JP6070411B2 - GAS BARRIER FILM, GAS BARRIER FILM MANUFACTURING METHOD, AND ORGANIC ELECTROLUMINESCENT ELEMENT - Google Patents

Description

The present invention relates to a gas barrier film , a method for producing a gas barrier film, and an organic electroluminescence element. In particular, the present invention relates to a gas barrier film in which deterioration is suppressed even in a high temperature and high humidity environment, a method for producing the same, and an organic electroluminescence device including the same.

  An organic electroluminescent element (also referred to as “organic EL element” or “organic electroluminescent element”) using electroluminescence (hereinafter referred to as EL) of an organic material has a low voltage of about several volts to several tens of volts. It is a thin-film type complete solid-state device capable of emitting light with a high brightness, high luminous efficiency, thinness, and light weight. For this reason, it has been attracting attention in recent years as surface light emitters such as backlights for various displays, display boards such as signboards and emergency lights, and illumination light sources.

  Gas barrier properties that block the penetration of various gases such as water vapor and oxygen into the organic EL element in an organic EL element using a resin base material to make it a thin, lightweight and flexible element A film may be provided. By providing the gas barrier film, the deterioration of the function of the organic EL element is suppressed.

  The shape of the flexible organic EL element can be maintained in a curved surface state, but there is a problem that the performance deteriorates if the curved surface state is maintained for a long time. One of the causes is the deterioration of the gas barrier film provided on the resin base material. This is because the gas barrier film has a laminated structure in which a plurality of organic layers, inorganic layers, etc. are laminated, and the curved surface state lasts for a long time, causing cracks in any of the constituent layers, This is thought to be due to peeling.

  With respect to such a problem, in Patent Document 1, a metal oxide layer formed on a film substrate by a physical vapor deposition method (PVD method) or a low temperature plasma vapor deposition method (CVD method), and a silicon-based metal Flexibility is improved by laminating an alkoxide or its derivative, an aluminum compound, and, if necessary, an inorganic / organic hybrid polymer layer (ORMOCER layer) formed by applying a compound containing another metal element. It is described that a gas barrier film can be provided. The same document also proposes a gas barrier film having improved bending resistance by setting the thickness of the ORMOKER layer in the range of 0.05 to 0.95 μm.

  However, although the conventional gas barrier film described above has excellent bending resistance, the adhesion between the metal oxide layer and the inorganic / organic hybrid polymer layer when exposed to a high temperature and high humidity environment for a long period of time. There has been a problem that the gas barrier property is deteriorated. For this reason, when such a gas barrier film was used for an organic EL element, there existed a problem that the light emission performance of an organic EL element also deteriorated due to deterioration of a gas barrier film.

JP 2002-46208 A

The present invention has been made in view of the above-mentioned problems and situations, and its solution is a gas barrier film that can be prevented from being deteriorated even in a high-temperature and high-humidity environment, a method for producing the same, and an organic material including the same. It is to provide an electroluminescent device.

As a result of investigating the cause of the above-mentioned problems in order to solve the above-mentioned problems according to the present invention, a gas barrier layer, which is a vapor-deposited film containing at least silicon atoms, oxygen atoms and carbon atoms, on the resin substrate, and the gas A gas barrier film comprising a polysilazane modified layer provided on the barrier layer and having a coating film containing at least polysilazane reformed, and suppressing deterioration between the resin substrate and the gas barrier layer It has been found that by providing the layer, a gas barrier film in which deterioration is suppressed even under a high temperature and high humidity environment can be obtained.
That is, the subject concerning this invention is solved by the following means.

1. A gas barrier layer that is a deposited film containing at least silicon atoms, oxygen atoms, and carbon atoms on a resin substrate, and a coating film that is provided adjacent to the gas barrier layer and contains at least polysilazane is modified. A polysilazane modified layer, and a gas barrier film comprising:
A gas barrier film comprising an ultraviolet absorbing layer containing metal oxide particles having ultraviolet absorbing ability and a fluorine-containing polymer between the resin substrate and the gas barrier layer.

2. 2. The gas barrier film according to claim 1, wherein a layer thickness ratio of the gas barrier layer to the ultraviolet absorbing layer is in a range of 0.01 to 0.05.

3 . A gas barrier layer that is a deposited film containing at least silicon atoms, oxygen atoms, and carbon atoms on a resin substrate, and a coating film that is provided adjacent to the gas barrier layer and contains at least polysilazane is modified. A polysilazane modified layer, and a method for producing a gas barrier film comprising:
Between the resin base material and the gas barrier layer, an ultraviolet absorbing layer containing metal oxide particles having ultraviolet absorbing ability and a fluorine-containing polymer is provided,
It said gas barrier layer, the manufacturing method of the characteristics and to Ruga Subaria film to be formed by vapor deposition of the opposing roll method.

4 . An organic electroluminescence device comprising the gas barrier film according to item 1 or 2 .

According to the present invention, it is possible to provide a gas barrier film whose deterioration is suppressed even in a high-temperature and high-humidity environment, a method for producing the same, and an organic electroluminescence device including the same.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
The gas barrier film according to the present invention is provided with a deterioration suppressing layer between the resin base material and the gas barrier layer, so that any residue generated from the resin base material due to the oligomer component contained in the resin base material or aging. It is possible to suppress the component, possibly the oligomer component, from reaching the interface between the gas barrier layer and the polysilazane modified layer. Thereby, it is speculated that the lowering of the adhesion between the gas barrier layer and the polysilazane modified layer due to the oligomer component is suppressed, and the above-mentioned effect of the present invention can be obtained.

Schematic configuration diagram showing an organic electroluminescence device of the present invention Diagram showing silicon distribution curve, oxygen distribution curve and carbon distribution curve The figure which expanded the carbon distribution curve shown in FIG. Diagram showing the refractive index profile of the gas barrier layer Schematic configuration diagram showing a gas barrier layer manufacturing apparatus

The gas barrier film of the present invention is provided on a resin base material, which is a vapor barrier film containing at least silicon atoms, oxygen atoms and carbon atoms, on the gas barrier layer, and contains at least polysilazane. A gas barrier film comprising a polysilazane modified layer obtained by modifying a coating film, wherein metal oxide particles and fluorine having an ultraviolet absorbing ability are provided between the resin substrate and the gas barrier layer. An ultraviolet absorption layer containing the containing polymer is provided. This feature is a technical feature common to claims 1 to 4 .
In the present invention, it is preferable that a layer thickness ratio of the gas barrier layer to the ultraviolet absorbing layer is in a range of 0.01 to 0.05. Thereby, deterioration of the gas barrier film in a high-temperature and high-humidity environment and the organic EL element including the same can be more effectively suppressed.
In the present invention, the resin base material preferably contains at least hydrolysis-resistant polyethylene terephthalate. Thereby, deterioration of the gas barrier film in a high-temperature and high-humidity environment and the organic EL element including the same can be more effectively suppressed.
In addition, the method for producing a gas barrier film of the present invention includes a gas barrier layer, which is a deposited film containing at least silicon atoms, oxygen atoms, and carbon atoms, on a resin substrate, and adjacent to the gas barrier layer. A polysilazane modified layer provided by modifying a coating film containing at least polysilazane, wherein between the resin base material and the gas barrier layer, the ultraviolet absorbing layer containing metal oxide particles and a fluorine-containing polymer having an ultraviolet absorbing ability is provided, the gas barrier layer, and forming by vapor phase deposition of the opposing roll method. Thereby, deterioration of the gas barrier film in a high temperature and high humidity environment and the organic EL element provided with the film can be further suppressed. Although the reason for this is not clear, the gas barrier layer formed by the opposite roll type vapor phase growth method has a non-uniform carbon atom concentration in the layer as compared with the layer formed by the conventional CVD method. It is speculated that this suppresses the deterioration of the gas barrier layer caused by the oligomer component of the resin base material. In addition, since the gas barrier layer is formed by the facing roll type vapor phase growth method, the time required to form the gas barrier layer can be shortened, and the productivity of the gas barrier film and the organic EL element is improved. Can be made.

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

<< Structure of organic electroluminescence element >>
Hereinafter, specific embodiments of the organic electroluminescence element of the present invention (hereinafter also referred to as “organic EL element”) will be described.
In FIG. 1, the schematic block diagram (sectional drawing) of an organic EL element is shown. As shown in FIG. 1, the organic EL element 10 includes a gas barrier film 11, a first electrode 16, an organic functional layer 17, a second electrode 18, a sealing resin layer 19, and a sealing member 20. The gas barrier film 11 is configured by laminating a deterioration suppressing layer 13, a gas barrier layer 14, and a polysilazane modified layer 15 in this order on a resin substrate 12. In the organic EL element 10 shown in FIG. 1, an organic functional layer 17 including a light emitting layer and a second electrode 18 serving as a cathode are laminated on a first electrode 16 serving as an anode, and further, a gas barrier film 11 and a sealing layer are sealed. The structure is solid-sealed by the stop resin layer 19 and the sealing member 20. Among these, the 1st electrode 16 used as an anode is comprised as a translucent electrode. In such a configuration, only a portion where the organic functional layer 17 is sandwiched between the first electrode 16 and the second electrode 18 becomes a light emitting region in the organic EL element 10. In the example shown in FIG. 1, the organic EL element 10 is configured as a bottom emission type in which generated light (hereinafter referred to as emitted light h) is extracted from at least the gas barrier film 11 side.

  In the organic EL element 10, a sealing member 20 is bonded on one surface of the gas barrier film 11 via a sealing resin layer 19 that covers the first electrode 16, the organic functional layer 17, and the second electrode 18. By doing so, it is solid-sealed. In the solid-sealed organic EL element 10, an uncured resin material is applied to the bonding surface of the sealing member 20 or the polysilazane modified layer 15 and the second electrode 18 of the gas barrier film 11. The gas barrier film 11 and the sealing member 20 are integrated by thermocompression bonding with the resin material interposed therebetween.

  The organic EL element 10 is not limited to the bottom emission type, and may be, for example, a top emission type configuration in which light is extracted from the second electrode 18 side or a dual emission type configuration in which light is extracted from both sides. If the organic EL element 10 is a top emission type, the second electrode 18 is made of a transparent material and the emitted light h is extracted from the second electrode 18 side. Further, if the organic EL element 10 is a double-sided light emitting type, a transparent material is used for the second electrode 18 and the emitted light h is extracted from both sides.

  Hereinafter, detailed configurations of the gas barrier film 11, the first electrode 16, the second electrode 18, the organic functional layer 17, the sealing resin layer 19, and the sealing member 20 will be described. In addition, in the organic EL element 10 of this example, translucency means that the light transmittance in wavelength 550nm is 50% or more.

<Gas barrier film>
The gas barrier film 11 of the present invention is a deterioration suppressing layer 13 containing metal oxide particles having ultraviolet absorbing ability on a resin substrate 12, and a vapor deposition film containing at least silicon atoms, oxygen atoms and carbon atoms. A gas barrier layer 14 and a polysilazane modified layer 15 which is provided adjacent to the gas barrier layer 14 and is formed by modifying a coating film containing at least polysilazane are laminated in this order.

<Resin substrate>
The resin base material 12 is not particularly limited as long as it is a flexible base material that can give flexibility to the gas barrier film 11 and the organic EL element 10. An example of the flexible base material is a transparent resin film.

Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Is mentioned.
In the present invention, the material of the resin base 12 is preferably polyethylene terephthalate (PET), and particularly preferably a hydrolysis-resistant polyester (PET) film from the viewpoint of maintaining barrier performance during high temperature and high humidity storage. As the hydrolysis-resistant PET film, a flexible substrate such as a commercially available Lumirror X10 (manufactured by Toray Industries, Inc.) or Shine Beam (manufactured by Toyobo Co., Ltd.) can be used.

<Deterioration suppression layer>
The deterioration suppressing layer 13 constituting the gas barrier film 11 of the present invention is characterized by containing metal oxide particles, particularly metal oxide particles having ultraviolet absorbing ability. In the present invention, the deterioration suppressing layer 13 is provided for the purpose of suppressing deterioration of the gas barrier film 11.

  As a formation method of the deterioration suppression layer 13, it may be formed by coating on the resin base material 12, or may be bonded to the resin base material 12 after being formed into a sheet shape.

Moreover, it is preferable that the layer thickness of the deterioration suppression layer 13 which concerns on this invention is 5-500 micrometers. By making the layer thickness 5 μm or more, the effect of the present invention can be easily obtained, and by making the layer thickness 500 μm or less, the cost can be reduced. The layer thickness of the deterioration suppressing layer 13 is more preferably 10 to 50 μm.
In the present invention, the thickness of each layer such as the degradation suppressing layer 13 can be measured using, for example, a micro gauge.

  Moreover, it is preferable that the refractive index of the deterioration suppression layer 13 is 1.4-2.5. Most preferably, it is 1.5-2.0. The adjustment of the refractive index can be appropriately selected depending on the mixing ratio of metal oxide particles and a binder described later.

(1) Metal oxide particles having ultraviolet absorbing ability In the present invention, the ultraviolet absorbing ability refers to an action of absorbing light in any band of wavelengths of 340 nm to 390 nm.

  As the metal oxide particles having ultraviolet absorbing ability used in the present invention, a metal oxide having a semiconductor property having a band gap in the vicinity of 3.1 eV is suitable. Examples of such metal oxides include zinc oxide, titanium oxide, cerium oxide, tungsten titanium trioxide, and strontium titanate. In the present invention, these are preferably used alone or in a mixture. Among these, zinc oxide and titanium oxide are relatively inexpensive and are preferably used. In particular, zinc oxide is superior in transparency because it has a higher absorption edge of ultraviolet rays of 380 nm and a lower refractive index than titanium oxide.

In the present invention, the amount of the metal oxide particles contained in the deterioration suppressing layer 13 is preferably 5 g or more and 20 g or less per 1 m ² . The amount of the metal oxide particles contained in the deterioration suppressing layer 13 is more preferably 7 g or more and 20 g or less per 1 m ² , and further preferably 10 g or more and 20 g or less per 1 m ² . When the amount of the metal oxide particles contained in the deterioration suppressing layer 13 is 5 g or more per 1 m ² , the deterioration suppressing layer 13 exhibits an excellent ultraviolet shielding effect. This is preferable because it can maintain flexibility.

Moreover, in order to ensure the transparency of the deterioration suppression layer 13, it is necessary to reduce the scattering of the metal oxide particles in the visible light region. For this purpose, it is important to make the particle size of the metal oxide particles sufficiently smaller than the wavelength of visible light. In the present invention, the average particle size of the metal oxide particles having ultraviolet absorbing ability is set to 0.1 μm or less. It is preferable. The average particle diameter of the metal oxide particles is more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. If the average particle size is reduced as described above, the transparency of the deterioration suppressing layer 13 can be sufficiently secured, and the ultraviolet shielding effect is also increased by reducing the average particle size.
Moreover, since it becomes difficult to obtain a uniform dispersion of less than 0.01 μm from the viewpoint of the surface energy of the particles, the average particle size of industrially obtained particles is 0.01 μm or more. Therefore, the lower limit value of the average particle diameter of the metal oxide particles is preferably 0.01 μm or more.
The method for measuring the average particle diameter is not particularly limited. For example, the metal oxide particles are photographed by setting the magnification to 10,000 times using a transmission electron microscope, and 100 random images are taken on the photographic image. A method of extracting and calculating metal oxide particles can be used. Specifically, from observation with an electron microscope of metal oxide particles, 100 or more metal oxide particles that can be observed as a circle, an ellipse, or a substantially circle or ellipse are randomly observed, and each metal oxide particle is observed. The average particle diameter of the metal oxide particles can be obtained by obtaining the diameter and obtaining the number average value thereof. Here, the particle diameter according to the present invention refers to the minimum distance among the distances between the two parallel lines that surround the outer edge of the metal oxide particles that can be observed as a circle, an ellipse, or a substantially circle or ellipse. . In measuring the average particle diameter, the ones that clearly represent the side surfaces of the metal oxide particles are not measured.

(2) Binder The deterioration suppressing layer 13 may contain a fluorine-containing polymer as a binder for the metal oxide particles. As the fluorine-containing polymer, a polymer formed from a fluoropolymer having a fluorinated resin and a curable functional group, a monomer, or the like is used. The binder contained in the deterioration suppressing layer 13 is not limited to the fluorine-containing polymer, and a conventionally known coating liquid binder can be used. For example, a thermosetting binder, an ultraviolet curable binder, a water-soluble binder can be used. A functional polymer.

  The content of the fluorine-containing polymer in the deterioration suppressing layer 13 is preferably 50% by mass or more, and more preferably 70% by mass or more.

  The fluorine-containing polymer is not particularly limited, but is selected from the group consisting of ethylene / tetrafluoroethylene copolymer [ETFE], polychlorotrifluoroethylene [PCTFE], and tetrafluoroethylene / hexafluoropropylene copolymer [FEP]. It is preferable that it is at least one.

  The fluorine-containing polymer may be a ternary or higher copolymer including not only the monomers exemplified above but also a comonomer copolymerizable with the monomers. The FEP is a concept that may include, for example, an ethylene / tetrafluoroethylene / hexafluoropropylene copolymer.

  The fluorine-containing polymer can be prepared by a conventionally known method such as suspension polymerization, solution polymerization, emulsion polymerization or bulk polymerization. The conditions for each polymerization can be appropriately selected according to the composition and amount of the fluorine-containing polymer to be prepared.

  When the deterioration suppressing layer 13 contains a fluorine-containing polymer, the method for forming the deterioration suppressing layer 13 is not particularly limited, but after mixing and kneading the metal oxide particles and the fluorine-containing polymer, A method in which a sheet formed by stretching is pressure-bonded to the resin substrate 12 is preferably used.

  The fluorine-containing polymer preferably has a curable functional group. Examples of the fluorine-containing polymer having a curable functional group include a perfluoroolefin-based polymer mainly composed of perfluoroolefin units, a CTFE-based polymer mainly composed of chlorotrifluoroethylene (CTFE) units, and vinylidene fluoride (VdF). Examples thereof include VdF polymers mainly composed of units, and fluoroalkyl group-containing polymers mainly composed of fluoroalkyl units.

  Specific examples of perfluoroolefin-based polymers mainly composed of perfluoroolefin units include tetrafluoroethylene (TFE) homopolymers, TFE and hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE). And copolymers with other monomers copolymerizable with these.

  Examples of other copolymerizable monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, cyclohexyl carboxyl. Carboxylic acid vinyl esters such as vinyl acid vinyl, vinyl benzoate, para-t-butyl vinyl benzoate; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether; ethylene, propylene, n-butene, isobutene, etc. Non-fluorinated olefins; vinylidene fluoride (VdF), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), fluorovinyl ether, and other fluorine-based monomers are listed. The present invention is not limited.

  Of these, TFE-based polymers mainly composed of TFE are preferable in terms of excellent dispersibility, weather resistance, copolymerization, and chemical resistance of the metal oxide particles.

  Specific examples of the curable functional group-containing perfluoroolefin polymer include, for example, TFE / isobutylene / hydroxybutyl vinyl ether / copolymer of other monomers, TFE / vinyl versatate / hydroxybutyl vinyl ether / other monomers Copolymer, TFE / VdF / hydroxybutyl vinyl ether / other monomer copolymer, etc., especially TFE / isobutylene / hydroxybutyl vinyl ether / other monomer copolymer, TFE / Versatic A copolymer of vinyl acid / hydroxybutyl vinyl ether / other monomers is preferred.

  Examples of the TFE-based curable polymer coating composition include the Zaffle GK series manufactured by Daikin Industries, Ltd.

  Specific examples of the CTFE-based polymer mainly composed of chlorotrifluoroethylene (CTFE) units include, for example, a copolymer of CTFE / hydroxybutyl vinyl ether / other monomers.

  Examples of CTFE-based curable polymer coating compositions include Lumiflon manufactured by Asahi Glass Co., Ltd., Fluoronate manufactured by DIC Co., Ltd., Cefral Coat manufactured by Central Glass Co., Ltd., and ZAFLON manufactured by Toagosei Co., Ltd. it can.

  Specific examples of the VdF-based polymer mainly composed of vinylidene fluoride (VdF) units include, for example, a copolymer of VdF / TFE / hydroxybutyl vinyl ether / other monomers.

Moreover, as a specific example of the fluoroalkyl group-containing polymer mainly composed of fluoroalkyl units, for example, CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCOCH═CH ₂ (mixture of n = 3 and 4) / 2-hydroxyethyl methacrylate / stearyl acrylate copolymer and the like.

  Examples of the fluoroalkyl group-containing polymer include Unidyne and Ftone manufactured by Daikin Industries, Ltd., and Zonyl manufactured by DuPont.

  Of these, a perfluoroolefin polymer is preferred from the viewpoint of weather resistance and moisture resistance.

  As a coating composition using a fluorine-containing polymer having these curable functional groups as a film-forming component, a solvent-type coating composition, an aqueous-type coating composition, and a powder-type coating composition are respectively used in a conventional manner. Can be prepared. Among these, it is preferable to prepare a solvent-type coating composition from the viewpoints of film formation ease, curability, drying property, and the like.

  Moreover, the fluorine-containing polymer coating composition having a curable functional group contains the metal oxide particles, and various additives can be blended according to required characteristics. Examples of the additive include a curing agent, a curing accelerator, a pigment dispersant, an antifoaming agent, a leveling agent, an ultraviolet absorber, a light stabilizer, a thickening agent, an adhesion improving agent, and a matting agent.

  The curing agent is selected according to the functional group of the curable polymer. For example, an isocyanate curing agent, a melamine resin, a silicate compound, an isocyanate group-containing silane compound and the like can be preferably exemplified for the hydroxyl group-containing fluorine-containing polymer. . In addition, amino curing agents and epoxy curing agents are used for carboxy group-containing fluorine-containing polymers, and carbonyl group-containing curing agents, epoxy curing agents and acid anhydride curing agents are used for amino group-containing fluorine-containing polymers. Can be used.

(3) Protective layer containing fluorine-containing polymer Further, on the deterioration suppressing layer 13 formed on the resin substrate 12, the protective layer further does not contain the metal oxide particles and contains the fluorine-containing polymer. It is also a preferred embodiment of the present invention to install the slab. The protective layer preferably used in the present invention preferably comprises 50% by mass or more of a fluorine-containing polymer, and particularly preferably 70% by mass or more of a fluorine-containing polymer. As the fluorine-containing polymer contained in the protective layer, the same polymer as that used in the deterioration suppressing layer 13 can be used. As a formation method of a protective layer, the method of forming by application | coating on the deterioration suppression layer 13 may be sufficient, and the method of bonding to the deterioration suppression layer 13 after forming in a sheet form may be sufficient.

《Gas barrier layer》
A gas barrier layer 14 is provided on the resin substrate 12 with the deterioration suppressing layer 13 interposed therebetween. Such a gas barrier layer 14 has a water vapor permeability (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS-K-7129-1992, 0.01 g / ( m ² · 24 hours) or less. Moreover, the oxygen permeability measured by the method based on JIS-K-7126-1987 is 1 × 10 ⁻³ ml / (m ² · 24 hours · atm) or less, and the water vapor permeability is 1 × 10 ⁻⁵ g / (M ² · 24 hours) or less is preferable.

  As a material for forming the gas barrier layer 14, a material having a function of suppressing intrusion of elements such as moisture and oxygen that cause deterioration of the resin base material 12 is used. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Furthermore, in order to improve the brittleness of the gas barrier layer 14, it is more preferable to have a laminated structure of these inorganic layers and layers (organic layers) made of an organic material. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

  The formation method of the gas barrier layer 14 is not particularly limited. For example, the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used. In particular, the atmospheric pressure plasma polymerization method described in JP-A-2004-68143 can be preferably used.

(1) Configuration of Gas Barrier Layer As the gas barrier layer 14 applied to the organic EL element 10, an inorganic film having a refractive index distribution in the layer thickness direction and having one or more extreme values in the refractive index distribution. It is preferable that it is comprised from these. The gas barrier layer 14 is made of a material containing silicon, oxygen, and carbon, and has a laminated structure including a plurality of layers having different silicon, oxygen, and carbon contents.
And the gas barrier layer 14 is a ratio (atomic ratio) between the distance from the surface of the gas barrier layer 14 (interface with the polysilazane modified layer 15) in the layer thickness direction and the atomic weight of each element (silicon, oxygen or carbon). ) And the distribution curve of each element showing the relationship.

In addition, the atomic ratio of silicon, oxygen, or carbon is represented by the ratio [(Si, O, C) / (Si + O + C)] of silicon, oxygen, or carbon to the total amount of each element of silicon, oxygen, and carbon.
The silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve indicate the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon at a distance from the surface of the gas barrier layer 14. Further, a distribution curve showing the relationship between the distance from the surface of the gas barrier layer 14 in the layer thickness direction (interface with the polysilazane modified layer 15) and the ratio (atomic ratio) of the total atomic weight of oxygen and carbon, The oxygen carbon distribution curve.

The gas barrier layer 14 may further contain nitrogen in addition to silicon, oxygen and carbon. By containing nitrogen, the refractive index of the gas barrier layer 14 can be controlled. For example, the refractive index of SiO ₂ is 1.5, whereas the refractive index of SiN is about 1.8 to 2.0. For this reason, it becomes possible to set it as 1.6-1.8 which is a preferable refractive index value by making the gas barrier layer 14 contain nitrogen and forming SiON in the gas barrier layer 14. Thus, the refractive index of the gas barrier layer 14 can be controlled by adjusting the nitrogen content.

When the gas barrier layer 14 contains nitrogen, the distribution curve of each element (silicon, oxygen, carbon, or nitrogen) constituting the gas barrier layer 14 is as follows.
In the case of containing nitrogen in addition to silicon, oxygen and carbon, the atomic ratio of silicon, oxygen, carbon or nitrogen is the ratio of silicon, oxygen, carbon or nitrogen to the total amount of each element of silicon, oxygen, carbon and nitrogen [(Si, O, C, N) / (Si + O + C + N)].
The silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve represent the atomic ratio of silicon, the atomic ratio of oxygen, the atomic ratio of carbon, and the atomic ratio of nitrogen at a distance from the surface of the gas barrier layer 14. Indicates the ratio.

(2) Relationship Between Element Distribution Curve and Refractive Index Distribution The refractive index distribution of the gas barrier layer 14 can be controlled by the amount of carbon and the amount of oxygen in the thickness direction of the gas barrier layer 14.
FIG. 2 shows an example of a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and a nitrogen distribution curve of the gas barrier layer 14. 3 shows an enlarged carbon distribution curve from the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve shown in FIG. 2 and 3, the horizontal axis indicates the distance [nm] from the surface of the gas barrier layer 14 in the layer thickness direction. The vertical axis represents the atomic ratio [at%] of silicon, oxygen, carbon, or nitrogen with respect to the total amount of each element of silicon, oxygen, and carbon.
In addition, the detail of the measuring method of a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and a nitrogen distribution curve is mentioned later.

  As shown in FIG. 2, the atomic ratio of silicon, oxygen, carbon, and nitrogen changes depending on the distance from the surface of the gas barrier layer 14. In particular, for oxygen and carbon, the atomic ratio varies greatly depending on the distance from the surface of the gas barrier layer 14, and each distribution curve has a plurality of extreme values. In addition, the oxygen distribution curve and the carbon distribution curve are correlated, and the oxygen atomic ratio decreases at a distance where the carbon atomic ratio is large, and the oxygen atomic ratio increases at a distance where the carbon atomic ratio is small.

  FIG. 4 shows a refractive index distribution curve of the gas barrier layer 14. In FIG. 4, the horizontal axis indicates the distance [nm] from the surface of the gas barrier layer 14 in the layer thickness direction. The vertical axis represents the refractive index of the gas barrier layer 14. The refractive index of the gas barrier layer 14 shown in FIG. 4 is a measured value of the distance from the surface of the gas barrier layer 14 in the layer thickness direction and the refractive index of the gas barrier layer 14 with respect to visible light at this distance. The refractive index distribution of the gas barrier layer 14 can be measured using a known method, for example, a spectroscopic ellipsometer (ELC-300 manufactured by JASCO Corporation) or the like.

As shown in FIGS. 3 and 4, there is a correlation between the atomic ratio of carbon and the refractive index of the gas barrier layer 14. Specifically, in the gas barrier layer 14, the refractive index of the gas barrier layer 14 also increases at a position where the carbon atomic ratio increases. Thus, the refractive index of the gas barrier layer 14 changes according to the atomic ratio of carbon. That is, in the gas barrier layer 14, the refractive index distribution curve of the gas barrier layer 14 can be controlled by adjusting the distribution of the atomic ratio of carbon in the layer thickness direction.
Since the carbon atomic ratio and the oxygen atomic ratio are also correlated as described above, the refractive index distribution curve of the gas barrier layer 14 is controlled by controlling the oxygen atomic ratio and the distribution curve. be able to.

  By providing the gas barrier layer 14 having an extreme value in the refractive index distribution, reflection and interference occurring at the interface of the resin substrate 12 can be suppressed. For this reason, the light transmitted through the organic EL element 10 is emitted without being affected by total reflection or interference due to the action of the gas barrier layer 14. Accordingly, the amount of light is not reduced, and the light extraction efficiency of the organic EL element 10 is improved.

(3) Conditions for Distribution Curve of Each Element It is preferable that the gas barrier layer 14 has an atomic ratio of silicon, oxygen, and carbon, or a distribution curve of each element that satisfies the following conditions (i) to (iii).

(I) In a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the layer thickness of the gas barrier layer 14, the following formula (A):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (A)
The condition represented by is satisfied.
Alternatively, in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the layer thickness of the gas barrier layer 14, the following formula (B):
(Atomic ratio of carbon)> (Atomic ratio of silicon)> (Atomic ratio of oxygen) (B)
The condition represented by is satisfied.

(Ii) The carbon distribution curve has at least one local maximum and local minimum.

(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.

  The gas barrier layer 14 preferably satisfies all the conditions (i) to (iii). Two or more gas barrier layers 14 that satisfy all of the above conditions (i) to (iii) may be provided. When two or more gas barrier layers 14 are provided, the materials of the plurality of thin film layers may be the same or different. When two or more gas barrier layers 14 are provided, the two or more gas barrier layers 14 may be formed on the deterioration suppression layer 13, or the deterioration suppression of the deterioration suppression layer 13 and the resin base material 12. Each may be formed on the surface opposite to the layer 13.

  The refractive index of the gas barrier layer 14 can be controlled by the atomic ratio of carbon or oxygen as shown in the correlation shown in FIGS. For this reason, the refractive index of the gas barrier layer 14 can be adjusted to a preferable range by the above conditions (i) to (iii).

(4) Carbon distribution curve The gas barrier layer 14 needs to have at least one extreme value in the carbon distribution curve. In such a gas barrier layer 14, it is more preferable that the carbon distribution curve has at least two extreme values, and it is even more preferable that the carbon distribution curve has at least three extreme values. Furthermore, it is preferable that the carbon distribution curve has at least one maximum value and one minimum value.

When the carbon distribution curve has no extreme value, the light distribution of the obtained gas barrier layer 14 becomes insufficient. For this reason, it becomes difficult to eliminate the light angle dependency of the organic EL element 10 obtained through the first electrode 16.
When the gas barrier layer 14 has three or more extreme values, one extreme value of the carbon distribution curve and another extreme value adjacent to the extreme value are obtained from the surface of the gas barrier layer 14. The difference in the distance in the layer thickness direction is preferably 200 nm or less, and more preferably 100 nm or less.

(5) Extreme Value In the gas barrier layer 14, the extreme value of the distribution curve is the maximum value or the minimum value of the atomic ratio of the element to the distance from the surface of the gas barrier layer 14 in the layer thickness direction of the gas barrier layer 14, Or it is the measured value of the refractive index distribution curve corresponding to the value.

  In the gas barrier layer 14, the maximum value of the distribution curve of each element is a point where the value of the atomic ratio of the element changes from increase to decrease when the distance from the surface of the gas barrier layer 14 is changed. In addition, from this point, the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer 14 is further changed by 20 nm is reduced by 3 at% or more.

  In the gas barrier layer 14, the minimum value of the distribution curve of each element is a point where the value of the atomic ratio of the element changes from decrease to increase when the distance from the surface of the gas barrier layer 14 is changed. In addition, from this point, the value of the atomic ratio of the element at a position where the distance from the surface of the gas barrier layer 14 is further changed by 20 nm is increased by 3 at% or more.

Further, in the carbon distribution curve of the gas barrier layer 14, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is preferably 5 at% or more. Moreover, in such a gas barrier layer 14, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is more preferably 6 at% or more, and further preferably 7 at% or more. When the difference between the maximum value and the minimum value of the atomic ratio of carbon is less than the above range, the refractive index difference in the refractive index distribution curve of the obtained gas barrier layer 14 becomes small, and the light distribution becomes insufficient.
There is a correlation between the amount of carbon distribution and the refractive index, and when the absolute value of the maximum value and the minimum value of the preferable carbon atom is 7 at% or more, the absolute value of the difference between the maximum value and the minimum value of the obtained refractive index is It becomes 0.2 or more.

(6) Oxygen distribution curve The gas barrier layer 14 preferably has at least one extreme value in the oxygen distribution curve. In particular, the gas barrier layer 14 preferably has an oxygen distribution curve having at least two extreme values, and more preferably has at least three extreme values. Furthermore, it is preferable that the oxygen distribution curve has at least one maximum value and one minimum value.

When the oxygen distribution curve does not have an extreme value, the light distribution of the obtained gas barrier layer 14 becomes insufficient. For this reason, it becomes difficult to eliminate the light angle dependency of the organic EL element 10 obtained through the first electrode 16.
Further, when the gas barrier layer 14 has three or more extreme values, one extreme value of the oxygen distribution curve and another extreme value adjacent to the extreme value are obtained from the surface of the gas barrier layer 14. The difference in the distance in the layer thickness direction is preferably 200 nm or less, and more preferably 100 nm or less.

  In the oxygen distribution curve of the gas barrier layer 14, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen is preferably 5 at% or more. In such a gas barrier layer 14, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen is more preferably 6 at% or more, and further preferably 7 at% or more. When the difference between the maximum value and the minimum value of the atomic ratio of oxygen is less than the above range, the light distribution is insufficient from the refractive index distribution curve of the obtained gas barrier layer 14.

(7) Silicon distribution curve The gas barrier layer 14 preferably has an absolute value of a difference between the maximum value and the minimum value of the atomic ratio of silicon of less than 5 at% in the silicon distribution curve. Further, in such a gas barrier layer 14, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon is more preferably less than 4 at%, and further preferably less than 3 at%. When the difference between the maximum value and the minimum value of the atomic ratio of silicon is not less than the above range, the light distribution is insufficient from the refractive index distribution curve of the obtained gas barrier layer 14.

(8) Total amount of oxygen and carbon: oxygen carbon distribution curve In the gas barrier layer 14, the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms is expressed as oxygen. The carbon distribution curve.
The gas barrier layer 14 preferably has an absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon in the oxygen-carbon distribution curve of less than 5 at%, more preferably less than 4 at%. Preferably, it is particularly preferably less than 3 at%.
When the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon is not less than the above range, the light distribution is insufficient from the refractive index distribution curve of the obtained gas barrier layer 14.

(9) XPS depth profile The silicon distribution curve, oxygen distribution curve, carbon distribution curve, oxygen carbon distribution curve, and nitrogen distribution curve described above are measured by X-ray photoelectron spectroscopy (XPS), argon, and the like. By using together with the rare gas ion sputtering, it is possible to prepare by so-called XPS depth profile measurement in which the surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).

In the element distribution curve with the horizontal axis as the etching time, the etching time generally correlates with the distance from the surface of the gas barrier layer 14 in the layer thickness direction. For this reason, when measuring the XPS depth profile, the distance from the surface of the gas barrier layer 14 calculated from the relationship between the etching rate and the etching time is defined as “the distance from the surface of the gas barrier layer 14 in the layer thickness direction”. Can be adopted.
For XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and an etching rate (etching rate) is set to 0.05 nm / sec (SiO ₂ thermal oxide film equivalent value). It is preferable to do.

  Further, the gas barrier layer 14 is substantially in the plane direction (direction parallel to the surface of the gas barrier layer 14) from the viewpoint of forming a layer having a uniform and excellent light distribution on the entire layer surface. It is preferable that they are uniform. The fact that the gas barrier layer 14 is substantially uniform in the plane direction means that the number of extreme values of the distribution curves of the elements at the respective measurement locations is the same at any two locations on the surface of the gas barrier layer 14, And the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the distribution curve is the same as each other, or the difference between the maximum value and the minimum value is within 5 at%.

(10) Substantially continuous In the gas barrier layer 14, the carbon distribution curve is preferably substantially continuous. The carbon distribution curve being substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the distance (x, unit: nm) from the surface of the gas barrier layer 14 calculated from the etching rate and etching time, and the atomic ratio of carbon (C, unit: at%) are expressed by the following formula. (F1):
(DC / dx) ≦ 0.5 (F1)
The condition represented by is satisfied.

(11) Silicon atomic ratio, oxygen atomic ratio In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve, the silicon atomic ratio, oxygen atomic ratio, and carbon atomic ratio are 90% of the thickness of the gas barrier layer 14. It is preferable that the condition represented by the above formula (A) is satisfied in the region of% or more. In this case, the atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer 14 is preferably 25 to 45 at%, and 30 to 40 at%. It is more preferable.

The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier layer 14 is preferably 33 to 67 at%, and more preferably 45 to 67 at%. preferable.
Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer 14 is preferably 3 to 33 at%, more preferably 3 to 25 at%. preferable.

(12) Layer thickness of gas barrier layer The layer thickness of the gas barrier layer 14 is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and in the range of 100 to 1000 nm. Particularly preferred. When the thickness of the gas barrier layer 14 is out of the above range, the light distribution of the gas barrier layer 14 becomes insufficient.
When the gas barrier layer 14 is formed from a plurality of layers, the total thickness of the gas barrier layer 14 is set in the range of 10 to 10000 nm, preferably in the range of 10 to 5000 nm, More preferably, it is in the range of -3000 nm, and particularly preferably in the range of 200-2000 nm.

(13) Primer layer The gas barrier layer 14 may be provided with a primer coat layer, a heat-sealable resin layer, an adhesive layer, etc. between the gas barrier layer 14 and the deterioration suppressing layer 13. The primer coat layer can be formed using a known primer coat agent capable of improving the adhesion between the deterioration suppressing layer 13 and the gas barrier layer 14. Moreover, a heat-sealable resin layer can be suitably formed using well-known heat-sealable resin. Furthermore, the adhesive layer can be appropriately formed using a known adhesive, and a plurality of gas barrier layers 14 may be adhered by such an adhesive layer.

(14) Formation Method of Gas Barrier Layer In the organic EL element 10, it is preferable that the gas barrier layer 14 is a layer formed by a plasma chemical vapor deposition (plasma CVD) method. As the gas barrier layer 14 formed by the plasma chemical vapor deposition method, the resin base material 12 having the deterioration suppressing layer 13 formed on one surface is disposed on a pair of film forming rolls, and the pair of film forming rolls. More preferably, the layer is formed by a plasma chemical vapor deposition method in which plasma is generated by discharging in between. The plasma chemical vapor deposition method may be a Penning discharge plasma type plasma chemical vapor deposition method. Moreover, when discharging between a pair of film-forming rolls, it is preferable to reverse the polarity of a pair of film-forming rolls alternately.

When generating plasma in the plasma chemical vapor deposition method, it is preferable to generate plasma discharge in the space between the plurality of film forming rolls.
Further, as a method for forming the gas barrier layer, it is preferable to use a vapor phase growth method by a counter roll method. In the present invention, the vapor phase growth method using the facing roll method uses a pair of film forming rolls, and a resin base material 12 is disposed on each of the pair of film forming rolls, and discharge is performed between the pair of film forming rolls. This means that the layer is formed by generating plasma.

  In this manner, the resin base material 12 is disposed on a pair of film forming rolls, and a film is formed on the resin base material 12 existing on one film forming roll by discharging between the film forming rolls. be able to. At the same time, it is possible to form a film on the resin substrate 12 on the other film forming roll. For this reason, the film-forming rate can be doubled and a thin film can be manufactured efficiently. Furthermore, a film having the same structure can be formed on each resin substrate 12 on the pair of film forming rolls.

In the plasma chemical vapor deposition method, a film forming gas containing an organosilicon compound and oxygen is preferably used. The oxygen content in the film forming gas is preferably less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas.
The gas barrier layer 14 is preferably a layer formed by a continuous film forming process.

(15) Gas Barrier Layer Manufacturing Apparatus The gas barrier layer 14 is preferably formed on the resin substrate 12 by the roll-to-roll method from the viewpoint of productivity as described above. An apparatus capable of producing the gas barrier layer 14 by plasma enhanced chemical vapor deposition is not particularly limited, but includes at least a pair of film forming rolls and a plasma power source and can discharge between the film forming rolls. It is preferable that the device is configured.

  For example, when the manufacturing apparatus 30 shown in FIG. 5 is used, it is also possible to manufacture by a roll-to-roll method using a plasma chemical vapor deposition method. Hereinafter, the manufacturing method of the gas barrier layer 14 will be described with reference to FIG. FIG. 5 is a schematic diagram showing an example of a manufacturing apparatus suitable for manufacturing the gas barrier layer 14.

  The manufacturing apparatus 30 shown in FIG. 5 includes a delivery roll 31, transport rolls 32, 33, 34, 35, film formation rolls 36, 37, a gas supply pipe 38, a plasma generation power source 39, and a film formation roll 36. And 37, and magnetic field generators 41 and 42 installed inside 37, and a winding roll 43. In the manufacturing apparatus 30, at least film forming rolls 36 and 37, a gas supply pipe 38, a plasma generation power source 39, and magnetic field generation apparatuses 41 and 42 are disposed in a vacuum chamber (not shown). Further, in the manufacturing apparatus 30, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be adjusted by the vacuum pump.

  In the manufacturing apparatus 30, each film forming roll is connected to the plasma generation power source 39 so that the pair of film forming rolls (the film forming roll 36 and the film forming roll 37) can function as a pair of counter electrodes. It is connected. For this reason, in the manufacturing apparatus 30, it is possible to discharge to the space between the film forming roll 36 and the film forming roll 37 by supplying power from the plasma generating power source 39. Plasma can be generated in the space between the film forming roll 37. When the film forming roll 36 and the film forming roll 37 are used as electrodes, the material and design of the film forming roll 36 and the film forming roll 37 may be changed so that they can be used as electrodes. Further, in the manufacturing apparatus 30, the pair of film forming rolls (film forming rolls 36 and 37) are preferably arranged so that the central axes are substantially parallel on the same plane. By arranging the pair of film forming rolls (film forming rolls 36 and 37) in this way, the film forming rate can be doubled and a film having the same structure can be formed. For this reason, it is possible to at least double the extreme value in the carbon distribution curve. Then, according to the manufacturing apparatus 30, it is possible to form the gas barrier layer 14 on the surface of the film 40 by the CVD method, while depositing a film component on the surface of the film 40 on the film forming roll 36, Further, since the film component can be deposited on the surface of the film 40 also on the film forming roll 37, the gas barrier layer 14 can be efficiently formed on the surface of the film 40.

Further, inside the film forming roll 36 and the film forming roll 37, magnetic field generators 41 and 42 fixed so as not to rotate even when the film forming roll rotates are provided, respectively.
Furthermore, as the film forming roll 36 and the film forming roll 37, known rolls can be used. As the film forming rolls 36 and 37, it is preferable to use rolls having the same diameter from the viewpoint of forming a thin film more efficiently. The diameters of the film forming rolls 36 and 37 are preferably in the range of 5 to 100 cm from the viewpoint of discharge conditions, chamber space, and the like.

  Moreover, in the manufacturing apparatus 30, the film 40 is arrange | positioned on a pair of film-forming roll (The film-forming roll 36 and the film-forming roll 37) so that the surface of the film 40 may oppose, respectively. By disposing the film 40 in this manner, each surface of the film 40 existing between the pair of film-forming rolls when the plasma is generated by discharging between the film-forming roll 36 and the film-forming roll 37. At the same time, the gas barrier layer 14 can be formed. That is, according to the manufacturing apparatus 30, the film component can be deposited on the surface of the film 40 on the film forming roll 36 and further the film component can be deposited on the film forming roll 37 by the CVD method. The gas barrier layer 14 can be efficiently formed on the surface of the film 40.

  Moreover, a well-known roll can be used as the sending roll 31 and the conveyance rolls 32, 33, 34, 35 used for the manufacturing apparatus 30. The winding roll 43 is not particularly limited as long as it can wind the film 40 on which the gas barrier layer 14 is formed, and a known roll can be used.

  As the gas supply pipe 38, a pipe capable of supplying or discharging the raw material gas at a predetermined speed can be used. Further, as the plasma generating power source 39, a power source of a known plasma generating apparatus can be used. The plasma generating power source 39 supplies power to the film forming rolls 36 and 37 connected thereto, and enables the film forming rolls 36 and 37 to be used as counter electrodes for discharging. As the plasma generation power source 39, it is preferable to use an AC power source or the like capable of alternately reversing the polarity of the film-forming roll, because it is possible to perform plasma CVD more efficiently. Moreover, since it becomes possible to perform plasma CVD more efficiently, the applied power can be 0.1 to 10 kW, and the alternating current frequency can be 0.05 to 500 kHz. More preferably, the generating power source 39 is used. As the magnetic field generators 41 and 42, known magnetic field generators can be used. Furthermore, as the film 40, in addition to the resin base material 12 applicable to the organic EL element 10 described above, a resin base material 12 in which a gas barrier layer 14 is formed in advance can be used. As described above, by using the resin base material 12 on which the gas barrier layer 14 is formed in advance as the film 40, the thickness of the gas barrier layer 14 can be increased.

  As described above, using the manufacturing apparatus 30 shown in FIG. 5, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roll, and the film transport speed By adjusting the gas barrier layer 14, the gas barrier layer 14 can be manufactured. That is, by using the manufacturing apparatus 30 shown in FIG. 5 and discharging a film forming gas (raw material gas or the like) between the pair of film forming rolls (film forming rolls 36 and 37) while supplying it into the vacuum chamber, The film forming gas (raw material gas or the like) is decomposed by plasma, and the gas barrier layer 14 is formed on the surface of the film 40 on the film forming roll 36 and the surface of the film 40 on the film forming roll 37 by the plasma CVD method. The In film formation, the film 40 is conveyed by the delivery roll 31 and the film formation roll 36, respectively, so that a gas barrier is formed on the surface of the film 40 by a roll-to-roll continuous film formation process. Layer 14 is formed.

(16) Source Gas The source gas in the film forming gas used for forming the gas barrier layer 14 can be appropriately selected and used according to the material of the gas barrier layer 14 to be formed. As the source gas, for example, an organosilicon compound containing silicon can be used. Examples of the organosilicon compound include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propyl Examples thereof include silane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane should be used from the viewpoints of handleability in film formation and light distribution of the gas barrier layer 14 to be obtained. Is preferred. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for

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

  When the film forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the amount of the reactive gas that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessively higher than the ratio of. If the ratio of the reaction gas is excessive, the light distribution of the gas barrier layer 14 cannot be obtained sufficiently. Moreover, when the film-forming gas contains an organosilicon compound and oxygen, the amount is preferably less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film-forming gas.

Hereinafter, as an example, a case where hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O :) is used as a source gas and oxygen (O ₂ ) is used as a reaction gas will be described.
When a silicon-oxygen-based thin film is produced by reacting a film-forming gas containing hexamethyldisiloxane as a source gas and oxygen as a reaction gas by plasma CVD, the following reaction formula is given by the film-forming gas:
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
The following reaction occurs and silicon dioxide is produced. In this reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. For this reason, when 12 mol or more of oxygen is contained in 1 mol of hexamethyldisiloxane in the film forming gas and completely reacted, a uniform silicon dioxide film is formed. For this reason, the incomplete reaction is performed by controlling the gas flow rate ratio of the raw material to a flow rate equal to or lower than the theoretical reaction raw material ratio. That is, the amount of oxygen needs to be less than 12 moles of the stoichiometric ratio with respect to 1 mole of hexamethyldisiloxane.

  In the actual reaction in the plasma CVD chamber, since the raw material hexamethyldisiloxane and the reactive gas oxygen are supplied from the gas supply unit to the film formation region, the molar amount (flow rate) of the reactive gas oxygen is the raw material. Even if the molar amount (flow rate) is 12 times the molar amount (flow rate) of hexamethyldisiloxane, the reaction cannot actually proceed completely. That is, it is considered that the reaction is completed only when the oxygen content is supplied in a large excess compared to the stoichiometric ratio. For example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material.

  For this reason, it is preferable that the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer 14, and the desired gas barrier layer 14. Can be formed.

  If the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, unoxidized carbon atoms and hydrogen atoms are excessively taken into the gas barrier layer 14. Therefore, the transparency of the gas barrier layer 14 is lowered. For this reason, like the organic EL element 10, it cannot be used for a flexible substrate that requires transparency. From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. Preferably, the amount is more than 0.5 times.

(17) Degree of vacuum The pressure in the vacuum chamber (degree of vacuum) can be adjusted as appropriate according to the type of the raw material gas, but is preferably in the range of 0.5 to 100 Pa.

(18) Film formation roll In the plasma CVD method described above, in order to discharge between the film formation rolls 36 and 37, the power applied to the electrode drum connected to the plasma generating power source 39 depends on the type of source gas and the vacuum chamber. It can adjust suitably according to the internal pressure etc. For example, a range of 0.1 to 10 kW is preferable. If the applied power is less than 0.1 kW, particles tend to be generated. On the other hand, when the applied power exceeds 10 kW, the amount of heat generated during film formation increases, the temperature of the substrate surface during film formation rises, the resin substrate 12 loses heat, and wrinkles occur during film formation. End up.
In this example, the electrode drum is installed on the film forming rolls 36 and 37.

  The conveyance speed (line speed) of the film 40 can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, and the like, but is preferably in the range of 0.25 to 100 m / min. A range of 5 to 20 m / min is more preferable. When the line speed is less than 0.25 m / min, wrinkles due to heat tend to occur in the film, and when it exceeds 100 m / min, the thickness of the formed gas barrier layer 14 tends to be thin. It is in.

By including the gas barrier layer 14 formed by the above-mentioned plasma CVD method, including silicon, oxygen and carbon, and the distribution curve of each element satisfying the above conditions (i) to (iii), Adhesiveness with the sealing member 20 can be improved.
The gas barrier layer 14 is formed from an inorganic film containing silicon, oxygen, and carbon, and has a characteristic of excellent thermal diffusivity. In particular, the inclusion of carbon is considered to improve the thermal conductivity as compared with an inorganic film made only of silicon and oxygen. Since the gas barrier layer 14 has a carbon content distribution in the layer thickness direction, it is presumed that the gas barrier layer 14 has characteristics similar to a configuration in which a plurality of layers having different compositions are laminated. That is, excellent thermal diffusibility is obtained in a region having a high carbon content in the gas barrier layer 14, and the thermal diffusivity in the surface direction of the gas barrier layer 14 is improved. For this reason, the thermal diffusibility of the gas barrier layer 14 can be improved.
Therefore, when a thermosetting resin is used for the sealing resin layer 19 and the high temperature treatment is performed for a long time as the curing treatment, the gas barrier layer 14 dissipates the heat applied to the organic EL element 10, thereby Thermal damage to the material 12 can be reduced.

《Smooth layer》
A smooth layer (not shown) may be formed between the deterioration suppressing layer 13 and the gas barrier layer 14. The smooth layer is provided in order to planarize the surface of the deterioration suppressing layer 13. Such a smooth layer is basically formed by curing a photosensitive resin.

  Examples of the photosensitive resin used for forming the smooth layer include 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, Examples thereof include resin compositions in which polyfunctional acrylate monomers such as urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate are dissolved. 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.

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

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

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 in order to improve the film formability and prevent the generation of pinholes in the film.

  When forming a smooth layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent, examples of the solvent used include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol. , Terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, toluene, xylene, tetramethylbenzene Aromatic hydrocarbons such as, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate Acetic esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, Diethylene glycol dialkyl ether, dipropylene group Call dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. When the thickness is smaller than 10 nm, the coating property may be impaired when the coating means comes into contact with the surface of the smooth layer in the step of applying a silicon compound described later by a coating method such as a wire bar or a wireless bar. Moreover, when larger than 30 nm, it may become difficult to smooth the unevenness | corrugation after apply | coating a silicon compound.
The surface roughness is a roughness related to the amplitude of fine irregularities measured using an AFM (atomic force microscope). This surface roughness is calculated from the cross-sectional curve of the unevenness measured continuously by measuring a number of times within several tens of μm with a detector having a stylus having a minimum tip radius of AFM.

(1) Additive to smooth layer The smooth layer may contain an additive. The additive contained in the smooth layer is preferably reactive silica particles in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the photosensitive resin (hereinafter also simply referred to as “reactive silica particles”).

  Here, examples of the photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group. The photosensitive resin preferably contains a compound capable of undergoing a photopolymerization reaction with the photosensitive group introduced on the surface of the reactive silica particles, for example, an unsaturated organic compound having a polymerizable unsaturated group. The photosensitive resin may have a solid content adjusted by mixing a general-purpose diluent solvent with reactive silica particles or an unsaturated organic compound having a polymerizable unsaturated group.

Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By using the average particle diameter in the above range, a smooth layer having both optical properties such as light distribution and hard coat properties when used in combination with a matting agent composed of inorganic particles having an average particle diameter of 1 to 10 μm described later. It becomes easy to form.
In order to make it easier to obtain the above effect, the average particle diameter is preferably in the range of 0.001 to 0.01 μm. The smooth layer preferably contains the above inorganic particles in a mass ratio of 20% to 60%. By adding 20% or more, the adhesion between the resin substrate 12 and the gas barrier layer 14 is improved. On the other hand, if it exceeds 60%, the film may be bent or cracks may occur when heat treatment is performed, and optical properties such as transparency and refractive index of the gas barrier layer 14 may be affected.

In this example, as the reactive silica particles, a hydrolyzable silyl group is hydrolyzed to form a silyloxy group between the silica particles and chemically bonded to the polymerizable unsaturated group modified hydrolyzable. Silane can be used.
Examples of the hydrolyzable silyl group include a carboxylylated silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oximesilyl group, and a hydridosilyl group.
Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.

The smooth layer may contain a matting agent as another additive. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.
As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the smooth layer. It is preferable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.

(2) Layer thickness of smooth layer The layer thickness of the smooth layer is preferably 1 to 10 μm, more preferably 2 to 7 μm. By setting the thickness to 1 μm or more, the smoothness of the resin substrate 12 having a smooth layer is sufficient. Moreover, by making it 10 μm or less, it becomes easy to adjust the balance of optical characteristics, and it is possible to easily suppress curling when a smooth layer is provided only on one surface of the resin substrate 12.

<Bleed-out prevention layer>
The gas barrier layer 14 can be provided with a bleed-out prevention layer. When the film-like resin substrate 12 having the smooth layer and the deterioration suppressing layer 13 are heated, the bleed-out prevention layer is transferred from the resin substrate 12 to the surface by unreacted oligomers and the like. In order to suppress the phenomenon of contaminating the surface of 12, it is provided on the opposite surface of the resin substrate 12 having a smooth layer. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  As the bleed-out preventing layer, an unsaturated organic compound having a polymerizable unsaturated group can be used. Examples of the unsaturated organic compound include a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or a unit price unsaturated organic compound having one polymerizable unsaturated group in the molecule. Is preferably used.

  Here, as the polyunsaturated organic compound, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meta ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolprop Tetra (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Moreover, as a unit price unsaturated organic compound, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-e Xoxyethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

  The bleed-out prevention layer may contain, for example, a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like.

  Examples of the thermoplastic resin contained in the bleedout prevention layer include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, Vinyl resins such as vinylidene chloride and copolymers thereof, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins , Linear polyester resin, polycarbonate resin and the like.

  Examples of the thermosetting resin contained in the bleed-out prevention layer include thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicon Examples thereof include resins.

  Further, the ionizing radiation curable resin contained in the bleed-out prevention layer is prepared by mixing ionizing radiation (ultraviolet or electron) with an ionizing radiation curable coating obtained by mixing one or more of photopolymerizable prepolymer or photopolymerizable monomer. Can be cured by irradiation. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferable. As the acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. As the photopolymerizable monomer, the above polyunsaturated organic compounds can be used.

  Examples of the photopolymerization initiator contained in the bleedout prevention layer include acetophenone, benzophenone, Michler ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl. ) -2- (4-morpholinyl) -1-propane, α-acyloxime ester, thioxanthones and the like.

  The bleed-out prevention layer is prepared by blending a matting agent and other necessary components, and then preparing a coating solution with a diluting solvent as necessary, and applying this coating solution to the surface of the resin substrate 12 by a conventionally known coating method. It can be formed by irradiating the coating liquid with ionizing radiation and curing it. In addition, as ionizing radiation, ultraviolet rays having a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like are irradiated. Alternatively, an electron beam having a wavelength region of 100 nm or less emitted from a scanning type or curtain type electron beam accelerator is irradiated.

  The layer thickness of the bleed-out prevention layer is preferably 1 to 10 μm, and particularly preferably 2 to 7 μm. By setting the layer thickness to 1 μm or more, the heat resistance of the bleed-out prevention layer can be made sufficient. In addition, by adjusting the layer thickness to 10 μm or less, it becomes easy to adjust the balance of optical characteristics, and curling when a smooth layer is provided on one surface of the resin substrate 12 can be suppressed.

<Polysilazane modified layer>
The polysilazane modified layer 15 is a layer provided to smooth the irregularities on the surface of the gas barrier layer 14 and is a light-transmitting layer formed on the gas barrier layer 14. The polysilazane modified layer 15 is a layer formed by subjecting a coating film of a polysilazane-containing liquid to a modification treatment. The polysilazane modified layer 15 is mainly formed of a silicon oxide or a silicon oxynitride compound.

  As a method for forming the polysilazane modified layer 15, a layer containing a silicon oxide or a silicon oxynitride compound is applied by performing a modification treatment after applying a coating liquid containing at least one polysilazane compound on a substrate. The method of forming is mentioned.

  The silicon oxide or silicon oxynitride compound for forming the polysilazane modified layer 15 is supplied as a substrate rather than being supplied as a gas as in the CVD method (Chemical Vapor Deposition). A more uniform and smooth layer can be formed by applying to the surface. In the case of the CVD method or the like, it is known that particles are generated at the same time as the step of depositing the source material having increased reactivity in the gas phase on the substrate surface. As the generated particles are deposited on the base material, the smoothness of the base material surface is lowered. In the coating method, since the raw material does not exist in the gas phase reaction space, generation of particles can be suppressed. Therefore, the polysilazane modified layer 15 having a smooth surface can be formed by using a coating method.

  By providing the polysilazane modified layer 15 on the gas barrier layer 14, the irregularities on the surface of the gas barrier layer 14 can be alleviated, and defects due to a short circuit of the first electrode 16 can be prevented. Peeling of the layer 17 can be prevented.

(1) Coating film containing polysilazane The coating film containing polysilazane is formed by applying at least one layer of a coating liquid containing a polysilazane compound on a substrate.

  Any appropriate method can be adopted as a coating method. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method. The coating thickness can be appropriately set according to the purpose. For example, the coating thickness can be set so that the thickness after drying is preferably about 0.001 to 100 μm, more preferably about 0.01 to 10 μm, and most preferably about 0.01 to 1 μm.

“Polysilazane” is a polymer having a silicon-nitrogen bond, and is a ceramic precursor inorganic polymer such as SiO ₂ , Si ₃ N ₄ composed of Si—N, Si—H, N—H, etc., and both intermediate solid solutions SiOxNy. is there. Polysilazane is represented by the following general formula (I).

  In order to apply the film base material without damaging the film base material, it is preferable to use a ceramic material which is converted to silica at a relatively low temperature as described in JP-A-8-112879.

  In general formula (I), R1, R2, and R3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group, or the like.

  Perhydropolysilazane, in which all of R1, R2 and R3 are hydrogen atoms, is particularly preferred from the viewpoint of the denseness as the obtained gas barrier film.

  On the other hand, the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to the base substrate is improved and the polysilazane is hard and brittle. The ceramic film can be provided with toughness, and there is an advantage that generation of cracks can be suppressed even when the (average) film thickness is increased. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and can also be mixed and used.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  As another example of polysilazane which is ceramicized at a low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with the polysilazane represented by the above general formula (I) (Japanese Patent Laid-Open No. 5-238827), 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 Polysilazane containing fine particles JP-A-7-196986 publication), and the like.

  Specific examples of the organic solvent for preparing a liquid containing polysilazane include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, and fats. Ethers such as cyclic ethers can be used. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of solvents may be mixed. Note that alcohol-based or water-containing solvents are not preferable because they easily react with polysilazane.

  The polysilazane concentration in the polysilazane-containing coating solution is about 0.2 to 35% by mass, although it varies depending on the target silica layer thickness and the pot life of the coating solution.

  In order to promote the conversion to a silicon oxide compound, an amine or metal catalyst may be added. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.

(2) Moisture removal treatment for coating film It is preferable that the coating film containing polysilazane has moisture removed before the modification treatment. The method for removing moisture in the coating film is preferably divided into a first step for removing the solvent in the coating film and a subsequent second step for removing moisture in the coating film.

  In the first step, drying conditions for mainly removing the solvent can be appropriately determined by a method such as heat treatment, but the conditions may be such that moisture is removed at this time. The heat treatment temperature is preferably a high temperature from the viewpoint of rapid treatment, but the temperature and treatment time are determined in consideration of thermal damage to the resin substrate 12. For example, when a PET substrate having a glass transition temperature (Tg) of 70 ° C. is used for the resin substrate 12, the heat treatment temperature can be set to 200 ° C. or less. The treatment time is preferably set to a short time so that the solvent is removed and thermal damage to the resin base material 12 is reduced. If the heat treatment temperature is 200 ° C. or less, the treatment time can be set within 30 minutes.

  The second step is a step for removing moisture in the coating film, and the method for removing moisture is preferably in a form maintained in a low humidity environment. Since the humidity in the low humidity environment varies depending on the temperature, a preferable form of the relationship between the temperature and the humidity is indicated by the definition of the dew point temperature. A preferable dew point temperature is 4 degrees or less (temperature 25 degrees / humidity 25%), a more preferable dew point temperature is -8 degrees (temperature 25 degrees / humidity 10%) or less, and a more preferable dew point temperature is (temperature 25 degrees / humidity 1%). ) −31 degrees or less, and the maintained time varies depending on the thickness of the coating film. Under the condition that the thickness of the coating film is 1 μm or less, the preferable dew point temperature is −8 ° C. or less, and the maintained time is 5 minutes or more. Moreover, you may dry under reduced pressure in order to make it easy to remove a water | moisture content. The pressure in the vacuum drying can be selected from normal pressure to 0.1 MPa.

  As a preferable condition of the second step with respect to the condition of the first step, for example, when the solvent is removed at a temperature of 60 to 150 ° C. and a processing time of 1 to 30 minutes in the first step, the dew point of the second step is 4 degrees or less. The time can be selected from 5 to 120 minutes to remove moisture. The first process and the second process can be distinguished by changing the dew point, and can be classified by changing the dew point of the process environment by 10 degrees or more.

  The coating film is preferably subjected to a modification treatment after the moisture is removed in the second step and the state is maintained.

(3) Water content of the coating film The water content of the coating film can be detected by the following analysis method.

Headspace-gas chromatograph / mass spectrometry apparatus: HP6890GC / HP5973MSD
Oven: 40 ° C. (2 min), then heated to 150 ° C. at a rate of 10 ° C./min Column: DB-624 (0.25 mm × 30 m)
Inlet: 230 ° C
Detector: SIM m / z = 18
HS condition: 190 ° C, 30min

  The moisture content in the coating film is defined as a value obtained by dividing the moisture content obtained by the above analysis method by the volume of the coating film, and is preferably 0.1% or less in a state where moisture is removed by the second step. is there. A more preferable moisture content is 0.01% or less (below the detection limit).

(4) Modification Treatment For the modification treatment, a known method based on the conversion reaction of polysilazane can be selected. Production of a silicon oxide film or a silicon oxynitride film by a substitution reaction of a silazane compound requires heat treatment at 450 ° C. or higher, and is difficult to apply to a flexible substrate such as plastic. In order to apply to a plastic substrate, it is preferable to use a method such as plasma treatment, ozone treatment, or ultraviolet irradiation treatment that allows the conversion reaction to proceed at a low temperature.

(4-1) Plasma treatment As the plasma treatment as the modification treatment, a known method can be used, but atmospheric pressure plasma treatment is preferable. In the case of atmospheric pressure plasma treatment, nitrogen gas and / or Group 18 atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used as the discharge gas. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  As an example of plasma processing, atmospheric pressure plasma processing will be described. Specifically, the atmospheric pressure plasma is one in which two or more electric fields having different frequencies are formed in the discharge space, as described in International Publication No. 2007-026545, and the first high-frequency electric field and the second high-frequency electric field. It is preferable to form an electric field superimposed with the electric field.

In the atmospheric pressure plasma treatment, the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, The relationship with the intensity IV of the discharge start electric field is
V1 ≧ IV> V2 or V1> IV ≧ V2
And the output density of the second high-frequency electric field is 1 W / cm ² or more.

  By adopting such a discharge condition, for example, a discharge gas having a high discharge start electric field strength such as nitrogen gas can be started to discharge and maintain a high density and stable plasma state, and a high performance thin film can be formed. Can do.

  When the discharge gas is nitrogen gas according to the above measurement, the discharge start electric field intensity IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field intensity is , By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited into a plasma state.

Here, as the frequency of the first power supply, 200 kHz or less can be preferably used. Further, the electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz. On the other hand, as the frequency of the second power source, 800 kHz or more can be preferably used. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.
The formation of a high-frequency electric field from such two power sources is necessary for initiating discharge of a discharge gas having a high discharge start electric field strength by the first high-frequency electric field, and the second high-frequency electric field is high. A dense and good quality thin film can be formed by increasing the plasma density by the frequency and the high power density.

(4-2) Ultraviolet irradiation treatment As a method for the modification treatment, treatment by ultraviolet irradiation is also preferable. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and it is possible to produce silicon oxide films or silicon oxynitride films that have high density and insulation at low temperatures. It is.

By this ultraviolet irradiation, the substrate is heated, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. The conversion to ceramics is promoted, and the resulting ceramic film becomes denser. Irradiation with ultraviolet rays is effective at any time after the coating film is formed.

  In the present invention, any commonly used ultraviolet ray generator can be used.

  In this example, “ultraviolet rays” generally refers to electromagnetic waves having a wavelength of 10 to 400 nm, but in the case of ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, preferably 210 to 210. An ultraviolet ray of 350 nm is used.

  In the irradiation with ultraviolet rays, the irradiation intensity and the irradiation time are set within a range where the substrate carrying the coating film to be irradiated is not damaged.

Taking the case of using a plastic film as a base material, for example, a lamp of 2 kW (80 W / cm × 25 cm) is used, and the strength of the base material surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm ^2. The distance between the base material and the lamp is set so that the irradiation becomes 0.1 seconds to 10 minutes.

  Generally, when the base material temperature at the time of ultraviolet irradiation treatment is 150 ° C. or more, when a plastic film or the like is used as the base material, the base material is deformed or the strength of the base material is reduced. However, in the case of a highly heat-resistant film such as polyimide or a base material such as metal, processing at a higher temperature is possible. Therefore, there is no general upper limit to the substrate temperature at the time of ultraviolet irradiation, and a person skilled in the art can appropriately set it depending on the type of the substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generation methods 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. )), UV light laser and the like, and are not particularly limited. In addition, when irradiating the generated ultraviolet rays to the coating film, it is desirable to apply the ultraviolet rays from the generation source to the coating film after reflecting the ultraviolet rays from the generation source with a reflector in order to achieve uniform irradiation and improve efficiency. .

  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 coated. For example, in the case of batch processing, a base material having a coating film on the surface (for example, a silicon wafer) can be processed in an ultraviolet baking furnace equipped with the above-described ultraviolet light source. The ultraviolet baking furnace itself is generally known, and for example, it is possible to use those manufactured by I-Graphics Co., Ltd. In addition, when the substrate having a coating film on the surface is a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. can do. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate to be applied and the coating composition.

(4-3) Vacuum ultraviolet irradiation treatment; excimer irradiation treatment In the present invention, as a more preferable method of the modification treatment, a treatment by vacuum ultraviolet irradiation is exemplified. The treatment with 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 silazane compound, and bonds of atoms are only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of.
As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

Here, since noble gas atoms such as Xe, Kr, Ar, Ne and the like are chemically bonded to form a molecule, it is called an inert gas. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. When the rare gas is xenon,
e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ^{2 *} + Xe
Then, when the excited excimer molecule Xe ^{2 *} transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high.
Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

  In order to obtain excimer light emission, a method using dielectric gas barrier discharge is known. Dielectric gas barrier discharge is generated in a gas space by arranging a gas space through a dielectric (transparent quartz in the case of an excimer lamp) between both electrodes and applying a high frequency high voltage of several tens of kHz to the electrode. It is a very thin discharge called a micro discharge similar to lightning. When the micro discharge streamer reaches the tube wall (dielectric), the electric charge accumulates on the dielectric surface, and the micro discharge disappears. Thus, the dielectric gas barrier discharge is a discharge in which micro discharge spreads over the entire tube wall and is repeatedly generated and extinguished. For this reason, flickering of light that can be seen with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless electric field discharge can be used in addition to dielectric gas barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp and electrodes and their arrangement may be basically the same as for dielectric gas barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge, a long-life lamp without flickering can be obtained.

  In the case of dielectric gas barrier discharge, micro discharge occurs only between the electrodes, so the outer electrode covers the entire outer surface and allows light to pass through to extract light to the outside in order to discharge in the entire discharge space. Must be a thing. For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere.

  In order to prevent this, it is necessary to create an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the outer surface of the lamp. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric gas barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside. Therefore, a very inexpensive light source can be provided.

  Since the double cylindrical lamp is processed by closing both ends of the inner and outer tubes, it is more likely to be damaged by use and transportation than a thin tube lamp. Further, the outer diameter of the tube of the thin tube lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

  As the form of discharge, either dielectric gas barrier discharge or electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

  The Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. 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. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the coating film containing polysilazane can be modified in a short time. Therefore, compared to low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

  Since the excimer lamp has high light generation efficiency, it can be lit 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 at a single wavelength in the ultraviolet region, so that an increase in the surface temperature of the irradiation object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

(5) Smoothness: surface roughness Ra
The surface roughness (Ra) of the polysilazane modified layer 15 is preferably 2 nm or less, and more preferably 1 nm or less. When the surface roughness is in the above range, when the first electrode 16 is provided on the gas barrier film 11, the light transmission efficiency is improved by the smooth film surface with less unevenness, and the leakage current between the electrodes is reduced. Since energy conversion efficiency improves, it is preferable. The surface roughness (Ra) of the polysilazane modified layer 15 can be measured by the following method.

  The surface roughness is calculated from an uneven sectional curve continuously measured with an AFM (Atomic Force Microscope), for example, DI3100 manufactured by Digital Instruments, with a detector having a stylus with a minimum tip radius. This is a roughness related to the amplitude of fine irregularities measured by a stylus many times in a section whose measurement direction is several tens of μm.

<< First electrode >>
In the organic EL element 10, the first electrode 16 is a substantial anode. The organic EL element 10 is a bottom emission type element that passes through the first electrode 16 and extracts light from the resin substrate 12 side. For this reason, the 1st electrode 16 needs to be formed with a translucent conductive layer.

  The first electrode 16 is a layer formed using, for example, silver or an alloy containing silver as a main component. Examples of the alloy mainly composed of silver (Ag) constituting the first electrode 16 include silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), silver indium ( AgIn) and the like. In the first electrode, the main component means that the content in the electrode is 98% by mass or more.

  The first electrode 16 may be formed by laminating a plurality of layers of silver or an alloy containing silver as a main component.

  Examples of the method for forming the first electrode 16 include a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, and the like. And a method using the dry process. Of these, the vapor deposition method is preferably applied.

  Further, the first electrode 16 preferably has a thickness in the range of 4 to 12 nm. A thickness of 12 nm or less is preferable because the light absorption component and the reflection component can be kept low and the light transmittance can be secured. Further, it is preferable that the thickness is 4 nm or more because sufficient conductivity as an electrode can be secured.

Note that the first electrode 16 as described above may be covered with a protective film at the top, or may be laminated with another conductive layer. In this case, it is preferable that the protective film and the conductive layer have light transmittance so that the light transmittance of the organic EL element 10 is not impaired.
In addition, a layer according to need may be provided below the first electrode 16, that is, between the polysilazane modified layer 15 and the first electrode 16. For example, an improvement in the characteristics of the first electrode 16 or a base layer for facilitating the formation may be formed.
The first electrode 16 may have a configuration other than that containing silver as a main component. For example, various transparent conductive material thin films such as other metals and alloys, ITO, zinc oxide, tin oxide and the like may be used.
Further, when the organic EL element 10 is a top emission type in which the emitted light h is extracted from the second electrode 18 side, the first electrode 16 may not have translucency.

<< Second electrode >>
The second electrode 18 is an electrode layer that functions as a cathode for supplying electrons to the organic functional layer 17, and a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof is used as a material. Specifically, gold, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TiO ₂ and oxide semiconductors such as SnO ₂ .

  The second electrode 18 can be formed of these conductive materials by a method such as vapor deposition or sputtering. The sheet resistance as the second electrode 18 is several hundred Ω / sq. The following is preferable, and the thickness is usually selected in the range of 5 to 5000 nm, preferably 5 to 200 nm.

  In addition, when the organic EL element 10 is a top emission type or a double-sided emission type in which the emitted light h is extracted from the second electrode 18 side, a conductive material having good light transmittance is selected from the above-described conductive materials. Thus, the second electrode 18 is configured.

《Organic functional layer》
The organic functional layer 17 has a configuration in which a hole injection layer 17a / hole transport layer 17b / light emitting layer 17c / electron transport layer 17d / electron injection layer 17e are stacked in this order on the first electrode 16 serving as an anode. Although it is possible, it is necessary to have at least the light emitting layer 17c composed of an organic material. The hole injection layer 17a and the hole transport layer 17b may be provided as a hole transport / injection layer having a hole transport property and a hole injection property. The electron transport layer 17d and the electron injection layer 17e may be provided as an electron transport / injection layer having electron transport properties and electron injection properties. Of these organic functional layers 17, for example, the electron injection layer 17e may be composed of an inorganic material.

  In addition to these layers, the organic functional layer 17 may be laminated with a hole blocking layer, an electron blocking layer, or the like as necessary. Furthermore, the light emitting layer 17c has each color light emitting layer for generating emitted light in each wavelength region, and each of these color light emitting layers is laminated via a non-light emitting intermediate layer to form a light emitting layer unit. Also good. The intermediate layer may function as a hole blocking layer and an electron blocking layer.

<Light emitting layer>
The light emitting layer 17c contains, for example, a phosphorescent light emitting compound as a light emitting material.
The light-emitting layer 17c is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer 17d and holes injected from the hole transport layer 17b. Even within the layer, it may be an interface with an adjacent layer in the light emitting layer 17c.

  The light emitting layer 17c is not particularly limited in its configuration as long as the contained light emitting material satisfies the light emission requirements. There may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting intermediate layer (not shown) between the light emitting layers 17c.

  The total thickness of the light emitting layer 17c is preferably in the range of 1 to 100 nm, and more preferably 1 to 30 nm because it can be driven at a lower voltage. The total thickness of the light emitting layer 17c is a layer thickness including the intermediate layer when a non-light emitting intermediate layer exists between the light emitting layers 17c.

  When the light emitting layer 17c consists of a several layer, it is preferable to adjust to the range of 1-50 nm as a layer thickness of each light emitting layer, and it is more preferable to adjust to the range of 1-20 nm. When the plurality of stacked light emitting layers correspond to the respective emission colors of blue, green, and red, there is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.

  The light emitting layer 17c as described above can be formed of a light emitting material or a host compound, which will be described later, by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method.

  The light emitting layer 17c may contain a plurality of light emitting materials, and a phosphorescent light emitting material and a fluorescent light emitting material (also referred to as a fluorescent dopant or a fluorescent compound) may be mixed and used in the same light emitting layer 17c. good.

  The light-emitting layer 17c preferably includes a host compound (also referred to as a light-emitting host) and a light-emitting material (also referred to as a light-emitting dopant compound or a guest material) and emits light from the light-emitting material.

(1) Host compound As the host compound contained in the light emitting layer 17c, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C) of less than 0.1 is preferable. Furthermore, the compound whose phosphorescence quantum yield is less than 0.01 is preferable. The host compound preferably has a volume ratio in the layer of 50% or more among the compounds contained in the light emitting layer 17c.

  As a host compound, a well-known host compound may be used independently, or multiple types may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element 10 can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

  The host compound used may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light-emitting host). .

  As the known host compound, a compound that has a hole transporting ability and an electron transporting ability, prevents light emission from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable. Glass transition point (Tg) here is a value calculated | required by the method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry: Differential scanning calorimetry).

(2) Light-Emitting Material Examples of the light-emitting material that can be used for the organic EL element 10 include phosphorescent compounds (also referred to as phosphorescent compounds and phosphorescent materials).

  A phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. A preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, in the case where a phosphorescent compound is used in this example, the phosphorescence quantum yield (0.01 or more) is obtained in any solvent. It only has to be achieved.

  There are two types of light emission principles of the phosphorescent compound. One is that recombination of carriers occurs on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent compound to emit light from the phosphorescent compound. Energy transfer type. The other is a carrier trap type in which the phosphorescent compound becomes a carrier trap, and recombination of carriers occurs on the phosphorescent compound, and light emission from the phosphorescent compound is obtained. In either case, the condition is that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of a general organic EL device, but preferably contains a group 8-10 metal in the periodic table of elements. It is a complex compound. More preferred are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds), and rare earth complexes, and most preferred are iridium compounds.

  In the organic EL element 10, at least one light emitting layer 17c may contain two or more types of phosphorescent compounds, and the concentration ratio of the phosphorescent compounds in the light emitting layer 17c is the thickness of the light emitting layer 17c. It may change in the direction.

  The phosphorescent compound is preferably 0.1% by volume or more and less than 30% by volume with respect to the total amount of the light emitting layer 17c.

  Examples of the fluorescent light emitting material used for the light emitting layer 17c include, for example, a coumarin dye, a pyran dye, a cyanine dye, a croconium dye, a squalium dye, an oxobenzanthracene dye, a fluorescein dye, a rhodamine dye, Examples include pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

<< Injection layer: hole injection layer, electron injection layer >>
The injection layer is a layer provided between the electrode and the light emitting layer 17c in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and its forefront of industrialization (November 30, 1998, NT. 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of “S. Co., Ltd.”, and includes a hole injection layer 17a and an electron injection layer 17e.

  The injection layer can be provided as necessary. The hole injection layer 17a is disposed between the anode and the light emitting layer 17c or the hole transport layer 17b, and the electron injection layer 17e is disposed between the cathode and the light emitting layer 17c or the electron transport layer 17d.

  The details of the hole injection layer 17a are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Specific examples thereof include phthalocyanine represented by copper phthalocyanine. Examples thereof include a layer, an oxide layer typified by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the electron injection layer 17e are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specifically, strontium, aluminum and the like are represented. Examples thereof include a metal layer, an alkali metal halide layer typified by potassium fluoride, an alkaline earth metal compound layer typified by magnesium fluoride, and an oxide layer typified by molybdenum oxide. The electron injection layer 17e is desirably a very thin layer, and its thickness is preferably in the range of 0.001 to 10 μm although it depends on the material.

《Hole transport layer》
The hole transport layer 17b is made of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer 17a and the electron blocking layer are also included in the hole transport layer 17b. The hole transport layer 17b 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.

  Although the above-mentioned thing can be used as a positive hole transport material, It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styryl amine compound, especially an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two fused aromatic rings described in US Pat. No. 5,061,569. In the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308688 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) in which triphenylamine units described in the publication are linked in three starburst types Etc.

  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.

  Further, the hole transport layer 17b has a so-called p-type positive layer as described in JP-A-11-251067, J. Huang et.al., Applied Physics Letters, 80 (2002), p.139. A hole transport material can also be used. These materials are preferably used because a highly efficient light-emitting element can be obtained.

  The hole transport layer 17b is 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. be able to. Although there is no restriction | limiting in particular about the layer thickness of the positive hole transport layer 17b, Usually, about 5-5000 nm, Preferably it is 5-200 nm. The hole transport layer 17b may have a single layer structure composed of one or more of the above materials.

  Further, the material of the hole transport layer 17b can be doped with impurities to increase the p property. Examples thereof include those described in JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Appl. Phys., 95, 5773 (2004), and the like. .

  Thus, it is preferable to increase the p property of the hole transport layer 17b because an element with lower power consumption can be manufactured.

《Electron transport layer》
The electron transport layer 17d is made of a material having a function of transporting electrons. In a broad sense, the electron injection layer 17e and a hole blocking layer (not shown) are also included in the electron transport layer 17d. The electron transport layer 17d can be provided as a single layer structure or a stacked structure of a plurality of layers.

  As an electron transport material (also serving as a hole blocking material) constituting the layer portion adjacent to the light emitting layer 17c in the electron transport layer 17d having a single layer structure and the electron transport layer 17d having a multilayer structure, electrons injected from the cathode are used. What is necessary is just to have the function to transmit to the light emitting layer 17c. Such a material can be arbitrarily selected from conventionally known compounds. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Furthermore, in the 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 are also used as the material for the electron transport layer 17d. Can do. 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 (Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) Aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as the material of the electron transport layer 17d.

  In addition, even if it is metal-free or metal phthalocyanine, or even if the terminal thereof is substituted with an alkyl group or a sulfonic acid group, it can be preferably used as a material for the electron transport layer 17d. Further, a distyrylpyrazine derivative exemplified also as a material of the light emitting layer 17c can be used as a material of the electron transport layer 17d, and n-type-Si, n-type similarly to the hole injection layer 17a and the hole transport layer 17b. An inorganic semiconductor such as -SiC can also be used as the material of the electron transport layer 17d.

  The electron transport layer 17d can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method. Although there is no restriction | limiting in particular about the layer thickness of the electron carrying layer 17d, Usually, about 5-5000 nm, Preferably it is 5-200 nm. The electron transport layer 17d may have a single-layer structure made of one or more of the above materials.

  In addition, the electron transport layer 17d can be doped with impurities to increase the n property. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J. Appl. Phys., 95, 5773 (2004), etc. What has been described. Furthermore, it is preferable that the electron transport layer 17d contains potassium or a potassium compound. As the potassium compound, for example, potassium fluoride can be used. Thus, when the n property of the electron transport layer 17d is increased, an element with lower power consumption can be manufactured.

<Blocking layer: hole blocking layer, electron blocking layer>
As described above, the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  In a broad sense, the hole blocking layer has the function of the electron transport layer 17d. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of the electron carrying layer 17d mentioned later can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer 17c.

  On the other hand, the electron blocking layer has the function of the hole transport layer 17b in a broad sense. The electron blocking layer is made of a material that has a function of transporting holes but has a very small ability to transport electrons, and improves the probability of recombination of electrons and holes by blocking electrons while transporting holes. be able to. Moreover, the structure of the above-described hole transport layer 17b can be used as an electron blocking layer as necessary.

  The thickness of the blocking layer is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

<Sealing member>
The sealing member 20 covers the organic EL element 10, and the plate-like (film-like) sealing member 20 is fixed to the resin base material 12 side by the sealing resin layer 19. The sealing member 20 is provided in a state of covering at least the organic functional layer 17 and is provided in a state of exposing the terminal portions (not shown) of the organic EL element 10 and the second electrode 18. Further, an electrode may be provided on the sealing member 20 and the electrode and the terminal portion of the second electrode 18 may be electrically connected.

  Specific examples of the plate-like (film-like) sealing member 20 include a glass substrate and a polymer substrate. These substrate materials may be used in the form of a thinner film. Examples of the glass substrate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

  Among them, since the element can be thinned, a polymer substrate in the form of a thin film can be preferably used as the sealing member 20.

Furthermore, the polymer substrate in the form of a film has an oxygen permeability measured by a method according to JIS-K-7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, JIS-K. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method based on −7129-1992 is 1 × 10 ⁻³ g / (m ² · 24 h) or less. It is preferable that

  Further, the above substrate material may be processed into a concave plate shape and used as the sealing member 20. In this case, the above-described substrate member is subjected to processing such as sand blasting or chemical etching to form a concave shape.

  Moreover, not only this but a metal material may be used. Examples of the metal material include one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum. By using such a metal material as a sealing member 20 in the form of a thin film, the entire light-emitting panel provided with the organic EL element 10 can be thinned.

<Sealing resin layer>
The sealing resin layer 19 for fixing the sealing member 20 to the resin base material 12 side is used for sealing the organic EL element 10 sandwiched between the sealing member 20 and the resin base material 12. The sealing resin layer 19 is, for example, a photocurable or thermosetting adhesive having a reactive vinyl group of an acrylic acid-based oligomer or a methacrylic acid-based oligomer, an epoxy-based thermosetting or chemical curable (two-component). Mixed) adhesives, hot-melt type polyamides, polyesters, polyolefins, and cationic curing type ultraviolet curable epoxy resins.

  From the viewpoint of simplicity of the manufacturing process, it is preferable to form the sealing resin layer 19 with a thermosetting adhesive. Moreover, as a form of the sealing resin layer 19, it is preferable to use the thermosetting adhesive processed into the sheet form. When a sheet-like thermosetting adhesive is used, the adhesive exhibits non-fluidity at room temperature (about 25 ° C.) and exhibits fluidity at a temperature in the range of 50 to 130 ° C. when heated. (Sealant) is used.

As the thermosetting adhesive, any adhesive can be used. From the viewpoint of improving the adhesion between the sealing member 20 adjacent to the sealing resin layer 19 and the resin base material 12, a suitable thermosetting adhesive is appropriately selected. For example, as the thermosetting adhesive, it is possible to use a resin mainly composed of a compound having an ethylenic double bond at the terminal or side chain of a molecule and a thermal polymerization initiator. More specifically, a thermosetting adhesive made of an epoxy resin, an acrylic resin, or the like can be used. Moreover, according to the bonding apparatus and hardening processing apparatus which are used at the manufacturing process of the organic EL element 10, you may use a fusion type thermosetting adhesive.
Moreover, what mixed 2 or more types of above-mentioned adhesives may be used as an adhesive agent, and the adhesive agent equipped with both thermosetting property and ultraviolet-ray-curing property may be used.

<< Application of organic electroluminescence element >>
Since the organic EL element 10 is a surface light emitter as described above, it can be used as various light emission sources. For example, lighting devices such as home lighting and interior lighting, backlights for clocks and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, Examples include a light source of an optical sensor. Moreover, it is not limited to these light emission light sources, It can use also as another light source.
In particular, it can be effectively used for a backlight of a liquid crystal display device combined with a color filter and a light source for illumination.

  The organic EL element 10 may be used as a kind of lamp such as an illumination or exposure light source, a projection device that projects an image, or a display device that directly recognizes a still image or a moving image. (Display) may be used. In this case, the area of the light emitting surface may be increased by so-called tiling, in which the light emitting panels provided with the organic EL elements 10 are planarly joined together with the recent increase in the size of lighting devices and displays.

  The driving method when used as a display device for reproducing moving images may be a simple matrix (passive matrix) method or an active matrix method. In addition, a color or full-color display device can be manufactured by using two or more kinds of organic EL elements 10 having different emission colors.

<< Method for Manufacturing Organic Electroluminescent Element >>
As an example of the method for producing the organic EL element of the present invention, a method for producing the organic EL element 10 shown in FIG. 1 will be described.

  First, the deterioration suppressing layer 13 is formed on the resin base material 12 with a layer thickness of about 5 to 500 μm. For example, a coating liquid containing metal oxide particles having ultraviolet absorbing ability is applied to a predetermined thickness on the resin substrate 12 and dried. Thereby, the deterioration suppression layer 13 is formed.

  Next, the gas barrier layer 14 is formed to a thickness of about 0.005 to 3 μm. The gas barrier layer 14 is preferably formed by the plasma CVD method using the manufacturing apparatus shown in FIG. By this method, the gas barrier layer 14 containing silicon, oxygen, and carbon and each element having a predetermined element distribution curve can be formed.

  Next, the polysilazane modified layer 15 is formed on the gas barrier layer 14 with a layer thickness of about 0.001 to 100 μm. For example, a polysilazane-containing liquid is applied on the gas barrier layer 14 to a predetermined thickness. And the polysilazane modified layer 15 which consists of a polysilazane modified layer is formed in this coating film by performing an excimer process.

  Next, the first electrode 16 is formed on the polysilazane modified layer 15. The first electrode 16 is formed from a transparent conductive material. For example, an electrode having a thickness of about 3 to 15 nm mainly composed of silver or a transparent conductive material such as ITO of about 100 nm is formed. As a method for forming the first electrode 16, for example, a spin coating method, a casting method, an ink jet method, a vapor deposition method, a sputtering method, a printing method, or the like can be used. The vacuum deposition method is particularly preferable from the viewpoint of difficulty in formation. In addition, before and after the formation of the first electrode 16, an auxiliary electrode pattern is formed as necessary.

Next, a hole injection layer 17a, a hole transport layer 17b, a light-emitting layer 17c, an electron transport layer 17d, and an electron injection layer 17e are formed in this order, and the organic functional layer 17 is formed. As a method for forming each of these layers, for example, a spin coating method, a casting method, an ink jet method, a vapor deposition method, a sputtering method, a printing method, or the like can be used, but a homogeneous layer is easily obtained and a pinhole is generated. From the standpoint of difficulty, it is particularly preferable to use vacuum deposition or spin coating. Further, different formation methods may be used for each layer. When employing a vapor deposition method for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, etc., but generally the boat heating temperature storing the compound is 50 to 450 ° C., and the degree of vacuum is 1 × 10 ⁻⁶ to 1 ×. It is desirable to select each condition as appropriate within a range of 10 ⁻² Pa, a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −50 to 300 ° C., and a thickness of 0.1 to 5 μm.

  Next, the second electrode 18 serving as a cathode is formed by an appropriate forming method such as an evaporation method or a sputtering method. At this time, a pattern is formed in a shape in which a terminal portion is drawn from the upper side of the organic functional layer 17 to the periphery of the resin base material 12 while maintaining an insulating state with respect to the first electrode 16 by the organic functional layer 17.

  Next, solid sealing of the 1st electrode 16, the organic functional layer 17, and the 2nd electrode 18 provided on the resin base material 12 is performed. A sealing resin layer 19 is formed on one side of the sealing member 20. Then, the sealing resin layer 19 formation surface of the sealing member 20 is placed on the first electrode 16, so that the ends of the lead wires of the first electrode 16 and the second electrode 18 come out of the sealing resin layer 19. The organic functional layer 17 and the second electrode 18 are superimposed on the resin base material 12. After the resin base material 12 and the sealing member 20 are overlapped, pressure is applied to the resin base material 12 and the sealing member 20. Furthermore, in order to harden the sealing resin layer 19, the sealing resin layer 19 is heated. At this time, the sealing resin layer 19 is sufficiently cured so that there is no problem in the adhesion between the polysilazane modified layer 15 and the sealing resin layer 19.

  As described above, a solid-sealed organic EL element 10 including the deterioration suppressing layer 13, the gas barrier layer 14, and the polysilazane modified layer 15 on the resin substrate 12 is obtained. In the production of such an organic EL element 10, it is preferable to produce from the first electrode 16 to the second electrode 18 consistently by a single evacuation, but a different formation method is used by taking out from the vacuum atmosphere on the way. May be. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to a following example.

<< Production of Organic EL Element 101 >>
In production of the organic EL element 101, first, a transparent biaxially stretched polyethylene terephthalate film (NSC manufactured by Teijin Ltd., single-sided corona treatment) is used as a resin base material, and a deterioration suppressing layer is formed on one surface.
100 parts by mass of zinc oxide particles (ZnO particles) having an average primary particle size of 0.02 μm as metal oxide particles, a curable TFE copolymer (Zeffle GK570 manufactured by Daikin Industries, Ltd., solid content 65% by mass) , Hydroxyl value 65 mgKOH / g) after being dispersed in 200 parts by mass, 10 parts by mass of a curing agent (Coronate HX manufactured by Nippon Polyurethane Co., Ltd.) and a silane coupling agent (OCN-C ₃ H ₆ -Si (OCH) ₃ ) ₃ ) ₃ ) 3 parts by mass were added and diluted with butyl acetate to prepare a coating solution for forming a deterioration inhibiting layer. On the resin base material, the prepared coating solution was applied so as to have a dry layer thickness of 25 μm to form a deterioration suppressing layer. The refractive index of the formed deterioration suppressing layer was 1.7.

Next, a gas barrier layer is formed on the deterioration suppressing layer.
The resin base material on which the deterioration suppressing layer is formed is mounted on the gas barrier layer manufacturing apparatus shown in FIG. 5 and the gas barrier layer is formed on the resin base material under the following film forming conditions (plasma CVD conditions). It was formed with a predetermined layer thickness (opposite roll method).

Source gas (HMDSO) supply: 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 1.2 kW
Frequency of power source for plasma generation: 80 kHz
Film transport speed: 0.5 m / min

The layer thickness of the gas barrier layer is set so that the layer thickness ratio of the gas barrier layer to the deterioration suppression layer, that is, the layer thickness ratio represented by the following formula is 0.020.
Layer thickness ratio = layer thickness of gas barrier layer / layer thickness of deterioration suppression layer

Next, a polysilazane modified layer is formed on the gas barrier layer.
First, as a polysilazane-containing liquid, a 10 mass% dibutyl ether solution of perhydropolysilazane (PHPS; Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was prepared. The prepared polysilazane-containing liquid is applied on the gas barrier layer with a wireless bar so that the average layer thickness after drying is 300 nm, and dried by treating for 1 minute in an atmosphere of temperature 85 ° C. and humidity 55% RH. I let you. Further, the coating film containing polysilazane was formed by holding for 10 minutes in an atmosphere of temperature 25 ° C. and humidity 10% RH (dew point temperature −8 ° C.) for 10 minutes.

  The resin base material on which the coating film was formed was fixed on the operation stage, and a modification treatment was performed under the following modification treatment conditions using the following ultraviolet device to form a polysilazane modified layer on the resin substrate.

Ultraviolet irradiation device: excimer irradiation device manufactured by M.D.COM MODEL: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
Excimer lamp irradiation time: 5 seconds

  In this manner, a deterioration suppressing layer, a gas barrier layer, and a polysilazane modified layer were formed on the resin substrate, and a gas barrier film was provided.

  Next, the resin base material (gas barrier film) was fixed to a base material holder of a commercially available vacuum deposition apparatus, and the following compound No. 10 was put in a resistance heating boat made of tungsten, and the base material holder and the heating boat were mounted in the first vacuum chamber of the vacuum evaporation apparatus. 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.

After depressurizing the first vacuum chamber of the vacuum deposition apparatus to 4 × 10 ⁻⁴ Pa, Compound No. A heating boat containing 10 was energized and heated, and an underlayer of the first electrode was provided with a layer thickness of 10 nm at a deposition rate of 0.1 to 0.2 nm / second. The resin base material on which the base layer was formed was transferred to the second vacuum chamber while being vacuumed, and after the pressure in the second vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing silver was energized and heated. As a result, a first electrode made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 to 0.2 nm / second.

Next, after reducing the pressure to 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, the following compound HT-1 was deposited at a deposition rate of 0.1 nm / second while moving the resin substrate, to 20 nm. Hole transport layer (HTL).

  Next, the following compound A-3 (blue light emitting dopant), the following compound A-1 (green light emitting dopant), the following compound A-2 (red light emitting dopant) and the following compound H-1 (host compound) are converted into the compound A- The deposition rate was changed depending on the location so that 3 was 35% by mass to 5% by mass linearly with respect to the layer thickness, and each of compound A-1 and compound A-2 was 0.2% without depending on the layer thickness. The concentration of the compound H-1 was changed from 64.6% by mass to 94.6% by mass at a deposition rate of 0.0002 nm / sec. The light emitting layer was formed by co-evaporation.

Thereafter, the following compound ET-1 was deposited to form an electron transport layer having a layer thickness of 30 nm, and potassium fluoride (KF) was further deposited to form an electron injection layer having a layer thickness of 2 nm. Furthermore, aluminum was vapor-deposited to form a second electrode having a layer thickness of 110 nm.
In addition, said compound No. 10, Compound HT-1, Compound A-1 to Compound 3, Compound H-1, and Compound ET-1 are compounds shown below.

  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. Using the stop member, the resin base material prepared up to the second electrode was superposed. 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 wires of the first electrode and the second electrode were exposed.

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

The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a moisture content of 1 ppm or less, in accordance with JIS B 9920, with a measured cleanliness of class 100, a dew point temperature of −80 ° C. or less, and an oxygen concentration of 0.8 ppm or less. At atmospheric pressure. In addition, the description regarding formation of the lead-out wiring etc. from the 1st electrode and the 2nd electrode is omitted.
The organic EL element 101 was produced through the above steps. The organic EL element 101 was produced so that the area of the light emitting region was 5 cm × 5 cm.

<< Production of Organic EL Element 102 >>
In the formation of the deterioration suppressing layer, 100 parts by mass of titanium oxide particles (TiO ₂ particles) having an average primary particle size of 0.02 μm are used as metal oxide particles instead of zinc oxide particles, and the layer thickness of the gas barrier layer is used. Was prepared in the same manner as the organic EL element 101 except that the layer thickness ratio of the gas barrier layer to the deterioration suppressing layer was set to 0.005.

<< Production of Organic EL Elements 103 to 107 >>
As the resin base material, hydrolysis resistant PET (Lumirror X10 manufactured by Toray Industries, Inc.) is used instead of the biaxially stretched polyethylene terephthalate film, and the layer thickness of the gas barrier layer is set to the layer thickness of the gas barrier layer with respect to the deterioration suppressing layer. Organic EL elements 103 to 107 were produced in the same manner as the production of the organic EL element 101 except that the ratio was set to the value described in Table 1.

<< Preparation of Organic EL Element 108 >>
An organic EL element 108 was produced in the same manner as the organic EL element 101 except that a conventionally known parallel plate CVD method was used as a method for forming the gas barrier layer.

<< Production of Organic EL Element 109 >>
As the resin base material, hydrolysis-resistant PET (Lumirror X10 manufactured by Toray Industries, Inc.) is used in place of the biaxially stretched polyethylene terephthalate film, and in the formation of the degradation suppressing layer, primary instead of zinc oxide particles is used as the metal oxide. Using 100 parts by mass of titanium oxide particles (TiO ₂ particles) having an average particle diameter of 0.02 μm, the layer thickness ratio of the gas barrier layer to the deterioration suppressing layer is set to 0.05. An organic EL element 109 was produced in the same manner as in the production of the organic EL element 101 except that the above was set.

<< Production of Organic EL Element 110 >>
As a resin base material, hydrolysis resistant PET (Lumilar X10 manufactured by Toray Industries, Inc.) is used instead of the biaxially stretched polyethylene terephthalate film, and in the formation of the deterioration suppressing layer, instead of zinc oxide particles as metal oxide particles Using 100 parts by mass of cerium oxide particles (CeO ₂ particles) having an average primary particle size of 0.02 μm, the layer thickness ratio of the gas barrier layer to the deterioration inhibiting layer is 0.05. The organic EL element 110 was produced in the same manner as the production of the organic EL element 101 except that the setting was made as described above.

<< Production of Organic EL Element 111 >>
As a resin base material, hydrolysis resistant PET (Lumilar X10 manufactured by Toray Industries, Inc.) is used instead of the biaxially stretched polyethylene terephthalate film, and in the formation of the deterioration suppressing layer, instead of zinc oxide particles as metal oxide particles Using 100 parts by mass of strontium titanate particles (SrTiO ₃ particles) having an average primary particle size of 0.03 μm, the layer thickness ratio of the gas barrier layer to the deterioration suppressing layer is 0.05. An organic EL element 111 was produced in the same manner as in the production of the organic EL element 101 except that the setting was made.

<< Production of Organic EL Element 112 >>
In the production of the organic EL element 101, a non-deterioration suppressing layer is formed using a coating solution prepared without dispersing zinc oxide particles in a curable TFE copolymer in place of the deterioration suppressing layer, and modified with polysilazane. An organic EL element 112 was produced in the same manner as the organic EL element 101 except that no layer was formed.

<< Preparation of organic EL element 113 >>
In the production of the organic EL element 101, a non-deterioration suppressing layer is formed using a coating solution prepared without dispersing zinc oxide particles in a curable TFE copolymer in place of the deterioration suppressing layer, and a gas barrier layer. The organic EL element 113 was produced in the same manner as the organic EL element 101 except that the organic EL element 101 was not formed.

<< Production of Organic EL Element 114 >>
In the production of the organic EL element 101, a non-deterioration suppressing layer is formed using a coating solution prepared without dispersing zinc oxide particles in a curable TFE copolymer in place of the deterioration suppressing layer, and a gas barrier layer. The organic EL element 114 was manufactured in the same manner as the organic EL element 101 except that a conventionally known magnetron sputtering method was used.

<< Production of Organic EL Element 115 >>
In the production of the organic EL element 101, the above except that the non-deterioration suppressing layer was formed using a coating solution prepared without dispersing zinc oxide particles in the curable TFE copolymer instead of the deterioration suppressing layer. The organic EL element 115 was produced in the same manner as the production of the organic EL element 101.

<< Evaluation of Organic EL Elements 101-115 >>
Each organic EL element installed in a curved shape on a cylindrical member having a diameter of 400 mm is held at 85 ° C. and 85% RH for 80 minutes while maintaining its shape, and then the temperature is lowered to −40 ° C. over 90 minutes (the humidity progress) ), Held at −40 ° C. for 80 minutes, and then the temperature was raised to 85 ° C. (humidity 85% RH) over 90 minutes and held for 80 minutes, and 10 cycles were repeated. Thereafter, each organic EL element was held in an environment of 60 ° C. and 90% RH for 500 hours, then turned on using a constant voltage power source, and the generation rate (occurrence rate) of dark spots (non-light emitting portions) was measured.
The dark spot occurrence rate was obtained by photographing the light emitting surface of the organic EL element and applying predetermined image processing to the image data.
The measured dark spot generation rate was determined based on 5 to 5 criteria (5 is good), and the light emitting performance of the organic EL device was evaluated.
5 Evaluation: Dark spot generation rate is 0% (no dark spots are generated)
4 Evaluation: Dark spot occurrence rate is greater than 0% and less than 5% 3 Evaluation: Dark spot occurrence rate is 5% or more and less than 10% 2 Evaluation: Dark spot occurrence rate is 10% or more and less than 20% 1 Evaluation: Dark spot occurrence rate 20% or more The organic EL elements 101 to 115 were evaluated by measuring the dark spot generation rate 10 times each, and the average value of the evaluation is shown in Table 1.

  As shown in Table 1, on a resin substrate, a deterioration suppressing layer containing metal oxide particles having an ultraviolet absorbing ability, a gas barrier layer containing at least silicon atoms, oxygen atoms and carbon atoms, and a coating containing polysilazane The organic EL elements 101 to 111 in which the polysilazane modified layer formed by modifying the film was laminated had good results in the dark spot generation rate. Thus, the organic EL element provided with the gas barrier film of the present invention is suppressed from deteriorating in light emission characteristics in a high temperature and high humidity environment. Thereby, it is shown that deterioration of the gas barrier film of the present invention is suppressed.

  Further, from the results of the organic EL element 101 and the organic EL element 105, and the organic EL element 102 and the organic EL element 109, when hydrolysis resistant PET is used as the resin base material, a good result in the dark spot occurrence rate may be obtained. It is shown.

  In addition, the results of the organic EL elements 103 to 107 indicate that when the layer thickness ratio is a value of 0.01 to 0.05, the dark spot generation rate is satisfactory.

  In addition, the results of the organic EL element 101 and the organic EL element 108 show that when the gas barrier layer is formed by the vapor deposition method of the opposite roll method, the dark spot generation rate is satisfactory. .

  On the other hand, none of the organic EL elements 112 to 115 having a non-deterioration suppressing layer containing no metal oxide particles has obtained a good result in the dark spot generation rate, and contains metal oxide particles. It has been shown that the gas barrier film and the organic EL element that do not include the deterioration suppressing layer that cannot suppress deterioration under a high temperature and high humidity environment.

DESCRIPTION OF SYMBOLS 10 Organic EL element 11 Gas barrier film 12 Resin base material 13 Deterioration suppression layer 14 Gas barrier layer 15 Polysilazane modified layer 16 1st electrode 17 Organic functional layer 17a Hole injection layer 17b Hole transport layer 17c Light emitting layer 17d Electron transport Layer 17e Electron injection layer 18 Second electrode 19 Sealing resin layer 20 Sealing member 30 Manufacturing device 31 Delivery roll 32, 33, 34, 35 Transport roll 36, 37 Film formation roll 38 Gas supply pipe 39 Plasma generating power source 40 Film 41, 42 Magnetic field generator 43 Winding roll

Claims (4)

A gas barrier layer that is a deposited film containing at least silicon atoms, oxygen atoms, and carbon atoms on a resin substrate, and a coating film that is provided adjacent to the gas barrier layer and contains at least polysilazane is modified. A polysilazane modified layer, and a gas barrier film comprising:
A gas barrier film comprising an ultraviolet absorbing layer containing metal oxide particles having ultraviolet absorbing ability and a fluorine-containing polymer between the resin substrate and the gas barrier layer. 2. The gas barrier film according to claim 1, wherein a layer thickness ratio of the gas barrier layer to the ultraviolet absorbing layer is in a range of 0.01 to 0.05. A gas barrier layer that is a deposited film containing at least silicon atoms, oxygen atoms, and carbon atoms on a resin substrate, and a coating film that is provided adjacent to the gas barrier layer and contains at least polysilazane is modified. A polysilazane modified layer, and a method for producing a gas barrier film comprising:
Between the resin base material and the gas barrier layer, an ultraviolet absorbing layer containing metal oxide particles having ultraviolet absorbing ability and a fluorine-containing polymer is provided,
It said gas barrier layer, the manufacturing method of the characteristics and to Ruga Subaria film to be formed by vapor deposition of the opposing roll method. The organic electroluminescent device characterized by comprising a gas barrier film according to claim 1 or claim 2.

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