Second gas barrier layer forming coating solution)
The solvent for preparing the second gas barrier layer forming coating solution is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups (for example, hydroxyl group, easily reacting with polysilazane). Alternatively, an organic solvent which does not contain an amine group and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable. Specifically, the solvent is an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc. Hydrogen solvents; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like. The solvent is selected according to purposes such as the solubility of polysilazane 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 polysilazane in the second gas barrier layer forming coating solution is not particularly limited, and varies depending on the film thickness of the layer and the pot life of the coating solution. %, More preferably 10 to 40% by mass.

  The second gas barrier layer forming coating solution preferably contains a catalyst in order to promote reforming. As the 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 ', N'-tetramethyl-1,3-diaminopropane, amine catalysts such as N, N, N', N'-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of 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% by mass, more preferably 0.5 to 7% by mass, based on the silicon compound. By setting the addition amount of the catalyst within this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, decrease in film density, increase in film defects, and the like.

  In the second gas barrier layer forming coating solution, the following additives may be used as necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

(Method of applying the second gas barrier layer forming coating solution)
As a method of applying the second gas barrier layer forming coating solution, a conventionally known appropriate wet coating method may be employed. 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, die coating method, gravure printing method and the like. It is done.

  The coating thickness can be appropriately set according to the preferred thickness and purpose. As an example, the thickness of the coating liquid (coating film) after drying (when forming a coating film a plurality of times, the thickness per one time) is preferably 40 nm or more and 1000 nm or less, more preferably 100 nm or more. 300 nm or less.

  After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable second 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 material to apply, it is preferable that it is 50-200 degreeC. For example, when a polyethylene terephthalate base material having a glass transition temperature (Tg) of 70 ° C. is used as the base material, the drying temperature is preferably set to 150 ° C. or lower in consideration of deformation of the base material due to heat. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.

  The coating film obtained by applying the second gas barrier layer-forming coating solution may include a step of removing moisture before application of energy or during application of energy. As a method for removing moisture, a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature. A preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −5 ° C. or lower (temperature 25 ° C./humidity 10%), and the time to be maintained is that of the second gas barrier layer. It is preferable to set appropriately depending on the film thickness. Under the condition that the film thickness of the second gas barrier layer is 1.0 μm or less, it is preferable that the dew point temperature is −5 ° C. or less and the maintained time is 1 minute or more. The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher and preferably −40 ° C. or higher. From the viewpoint of promoting the dehydration reaction of the second gas barrier layer converted to silanol by removing water before or during the reforming treatment.

<Application of energy>
Subsequently, energy is applied to the coating film formed as described above, and a conversion reaction of polysilazane to silicon oxide or silicon oxynitride is performed, so that the second gas barrier layer can exhibit gas barrier properties. Modification to inorganic thin film.

  The conversion reaction of polysilazane to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method. Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment. However, in the case of modification by heat treatment, 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 higher, so that it is difficult to adapt to a flexible substrate such as plastic. . For this reason, it is preferable to perform the heat treatment in combination with other reforming treatments.

  Therefore, as the modification treatment, from the viewpoint of adapting to a plastic substrate, a plasma treatment capable of a conversion reaction at a lower temperature or a conversion reaction by ultraviolet irradiation treatment is preferable. Hereinafter, plasma treatment and ultraviolet irradiation treatment, which are preferable modification treatment methods, will be described.

(Plasma treatment)
In the present invention, a known method can be used for the plasma treatment that can be used as the reforming treatment, and an atmospheric pressure plasma treatment or the like can be preferably used. The atmospheric pressure plasma CVD method, which performs plasma CVD processing near atmospheric pressure, does not need to be reduced in pressure and is more productive than the plasma CVD method under vacuum. The film speed is high, and further, under a high pressure condition under atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free process is very short, so that a very homogeneous film can be obtained.

  In the case of atmospheric pressure plasma treatment, as the discharge gas, nitrogen gas or a gas containing Group 18 atoms of the long-period periodic table, specifically helium, neon, argon, krypton, xenon, radon, or the like is used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

(UV irradiation treatment)
As one of the modification treatment methods, treatment by ultraviolet irradiation is preferable. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures It is.

  The substrate is heated by this ultraviolet irradiation, and O contributes to ceramicization (silica conversion). ₂And H₂O, the ultraviolet absorber, and the polysilazane itself are excited and activated, so that the polysilazane is excited to promote the conversion of the polysilazane into a ceramic, and the obtained second gas barrier layer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

  In the ultraviolet irradiation treatment, any commonly used ultraviolet ray generator can be used.

  The ultraviolet ray referred to in the present invention generally refers to an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, it is preferably 210 to 375 nm. Use ultraviolet light.

  In the irradiation with ultraviolet rays, it is preferable to set the irradiation intensity and the irradiation time in a range in which the substrate carrying the second gas barrier layer to be irradiated is not damaged.

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

  In general, when the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more, in the case of a plastic film or the like, the properties of the substrate are impaired, such as deformation of the substrate or deterioration of its strength. Become. However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generating means include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by M.D. Com Co., Ltd.), UV light laser, and the like, but are not particularly limited. In addition, when irradiating the generated ultraviolet light to the second gas barrier layer, from the viewpoint of achieving efficiency improvement and uniform irradiation, the ultraviolet light from the generation source is reflected by the reflector and then applied to the second gas barrier layer. It is preferable to apply.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, the laminated body having the second gas barrier layer on the surface can be processed in an ultraviolet baking furnace equipped with the ultraviolet ray generation source as described above. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. Moreover, when the laminated body which has a 2nd gas barrier layer on the surface is a elongate film form, it irradiates with an ultraviolet-ray continuously in the drying zone provided with the above ultraviolet-ray generation sources, conveying this. Can be made into ceramics. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate used and the second gas barrier layer.

(Vacuum ultraviolet irradiation treatment: excimer irradiation 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 irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together as mentioned above.

  The radiation source in the present invention is not limited as long as it generates light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator having a maximum emission at about 172 nm (for example, Xe excimer lamp), and has an emission line at about 185 nm. Low pressure mercury vapor lamps, and medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having maximum emission at about 222 nm.

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

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), and preferably 50 to 10,000 volume ppm (0.005 to 1 volume%). More preferably. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

In vacuum ultraviolet irradiation step, more that illuminance of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is preferable to be ^{1mW / cm 2 ~10W / cm 2} , a 30mW / cm ² ~200mW / cm 2 ^preferably, further preferably at ^{50mW / cm 2 ~160mW / cm 2} . If it is 1 mW / cm ² or more, the reforming efficiency is improved, and if it is 10 W / cm ² or less, ablation that can occur in the coating film and damage to the substrate can be reduced.

The amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the coating surface is preferably 100 mJ / cm ^{2 to} 50 J / cm ² , more preferably 200 mJ / cm ^{2 to 20} J / cm ² , and 500 mJ / cm 2. More preferably, it is ^{2 to} 10 J / cm ² . If it is 100 mJ / cm ² or more, modification is sufficient, and if it is 50 J / cm ² or less, generation of cracks due to excessive modification and thermal deformation of the substrate can be suppressed.

Further, the vacuum ultraviolet ray to be used may be generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.

  In addition, the composition distribution and thickness in the thickness direction of the region (c) according to the present invention can be obtained by measurement by a method using XPS (photoelectron spectroscopy) analysis as described below.

Since the etching rate of the region (c) according to the present invention varies depending on the composition, in the present invention, the thickness in the XPS analysis is obtained once based on the etching rate in terms of SiO ₂ , and the cross-section TEM of the same sample. Based on the image, the interface between each region of the region formed by stacking is specified to determine the thickness per region, and this is compared with the composition distribution in the thickness direction obtained from XPS analysis. Each region in the longitudinal composition distribution is specified, and each thickness obtained from the XPS analysis so that the thickness of each region obtained from the XPS analysis corresponding to each region matches the thickness of each region obtained from the cross-sectional TEM image. Correction in the thickness direction is performed by uniformly applying a coefficient to the thickness of the region.

  The XPS analysis in the present invention was performed under the following conditions, but even if the apparatus and measurement conditions are changed, any measurement method that conforms to the gist of the present invention can be applied without any problem.

  The measurement method according to the gist of the present invention is mainly resolution in the thickness direction, and the etching depth per measurement point (corresponding to the conditions of the following sputter ion and depth profile) is 1 to 15 nm. It is preferable that the thickness is 1 to 10 nm.

  << XPS analysis conditions >>
  ・ Equipment: ULVAC-PHI QUANTERASXM
  ・ X-ray source: Monochromatic Al-Kα
  Measurement area: Si2p, C1s, N1s, O1s
  ・ Sputtering ion: Ar (2 keV)
  Depth profile: repeats measurement after sputtering for a certain time. One measurement is SiO ₂Adjust the sputtering time so that the thickness is equivalent to approximately 2.8 nm.
  Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Data processing uses MultiPak manufactured by ULVAC-PHI.

  In this way, primary data of the profile of the composition distribution in the film thickness direction of the second gas barrier layer is obtained.

  Moreover, the cross section of each sample is image | photographed with TEM, and each film thickness of a laminated structure is calculated | required. The composition distribution profile in the film thickness direction obtained above is corrected using the actual film thickness data obtained from the TEM image to obtain the composition distribution in the film thickness direction of the region. Based on this, the thickness of the region (c) is obtained.

  As a method for obtaining the thickness per region from the TEM image, a gas barrier film may be prepared by observing a cross-section TEM according to a conventional method after producing a thin piece by the following FIB processing apparatus. In this way, the thickness of each region can be calculated. An example that can be used for FIB processing and TEM observation is shown below.

《FIB processing》
・ Apparatus: SII SMI2050
・ Processed ions: (Ga 30 kV)
Sample thickness: 100 nm to 200 nm
<< TEM observation >>
Apparatus: JEM2000FX (acceleration voltage: 200 kV) manufactured by JEOL Ltd.

  The second gas barrier layer may be a single layer or a laminated structure of two or more layers. When the second gas barrier layer has a laminated structure of two or more layers, the second gas barrier layers may have the same composition or different compositions.

  The thickness of the second gas barrier layer (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 1000 nm, and more preferably 50 to 600 nm. If it is this range, the balance of gas barrier property and durability becomes favorable and is preferable. The thickness of the second gas barrier layer can be measured by TEM observation.

[(D) Layer containing a metal oxide whose oxidation-reduction potential is lower than that of silicon as a main component and having a refractive index of light having a wavelength of 450 nm of 2.0 or more]
The (D) layer according to the present invention contains, as a main component, a metal oxide having a lower oxidation-reduction potential than silicon, and the refractive index of light having a wavelength of 450 nm is 2.0 or more. Such a layer (D) alone does not have, for example, a high gas barrier property sufficient to reduce the dark spots of the organic EL element, but in a high temperature and high humidity environment, the second gas barrier layer having the region (c). Will be oxidized first. Therefore, it is considered that the effect of suppressing the oxidation of the surface of the second gas barrier layer in a high temperature and high humidity environment is exhibited, and the spot-like gas barrier property is hardly reduced. Therefore, the gas barrier film of this invention provided with this (D) layer is excellent in durability in a high-temperature, high-humidity environment.

  Here, “comprising a metal oxide having a lower redox potential than silicon as a main component” means that the content of the metal oxide having a lower redox potential than silicon is the total mass of the layer (D). It means that it is 50% by mass or more. The content is more preferably 80% by mass or more, further preferably 95% by mass or more, particularly preferably 98% by mass or more, and 100% by mass (that is, the (D) layer. Is most preferably made of a metal oxide having a lower redox potential than silicon).

  Specific examples of the metal having a lower redox potential than silicon include niobium, tantalum, zirconium, titanium, hafnium, magnesium, yttrium, and aluminum. These metals may be used alone or in combination of two or more.

  Among these, at least one metal selected from the group consisting of niobium, tantalum, zirconium, and titanium is preferable. That is, the (D) layer preferably contains, as a main component, an oxide of at least one metal selected from the group consisting of niobium, tantalum, zirconium, and titanium.

  The standard oxidation-reduction potentials of major metals and the refractive indexes of light of these metal oxides having a wavelength of 450 nm are shown in the following table. The refractive index of light having a wavelength of 450 nm of the following metal oxide can be measured using, for example, a spectroscopic ellipsometer.

  The oxide of at least one metal selected from the group consisting of niobium, tantalum, zirconium, and titanium alone has a refractive index of light having a wavelength of 450 nm exceeding 2.0. Since it becomes easy to control the refractive index of light to 2.0 or more, it is preferable. Furthermore, for example, from the viewpoint that generation of dark spots in the organic EL element can be further suppressed, the layer (D) preferably contains an oxide of at least one of niobium and tantalum as a main component.

  As a preferred embodiment, the layer (D) is a metal oxide having a redox potential lower than that of silicon and containing a metal oxide having a refractive index of light having a wavelength of 450 nm of 2.0 or more as a main component. For example, other compounds may be included. Examples of other compounds include hafnium, magnesium, yttrium, and aluminum. These other compounds can be used alone or in combination of two or more.

  The (D) layer has a refractive index of light having a wavelength of 450 nm of 2.0 or more. The gas barrier film of the present invention including the (D) layer having such a refractive index is excellent in blue light transmittance (light extraction property) near a wavelength of 450 nm, and an electronic device using the gas barrier film is blue light. The light emission efficiency is excellent. When the refractive index of light having a wavelength of 450 nm is less than 2.0, the light extraction property is lowered. The refractive index of light having a wavelength of 450 nm of the layer (D) is preferably 2.05 or more, more preferably 2.10 or more. The upper limit of the refractive index is not particularly limited, but is preferably 3.00 or less, and more preferably 2.90 or less.

  (D) Specifically, the refractive index of light having a wavelength of 450 nm can be measured using a general spectroscopic ellipsometer, a non-contact film thickness refractive index measurement system FilmTek series manufactured by Scientific Computing International, or the like. it can. In addition, the refractive index of light having a wavelength of 450 nm of the layer (D) is, for example, from a metal oxide (for example, niobium, tantalum, zirconium, and titanium) having a refractive index of light having a wavelength of 450 nm as a constituent material. An oxide of at least one metal selected from the group consisting of: a target having a compound whose main component is a compound having a lower oxidation state than that of complete oxidation (oxygen-deficient) as a main component. It can be controlled by adjusting the amount of oxygen introduced and changing the degree of oxidation.

  The method for forming the (D) layer is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, and ion plating, plasma CVD (chemical vapor deposition), and ALD (Atomic Layer Deposition). ) Or the like. In particular, the film formation is possible without damaging the second gas barrier layer provided in the lower part, and it is preferable to form the film by sputtering because it has high productivity.

  Film formation by sputtering uses conventional techniques such as DC (direct current) sputtering, RF (high frequency) sputtering, a combination of these magnetron sputtering, and dual magnetron (DMS) sputtering using an intermediate frequency region. These can be used alone or in combination of two or more. In addition, a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used. By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable. When performing DC sputtering or DMS sputtering, a metal having a lower redox potential than silicon is used as the target, and oxygen is introduced into the process gas to oxidize a metal having a lower redox potential than silicon. A thin film of an object can be formed. In the case of forming a film by an RF (high frequency) sputtering method, a metal oxide target having a lower oxidation-reduction potential than silicon can be used. As the process gas, an inert gas such as He, Ne, Ar, Kr, or Xe, or at least one process gas selected from oxygen, nitrogen, carbon dioxide, and carbon monoxide can be used. Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, film material, film thickness, and the like.

  Among these, a sputtering method using a metal oxide having a lower oxidation-reduction potential than silicon as a target is preferable because it has a higher film formation rate and higher productivity.

  The layer (D) may be a single layer or a laminated structure of two or more layers. When the (D) layer has a laminated structure of two or more layers, the (D) layer may have the same composition or different compositions.

  The thickness of the (D) layer (the total thickness in the case of a laminated structure of two or more layers) is not particularly limited, but is preferably 1 to 500 nm, and more preferably 5 to 200 nm. If it is this range, the advantage that sufficient gas-barrier property improvement effect is acquired within the range of the film-forming tact time with high productivity is acquired.

[Layers with various functions]
In the gas barrier film according to the present invention, layers having various functions can be provided.

(Anchor coat layer)
An anchor coat layer is formed on the surface of the resin substrate on the side on which the gas barrier layer (first gas barrier layer, second gas barrier layer) according to the present invention is formed for the purpose of improving adhesion with the gas barrier layer. May be.

  As anchor coating agents used for the anchor coat layer, polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, alkyl titanates, etc. are used alone Or in combination of two or more.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5.0 g / m ² (dry state).

  The anchor coat layer can also be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like. Alternatively, by forming an anchor coat layer as described in Japanese Patent Application Laid-Open No. 2004-314626, when an inorganic thin film is formed thereon by a vapor phase method, the gas generated from the substrate side is blocked to some extent. Thus, an anchor coat layer can be formed for the purpose of controlling the composition of the inorganic thin film.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

(Smooth layer)
The gas barrier film according to the present invention may have a smooth layer between the resin substrate and the first gas barrier layer. The smooth layer used in the present invention flattens the rough surface of the resin base material on which protrusions and the like exist, or flattens the unevenness and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the resin base material. Provided for. Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.

  As the photosensitive material of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. Specifically, a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Co., Ltd., Nanohybrid Silicone manufactured by Adeka, and Unidic manufactured by DIC. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), various silicon resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd. Examples include coats, thermosetting urethane resins composed of acrylic polyols and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicon resins. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

  The method for forming the smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

  The thickness of the smooth layer is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 7 μm from the viewpoint of improving the heat resistance of the film and facilitating the balance adjustment of the optical properties of the film. Is preferred.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601: 2001, and the ten-point average roughness Rz is preferably 10 nm or more and 30 nm or less. If it is this range, even if it is a case where a barrier layer is apply | coated with an application | coating form, even if it is a case where a coating means contacts the smooth layer surface by application methods, such as a wire bar and a wireless bar, applicability | paintability will be impaired. In addition, it is easy to smooth the unevenness after coating.

[Electronic device body]
The gas barrier film of the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, the present invention provides an electronic device comprising the gas barrier film of the present invention and an electronic device body formed on the surface of the (D) layer opposite to the surface having the second gas barrier layer. provide.

  Examples of the electronic device body used in the electronic device of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. be able to. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

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

  Although the preferable specific example of the layer structure of an organic EL element is shown 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 / light emitting layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode (anode)
As the anode (transparent electrode) in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used.

  For the anode, these electrode materials may be formed as a thin film by a method such as vapor deposition or sputtering, and the thin film may be formed into a desired shape pattern by photolithography, or if the pattern accuracy is not required ( The pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.

  When light emission is taken out from the anode, it is desirable that the transmittance be larger than 10%. The sheet resistance as the anode is preferably several hundred Ω / □ 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 the range of 10-200 nm.

(cathode)
As the cathode in the organic EL element, a material having a small work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof 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 and the like. Among these, from the point of durability against electron injection and oxidation, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are suitable as the cathode.

  The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less. The film thickness of the cathode is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after manufacturing the said metal quoted by description of the cathode with the film thickness of 1-20 nm, the transparent transparent or semi-transparent cathode is produced by producing the electroconductive transparent material quoted by description of the anode on it. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

(Injection layer: electron injection layer, hole injection layer)
The injection layer includes an electron injection layer and a hole injection layer. An electron injection layer and a hole injection layer are provided as necessary, and between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport. Exist between the layers.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes 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, and the like. Examples thereof include a phthalocyanine buffer layer typified by phthalocyanine, an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  Details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium Metal buffer layer typified by aluminum and aluminum, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. Is mentioned. The buffer layer (injection layer) is desirably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 5 μm.

(Light emitting layer)
The light emitting layer in the organic EL element is a layer that emits light by recombination of electrons and holes injected from the electrode (cathode, anode) or electron transport layer, hole transport layer, and the light emitting portion is the light emitting layer. It may be in the layer or the interface between the light emitting layer and the adjacent layer.

  The light emitting layer of the organic EL device preferably contains the following dopant compound (light emitting dopant) and host compound (light emitting host). Thereby, the luminous efficiency can be further increased.

(Luminescent dopant)
There are two types of luminescent dopants: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.

  Representative examples of fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.

  As a typical example of the phosphorescent dopant, preferably a complex compound containing a metal of Group 8, Group 9, or Group 10 in the periodic table of elements, more preferably an iridium compound or an osmium compound, Of these, iridium compounds are the most preferred. The light emitting dopant may be used by mixing a plurality of kinds of compounds.

(Light emitting host)
A light-emitting host (also simply referred to as a host) means a compound having the largest mixing ratio (mass) in a light-emitting layer composed of two or more kinds of compounds. It is also simply called a dopant). For example, if the light emitting layer is composed of two types of 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, if a light emitting layer is comprised from 3 types of a compound A, a compound B, and the compound C and the mixing ratio is A: B: C = 5: 10: 85, the compound A and the compound B are dopant compounds, and a compound C is a host compound.

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

  The light emitting layer can be formed by depositing the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. Although the film thickness as a light emitting layer does not have a restriction | limiting in particular, Usually, 5 nm-5 micrometers, Preferably it is chosen in the range of 5-200 nm. This light emitting layer may have a single layer structure in which the dopant compound and the host compound are one kind or two or more kinds, or may have a laminated structure made up of a plurality of layers having 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 has any one of hole injection or transport and 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, particularly thiophene oligomers. The above-mentioned materials can be used as the hole transport material, 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, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, 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 can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. 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 have 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 only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and the material can be selected and used from conventionally known compounds. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq3), 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), and the like, and the central metal of these metal complexes is 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 having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. Similarly to the hole injection layer and the hole transport layer, an inorganic semiconductor such as n-type-Si or n-type-SiC can also be used as the electron transport material.

  The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. 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 have a single layer structure composed of one or more of the above materials.

(Method for producing organic EL element)
A method for manufacturing the organic EL element will be described.

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

  First, a desired electrode material, for example, a thin film made of an anode material is formed on a gas barrier film so as to have a thickness of 1 μm or less, preferably 10 to 200 nm, for example, by vapor deposition, sputtering, plasma CVD, or the like. To produce 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 are organic EL element materials, is formed thereon. As a method for forming this organic compound thin film, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method), etc., but a homogeneous film is easily obtained and pinholes are not easily generated. From the point of view, the vacuum deposition method, the spin coating method, the ink jet method, and the printing method are particularly preferable. Further, different film forming methods may be applied for each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a vacuum degree of 10 ⁻⁶ to 10 ⁻² Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within 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 these layers are formed, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained.

  The organic EL device is preferably manufactured from the anode and the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere. In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.

  When a DC voltage is applied to a multicolor display device (organic EL panel) provided with the organic EL element thus obtained, a voltage of about 2 to 40 V is applied with the positive polarity of the anode and the negative polarity of the cathode. Then luminescence can be observed. An alternating voltage may be applied. The alternating current waveform to be applied 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 only to the following examples.

[Resin substrate]
A PET film with a double-sided hard coat (total thickness: 136 μm, PET thickness: 125 μm, manufactured by Kimoto Co., Ltd., trade name: KB film (trademark) 125G1SBF) was used.

[Formation of first gas barrier layer]
Roll-to-roll type CVD in which two apparatuses each having a film forming unit composed of opposing film forming rolls described in Japanese Patent No. 4268195 are connected (having a first film forming unit and a second film forming unit) A film forming apparatus was used (see FIG. 2). The effective film formation width is 1000 mm, and the film formation conditions are: conveyance speed, supply amount of source gas (HMDSO) of each of the first film formation unit and the second film formation unit, supply amount of oxygen gas, degree of vacuum, applied power, The frequency was adjusted by the frequency of the power supply and the number of film formation (number of passes of the apparatus). In contrast to the first pass, the substrate is transported in the direction of rewinding the substrate in the second pass. However, even when the pass directions are different, the first film forming unit passes through the first film forming unit, and the component that passes next. The film part was used as the second film forming part.

  As other conditions, the power supply frequency was 84 kHz, and the film forming roll temperatures were all 30 ° C. As the substrate used, a substrate obtained by pasting and winding a heat-resistant protective film on the surface opposite to the film formation surface was used. In the case of film formation on both sides, a heat-resistant protective film is further bonded to the film-formed surface of the base material after single-sided film formation, and then the protective film on the opposite surface, which is the next film formation surface, is peeled off. What was wound up was used. The film thickness was determined by cross-sectional TEM observation.

  The film forming conditions of the first film forming unit and the second film forming unit are shown in Table 1 below. Under the conditions of V4 in Table 1, the first gas barrier layer was formed by magnetron sputtering.

[Formation of Second Gas Barrier Layer]
The second gas barrier layer was formed by applying a coating liquid containing polysilazane as shown below to form a coating film, and then performing modification by vacuum ultraviolet irradiation.

  Dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) )) And a perhydropolysilazane 20 mass% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) at a ratio of 4: 1 (mass ratio), and further for dry film thickness adjustment A coating solution was prepared by appropriately diluting with dibutyl ether.

  The resin base material on which the first gas barrier layer was formed was prepared by cutting it into a sheet. The coating film was formed on the surface of the first gas barrier layer that had already been formed. The coating solution was applied by spin coating so as to have a dry film thickness shown in Table 2 below, and dried at 80 ° C. for 2 minutes. Next, the dried coating film was subjected to a vacuum ultraviolet ray irradiation treatment using an Xe excimer lamp with a wavelength of 172 nm under the conditions of oxygen concentration and irradiation energy shown in Table 2 below to form a second gas barrier layer.

  Details of the film forming conditions are shown in Table 2 below.

  The composition distribution in the thickness direction of the region (c) included in the second gas barrier layer was determined by measurement using the following XPS analysis method.

  (XPS analysis conditions)
  ・ Equipment: ULVAC-PHI QUANTERASXM
  ・ X-ray source: Monochromatic Al-Kα
  Measurement area: Si2p, C1s, N1s, O1s
  ・ Sputtering ion: Ar (2 keV)
  Depth profile: repeats measurement after sputtering for a certain time. One measurement is SiO ₂Sputtering time was adjusted so that the thickness was equivalent to about 2.8 nm.
  Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. For data processing, MultiPak manufactured by ULVAC-PHI was used.

  In this way, primary data of the profile of the composition distribution in the film thickness direction in the second gas barrier layer was obtained. The obtained profile of the composition distribution in the film thickness direction was corrected using the actual film thickness data obtained from the TEM image, the composition distribution in the film thickness direction was obtained, and the thickness of the region (c) was determined.

  The film thickness of the second gas barrier layer was determined by cross-sectional TEM observation.

[(D) Formation of layer]
The layer (D) was formed using a magnetron sputtering apparatus with the targets and conditions shown in Table 3 below. The refractive index of the (D) layer was measured using a spectroscopic ellipsometer.

(Comparative Example 1)
A first gas barrier layer was formed on one surface of the resin base material under the conditions of V2 in Table 1 above. Next, a second gas barrier layer was formed on the first gas barrier layer under the conditions of P4 in Table 2 above to produce a gas barrier film (sample No. 1).

(Comparative Example 2)
A gas barrier film (sample No. 2) was produced in the same manner as in Comparative Example 1 except that the conditions of P4 in Table 2 were repeated twice to form a second gas barrier layer.

Example 1
A first gas barrier layer was formed on one surface of the resin base material under the conditions of V2 in Table 1 above. Next, a second gas barrier layer was formed on the first gas barrier layer under the conditions of P4 in Table 2 above. Further, a layer (D) was formed on the second gas barrier layer under the condition of M1 in Table 3 above, and a gas barrier film (sample No. 3) was produced.

(Comparative Example 3)
A first gas barrier layer was formed on one surface of the resin base material under the conditions of V3 in Table 1 above. Next, a second gas barrier layer was formed on the first gas barrier layer under the conditions of P2 in Table 2 above. Further, a layer (D) was formed on the second gas barrier layer under the condition of M2 in Table 3 above, to produce a gas barrier film (sample No. 4).

(Example 2)
A first gas barrier layer was formed on one surface of the resin base material under the conditions of V2 in Table 1 above. Next, a second gas barrier layer was formed on the first gas barrier layer under the conditions of P3 in Table 2 above. Further, a layer (D) was formed on the second gas barrier layer under the condition of M3 in Table 3 above, to produce a gas barrier film (sample No. 5).

(Example 3)
A first gas barrier layer was formed on one surface of the resin base material under the conditions of V1 in Table 1 above. Next, on the first gas barrier layer, the conditions of P4 in Table 2 were repeated twice to form a second gas barrier layer. Further, a layer (D) was formed on the second gas barrier layer under the condition of M2 in Table 3 above, and a gas barrier film (Sample No. 6) was produced.

Example 4
A first gas barrier layer was formed on one surface of the resin substrate under the conditions of P4 in Table 2 above. Next, on the first gas barrier layer, the conditions of P4 in Table 2 were repeated twice to form a second gas barrier layer. Further, a layer (D) was formed on the second gas barrier layer under the conditions of M1 in Table 3 above, and a gas barrier film (Sample No. 7) was produced.

(Example 5)
A first gas barrier layer was formed on one surface of the resin base material under the conditions of V4 in Table 1 above. Next, a second gas barrier layer was formed on the first gas barrier layer under the conditions of P4 in Table 2 above. Further, the (D) layer was formed on the second gas barrier layer under the condition of M2 in Table 3 above, and a gas barrier film (Sample No. 8) was produced.

(Example 6)
A first gas barrier layer was formed on one surface of the resin base material under the conditions of V2 in Table 1 above. Next, the conditions of P4 in Table 2 were repeated three times to form a second gas barrier layer. Further, a layer (D) was formed on the second gas barrier layer under the conditions of M1 in Table 3 above, to produce a gas barrier film (sample No. 9).

(Example 7)
A first gas barrier layer was formed on one surface of the resin base material under the conditions of V2 in Table 1 above. Next, the conditions of P4 in Table 2 were repeated twice to form a second gas barrier layer. Further, a layer (D) was formed on the second gas barrier layer under the condition of M4 in Table 3 above, and a gas barrier film (Sample No. 10) was produced.

(Example 8)
A gas barrier film (sample No. 11) was produced in the same manner as in Example 7 except that the layer (D) was formed under the condition M5 in Table 3 instead of the condition M4 in Table 3 above. .

Example 9
A gas barrier film (sample No. 12) was produced in the same manner as in Example 7 except that the layer (D) was formed under the condition M6 in Table 3 instead of the condition M4 in Table 3 above. .

(Comparative Example 4)
A first gas barrier layer was formed on one surface of the resin base material under the conditions of V2 in Table 1 above. Next, the conditions of P5 in Table 2 were repeated three times to form a second gas barrier layer. Further, a layer (D) was formed on the second gas barrier layer under the condition of M2 in Table 3 above, and a gas barrier film (Sample No. 13) was produced.

(Comparative Example 5)
A gas barrier film (Sample No. 14) was produced in the same manner as in Example 1 except that the layer (D) was formed under the condition M7 in Table 3 instead of the condition M1 in Table 3 above. .

  Table 4 below shows the structure of each layer obtained in Examples and Comparative Examples.

≪Method for manufacturing organic EL element≫
Using the gas barrier films obtained in Examples 1 to 9 and Comparative Examples 1 to 5, a bottom emission type organic electroluminescence device was formed by the method shown below so that the area of the light emitting region was 5 cm × 5 cm. (Organic EL element) was produced.

(Formation of underlayer and first electrode)
The gas barrier film is fixed to a substrate holder of a commercially available vacuum deposition apparatus, compound 118 is placed in a resistance heating boat made of tungsten, and the substrate holder and the heating boat are attached in the first vacuum chamber of the vacuum deposition apparatus. It was. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

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

  Next, the base material formed up to the base layer is transferred to the second vacuum chamber while being vacuumed, and the second vacuum chamber is moved to 4 × 10. ^-4After reducing the pressure to Pa, the heating boat containing silver was energized and heated. Thus, a first electrode made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.

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

  Next, compound A-3 (blue light-emitting dopant), compound A-1 (green light-emitting dopant), compound A-2 (red light-emitting dopant) and compound H-1 (host compound), compound A-3 is film thickness In contrast, the vapor deposition rate was changed depending on the location so that it was linearly from 35% by mass to 5% by mass, and Compound A-1 and Compound A-2 each had a concentration of 0.2% by mass without depending on the film thickness. Thus, at a deposition rate of 0.0002 nm / second, the vapor deposition rate was changed depending on the location so that the compound H-1 was 64.6% by mass to 94.6% by mass, so that the thickness was 70 nm. A light emitting layer was formed.

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

  The compound 118, compound HT-1, compound A-1 to compound 3, compound H-1, and compound ET-1 are the compounds shown below.

(Solid sealing)
Next, an aluminum foil with a thickness of 25 μm is used as a sealing member, and a thermosetting sheet adhesive (epoxy resin) is bonded as a sealing resin layer on one surface of the aluminum foil with a thickness of 20 μm. The stopper member was used to superimpose the sample up to the second electrode. At this time, the adhesive forming surface of the sealing member and the organic functional layer surface of the element were continuously overlapped so that the ends of the lead electrodes of the first electrode and the second electrode were exposed.

  Next, the sample was placed in a decompression device, and the laminated base material and the sealing member were pressed and held for 5 minutes under a decompression condition of 0.1 MPa at 90 ° C. Subsequently, the sample was returned to an atmospheric pressure environment and further heated at 120 ° C. for 30 minutes to cure the adhesive.

  The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a water content of 1 ppm or less in accordance with JIS B 9920: 2002. The measured cleanliness is class 100, the dew point temperature is −80 ° C. or less, and the oxygen concentration is 0.00. It was performed at an atmospheric pressure of 8 ppm or less. In addition, the description regarding formation of the lead-out wiring from an anode and a cathode is abbreviate | omitted.

  In this manner, four electronic devices having a light emitting region size of 5 cm × 5 cm were manufactured for one level.

(Dark spot (DS) evaluation)
The organic EL device obtained as described above was energized for 200 hours in an environment of 85 ° C. and 85% RH, and the number of dark spots with a circular equivalent diameter of 300 μm or more was determined for the generated dark spots. The average was obtained for four devices.

(Improved luminous efficiency at a wavelength of 450 nm)
The presence or absence of the light emission efficiency improvement effect of the light of wavelength 450nm by having provided (D) layer on the 2nd gas barrier layer was evaluated. (D) When the light emission at a wavelength of 450 nm of an organic EL device using a gas barrier film having no layer is defined as 100, when a gas barrier film having the same configuration is used except that the (D) layer is provided The light emission at a wavelength of 450 nm of the organic EL element was shown as a relative value. If this value is 102 or more, it indicates that there is an improvement effect, and is shown in the following Table 5 as ◯. If it was less than 98, it was shown as x in Table 5 below as deterioration. If it was 98-102, it was set as there was no change and it showed by-in the following Table 5. Note that Comparative Example 4 could not be evaluated because a crack occurred in the second gas barrier layer.

  The above evaluation results are shown in Table 5 below.

  As apparent from Table 5 above, the gas barrier film of the present invention is excellent in durability in a high-temperature and high-humidity environment and excellent in blue light transmission around a wavelength of 450 nm. In particular, in Example 6, no dark spot was generated, which is probably because the region (c) is thick. The region (c) has a moisture capturing ability, and the thicker it is in the range where it does not break, the longer the time until dark spots are generated. Therefore, it can be said that a dark spot is not substantially generated if it has a moisture capturing ability (time conversion) that exceeds the service life required for an electronic device.

  Furthermore, this application is based on Japanese Patent Application No. 2014-104698 filed on May 20, 2014, the disclosure of which is referred to and incorporated in its entirety.

Claims (5)

(A) resin base material,
(B) a first gas barrier layer containing an inorganic compound,
(C) formed by applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane; and SiO _w N _x (where 0.2 <w ≦ 0.55, 0.66 <x A second gas barrier layer satisfying the composition range represented by ≦ 0.75) and having a region having a thickness of 50 to 1000 nm, and (D) an oxide of a metal having a lower redox potential than silicon. A layer containing as a main component and having a refractive index of light having a wavelength of 450 nm of 2.0 or more,
A gas barrier film containing the materials in this order.   2. The gas barrier film according to claim 1, wherein the (D) layer contains, as a main component, an oxide of at least one metal selected from the group consisting of niobium, tantalum, zirconium, and titanium.   The gas barrier film according to claim 2, wherein the layer (D) contains an oxide of at least one of niobium and tantalum as a main component.   The gas barrier film according to any one of claims 1 to 3, wherein application of energy in the formation of the second gas barrier layer is performed by irradiation with vacuum ultraviolet rays. The gas barrier film according to any one of claims 1 to 4,
An electronic device body formed on a surface of the (D) layer opposite to the surface having the second gas barrier layer;
Including electronic devices.