JP2015103389A - Organic el device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic EL device including a barrier film having a high barrier performance.SOLUTION: An organic EL device comprises: a first flexible resin film base; and a barrier film including a barrier layer provided on the first flexible resin film base by ALD method, in which the barrier layer herein has a thickness of 10-100 nm, and of which the water vapor permeability is 1×10to 9×10g/m/day; an organic EL layer provided on the barrier film; a second flexible resin film base provided on the organic EL layer; and an adhesive layer for adhering to the second flexible resin film base while covering the organic EL layer.

Description

  The present invention relates to an organic EL device using a barrier film having a high barrier property against bending.

  Conventionally, the use of a barrier film that blocks various gases such as moisture and oxygen has been studied as a substrate for organic electroluminescence (organic EL) element display. Since such a barrier film is required to be transparent, an opaque barrier film such as an aluminum foil is not suitable.

  Furthermore, for transparent barrier films that are being applied to organic EL elements and the like, in recent years, roll-to-roll (hereinafter referred to as “ R2R ") is possible, and there are high demands such as long-term reliability and high degree of freedom in shape, and curved surface display. Therefore, a transparent resin film has begun to be used in place of a glass substrate that is heavy, easily broken, and difficult to increase in area. For example, Patent Documents 1 and 2 disclose a substrate using a polymer film as a substrate for an organic EL element.

  However, the transparent resin film is inferior in barrier properties and surface flatness to glass. If a film with poor barrier properties is used as the substrate of the organic EL element, moisture or air penetrates the substrate and reaches the organic EL layer to deteriorate the organic EL layer. It becomes a factor that etc. are damaged.

  As a method for solving such a problem, it is known to form a barrier film by forming an inorganic thin film such as a metal oxide on a resin film substrate. Such a barrier film forms a layer of an inorganic oxide or an inorganic nitride on a resin film using a sputtering method, an ion assist method, a plasma CVD (Chemical Vapor Deposition) method, an ALD (Atomic Layer Deposition) method, or the like. It is obtained by doing. Or the barrier film (for example, refer nonpatent literature 1) which vapor-deposited silicon oxide on the resin film, the barrier film (for example, refer nonpatent literature 2) which vapor-deposited aluminum oxide, etc. are known.

By the way, in the ALD method, two kinds of source gases (precursor gases) are alternately introduced into a chamber to adsorb the source gases on the substrate surface, and unnecessary gases are removed with N _2. The reaction product film is formed one atomic layer at a time by introducing and reacting with other raw material gases or the like, or by reacting with active oxygen plasma or ozone gas to form a thin film of several tens of nm. Is the method. The ALD film formed by this method is dense, and furthermore, because of its high coverage, it is formed following the cracks and shape of the substrate, so that a barrier film having high barrier properties can be obtained stably. Is suitable.

  However, the ALD film suffers from problems such as mechanical stress in the barrier layer during the organic EL device deposition process, cracking of the barrier layer due to heat treatment, or deterioration of barrier properties due to degassing from unreacted substances. There is. Furthermore, in order to obtain a desired film thickness, it is necessary to repeat the process of laminating the reaction product film by one atomic layer several hundred times, and there is a problem that it takes much time. As an attempt to shorten the time required for such a lamination process, an ALD film forming technique using an R2R process has been reported (for example, see Patent Documents 3 and 4).

  As the ALD method, a thermal ALD method, an ozone ALD method, a plasma ALD method, or the like is known. In the thermal ALD method, it is necessary to complete the process of forming one atomic layer in a short time of less than one second. For this reason, it becomes difficult to adsorb water having a large adsorbing power to the source gas and to completely remove unnecessary gas, and the unreacted substances in the formed film are degassed. Loss of barrier properties and heat resistance are likely to occur. Moreover, the subject that the film-forming speed cannot be made high arises by these. On the other hand, the ozone ALD method and the plasma ALD method do not use water, and thus do not have the above-described problems and have high productivity.

  In addition, in an organic EL element in which an organic EL layer is formed on the barrier film via an adhesive layer, in addition to moisture intrusion from the barrier film, moisture intrusion occurs from the side surfaces of the element, end faces of the adhesive layer, and the like. Cheap. For this reason, in the element used for a long time, there exists a subject which the quenching of the edge part of a light emission surface advances.

JP-A-2-251429 JP-A-6-124785 JP 2009-516077 A JP 2010-538165 A

M.Soderlund, ICFPE 2012, September 6, Tokyo, Japan, “Flexible Thin-Film Moisture Barriers by Atomic Layer Deposition Technology.” B. Danforth, W. Barrow, and E. Dickey, Lotus Applied Technology, Hillsboro, Finalprogram for the 2013 SVC Annual TechCon, Rhode Island Convention Center Province, Phode Island USA, '' W-9 UV-Curable Top Coat Protection against mechanical, p. 22. Abrasion for ALD Thin Film BarrierCoatings. ”

  The present invention has been made in view of the conventional drawbacks, and an object of the present invention is to provide an organic EL device using a barrier film having high barrier performance. The object of the present invention is to provide an organic EL device using a barrier film that can achieve high barrier performance against bending. Further, the object of the present invention is to have high barrier properties without breaking the barrier film against bending. Another object of the present invention is to provide an organic EL element that is resistant to mechanical impact. Furthermore, the object of the present invention is to produce an organic EL element by roll-to-roll.

The present invention relates to a barrier film comprising a first flexible resin film substrate and a barrier layer provided on the first flexible resin film substrate by an ALD method, wherein the barrier layer has a thickness of 10 nm. The barrier film has a water vapor permeability of 1 × 10 ^{−3 to} 9 × 10 ⁻² g / m ² / day, and is disposed on the organic EL layer provided on the barrier film. Provided is an organic EL element provided with a second flexible resin film substrate provided, an adhesive layer for covering the organic EL layer and adhering to the second flexible resin film substrate.

  When the barrier film is bent within a radius of curvature (R) of 1.5 mm or more and 10 mm or less, an arc-shaped crack is generated from the cut end of the barrier layer toward the inside, and the spread of the crack is less than 200 μm. Preferably there is.

  The spread of cracks is preferably less than 100 μm.

  The water vapor permeability is preferably a value obtained by allowing the barrier film to stand at room temperature in a dry nitrogen atmosphere to remove moisture and then measuring by atmospheric pressure ionization mass spectrometry and / or using a laser moisture meter.

Moreover, this invention is a barrier film provided with the 1st flexible resin film base material and the barrier layer provided by the ALD method on the 1st flexible resin film base material, and here, a barrier layer is thickness; 10 nm to 100 nm, the water vapor permeability of the barrier film is 1 × 10 ^{−3 to} 9 × 10 ⁻² g / m ² / day, and the organic EL layer provided on the barrier film is formed on the organic EL layer. The organic EL element includes an arranged second flexible resin film base material and an adhesive layer that covers the organic EL layer and adheres to the second flexible resin film base material. When bent in a range of 5 mm or more and 10 mm or less, an arc-shaped crack is generated from the cut end of the barrier layer to the inside, and the spread of the crack is less than 200 μm. The water vapor permeability of the organic EL device is a value obtained by allowing the barrier film to stand at room temperature in a dry nitrogen atmosphere to remove moisture and then measuring it with atmospheric pressure ionization mass spectrometry and / or with a laser moisture meter I will provide a.

  The organic EL element preferably includes a temporary sealing barrier layer provided by an ALD method so as to cover the organic EL layer.

The barrier film includes a first protective barrier layer having a thickness of 100 to 1000 nm provided by a sputtering method between the barrier layer and the first flexible resin film substrate, and the water vapor permeability of the barrier film is 9 It is preferable to provide not more than × 10 ⁻² g / m ² / day.

The barrier film includes a first protective barrier layer having a thickness of 100 to 3000 nm provided by a CVD method between the barrier layer and the first flexible resin film substrate, and the water vapor permeability of the barrier film is 9 It is preferable to have x10 < ^-3 > g / m < ² > / day or less.

  The organic EL element preferably includes a second protective barrier layer formed by a sputtering method between the organic EL layer and the barrier layer.

  The organic EL element preferably includes a substrate back surface barrier layer provided on the opposite surface of the first flexible resin film substrate on which the organic EL layer is formed.

  The barrier film preferably includes a first flat layer between the first flexible resin film substrate and the barrier layer.

  The barrier film preferably includes a second flat layer between the barrier layer and the organic EL layer.

  The flatness of the first planarization layer and the second planarization layer is preferably 20 nm or less in Ra (50 μm).

The barrier layer may be composed of an Al ₂ O ₃ layer, a TiO ₂ layer, a ZrO ₂ layer, or a laminate of these materials formed by using heat or plasma, an ozone ALD method, or an ALD method using roll-to-roll. preferable.

The first protective barrier layer and the second protective barrier layer is preferably made of SiN formed using a SiO _x C _y, a sputtering method is formed by a CVD method.

The barrier film includes a second flat layer between the barrier layer and the organic EL layer, and a 100-3000 nm thick first layer provided by a CVD method between the barrier layer and the first flexible resin film substrate. 1 protective barrier layer, and the water vapor permeability of the barrier film is preferably 9 × 10 ⁻³ g / m ² / day or less.

  ADVANTAGE OF THE INVENTION According to this invention, the organic EL element using the barrier film which has high barrier performance can be provided. In addition, according to the present invention, it is possible to provide an organic EL element having high barrier properties and resistance to mechanical impact without breaking the barrier film against bending. Furthermore, according to the present invention, an organic EL element can be produced by roll-to-roll.

It is a schematic cross section which shows one Embodiment of the organic EL element which concerns on this invention. It is a schematic cross section which shows another embodiment of the organic EL element which concerns on this invention. It is a schematic cross section which shows another embodiment of the organic EL element which concerns on this invention. It is a top view which shows the result of having observed the spreading of the arc-shaped crack which arises in the bending test of the barrier film in an Example and a comparative example.

  Hereinafter, a preferred embodiment of an organic EL device according to the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing the configuration of the organic EL element according to this embodiment. As shown in FIG. 1, the organic EL element 1 includes a barrier film 4 having a first flexible resin film substrate 2 and a barrier layer 3 provided on the first flexible resin film substrate, and a barrier film 4. An organic EL layer 5 provided on the barrier layer 3 side, an adhesive layer 6 provided so as to cover the organic EL layer 5, and a second flexible resin film base adhered to the organic EL layer 5 via the adhesive layer 6 Material 7 is provided.

[Barrier film]
In the barrier film 4, the barrier layer 3 for preventing moisture from entering the organic EL layer 5 is provided on the first flexible resin film substrate 2. The barrier film 4 is preferably transparent. When the barrier film 4 is transparent, it can be used as a transparent substrate of an organic EL element. The light transmittance of the barrier film 4 is, for example, preferably 80% or more at a wavelength of 550 nm, and more preferably 90% or more.

(First flexible resin film substrate)
The 1st flexible resin film base material 2 (henceforth a "resin film base material" only) which concerns on this embodiment is demonstrated. The resin film substrate is preferably transparent. By using a transparent resin film substrate as a substrate, light can be extracted through the substrate. A resin film base material is a base material which can hold | maintain the barrier layer 3 which has barrier property, and if it was formed with the organic material, it will not specifically limit.

  Examples of the organic material for forming the resin film substrate include acrylic acid ester, methacrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride ( PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide and the like. As the resin film substrate, a resin film formed of these organic materials can be used as a single layer or as a laminate of two or more layers. The thickness of the resin film substrate is preferably 5 to 500 μm, more preferably 25 to 250 μm.

  The resin film substrate can be produced by a conventionally known general method, and may be an unstretched film or a stretched film. For example, an unstretched resin film substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the flow of the resin film substrate (vertical axis) is obtained by a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. ) Direction or a direction perpendicular to the flow direction of the resin film substrate (horizontal axis), a stretched resin film substrate can be produced. Although the draw ratio in this case can be suitably selected according to the resin used as the raw material of the resin film substrate, it is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction. Moreover, you may perform a corona treatment before depositing an inorganic barrier layer with respect to the resin film base material which concerns on this embodiment.

Furthermore, an anchor coat agent layer may be formed on the surface of the resin film substrate according to the present embodiment for the purpose of improving adhesion and flatness with an inorganic material barrier film. Examples of the anchor coating agent used in this anchor coating agent layer include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicone resins, and alkyl titanates. Can be used singly or in combination of two or more. These anchor coating agents can be added with conventionally known additives, materials selected from flattening layer materials described later, and the like. The above anchor coating agent is coated on a resin film substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and the solvent, diluent, etc. are removed by drying. Can be coated. As an application quantity of said anchor coating agent, 0.1-5 g / m < ² > (dry state) is preferable.

(Barrier layer)
The barrier layer 3 constituting the barrier film is provided between the first flexible resin film substrate 2 and the organic EL layer 5. The barrier layer 3 only needs to be made of a film that blocks the permeation of moisture, and the composition thereof is not particularly limited. The material constituting the barrier layer 3 is preferably an inorganic oxide or inorganic nitride, such as silicon oxide, aluminum oxide, silicon oxynitride, silicon nitride, aluminum oxynitride, magnesium oxide, titanium oxide, zirconia oxide, zinc oxide, Examples thereof include indium oxide and tin oxide.

  The barrier layer 3 is formed by an ALD method. The ALD method is a thin film forming method in which a plurality of kinds of source gases (precursor gases) are alternately introduced into a chamber, and reaction products are deposited one atomic layer on the surface of a substrate installed in the chamber. As the ALD method, water is used as a raw material and a high temperature is required (thermal ALD method). In order to accelerate the lowering and / or speeding up of the reaction of the raw material gas, highly reactive oxygen plasma is used instead of water. A method of using a raw material (plasma ALD method) or the like is known, and any method is applicable.

When the barrier layer 3 is specifically formed by the ALD method, a first precursor gas and a second precursor gas are used. Examples of the first precursor gas include TMA (trimethyl aluminum; (CH ₃ ) ₃ Al). Examples of the second precursor gas include water (H ₂ O) in the case of the thermal ALD method, and oxygen and the like in the case of the ozone ALD method and the plasma ALD method.

Among these, an Al ₂ O ₃ film formed by TMA is preferable because it has excellent moisture barrier properties. On the other hand, the Al ₂ O ₃ film has a drawback that the barrier property is remarkably lowered when it is placed in a high humidity state of 90% or more, or when it comes into contact with high concentration of water or water such as when water droplets adhere. In order to compensate for these disadvantages and to provide a high concentration of moisture or a barrier property against water, the precursor gas is titanium tetrachloride; TiCl ₄ , titanium (IV) isopropoxide; Ti [(OCH) (CH ₃ ) ₂ ] ₄ , Lakis (dimethylamido) titanium (IV); [(CH ₃ ) ₂ N] ₄ Ti, Tetrakis (dimethylimide) zirconium (IV); [(CH ₃ ) ₂ N] ₄ Zr, Al It is preferable to provide a TiO ₂ film or a ZrO ₂ film under the same reaction conditions adjacent to the side where moisture enters the ₂ O ₃ film.

In the ALD method, as described above, a source gas is adsorbed on the substrate surface, an unnecessary gas is removed with N ₂ , and another source gas is reacted with the adsorbed single molecule by using heat or plasma to generate one atom. A batch type ALD film forming method is generally used in which a reaction product film is formed layer by layer, and this is repeated to form a thin film of several tens of nanometers. In addition, Al ₂ O ₃ layers in which a number of atomic layers are laminated one by one or a laminated type barrier layer of Al ₂ O ₃ and TiO ₂ is excellent in covering and filling characteristics against defects such as cracks in the lower layer. It is excellent in that high barrier properties can be obtained stably with a thin film. On the other hand, in such a batch type ALD film forming method, it is usually necessary to repeat a single atomic layer film forming reaction 200 times or more to form a 20 nm film. There is a problem.

In order to solve this problem, a roll-to-roll ALD method (R2R-ALD method) is known. In this method, an ALD film can be formed at a line speed of 0.1 m / min to 100 m / min by repeating the process of supplying and reacting two kinds of source gases and cleaning N ₂ gas at high speed. .

As a method of repeatedly depositing by causing a single atomic layer reaction at a high speed, (1) a plurality of slits placed close to a film substrate in a vacuum or in the atmosphere are in a proximity state of 0.1 to 1 mm with respect to the substrate. while retaining moved at high speed, and supplying a plurality of raw material gas and cleaning N ₂ gas are alternately, one by one atomic layer to cause a film formation reaction, R2R-ALD deposition of slit coating type repeating the reaction at a high speed Method (see, for example, JP 2009-516077 A, JP 2010-538165 A), (2) A plurality of different source gases are filled using partition walls provided with narrow slits through which the transport film substrate can pass. In a large vacuum reaction vessel partitioned into separate chambers, the film substrate is sequentially conveyed at high speed through a slit through a chamber filled with different gases. , R2R-ALD film forming method of different source gas compartment reaction vessel type in which single atomic layer reaction is repeatedly induced on a flexible substrate at high speed and a barrier film is formed at high speed (for example, refer to JP2013-508544A) ) Etc. are known.

  In such an R2R-ALD method, it is necessary to complete each step of film formation of the above-mentioned single atomic layer in a time of less than 1 second, and it is difficult to remove water having a large adsorptive power on the substrate at a high speed. . Moreover, the loss of the barrier property and the decrease in heat resistance are likely to occur due to degassing derived from unreacted substances in the formed film. Further, there is a problem that the film forming speed cannot be increased due to these reasons.

  On the other hand, in the ozone R2R-ALD method and the plasma R2R-ALD method, since the reaction with ozone or oxygen plasma is used without using water, there is no problem like the thermal ALD method, and the productivity is high.

In the case of the batch type and the thermal type ALD method of reduced pressure and atmospheric R2R method, the reduced pressure condition is 1 × 10 ^{−3 to} 9 × 10 ⁻¹ Pa, and the reaction temperature as the film forming condition is 70 to 150 ° C., preferably 80 to 130 ° C.

  When the film formation temperature is extremely low, bubbles and particles are mixed in by degassing components such as unreacted substances, resulting in a decrease in refractive index and a barrier property against moisture. Degassing generated in the barrier layer during the baking process deteriorates the organic EL member, and as a result, quenching (destruction) of the organic EL element easily occurs. On the other hand, when the film formation temperature is extremely high, a dense film can be obtained and an improvement in refractive index and barrier property can be seen. However, the film is inferior in flexibility and easily cracks when the barrier film is bent.

  Since water is not used in the ALD method using oxygen plasma or ozone, it is not necessary to remove water adsorbed on the substrate. For example, the temperature is 60 to 150 ° C., preferably 70 to 100 ° C., more preferably 70 to 90 ° C. The film can be formed under a low temperature condition, and the film can be formed even on a flexible substrate having a low softening temperature such as PET, which is preferable. In particular, oxygen plasma having high reaction activity is preferable because high-speed film formation is possible.

The barrier layer 3 is preferably a laminate of two or more layers for the purpose of improving the barrier properties. For example, the barrier layer 3 may be a barrier layer formed by alternately stacking the Al ₂ O layers ₃ and the TiO ₂ layers by repeating the film forming process of the Al ₂ O ₃ film and the TiO ₂ film a plurality of times. it can. This barrier layer is prevented by the TiO ₂ layer in which the growth of cracks generated during the Al ₂ O ₃ film formation is laminated. For this reason, when the film thickness of the entire Al ₂ O ₃ layer in the multilayer barrier layer is the same as the film thickness of the single-layer Al ₂ O ₃ single layer, the multilayer type can obtain higher barrier properties. Further, by providing the TiO ₂ layer, to improve the flexibility of the barrier layer, it is possible to set the film thickness of the entire _{the Al} 2 _{O 3} layer than _Al 2 _{O 3} single layer. Further, a ZrO ₂ layer or the like can be preferably used instead of the TiO ₂ layer.

  The film thickness of the barrier layer 3 is 10 nm to 100 nm (in the case of a barrier layer in which two or more layers are laminated, the total film thickness of all the layers is shown), preferably 15 nm to 90 nm. Preferably, it is 20 nm to 80 nm. When the film thickness is less than 10 nm, the barrier property is inferior, and when the film thickness exceeds 100 nm, the flexibility is lowered, and cracking is likely to occur due to external factors such as bending and pulling after film formation. It tends to decrease.

The water vapor permeability of the laminate composed of the first flexible resin film substrate 2 and the barrier layer 3 is 1 × 10 ^{−3 to} 9 × 10 ⁻² g / m ² / day, preferably 1 × 10 ^{−. 3 to} 7 × 10 ⁻² g / m ² / day, more preferably 1 × 10 ^{−3 to} 5 × 10 ⁻² g / m ² / day. In such an evaluation of the barrier property (water vapor permeability) of the barrier layer, conventional PERMATRAN (MOCON / IR sensor), AQUATRAN (MOCON): MODEL7001 (Illinois / Coulometric sensor), DELTAPERM (TECHNOLOX / Pressure gauge, Various evaluation methods such as test (Various / Ca film) have been proposed, and the water vapor permeability of a high barrier film using them has been reported. However, ISO / TC61-Plastics discusses machine differences in such evaluation methods (for example, 60th meeting of ISO / TC61-Plastics), and the value of water vapor permeability actually reported in the past is The value varies greatly depending on the pre-drying treatment conditions and apparatus (method) of the measurement sample. In the present invention, a sample is allowed to stand at room temperature in a dry nitrogen atmosphere for 2 days, and after sufficiently removing moisture, there is a report of a measuring apparatus with higher accuracy and reliability than the ISO / TC61-Plastics. The laser system (CRDS system) moisture meter HALO-H20 Moisture Analyzer (LASERTRACE-H ₂ O) manufactured by Tiger Optics, Inc., which is adopted in the Japan API Corporation atmospheric pressure ionization mass spectrometer (API-BA60) or a trace moisture region standard engine. The water vapor transmission rate is measured by a method using two types of devices, preferably CRDS type devices that directly measure the amount of water from the absorption of water.

The barrier film 4 according to the present embodiment obtained as described above hardly cracks or curls in the barrier layer and exhibits high barrier properties. Specifically, the barrier film is subjected to the following bending evaluation test:
(1) Bending the barrier film so that the radius of curvature is not less than 1.5 mm and not more than 10 mm with the barrier layer on the outer peripheral side (bending step)
(2) The barrier layer surface is observed after returning the bent barrier film to the state before the bending step (observation step).
In the observation step, the barrier film 4 according to the present embodiment is preferably 200 μm or more, more preferably 100 μm or more, and even more preferably 50 μm or more from the outer edge of the barrier layer surface in the observation step. Is not observed.

The barrier film preferably further has one or more layers selected from the group consisting of the following layers (a) to (e).
(A) First protective barrier layer provided between the first flexible resin film substrate 2 and the barrier layer 3 (b) Provided on the opposite side of the barrier layer 3 from the first flexible resin film substrate 2 The second protective barrier layer (c) the substrate back surface barrier layer provided on the opposite side of the barrier layer 3 of the first flexible resin film substrate 2 (d) the first flexible resin film substrate 2 and the barrier 1st planarization layer provided between the layers 3 (e) 2nd planarization layer provided in the opposite side to the 1st flexible resin film base material 2 of the barrier layer 3

  As a more preferred embodiment of the barrier film, specifically, for example, a barrier film 24 as shown in FIG. The barrier film 24 includes the substrate back surface barrier layer 8, the first flexible resin film substrate 2, the first planarization layer 9, the first protective barrier layer 10, the barrier layer 3, and the second A planarizing layer 11 and a second protective barrier layer 12 are provided in this order.

The first protective barrier layer 10 is provided to protect the barrier layer ₃ such as an Al ₂ O ₃ layer that is vulnerable to moisture from moisture penetrating the first flexible resin film substrate 2. The second protective barrier layer 12 protects the organic EL layer 5 from moisture penetrating from the planarization layers 9 and 11 described later, a part of the material constituting the planarization layers 9 and 11, and degassing. Is provided. The base material back surface barrier layer 8 is provided in order to improve the water vapor barrier property on the surface of the first flexible resin film base material 2 on the side opposite to the barrier layer 3.

  The substrate back surface barrier layer 8, the first protective barrier layer 10, and the second protective barrier layer 12 (hereinafter sometimes collectively referred to as “barrier layers 8, 10, 12”) are permeable to moisture. If it can suppress, the composition etc. will not be specifically limited. The material constituting the barrier layers 8, 10, and 12 is preferably an inorganic oxide or an inorganic nitride. Silicon oxide, silicon carbide oxide, aluminum oxide, silicon oxynitride, silicon nitride, aluminum oxynitride, magnesium oxide, titanium oxide , Zirconia oxide, zinc oxide, indium oxide, tin oxide and the like.

The barrier layers 8 and 12 can be configured similarly to the barrier layer 3, for example. Further, when the barrier layer 10 is in contact with the barrier layer 3 via the first planarizing layer 9 (for example, in the case of the configuration shown in FIG. 3), the barrier layer 10 has the same configuration as the barrier layer 3, for example. Can do. As the material constituting the other barrier layers _{8,10,12, SiO x C y (x} = 1.5~2.0, y = 0.01~0.5), SiO 2, SiO v N w (V = 0.01 to 2.0, w = 0.01 to 1), or an inorganic compound of SiN is preferable. Among these, SiO _x C _y and SiN are more preferable from the viewpoint of barrier properties and light transmittance.

The barrier layers 8, 10, and 12 made of the inorganic compound include, for example, combining at least one of O atoms and N atoms and Si atoms by combining an organic silicon compound and oxygen gas or nitrogen gas at a predetermined ratio. It becomes a containing layer. In particular, when forming the barrier layer 8, 10, and 12 in _SiO x _{C y,} without the use of highly toxic, such as silane raw material, because it can form a barrier layer Hexamethyldisiloxane the (HMDSO) as a raw material, equipment cost It is preferable because it can be kept low and a high barrier property can be easily obtained.

  As a method for forming the barrier layers 8, 10, and 12, it is preferable to use a sputtering method, a plasma CVD method, a plasma ALD method, or the like. Hereinafter, the sputtering method and the plasma CVD method will be described. The plasma ALD method is the same as that described for the barrier layer 3.

<Sputtering method>
In the sputtering method, accelerated ions are irradiated onto a material substance (called a target). The ions collide with the target, and the kinetic energy releases atoms or molecules on the surface of the target into the space to form a thin film on the substrate. Since the kinetic energy of the target atoms (molecules) is larger than that of the vacuum deposition method, a strong (hard to peel off) film can be formed. In addition, a thin film of SiN or SiO ₂ which is a refractory metal can be formed. Usually, argon gas is injected to make an ion state, and the target is irradiated. In general, the film forming chamber is in a high vacuum state of about 1 × 10 ^{−3 to} 9 × 10 ⁻² Pa, and argon gas of about 10 SCCM is injected.

In this embodiment, for example, a SiN film having excellent barrier properties is obtained by reactive sputtering using SiN as a target or reacting with N ₂ using Si as a target. The temperature at the time of sputtering is usually 50 to 200 ° C, preferably 70 to 150 ° C, more preferably 80 to 120 ° C. For example, when forming a SiN film, the film thickness is usually 1 to 500 nm, preferably 20 to 300 nm, and more preferably 40 to 200 nm.

<Plasma CVD method>
In plasma CVD, inorganic materials such as metal carbides, metal nitrides, metal oxides, and metal sulfides are selected by selecting conditions such as organometallic compounds, decomposition gases, decomposition temperatures, and input power as raw materials (also referred to as raw materials). The film is preferable because an inorganic film made of a mixture thereof (metal oxynitride, metal nitride carbide, etc.) can be formed separately.

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

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

  In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples thereof include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  These reactive gases are mixed mainly with a discharge gas that tends to be in a plasma state, and the discharge gas is sent to the plasma discharge generator. As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  The discharge gas and the reactive gas are mixed, and a film is formed by supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% by volume or more with respect to the entire mixed gas.

  The thicknesses of the barrier layers 8, 10, and 12 formed by the sputtering method and the plasma CVD method as described above are appropriately selected depending on the type and configuration of the materials used, and preferably 10 to 3000 nm. More preferably, it is in the range of 100 to 3000 nm, more preferably 100 to 2000 nm, and particularly preferably 100 to 1000 nm. When the thickness of the barrier layers 8, 10, and 12 is thinner than the above range, a uniform film cannot be obtained, and it becomes difficult to obtain a barrier property against gas and moisture. Further, when the thickness of the barrier layers 8, 10, 12 is larger than the above range, warping due to internal stress between the barrier layers 8, 10, 12 and the first flexible resin film substrate 2 occurs. It is easy and it becomes difficult to maintain flexibility. As a result, there is a possibility that the barrier property may be deteriorated by cracking of the barrier film or peeling of the barrier layer due to external factors such as bending and pulling after the film formation.

The barrier layers 8, 10, and 12 formed by the sputtering method and the plasma CVD method are respectively a laminate of the first flexible resin film substrate 2 and the substrate back surface barrier layer 8, and the first flexible resin film substrate 2. 1 × 10 ⁻⁵ to 10 ⁻² g / m ² / a laminate of the first protective barrier layer 10 and the laminate of the first flexible resin film substrate 2 and the second protective barrier layer 12. The water vapor permeability (barrier property) of day is given.

When using the _{the Al} 2 _{O 3} layer as the barrier layer 3, a first protective barrier layer 10, it is preferable to use _Al 2 _{O 3} layer formed by ALD. In this case, the barrier layer formed by the ALD method is excellent in coverage and followability to unevenness such as cracks and cracks in adjacent layers. For this reason, since it has a function of embedding defects such as cracks and cracks in adjacent layers and improving the barrier property, a high barrier layer is easily obtained.

In addition, the barrier layer 3 composed of a stack of an Al ₂ O ₃ layer, an Al ₂ O ₃ layer, and a TiO ₂ layer is composed of the SiO _{x Cy} layer or SiN layer that is the first protective barrier layer 10 and the second planarization layer. 11, the first protective barrier layer 10 and the second flatness having low adhesiveness are improved while improving the barrier property against moisture penetrating from the first flexible resin film substrate 2 side. It becomes possible to improve adhesiveness with the chemical layer 11. For example, even after high temperature and high humidity accelerated storage at 60 ° C. and 90%, peeling between the first protective barrier layer 10 and the second planarizing layer 11 in a bent state, which occurs when an organic EL element is manufactured by R2R, etc. Can be prevented. In particular, this effect becomes remarkable when a SiO _{x Cy} layer is used as the protective barrier layer 10.

(Flattening layer)
The first flattened layer 9 and the second flattened layer (hereinafter sometimes collectively referred to as “flattened layer”) are rough surfaces of the first flexible resin film substrate 2 on which protrusions and the like are present. Is provided, or the projections and depressions generated in the inorganic compound layer such as the barrier layer 3 by the protrusions are filled and flattened. Such a planarization layer can be formed by curing a thermosetting resin or a photosensitive resin. In the case of a photosensitive resin, the planarizing material solution is applied and dried on a flat resin flexible substrate, or coated and dried on a temporary substrate (such as a PET film) and laminated onto the resin flexible substrate by laminating or the like. The flat layer surface obtained by the transfer can be cured with light in a time usually within several minutes. Therefore, it is easy to fix the flattened surface shape at the time of coating and drying, and the curing time should be very short compared to thermosetting resins that are generally cured at 80 to 120 ° C. for 30 minutes to 1 hour. Can do. As a result, the entry of dust and the like from the air that causes the generation of dark spots (DS) can be suppressed, and deterioration of the coating surface flatness due to hot melt deformation can also be suppressed.

  Examples of the photosensitive resin used for the planarization 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 n-pentyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, benzyl acrylate, butoxyethyl acrylate, cyclohexyl acrylate, dicyclohexane. Pentanyl acrylate, 2-ethylhexyl acrylate, glycidyl 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, Lyserol 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-buta Diol triacrylate, 2,2,4-trimethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and the above acrylate replaced with methacrylate , Γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used individually by 1 type or in mixture of 2 or more types, or as a mixture with another compound.

  The composition of the photosensitive resin contains a photopolymerization initiator. As photopolymerization initiators, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino-acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyldichloroacetophenone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin methyl ether, benzoin butyl ether 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-prop Trione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1- Examples thereof include a combination of propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride, and the like. These photopolymerization initiators may be used alone or in combination. It can be used in combination of more than one species.

  The method for forming the planarizing layer is not particularly limited, but it is preferably formed by a wet coating method such as die coating, spin coating method, spray method, blade coating method, dip method, or dry coating method such as vapor deposition method. .

  In the formation of the planarization 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 of the flattening layer, in any flattening layer, an appropriate resin or additive other than those described above is further used in order to improve the film formability and prevent pinhole generation in the film. Also good.

  As other resin materials used for forming the planarizing layer, it is preferable that a resin such as a thermoplastic resin or a thermosetting resin is a main component. Among these, those having excellent surface smoothness after coating film formation, low gas permeability to oxygen and moisture, and excellent adhesion to the base resin and the inorganic barrier layer are desirable.

  Specific examples of the flattening layer forming resin include, for example, epoxy resins, phenoxy resins, phenoxy ether resins, phenoxy ester resins, acrylic resins, melamine resins, phenol resins, urethane resins, alkyd resins, silicone resins, and mixtures thereof. Polyester, polyvinyl alcohol, polyvinyl pyrrolidone, ethylene vinyl alcohol copolymer, polyvinylidene chloride, polyvinylidene fluoride, polychlorotrifluoroethylene, tetrafluoroethylene, tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene / hexafluoropropylene copolymer Examples thereof include a polymer and a tetrafluoroethylene / perfluoroalkoxyethylene copolymer. These resins can be used singly or in combination of two or more. A flattening layer is formed by applying a monomer, a solution, an emulsion, or the like of these resins by an existing coating film forming method alone, followed by drying or curing.

  Moreover, it is formed from a base film or an inorganic thin film layer and a polymer by including a hydrolysis / condensation product of alkoxysilane such as tetramethoxysilane or tetraethysilane or a silane coupling material in the planarizing layer. Adhesion with the planarization layer can be enhanced. A flattened layer is formed by applying a solution-like or suspension-like mixture of these resins by an existing coating film forming method, followed by drying and / or curing.

  In order to further improve the smoothness of the planarizing layer, a leveling agent may be added to the resin material for forming the planarizing layer. The leveling agent that can be used is not particularly limited. For example, a coating leveling agent such as a fluorine nonionic surfactant, a special acrylic resin leveling agent, or a silicone leveling agent can be used. The addition amount of the leveling agent is usually 5 to 50,000 ppm, preferably 10 to 20,000 ppm.

  The thickness of the planarizing layer is not particularly limited, but is 0.02 to 50 μm, more preferably 0.1 to 10 μm, and further preferably 0.2 to 5 μm. Further, the transparency of the flattening layer is preferably 80% or more at a light transmittance of 550 nm as in the case of the substrate.

  As a solvent used when forming a planarization layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent, alcohols such as n-propanol, isopropanol, ethylene glycol, propylene glycol, α- or β -Terpenes such as terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, and aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, etc. , Glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl celloso Examples thereof include acetates such as rubacetate and carbitol acetate, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, ethyl 3-ethoxypropionate, methyl benzoate and the like. Moreover, the organic inorganic hybrid polymer etc. which are used as a stress relaxation layer by the Japanese translations of PCT publication No. 2010-026852 can also be applied.

  In order to form a planarized layer having high smoothness, in the case of the above-described wet coating method, it is preferable to adjust the coating solution solid content concentration so that the viscosity of the coating solution is lowered. Usually, the coating solution viscosity at 25 ° C. is 1 to 100 cP (1 to 100 mPa · s), more preferably 2 to 30 cP (2 to 30 mPa · s). Further, when the drying temperature is also high, convection occurs in the film in the middle of drying, making it difficult to obtain sufficient smoothness. On the other hand, when the drying is performed at a temperature lower than necessary, the film flows during the drying due to a delay in the drying speed, and thickness unevenness is liable to occur, so that stable smoothness cannot be obtained. The drying temperature for obtaining high smoothness is usually 20 to 120 ° C, preferably 30 to 100 ° C.

  The surface roughness is calculated from an uneven cross-sectional curve measured with a non-contact surface / layer cross-sectional shape measurement system “VertScan 2.0” manufactured by Ryoka System Co., Ltd., and is a parameter Ra (arithmetic) representing the surface roughness at 50 μm. The average roughness) is preferably 100 nm, more preferably 50 nm, and even more preferably 20 nm.

If necessary, the flattening layer can be applied to a resin film temporary support, such as PET, using a film in which the flattening layer material is liquid-coated. Furthermore, before laminating, the flattening layer is heated to a temperature at which it melts, the bubbles in the adhesive layer are removed by vacuum, and then laminated at vacuum or atmospheric pressure, and then heat-treated as necessary. It is preferable. The temperature during defoaming treatment, laminating, and thermosetting is usually 70 to 150 ° C., more preferably 90 to 120 ° C., and the treatment time is preferably 1 minute to 1 hour for the defoaming treatment time of a 100 cm ² sample. 1 to 10 minutes. Moreover, the laminating time of a 100 cm < ² > sample is 1 minute-1 hour, Preferably it is 1-10 minutes. The heat curing time is 10 minutes to 2 hours, preferably 20 minutes to 1 hour.

  As one of the preferred embodiments of the planarizing layer, reactive silica particles in which a photosensitive group having photopolymerization reactivity is introduced into the surface of the above-described photosensitive resin (hereinafter also simply referred to as “reactive silica particles”). ). Here, examples of the photosensitive group having photopolymerization reactivity include polymerizable unsaturated groups represented by (meth) acryloyloxy groups. The photosensitive resin also contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be a thing. Moreover, as a photosensitive resin, what adjusted solid content by mixing a general purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.

  Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By setting the average particle size in such a range, the antiglare property and the resolution, which are the effects of the present invention, can be obtained by using in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 μm described later. It becomes easy to form a flattened layer having both optical properties satisfying a good balance and hard coat properties. From the viewpoint of making it easier to obtain such an effect, it is more preferable to use an average particle diameter of 0.001 to 0.01 μm.

  In the present embodiment, the polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to the silica particles by generating a silyloxy group by a hydrolysis reaction of the hydrolyzable silyl group. Can be used as reactive silica particles.

  Examples of the hydrolyzable silyl group include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl 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.

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.001 to 5 μm, preferably 0.002 to 2 μm are preferable.

  As such inorganic particles, silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide, etc. may be used alone or in combination of two or more. Can do.

  Here, the matting agent composed of inorganic particles is preferably mixed in a proportion of 2 parts by mass or more, more preferably 4 parts by mass or more, and further preferably 6 parts by mass or more with respect to 100 parts by mass of the solid content of the hard coat agent. Moreover, it is preferably mixed at a ratio of 80 parts by mass or less, more preferably 70 parts by mass or less, and further preferably 30 parts by mass or less.

  In addition, the planarizing layer according to this embodiment includes a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, a moisture or oxygen scavenging getter agent as other components of the hard coating agent and the matting agent. (Described in JP-A-2002-124374 and the like) may be contained.

  Examples of such thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof. Vinyl resins such as polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Examples thereof include resins.

  Further, as the thermosetting resin, thermosetting urethane resin, phenol resin, urea melamine resin, epoxy resin (Japanese Patent Laid-Open No. 2006-179318, Japanese Patent Laid-Open No. 2006-070221, JP-A-2005-004063, JP-A-2010-126699, JP-A-2004-139777, JP-A-2007-1212956, etc.), unsaturated polyester resins, silicone resins and the like.

  Moreover, as ionizing radiation curable resin, it hardens | cures by irradiating ionizing radiation (an ultraviolet ray or an electron beam) to the ionizing radiation hardening coating material containing 1 type, or 2 or more types of photopolymerizable prepolymers, photopolymerizable monomers, etc. Can be used. 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 preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.

  The thickness of the planarization layer is preferably 0.01 to 100 μm, more preferably 0.1 to 10 μm, and still more preferably 0.5 to 5 μm. By making it 0.01 μm or more, it becomes easy to make the smoothness as a film having a flattening layer sufficient, and by making it 100 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film and to make it flat. When the layer is provided only on one surface of the resin film substrate, curling of the film can be easily suppressed.

  The flattening layer as described above is blended with a hard coat agent, a matting agent, and other components as necessary, and is prepared as a coating solution by using a diluent solvent as necessary, and the coating solution is supported on the support. It can be formed by coating the film surface with a conventionally known coating method and then curing it by irradiating with ionizing radiation. In addition, as a method of irradiating with ionizing radiation, ultraviolet rays in 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, etc., or Examples include a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning type or curtain type electron beam accelerator.

[Adhesive layer]
The adhesive layer 6 is used for adhering the second flexible resin film substrate 7 to the organic EL layer 5, and specifically, the photo-curing or thermosetting used for the above-described planarization layer. Made of a functional acrylate resin or epoxy resin. Other commonly used resin films that can be fused with an impulse sealer, such as ethylene vinyl acetate copolymer (EVA), polypropylene (PP) film, polyethylene (PE) film, polybutadiene (PB) film, etc. You can also

  As an adhesive used for the adhesive layer 6, the barrier film 4, the organic EL layer 5, and the adhesive layer 6 are formed by a thermosetting process when the second flexible resin film substrate 7 and the organic EL layer 5 are bonded. High adhesiveness, significant heat shrinkage of adhesive, peeling of organic EL layer due to stress on organic EL layer, generation of components that adversely affect organic EL layer from heat-cured adhesive layer, and high barrier property and darkness A thermosetting epoxy resin type adhesive having a high effect of suppressing the generation / growth of spots is preferred.

  Examples of the thermosetting epoxy resin type adhesive include, for example, JP-A-2002-56970, JP-A-2006-179318, JP-A-2006-070221, JP-A-2005-004063, JP-A-2010-126699. And thermosetting compositions containing a high molecular weight epoxy resin described in JP-A No. 2004-139777, JP-A No. 2007-112956, and an epoxy thermosetting initiator. Such a thermosetting composition exhibits fluidity in the range of 50 ° C to 100 ° C when heated. Specifically, as a high molecular weight epoxy resin, it has at least two or more glycidyl groups in one molecule such as bisphenol A type epoxy resin, bisphenol type epoxy resin, hydrogenated bisphenol type epoxy resin, phenol novolac type resin, Low molecular weight epoxy resins having a molecular weight of 200 to 2000, high molecular weight epoxy resins having 2000 to 70000 epoxy resins such as solid bisphenol A type epoxy resin, solid bisphenol F type epoxy resin, and phenoxy resin, and epoxy thermosetting agents 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimelli 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [ 2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-methyli An imidazole compound or sulfonium salt that is solid at room temperature, such as dazoline, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, and has a melting point or decomposition temperature of 80 ° C. or higher. Publication No. 2005/059002 etc.), “Sanyo Chemical Industry Co., Ltd. Technical Report No. SA13012013 February” and “Sanshin Chemical Industry Co., Ltd. Technical Report STR-16107R”, etc. Is mentioned.

In addition, for thermosetting epoxy resin type adhesives, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl are used for the purpose of improving adhesion and coating properties with adjacent layers as necessary. Methyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3 -Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (Vinylbenzylamino) ethyl) 3-aminopropyltri Tokishishiran hydrochloride, 3-methacryloxypropyl trimethoxysilane silane coupling agent can be blended in an amount. Further, for the purpose of improving the barrier property against moisture and oxygen of the adhesive layer 6, a getter agent described in JP-A-2002-124374 can be blended, and the getter material is dispersed in the adhesive. You can also. As a getter agent for the purpose of capturing moisture, a material having an effect of adsorbing moisture, such as CaO (calcium oxide), BaO (barium oxide), silicon oxide (SiO ₂ ) and calcium chloride (CaCl ₂ ), Furthermore, materials that readily adsorb moisture, such as materials that easily react with water, such as alkali metals and alkaline earth metals, and materials that are difficult to liquefy (preferably not liquefied) can be used. The material that can be used is not limited by the adsorption mechanism. As a getter agent for the purpose of capturing oxygen, an activated metal material such as Ba (barium), Ca (calcium), Ti (titanium) or the like can be used.

  The compounding ratio of the silane coupling agent is usually 0 to 10% by weight, preferably 0 to 5% by weight. If it is excessively blended, the storage stability of the adhesive is lowered. The blending ratio of the getter material is usually 0 to 50% by weight, preferably 0 to 40% by weight. When the blending ratio is remarkably increased, the storage stability is improved, but the adhesiveness of the adhesive layer is lowered, and peeling from the adhesive layer such as a barrier film is likely to occur in the refractive state. The adhesive layer 6 can be applied and laminated and formed by the same method as the above-described planarization layer.

  The film thickness of the adhesive layer 6 is preferably 1.0 to 100 μm, more preferably 2 to 50 μm, and still more preferably 3 to 40 μm. If the film thickness is remarkably thin, the organic EL layer surface unevenness or mixed dust cannot be sufficiently embedded, and they tend to cause mechanical stress on the organic EL material and cause dark spots. On the other hand, when the film thickness is extremely thick, it is easily affected by moisture entering from the end face of the adhesive layer. However, when the amount of adhesive applied is too large, tunneling, seepage, crimping, etc. may occur.

  As a method for forming the adhesive layer 6, there is a hot melt lamination method. The hot melt lamination method is a method in which a hot melt adhesive is melted and an adhesive layer is coated on a support, and the thickness of the adhesive layer is generally set within a wide range of 1 to 50 μm. EVA, EEA, polyethylene, butyl rubber, etc. are used as the base resin of the adhesive generally used in the hot melt lamination method, and rosin, xylene resin, terpene resin, styrene resin, etc. are used as tackifiers, waxes Etc. are added as plasticizers.

  Further, as a method of forming the adhesive layer 6, there is an extrusion laminating method. The extrusion laminating method is a method in which a resin melted at a high temperature is coated on a support using a die, and the thickness of the adhesive layer can generally be set in a wide range of 10 to 50 μm. In general, LDPE, EVA, PP or the like is used as a resin used in the extrusion laminating method.

[Temporary sealing barrier layer]
As shown in FIG. 2, a temporary sealing barrier layer 13 may be further provided between the organic EL layer 5 and the adhesive layer 6 so as to cover the organic EL layer 5. The temporary sealing barrier layer 13 is configured in the same manner as the barrier layers 8, 10, and 12.

[Second flexible resin film substrate]
A 2nd flexible resin film base material is 10-200 micrometers in film thickness in the above-mentioned transparent barrier film 4,24,34 or the 1st flexible resin film base material 2, Preferably it is 1 * 10 < ^-4 > g / m < ² >. An opaque base material obtained by laminating an aluminum foil having a thickness of 20 to 50 μm having a water vapor permeability of not more than / day can be suitably used. In particular, a film substrate (Al-PEN) obtained by bonding an aluminum foil with a thickness of 30 μm to a PEN film with a thickness of 100 μm has a low water vapor of 1 × 10 ⁻⁴ g / m ² / day or less as measured by the CRDS method. It has transparency and high flexibility, which is preferable.

[Organic EL layer]
The configuration of the organic EL layer according to this embodiment will be described in detail. In the present embodiment, preferred specific examples of the configuration of the organic EL layer are shown below, but are not limited thereto.

(1) Anode / light emitting layer / electron transport layer / cathode (2) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (3) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (4) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (5) anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode

(anode)
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO and IZO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

(cathode)
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either the anode or the cathode of the organic EL layer is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after producing the metal with a film thickness of 1 to 20 nm on the cathode, a transparent or translucent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

(Injection layer: electron injection layer, hole injection layer)
Next, an injection layer, a blocking layer, an electron transport layer, and the like used as a constituent layer of the organic EL element of the present invention will be described.

  The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer. May be.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

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

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

(Blocking layer: hole blocking layer, electron blocking layer)
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.

  The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.

(Light emitting layer)
The light emitting layer according to this embodiment is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. Alternatively, it may be the interface between the light emitting layer and the adjacent layer.

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

  The light-emitting dopant is roughly classified into two types: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.

  Typical examples of the former (fluorescent dopant) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, Examples include perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

  Typical examples of the latter (phosphorescent dopant) are preferably complex compounds containing metals of Group 8, Group 9, and Group 10 in the periodic table of elements, and more preferably iridium compounds and osmium compounds. Of these, iridium compounds are most preferred. The light emitting dopant may be used by mixing a plurality of kinds of compounds.

  A light-emitting host (also simply referred to as a host) means a compound having the largest mixing ratio (mass) in a light-emitting layer composed of two or more compounds. For other compounds, “dopant compound ( Simply referred to as a dopant). " For example, if the light emitting layer is composed of two types of compound A and compound B and the mixing ratio is A: B = 10: 90, compound A is a dopant compound and compound B is a host compound. Furthermore, if a light emitting layer is comprised from 3 types of compound A, compound B, and compound C, and the mixing ratio is A: B: C = 5: 10: 85, compound A and compound B are dopant compounds, Compound C is a host compound.

  The light-emitting host used in the present invention is not particularly limited in terms of structure, but is typically a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, an oligo Those having a basic skeleton such as an arylene compound, or a carboline derivative or a diazacarbazole derivative (here, a diazacarbazole derivative is a nitrogen atom in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is a nitrogen atom) And the like.) And the like. Of these, carboline derivatives, diazacarbazole derivatives and the like are preferably used.

  The light emitting layer can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. Although the film thickness as a light emitting layer does not have a restriction | limiting in particular, Usually, 5 nm-5 micrometers, Preferably it is chosen in the range of 5-200 nm. This light emitting layer may have a single layer structure in which these phosphorescent compounds and host compounds are one or more kinds, or may have a laminated structure formed of a plurality of layers having the same composition or different compositions.

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

  The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

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

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

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

  Examples of the resin film constituting the barrier film that can be used in the organic EL layer according to this embodiment include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, and cellulose diacetate. , Cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), cellulose acetate phthalate (TAC), cellulose esters such as cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, Shinji Tactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimide, poly Cyclones such as ether sulfone (PES), polysulfones, 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) Examples include olefin resins.

(Method for producing organic EL layer)
A method for manufacturing the organic EL layer will be described in detail below.

  As an example of the organic EL layer, a method for producing an organic EL element composed of an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.

  First, on the barrier films 4 and 24 according to the present embodiment, a desired electrode material, for example, a thin film made of an anode material is deposited or sputtered to a thickness of 1 μm or less, preferably 10 to 200 nm. An anode is formed by a method such as plasma CVD. Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer is formed thereon.

There are vapor deposition methods, wet processes (spin coating method, casting method, ink jet method, printing method), etc. as methods for thinning this organic compound thin film, but it is easy to obtain a uniform film and pinholes are generated. From the viewpoint of difficulty, vacuum deposition, spin coating, ink jet, and printing are particularly preferable. Further, different film forming methods may be applied for each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 1 × 10 ^{−6 to} 9 × 10 ⁻² Pa, and a deposition rate. It is desirable to select appropriately within a range of 0.01 to 50 nm / second, a substrate temperature of −50 to 300 ° C., and a film thickness of 0.1 nm to 5 μm, preferably 5 to 200 nm.

  After forming these layers, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL layer can be obtained. The organic EL layer is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but it may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

[Side barrier layer]
In the organic EL element according to the present embodiment, in addition to moisture intrusion from the flexible resin film substrate, moisture intrusion occurs from the side surface of the element, the end face of the adhesive layer or the flattening layer. In this case, the extinction of the outer edge of the light emitting surface proceeds. Therefore, the side surface of the element, be formed by the ALD method comprised the side barrier layer and the like laminated with trackability good _{as Al} 2 _{O 3} and _Al 2 _{O 3} and TiO ₂ preferably.

Furthermore, when providing a side barrier layer, the 1st flexible resin film base material 2 and the 2nd flexible resin film base material 7 are bonded together. In addition, a side barrier layer made of the above-described Al ₂ O ₃ or a laminate of Al ₂ O ₃ and TiO ₂ is formed by ALD on the end face where a recess (insertion shape) has occurred so as to bite into the organic EL element. By doing so, the side surface of the organic EL element can be sealed.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

(Example 1 of formation of first protective barrier layer by CVD method)
After the first flexible resin film substrate (Q65FA, manufactured by Teijin DuPont Films, Ltd., width 300 mm, length 100 m, thickness 125 μm) is washed with a brush and ultrasonic waves and dried at 100 ° C. for 1 minute. And wound in a roll shape along the length direction (roll A). At the time of winding, both ends of the first protective barrier layer film-forming surface of the first flexible resin film substrate have a width of 50 mm and a thickness of 75 μm along the length direction of the first flexible resin film substrate. A PET spacer ribbon was placed. Thereby, when forming into a roll shape after forming a 1st protective barrier layer, it can prevent that a 1st protective barrier layer and the back surface of a 1st flexible resin film base material contact. After roll A is mounted on a CVD film forming apparatus (W35-350C, manufactured by Kobe Steel, Ltd.), a mixed gas of oxygen and HMDSO (450: 50 by volume) is formed on the first flexible resin film substrate. Then, the SiO _x C _y film was formed as a first protective barrier layer by CVD while the first flexible resin film substrate was transported at a rate of 0.5 m / min at room temperature. The film thickness of the _SiO x _{C y} film formed by a single film is 0.125 .mu.m, a first protective barrier layer made of _SiO x _{C y} film with a thickness of 1μm repeating this film formation 8 times It was formed on a flexible resin film substrate (thus formed a _SiO x _{C y} film hereinafter referred to as "CVD-A1".). The obtained film was wound up while disposing a spacer ribbon in the same manner as described above to obtain a roll film (roll B).

(Measurement of water vapor permeability)
A sample was cut into a 100 mm square and dried for 2 days. Thereafter, humidification at 40 ° C. and 90% is performed for 1 week from the surface side on which the first protective barrier layer is formed, and an atmospheric pressure ionization mass spectrometer (API-BA60) manufactured by Japan API Corporation and a laser manufactured by Tiger Optics Co., Ltd. The moisture permeating through the resin film substrate was measured with a method (CRDS method) moisture meter (HALO-H20), and the water vapor permeability was determined.

(Example 1 of formation of barrier layer by batch ALD method)
A sample is cut out to 100 mm square from the roll B, and the sample is kept at 105 ° C. using an ALD film forming apparatus (LabNanoTM 9100) for 6-inch substrate, and water is contained on the surface of the first protective barrier layer. Water molecules were adsorbed by contacting N ₂ gas. Then, N ₂ to remove unwanted moisture by the gas, the first supplying N ₂ gas containing TMA on the protective barrier layer, Al ₂ O ₃ of 1 atomic by reacting TMA water molecules adsorbed A layer was formed. Furthermore, unnecessary TMA was removed with N ₂ gas. This operation is repeated 200 times, 30 nm _{the Al} 2 _{O 3} layer of the formation of the (barrier layer) (thus formed _{the Al} 2 _{O 3} layer hereinafter referred to as "ALD-A1". The 100mm obtained in this manner The corner sample is hereinafter referred to as “film substrate A”). Similarly, a film “ALD-RF1” having a 5 nm Al ₂ O ₃ layer, and a 3 nm Al ₂ O ₃ layer and a 3 nm TiO ₂ layer are alternately and repeatedly formed 5 times to form a 30 nm Al ₂ O _{3 layer.} : A film “ALD-A2” having a TiO ₂ laminate was produced.

(Example 2 of barrier layer formation by R2RALD method)
1. The PEN film base material provided with the SiO _x C _y barrier layer was mounted on the film unwinding core of a slit nozzle type R2R-ALD film forming apparatus (manufactured by Beneck Co., Ltd., WCS-600). The film substrate was pulled out together with the spacer, passed through the ALD reaction material supply nozzle device, and fixed to the film material winding core. The film formation container was decompressed and the temperature of the film was adjusted to 105 ° C. Thereafter, N ₂ gas containing water is supplied from the slit nozzle onto the SiO _x C _y surface of the film while the film substrate is conveyed at a speed of 0.1 m / min, and is contacted and adsorbed. Molecules were adsorbed. Thereafter, unnecessary moisture is removed by N ₂ gas supplied from the N ₂ slit nozzle, and then N ₂ gas containing TMA is supplied from the slit nozzle to react therewith to form a 1 atom Al ₂ O ₃ layer. Made a film. It was then removed by N2 gas supplied unnecessary TMA from N ₂ slit nozzle. This operation was repeated 200 times to form a 30 nm Al ₂ O ₃ layer (ALD-B1 in Table 1). Then, this film base material was wound up with a spacer film, two types of barrier layers were laminated, and the roll (roll C) which provided the barrier layer in the resin film was produced.

Above 1. And 30 nm Al ₂ O ₃ layer (ALD-C1), 60 nm Al ₂ O ₃ layer (ALD-C2), 120 nm at a rate of 0.5 m / min in air at 130 ° C. A roll having an Al ₂ O ₃ layer (ALD-RF2) was prepared.

3. A PEN film substrate having a thickness of 100 μm was obtained by providing a partition partitioned by N ₂ gas provided with a narrow slit through which a transport film substrate could pass through in a reaction vessel maintained at 75 ° C. under reduced pressure. TMA gas, oxygen plasma gas, and TiCl ₄ gas are supplied to each of the plurality of gas chambers. Then, the slits of these different gas chambers are passed through the film base at a speed of 1 m / min, and the Al ₂ O ₃ layer formed by the reaction of TMA and oxygen plasma on both sides of the substrate is followed by TiCl ₄ and oxygen plasma. After forming a TiO ₂ layer by reaction, this operation was repeated to produce a 30 nm thick barrier layer in which Al ₂ O ₃ and TiO ₂ were alternately laminated on a film substrate (ALD-D1).

(Measurement of barrier layer thickness)
The barrier layer is formed by covering the PEN film with a Kapton tape before film formation and peeling the Kapton tape after film formation. It calculated | required by measuring using a tomographic measurement system (Vert Scan).

(Formation of planarization layer)
The roll C was mounted on an R2R-slit coating device, and the film was passed through the die coater unit while winding the spacer ribbon of the roll C, and conveyed to a drying unit at 100 ° C. Thereafter, the film was set to be wound around the winding portion while a new spacer ribbon was arranged. After that, a film for flattening layer (Z770UH, manufactured by Aika Industry Co., Ltd., acrylic resin) is applied so that the film thickness becomes 1 μm while transporting the film at a speed of 1.5 m / min, and dried for 2 minutes to be flat. A planarized layer was obtained (the planarized layer thus obtained is hereinafter referred to as “UC1-A1”).

  On the other hand, the film substrate A was dried by spin coating and a hot plate at 100 ° C., and a planarizing layer was provided so as to have a film thickness of 1 μm. About these barrier film base materials with a planarization layer, the unevenness | corrugation of the surface was evaluated by the above-mentioned VertScan. Ra (50 μm) of the obtained flattened layer was less than 5 nm.

(Formation of organic EL layer and temporary sealing barrier layer)
A transparent electrode of 2 mm square (IZO (indium zinc oxide), 160 nm) is formed by sputtering, and holes are injected by vapor deposition at a position moved 14 mm inward along the diagonal line from the corner of the barrier film with a 30 mm square flattening layer. Layer (MoO ₃ (molybdenum oxide), 25 nm), hole transport layer (α-NPD (compound represented by the following structural formula (I)), 45 nm), green dopant (Alq ₃ (the following structural formula (II)) Compound), 60 nm), an electron injection layer (LiF (lithium fluoride), 1.6 nm) in this order, a 4 mm square organic layer, and a 2 mm square cathode (Al (aluminum), 100 nm) by the same method. (The organic EL layer thus formed is hereinafter referred to as “EL-G1”). On this substrate, a temporary sealing barrier layer (the layer formed in this way) made of 100 nm SiN by sputtering (reaction temperature 100 ° C., film formation time 1 hour) by a ULVAC sputtering apparatus (model SBH-2306) "SP-A1") was formed. The structure of the organic EL layer is summarized in Table 2.

(Production of laminate sealing element)
In the glove box, a delayed photo-curing type adhesive (XV-ZEN1-83, injected into a 10 ml syringe on the surface of the central temporary sealing layer of the barrier film provided with the organic EL layer and the temporary sealing barrier layer. After dropping 2 drops of UV & thermosetting epoxy resin manufactured by Panasonic Corporation (hereinafter referred to as “SS-A1”), it is exposed to 500 mJ / cm ² by a high pressure mercury lamp SEN LIGHTS CORP PL17-110 for 5 minutes under reduced pressure. To remove bubbles in the liquid. Next, as a second flexible resin film base material, a 100 μm thick PEN type barrier film (Al-PEN) laminated with 30 mm square and 30 μm thick aluminum foil is laminated so that the aluminum foil side faces the organic EL layer side. In addition, the distance between the outer edge of the organic EL layer and the outer edge of Al-PEN (sealing edge width) was shifted to 1 nm or 4 mm, and then held for 10 minutes in a laminate under reduced pressure, followed by 100 ° C. for 30 minutes. Was cured by heating.

(High temperature and high humidity (60 ° C 90%) storage test)
The produced organic EL device was stored for 300,500,800 hours using a small environmental tester SH-221 manufactured by Espec Co., Ltd. set to 60 ° C. and 90%, and then the change in the light emitting area before and after storage was evaluated. In addition, it evaluated by AD as follows by the value (%) of the light emission area before storage-the light emission area after a storage-the light emission area before a storage.
A: Less than 10%, B: 10% or more and less than 20%, C: 20% or more and less than 30%, D: 30% or more.

(Barrier film bending test)
For the barrier film formed on the Teijin 125 μm PEN film (PQDA5) cut into 30 nm square, the barrier film is bent so that the radius of curvature is 2.5 mm with the barrier layer on the outer peripheral side, After returning the bent barrier film to the original state, the surface of the barrier layer was observed. At this time, A in which an arc-shaped crack is not observed in a region 50 μm or more from the outer edge of the barrier layer surface, A in which an arc-shaped crack is observed in a region from 50 μm or more to less than 100 μm from the outer edge of the barrier layer surface B, C indicates that an arc-shaped crack is observed in the region 100 μm or more and less than 200 μm from the outer edge of the barrier layer surface, and D indicates that an arc-shaped crack is observed in the region 200 μm or more from the outer edge of the barrier layer surface. evaluated. A part of the results is shown in FIG.

(Evaluation of flatness of barrier film)
The surface roughness Ra (arithmetic mean roughness) at a linear distance of 50 μm on the barrier film surface is measured using a non-contact surface / layer cross-sectional shape measurement system “VertScan 2.0” manufactured by Ryoka System Co., Ltd. Ra was determined. The Ra on the surface of the barrier film used in Examples 1 to 10 and Comparative Examples 1 to 4 described later were all 5 nm or less.

(Measurement of sealing edge width)
The distance between the outer edge of the organic EL layer of the fabricated element and the outer edge of Al-PEN was determined, and this was taken as the sealing edge width.

(Bending evaluation of organic EL elements)
A 30 mm square organic EL was stored at 60 ° C. and 90% for 500 hours, wound around a cylinder with a diameter of 30 mm and allowed to stand for 5 minutes, and then returned to the original flat state. Presence or absence of peeling between the element constituent parts from the first planarization layer to the second flexible resin film substrate and the element constituent parts from the first protective layer to the first flexible resin film substrate at that time Were evaluated according to the following criteria.
A: The peeled portion is less than 10% of the total adhesion area B: The peeled portion is 20% or more and less than 30% of the total adhesion area C: The peeled portion is 30% or more and less than 50% of the total adhesion area D: Peeled part is 50% or more of the total adhesion area

  The characteristics of each barrier film are shown in Table 1. FIG. 4A shows an observation result (a result of observing the surface of the PEN film) when only the PEN film is bent. Moreover, in FIG.4 (b) and FIG.4 (c), the observation result (the result of having observed the surface by the side of the barrier layer of a barrier film) at the time of bending evaluation about ALD-C2 and ALD-RF2 is shown, respectively. .

1) The water vapor permeability of a barrier film having a barrier layer formed on Teijin's 125 μm (PQDA5) was measured.

Example 1
On the first flexible resin film substrate (PQDA5, manufactured by Teijin Ltd., 125 μm PEN film), CVD-A1 is used as the first protective barrier layer according to the above (Example 1 of forming the first protective barrier layer by the CVD method). Formed. Subsequently, ALD-A1 was formed as a barrier layer on the first protective barrier layer in accordance with the above (Example 1 of formation of barrier layer by batch ALD method). Subsequently, UC1-A1 was formed as a second planarization layer on the barrier layer according to the above (formation of planarization layer). Subsequently, ALD-A1 was formed as a second protective barrier layer on the second planarization layer according to the above (Example 1 of formation of barrier layer by batch ALD method). Thus, a barrier film was obtained.

  Next, an organic EL layer (EL-G1) and a temporary sealing barrier layer (SP-A1) were formed on the obtained barrier film according to the above (formation of an organic EL layer and a temporary sealing barrier layer).

  Furthermore, on the organic EL and the temporary sealing barrier layer, the adhesive layer SS-A1 and the second flexible resin film substrate Al-PEN were formed in accordance with the above (production of the laminate sealing element) to obtain an organic EL element. .

  Each evaluation was performed about the obtained barrier film or organic EL element according to the above (measurement of water vapor permeability), (high temperature and high humidity (60 ° C. 90%) storage test), and (bending evaluation of organic EL element). The results are shown in Table 3.

(Example 2)
An organic EL element was produced and evaluated in the same manner as in Example 1 except that the second protective barrier layer was changed to SP-A1. The results are shown in Table 3.

(Example 3)
Example 1 except that the first flexible resin film substrate was changed to Q65FA (Teijin Limited, 125 μm PEN film), the sealing edge width was changed to 1 mm, and the second protective barrier layer was not provided. Thus, an organic EL element was produced and evaluated. The results are shown in Table 3.

Example 4
The first flexible resin film substrate was changed to Q65FA (125 μm PEN film manufactured by Teijin Limited), and the organic EL device was prepared and evaluated in the same manner as in Example 1 except that the second protective barrier layer was not provided. went. The results are shown in Table 3.

(Example 5)
An organic EL device was produced and evaluated in the same manner as in Example 1 except that the barrier layer was changed to ALD-A2 and the second protective barrier layer was not provided. The results are shown in Table 3.

(Example 6)
An organic EL device was produced and evaluated in the same manner as in Example 1 except that the barrier layer was changed to ALD-B1 and the second protective barrier layer was not provided. The results are shown in Table 3.

(Example 7)
An organic EL device was produced and evaluated in the same manner as in Example 1 except that the barrier layer was changed to ALD-C1 and the second protective barrier layer was not provided. The results are shown in Table 4.

(Example 8)
Production and evaluation of organic EL device in the same manner as in Example 1 except that the barrier layer was changed to ALD-C1, the temporary sealing barrier layer was changed to ALD-A1, and the second protective barrier layer was not provided. Went. The results are shown in Table 4.

Example 9
An organic EL device was produced and evaluated in the same manner as in Example 1 except that the barrier layer was changed to ALD-C2 and the second protective barrier layer was not provided. The results are shown in Table 4.

(Example 10)
An organic EL element was produced and evaluated in the same manner as in Example 1 except that the first protective barrier layer and the second protective barrier layer were not provided. The results are shown in Table 4.

(Example 11)
UC1-A1 is provided as a first planarizing layer between the first flexible resin film substrate and the first protective barrier layer, the first protective barrier layer is changed to SP-A1, and the second flat An organic EL element was produced and evaluated in the same manner as in Example 1 except that the organic layer and the second protective barrier layer were not provided. The results are shown in Table 4.

(Example 12)
ALD-A1 is provided on the back surface of the first flexible resin film substrate as the substrate back surface barrier layer, the first flexible resin film substrate is changed to PET, and the first protective barrier layer and the second protective barrier layer The organic EL device was produced and evaluated in the same manner as in Example 1 except that the above was not provided. The results are shown in Table 4.

(Comparative Example 1)
An organic EL element was produced and evaluated in the same manner as in Example 8 except that the first protective barrier layer and the barrier layer were not provided. The results are shown in Table 5. From the comparison between Example 8 and Comparative Example 1, the presence of the first protective barrier layer and the barrier layer (particularly the barrier layer ALD-A1 by the ALD method) significantly improves the high-temperature and high-humidity storage stability of the organic EL element. You can see that

(Comparative Example 2)
An organic EL element was produced and evaluated in the same manner as in Example 3 except that the barrier layer was not provided. The results are shown in Table 5. From the comparison between Example 3 and Comparative Example 2, the presence of the barrier layer (particularly the barrier layer ALD-A1 by the ALD method) allows the first protective barrier layer and the second flat surface when the organic EL element is bent. It can be seen that peeling from the chemical layer can be suppressed.

(Comparative Example 3)
An organic EL device was produced and evaluated in the same manner as in Example 8 except that the barrier layer was changed to ALD-RF1 (film thickness 5 nm) and the first protective barrier layer was not provided. The results are shown in Table 5. From comparison between Example 8 and Comparative Example 3, it can be seen that the high-temperature and high-humidity storage stability of the organic EL element is significantly improved when the thickness of the barrier layer is 10 nm or more.

(Comparative Example 4)
An organic EL device was produced and evaluated in the same manner as in Example 8 except that the barrier layer was changed to ALD-RF2 (film thickness 120 nm) and the first protective barrier layer was not provided. The results are shown in Table 5. From the comparison between Example 8 and Comparative Example 4, it can be seen that the high-temperature and high-humidity storage stability of the organic EL element is significantly improved when the thickness of the barrier layer is 100 nm or less.

  In addition, the organic EL device of the present invention has an effect that the high-temperature and high-humidity storage stability decreases when the sealing edge width related to the barrier property of water vapor from the side surface is changed from 4 mm (Example 3) to 1 mm (Example 4). Is seen. Therefore, an organic EL device manufactured using a barrier film that generates a large arc crack of 200 μm or more from the outer edge of the barrier film barrier film such as ALD-RF2 has a significant shelf life when used for repeated bending. Is expected to decrease.

  DESCRIPTION OF SYMBOLS 1, 21, 31 ... Organic EL element, 2 ... 1st flexible resin film base material, 3 ... Barrier layer, 4, 24, 34 ... Barrier film, 5 ... Organic EL layer, 6 ... Adhesive layer, 7 ... 2nd Flexible resin film base material, 8 ... back surface barrier layer of substrate, 9 ... first planarization layer, 10 ... first protective barrier layer, 11 ... second planarization layer, 12 ... second protective barrier layer , 13 ... Temporary sealing barrier layer.

Claims (16)

A barrier film comprising a first flexible resin film substrate and a barrier layer provided on the first flexible resin film substrate by an ALD method, wherein the barrier layer has a thickness of 10 nm to 100 nm; The barrier film has a water vapor permeability of 1 × 10 ^{−3 to} 9 × 10 ⁻² g / m ² / day, and an organic EL layer provided on the barrier film, and the organic EL layer An organic EL element comprising: a second flexible resin film substrate disposed; and an adhesive layer that covers the organic EL layer and adheres to the second flexible resin film substrate.   When the barrier film is bent within a radius of curvature (R) of 1.5 mm or more and 10 mm or less, an arc-shaped crack is generated from the cut end of the barrier layer to the inside, and the spread of the crack is 200 μm. The organic EL device according to claim 1, wherein the organic EL device is less than 1.   3. The organic EL element according to claim 2, wherein the spread of the crack is less than 100 μm.   The water vapor permeability is a value obtained by allowing the barrier film to stand at room temperature in a dry nitrogen atmosphere to remove moisture and then measuring by atmospheric pressure ionization mass spectrometry and / or using a laser moisture meter. The organic EL element according to any one of claims 1 to 3. A barrier film comprising a first flexible resin film substrate and a barrier layer provided on the first flexible resin film substrate by an ALD method, wherein the barrier layer has a thickness of 10 nm to 100 nm; The barrier film has a water vapor permeability of 1 × 10 ^{−3 to} 9 × 10 ⁻² g / m ² / day, and an organic EL layer provided on the barrier film, and the organic EL layer The organic EL element includes a second flexible resin film substrate disposed and an adhesive layer that covers the organic EL layer and adheres to the second flexible resin film substrate. , When bent in the range of 1.5 mm or more and 10 mm or less, an arc-shaped crack is generated from the cut end of the barrier layer to the inside, and the spread of the crack is 200 μm. The water vapor permeability of the barrier film is obtained by allowing the barrier film to stand at room temperature in a dry nitrogen atmosphere to remove moisture, and then measuring by atmospheric pressure ionization mass spectrometry and / or using a laser moisture meter. Organic EL element which is the value.   6. The organic EL element according to claim 1, further comprising a temporary sealing barrier layer provided by an ALD method so as to cover the organic EL layer. The barrier film includes a first protective barrier layer having a thickness of 100 to 1000 nm provided by a sputtering method between the barrier layer and the first flexible resin film substrate, and water vapor permeability of the barrier film The organic EL device according to claim 1, comprising 9 × 10 ⁻² g / m ² / day or less. The barrier film includes a first protective barrier layer having a thickness of 100 to 3000 nm provided by a CVD method between the barrier layer and the first flexible resin film substrate, and water vapor permeability of the barrier film The organic EL device according to claim 1, comprising 9 × 10 ⁻³ g / m ² / day or less.   6. The organic EL element according to claim 1, further comprising a second protective barrier layer formed by a sputtering method between the organic EL layer and the barrier layer.   The organic EL element according to claim 1, further comprising a substrate back surface barrier layer provided on a surface opposite to the first flexible resin film substrate on which the organic EL layer is formed.   The organic EL device according to claim 1, wherein the barrier film includes a first flat layer between the first flexible resin film substrate and the barrier layer.   The organic EL element according to claim 1, wherein the barrier film includes a second flat layer between the barrier layer and the organic EL layer.   The organic EL element according to claim 11 or 12, wherein the flatness of the first planarization layer and the second planarization layer is 20 nm or less in Ra (50 µm). The barrier layer is made of Al ₂ O ₃ layer, TiO ₂ layer or ZrO ₂ layer formed by heat or plasma, ozone ALD method, or ALD method using roll-to-roll, or a laminate of these materials. The organic EL element according to claim 1 or 5. The first protective barrier layer and said second protective barrier layer, claim 7, characterized in that it consists of SiN formed using a SiO _x C _y, a sputtering method is formed by a CVD method or 8. The organic EL element according to 8. The barrier film includes a second flat layer between the barrier layer and the organic EL layer, and has a thickness provided by a CVD method between the barrier layer and the first flexible resin film substrate. The organic EL according to claim 1, further comprising a first protective barrier layer having a thickness of 100 to 3000 nm, wherein the barrier film has a water vapor permeability of 9 × 10 ⁻³ g / m ² / day or less. element.