WO2020262110A1

WO2020262110A1 - Method for manufacturing organic electronic device

Info

Publication number: WO2020262110A1
Application number: PCT/JP2020/023581
Authority: WO
Inventors: 匡哉下河原; 進一森島; 貴志藤井
Original assignee: 住友化学株式会社
Priority date: 2019-06-25
Filing date: 2020-06-16
Publication date: 2020-12-30
Also published as: JP2021005469A

Abstract

The present invention provides a method for manufacturing an organic electronic device of superior long-term shelf-life in which the occurrence of deformations, such as wrinkles, in a seal member is suppressed.　The present invention pertains to a method for manufacturing an organic electronic device, the method comprising: a step for forming an organic electronic device substrate comprising a first electrode, an organic functional layer, and a second electrode in that order on a main surface of a support substrate; a step for drying a seal member in which a resin layer, a metal layer, and an adhesive layer have been stacked in that order; and a step for bonding the dried seal member to the organic electronic device substrate via the adhesive layer, wherein the metal layer has a load capacity of 100–200 N/mm².

Description

Manufacturing method of organic electronic devices

The present invention relates to a method for manufacturing an organic electronic device.

Examples of organic electronic devices include organic electroluminescence devices (organic EL devices), organic solar cells, organic transistors, and the like. The organic electronic device has a first electrode, a functional layer having a predetermined function (for example, a hole injection layer, a light emitting layer, an electron injection layer, etc. in an organic EL device), and a second electrode, which are It is provided on the substrate. Organic electronic devices usually include an organic layer as one of the functional layers. Therefore, at least the functional layer is usually sealed with a sealing member. In Patent Document 1, a long organic electronic device base material having a first electrode, a functional layer, and a second electrode formed on a long substrate is conveyed by a roller while being conveyed by a roller. An organic electronic device is manufactured by laminating a shaku sealing member to an organic electronic device base material.

International Publication No. 2010/106853

The sealing member used in an organic electronic device has a sealing base material containing a resin layer and a metal layer such as an inexpensive and lightweight AlPET (composite material of Al and PET), and a viscous adhesive layer. The sealing base material is attached to the organic electronic device base material via the adhesive layer. Therefore, if the adhesive layer contains water, there is a problem that the long-term storage property of the manufactured organic electronic device is deteriorated. In order to avoid such a decrease in long-term storage property, it is conceivable to dry the sealing member in advance.

Here, when the sealing member is dried, the sealing member is heated to remove water. After drying, when the sealing member heated at a high temperature is cooled, the thermal expansion coefficient of each layer in the sealing member is different, so that stress is generated in the plane of each layer, and the sealing member is wrinkled. Is generated and deformed. Such deformation is likely to occur because the sealing member is rapidly cooled, especially when it comes into contact with the transport roller. When the sealing member is deformed, the adhesion between the organic electronic device base material and the sealing member is lowered due to the mixing of air bubbles or the like, so that the long-term storage property of the organic electronic device is lowered.

Therefore, an object of the present invention is to provide a method for manufacturing an organic electronic device having excellent long-term storage stability by suppressing the occurrence of deformation such as wrinkles in the sealing member.

The method for producing an organic electronic device of the present invention includes a step of forming an organic electronic device base material having a first electrode, an organic functional layer and a second electrode in this order on a main surface of a supporting base material, and a resin layer. , A step of drying the sealing member in which the metal layer and the adhesive layer are laminated in this order, and a step of bonding the dried sealing member to the organic electronic device base material via the adhesive layer. The metal layer has a strength of 100 to 200 N / mm ² .
In the method for manufacturing an organic electronic device of the present invention, the sealing member has a metal layer having a proof stress of 100 N / mm ² or more. Since such a metal layer is not easily deformed, it is possible to suppress deformation of the resin layer and the adhesive adhesive layer due to a temperature change after drying, and prevent deformation such as wrinkles. If the proof stress of the metal layer is too high, when the sealing member is conveyed by the roller, the sealing member is too hard to fit into the shape of the conveying path, and it becomes difficult to convey the sealing member. However, since the sealing member in the manufacturing method of the present invention uses a metal layer having a proof stress of 200 N / mm ² or less, it has appropriate flexibility and can be easily conveyed by a roller. ..
As the material of such a metal layer, work-hardened aluminum is preferable. Since aluminum has a small specific gravity, it is possible to suppress the load on the organic electronic device manufacturing apparatus. By using hard aluminum as the material of the metal layer, it is possible to more effectively prevent deformation such as wrinkles.

The method for producing an organic electronic device of the present invention includes a step of forming an organic electronic device base material having a first electrode, an organic functional layer and a second electrode in this order on a main surface of a supporting base material, and a resin layer. , A step of drying the sealing member in which the metal layer and the adhesive layer are laminated in this order, and a step of bonding the dried sealing member to the organic electronic device base material via the adhesive layer. The method may be such that the material of the metal layer is work-hardened aluminum.
Since the work-hardened aluminum is not easily deformed, it is possible to suppress the deformation of the resin layer and the adhesive adhesive layer due to the temperature change after drying, prevent the deformation such as wrinkles, and moderately possible. It has flexibility and is easy to convey with rollers. Further, since aluminum has a small specific gravity, it is possible to suppress the load of the organic electronic device manufacturing apparatus.
The proof stress of the metal layer is preferably 100 to 200 N / mm ² because it can more effectively prevent deformation such as wrinkles and tends to facilitate transportation by a roller.

It is preferable that the material of the metal layer is 1N30-H material.

A protective film is provided on the surface of the adhesive layer of the sealing member, and in the bonding step, the protective film is peeled off from the sealing member to make the sealing member a base material for an organic electronic device. It is preferable to bond them together.

According to the present invention, it is possible to provide a method for manufacturing an organic electronic device having excellent long-term storage property by suppressing deformation such as wrinkles in the sealing member.

FIG. 1 is a schematic view showing a configuration of an organic EL device which is an example of an organic electronic device manufactured by the method for manufacturing an organic electronic device according to an embodiment. FIG. 2 is a side view of a long sealing member with a protective film used for manufacturing an organic EL device. FIG. 3 is a flowchart of an example of the method for manufacturing the organic EL device shown in FIG. FIG. 4 is a drawing for explaining the configuration of an organic EL device base material (organic electronic device base material). FIG. 5 is a drawing for explaining a drying process and a bonding process.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The same elements are designated by the same reference numerals, and duplicate description will be omitted. The dimensional ratios in the drawings do not always match those described. Examples of the organic electronic device manufactured by the present invention include an organic EL device, an organic solar cell, an organic photodetector, and an organic transistor. Unless otherwise specified, the embodiments described below are embodiments of a method for manufacturing an organic EL device, which is an example of an organic electronic device.

As schematically shown in FIG. 1, the organic EL device 10 manufactured by the method for manufacturing an organic EL device according to one embodiment includes a substrate 12, an anode (first electrode) 14, and an organic EL. A unit 18 (organic functional layer) and a cathode (second electrode) 20 are provided. The organic EL device 10 is, for example, an organic EL lighting panel used for lighting.

The organic EL device 10 may include an extraction electrode 16 electrically connected to the cathode 20. The organic EL device 10 may include at least a sealing member 22 that seals the organic EL portion 18. The organic EL device 10 may take a form of emitting light from the anode 14 side or a form of emitting light from the cathode 20 side. Hereinafter, a mode in which a drawer electrode 16 and a sealing member 22 are provided as the organic EL device 10 and light is emitted from the anode 14 side will be described.

[substrate]
The substrate 12 is transparent to visible light (light having a wavelength of 400 nm to 800 nm). The substrate 12 may be in the form of a film, and the thickness of the substrate 12 is, for example, 30 μm or more and 700 μm or less.

The substrate 12 may be a flexible substrate having flexibility. The flexible substrate is a substrate having flexibility, and the flexibility means that the substrate can be bent without being sheared or broken even when a predetermined force is applied to the substrate. Board. An example of the substrate 12 is a plastic film or a polymer film. Examples of the material of the substrate 12 include polyether sulfone (PES); polyester resin such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resin such as polyethylene (PE), polypropylene (PP) and cyclic polyolefin; polyamide. Resins; polypropylene resins; polystyrene resins; polyvinyl alcohol resins; saponified products of ethylene-vinyl acetate copolymers; polyacrylonitrile resins; acetal resins; polyimide resins; epoxy resins and the like.

A drive circuit (for example, a circuit including a thin film transistor or the like) for driving the organic EL device 10 may be formed on the substrate 12. Such drive circuits are usually constructed of transparent material.

The substrate 12 may be provided with a moisture barrier layer. The moisture barrier layer may have a function of barriering gas (for example, oxygen) in addition to a function of barriering moisture. The moisture barrier layer can be, for example, a film made of silicon, oxygen and carbon, or a film made of silicon, oxygen, carbon and nitrogen. Specifically, examples of the material of the moisture barrier layer are silicon oxide, silicon nitride, silicon oxynitride and the like. An example of the thickness of the moisture barrier layer is 100 nm or more and 10 μm or less.

[anode]
The anode 14 is provided on the substrate 12. An electrode exhibiting light transmission may be used for the anode 14. As the electrode exhibiting light transmittance, a thin film such as a metal oxide, a metal sulfide, or a metal having high electric conductivity can be used, and a thin film having high light transmittance is preferably used. The anode 14 may have a network structure made of a conductor (for example, metal).

The thickness of the anode 14 can be determined in consideration of light transmission, electrical conductivity, and the like. The thickness of the anode 14 is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

Examples of the material of the anode 14 include indium oxide, zinc oxide, tin oxide, indium tin oxide (abbreviated as ITO), indium zinc oxide (indium Zinc Oxide: abbreviated as IZO), gold, platinum, silver, and copper. Among these, ITO, IZO, or tin oxide is preferable. The anode 14 can be formed as a thin film made of the illustrated materials. As the material of the anode 14, an organic substance such as polyaniline and its derivative, polythiophene and its derivative may be used. In this case, the anode 14 can be formed as a transparent conductive film. As described above, the anode 14 may have a network structure made of a conductor (for example, metal).

[Drawer electrode]
The extraction electrode 16 is provided on the substrate 12 in a state of being insulated from the anode 14. The extraction electrode 16 is connected to the cathode 20 and can be used to externally connect the cathode 20. The material and thickness of the extraction electrode 16 may be the same as that of the anode 14.

[Organic EL part]
The organic EL unit 18 includes a light emitting layer 181 and has a function of contributing to light emission of the organic EL device 10 such as carrier movement and carrier recombination according to electric power (for example, voltage) applied to the anode 14 and the cathode 20. It is a department.

In the present embodiment, the organic EL portion 18 is provided so as to cover a part of the anode 14, and a part of the organic EL portion 18 is between the anode 14 and the extraction electrode 16 as shown in FIG. It is also arranged on the substrate 12 of. As a result, a short circuit between the anode 14 and other electrodes (for example, the cathode 20 and the extraction electrode 16) is prevented.

In the example shown in FIG. 1, the organic EL unit 18 has a single-layer structure. That is, the organic EL unit 18 is composed of the light emitting layer 181. The light emitting layer 181 is a functional layer for an organic EL device (organic electronic device) provided on the anode 14. The thickness of the light emitting layer 181 is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 10 nm to 200 nm.

The light emitting layer 181 is usually formed of an organic substance that mainly emits at least one of fluorescence and phosphorescence, or an organic substance thereof and a dopant that assists the organic substance. Dopants are added, for example, to improve luminous efficiency and change the emission wavelength. The organic substance contained in the light emitting layer 181 may be a low molecular weight compound or a high molecular weight compound. The organic substance may be an organometallic complex. Examples of the light emitting material constituting the light emitting layer 181 include the following pigment-based materials, metal complex-based materials, polymer-based materials, and dopant materials.

Examples of the dye-based material include cyclopentamine or a derivative thereof, tetraphenylbutadiene or a derivative thereof, triphenylamine or a derivative thereof, oxadiazole or a derivative thereof, pyrazoloquinolin or a derivative thereof, distyrylbenzene or a derivative thereof, or di. Styrylarylene or its derivative, pyrrole or its derivative, thiophene ring compound, pyridine ring compound, perinone or its derivative, perylene or its derivative, oligothiophene or its derivative, oxaziazole dimer or its derivative, pyrazoline dimer or its derivative, Examples thereof include quinacridone or a derivative thereof, coumarin or a derivative thereof.

Examples of the metal complex material include rare earth metals such as Tb, Eu, and Dy, or Al, Zn, Be, Pt, and Ir as the central metal, and oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, and quinoline. Examples thereof include metal complexes having a structure or the like as a ligand. Examples of the metal complex include a metal complex that emits light from a triple-term excited state such as an iridium complex and a platinum complex, an aluminum quinolinol complex, a benzoquinolinol berylium complex, a benzoxazolyl zinc complex, a benzothiazole zinc complex, and an azomethylzinc complex. Examples thereof include a porphyrin zinc complex and a phenanthroline europium complex.

Examples of the polymer-based material include polyparaphenylene vinylene or a derivative thereof, polythiophene or a derivative thereof, polyparaphenylene or a derivative thereof, polysilane or a derivative thereof, polyacetylene or a derivative thereof, polyfluorene or a derivative thereof, polyvinylcarbazole or a derivative thereof, and the like. Examples thereof include materials obtained by polymerizing at least one of the above dye material and metal complex material.

Examples of the dopant material include perylene or its derivative, coumarin or its derivative, rubrene or its derivative, quinacridone or its derivative, squalium or its derivative, porphyrin or its derivative, styryl dye, tetracene or its derivative, pyrazolone or its derivative, decacyclene. Alternatively, a derivative thereof, phenoxazone or a derivative thereof, etc. may be mentioned.

FIG. 1 illustrates a form in which the organic EL unit 18 is a light emitting layer 181. However, the organic EL unit 18 may be a laminate including a light emitting layer 181 and another functional layer.

Examples of the functional layer provided between the anode 14 and the light emitting layer 181 include a hole injection layer and a hole transport layer. Examples of the functional layer provided between the cathode 20 and the light emitting layer 181 include an electron injection layer and an electron transport layer. The thicknesses of the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer can be appropriately set according to the device performance of the organic EL device 10.

The hole injection layer is a layer having a function of improving the hole injection efficiency from the anode 14 to the light emitting layer 181. A known hole injection material can be used as the material of the hole injection layer. Examples of the hole injection material include oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, phenylamine compounds, starburst amine compounds, phthalocyanine compounds, amorphous carbon, polyaniline, and polyethylenedioxythiophene. (PEDOT) and other polythiophene derivatives can be mentioned.

The hole transport layer is a layer having a function of improving the hole injection efficiency from the anode 14, the hole injection layer, or the hole transport layer closer to the anode 14 to the light emitting layer 181. A known hole transport material can be used as the material of the hole transport layer. Examples of the material of the hole transport layer include polyvinylcarbazole or its derivative, polysilane or its derivative, polysiloxane or its derivative having an aromatic amine in the side chain or main chain, pyrazoline or its derivative, arylamine or its derivative, and stylben. Or its derivative, triphenyldiamine or its derivative, polyaniline or its derivative, polythiophene or its derivative, polyarylamine or its derivative, polypyrrole or its derivative, poly (p-phenylene vinylene) or its derivative, or poly (2,5) -Thienylene vinylene) or its derivatives and the like. Examples of the material of the hole transport layer include the hole transport layer material disclosed in Japanese Patent Application Laid-Open No. 2012-144722.

The electron transport layer is a layer having a function of improving the electron injection efficiency from the cathode 20, the electron injection layer, or the electron transport layer closer to the cathode 20. A known material can be used as the electron transport material constituting the electron transport layer. Examples of the electron transporting material constituting the electron transporting layer include oxadiazole or a derivative thereof, anthracinodimethane or a derivative thereof, benzoquinone or a derivative thereof, naphthoquinone or a derivative thereof, anthraquinone or a derivative thereof, tetracyanoanthraquinodimethane or a derivative thereof. Derivatives, fluorenone or its derivatives, diphenyldicyanoethylene or its derivatives, diphenoquinone or its derivatives, metal complexes of 8-hydroxyquinoline or its derivatives, polyquinolin or its derivatives, polyquinoxalin or its derivatives, polyfluorene or its derivatives, etc. Can be done.

The electron injection layer is a layer having a function of improving the electron injection efficiency from the cathode 20 to the light emitting layer 181. The electron injection layer may form a part of the cathode 20. A known electron injection material can be used as the material of the electron injection layer. Examples of the material of the electron injection layer include alkali metals, alkaline earth metals, alkali metals and alloys containing one or more of alkaline earth metals, alkali metals or oxides of alkaline earth metals, alkali metals or alkaline soil. Examples thereof include halides of similar metals, carbonates of alkali metals or alkaline earth metals, or mixtures of these substances.

An example of the layer structure of the organic EL device 10 including the various functional layers described above is shown below.
(A) anode / light emitting layer / cathode (b) anode / hole injection layer / light emitting layer / cathode (c) anode / hole injection layer / light emitting layer / electron injection layer / cathode (d) anode / hole injection layer / Light emitting layer / electron transport layer / electron injection layer / cathode (e) anode / hole injection layer / hole transport layer / light emitting layer / cathode (f) anode / hole injection layer / hole transport layer / light emitting layer / Electron injection layer / cathode (g) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (h) anode / light emitting layer / electron injection layer / cathode (i) anode / Light emitting layer / electron transport layer / electron injection layer / cathode The symbol "/" means that the layers on both sides of the symbol "/" are joined to each other. The configuration of (a) above corresponds to the configuration shown in FIG.

The organic EL device 10 may have a single-layer light emitting layer 181 or may have two or more light emitting layers 181. In any one of the layer configurations (a) to (i) above, assuming that the laminated structure arranged between the anode 14 and the cathode 20 is the "structural unit I", the two light emitting layers 181 are formed. As the configuration of the organic EL device 10 to have, for example, the layer configuration shown in (j) below can be mentioned. The layer structure of the two (structural unit I) may be the same as or different from each other.
(J) Anode / (Structural unit I) / Charge generation layer / (Structural unit I) / Cathode Here, the charge generation layer is a layer that generates holes and electrons by applying an electric field. Examples of the charge generation layer include a thin film made of vanadium oxide, ITO, molybdenum oxide, and the like.

Assuming that "(structural unit I) / charge generation layer" is "structural unit II", examples of the configuration of the organic EL device 10 having three or more light emitting layers 181 include the layer configuration shown in (k) below. be able to.
(K) Anode / (Structural unit II) x / (Structural unit I) / Cathode The symbol "x" represents an integer of 2 or more, and "(Structural unit II) x" has (Structural unit II) in x stages. Represents a laminated body. The layer structure of the plurality of (structural unit II) may be the same or different.

The organic EL device 10 may be configured by directly laminating a plurality of light emitting layers 181 without providing a charge generation layer.

[cathode]
The cathode 20 is provided on the organic EL unit 18. In the embodiment in which the organic EL device 10 has the extraction electrode 16 as in the present embodiment, the cathode 20 is provided on the organic EL unit 18 so as to be connected to the extraction electrode 16, and in this case, one of the cathodes 20. The unit may be arranged on the substrate 12. The optimum value of the thickness of the cathode 20 differs depending on the material used, and is set in consideration of electrical conductivity, durability, and the like. The thickness of the cathode 20 is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

In order to reflect the light from the light emitting layer 181 toward the anode 14 side by the cathode 20, the material of the cathode 20 is preferably a material having high visible light reflectance. Examples of the material of the cathode 20 include alkali metals, alkaline earth metals, transition metals, and Group 13 metals in the periodic table. As the cathode 20, a transparent conductive electrode made of a conductive metal oxide, a conductive organic substance, or the like may be used.

[Sealing member]
The sealing member 22 is a member for sealing at least the organic EL portion 18. The sealing member 22 is provided on the cathode 20. In the present embodiment, the sealing member 22 is provided so that a part of the anode 14 and a part of the extraction electrode 16 project from the sealing member 22. The portion of the anode 14 and the extraction electrode 16 located outside the sealing member 22 functions as a region for external connection. The sealing member 22 has an adhesive layer 222, a metal layer 223, and a resin layer 224 in this order when viewed from the substrate 12 side.

The resin layer 224 is located on the outermost surface of the organic EL device 10 on the opposite side of the substrate 12. Examples of the material of the resin layer 224 include a transparent plastic film such as PET.
The resin layer 224 preferably has a thickness of 6 to 51 μm.

The metal layer 223 is a layer containing a metal as a main component, and the metal may be a simple substance of a metal or an alloy. The metal layer 223 in the organic EL device 10 of the present embodiment has a proof stress of 100 to 200 N / mm ² , and at least one of the conditions that the material of the metal layer 223 is work-hardened aluminum. Satisfy the conditions.

Strength of the metal layer 223 is preferable to be 100 ~ 200N / mm ^2, more preferable to be 110 ~ 190N / mm ^2, further preferable to be 120 ~ 180N / mm ^2, is a 150 ~ 170N / mm ² Is particularly preferable. Since the sealing member of the present embodiment has a metal layer 223 having a proof stress of 100 to 200 N / mm ² , it is possible to suppress deformation such as wrinkles even if the temperature of the sealing member changes after the drying step. , Easy to transport with rollers. The "proof stress" referred to in the present specification means a 0.2% proof stress (offset method) defined in JISZ2241 (metal material tensile test method).

The thickness of the metal layer 223 is preferably 5 to 50 μm, more preferably 10 to 40 μm. When the thickness of the metal layer 223 is 5 to 50 μm, it is possible to achieve both transportability and sealing performance.

Examples of the material of the metal layer 223 include work-hardened aluminum (hereinafter, also referred to as hard aluminum) and copper. Hard aluminum is particularly preferable because it can suppress deformation such as wrinkles, tends to be easily conveyed by rollers, and has a small specific gravity, so that it tends to reduce the load on the device.

Here, the hard aluminum means an aluminum foil in a state of being work-hardened by being processed (rolled), and examples thereof include a foil after work hardening, a foil which has been subjected to an appropriate heat treatment after work hardening, and the like. Examples of the classification symbols HX1, HX2, HX3, HX4, HX5, HX6, HX7, HX8, and HX9 generally used in the JIS standard (JIS H0001) (however, X: 1 to 3) can be mentioned.

More specific materials of hard aluminum include, but are not limited to, 1N30-H defined by JIS H4160 and the like. Generally, the proof stress of 1N30-H is 150 to 170 N / mm ² .

The adhesive layer 222 is provided on the surface of the metal layer 223 on the substrate 12 side, and the metal layer 223 is adhered to the substrate 12 on which the anode 14, the organic EL portion 18, and the cathode 20 are formed. Used for moisture barrier. The adhesive layer 222 may have a thickness capable of embedding a laminated structure including an anode 14, an organic EL portion 18, and a cathode 20, but is preferably 1 μm to 100 μm, more preferably 5 μm to 60 μm. More preferably, it is 10 μm to 30 μm. When the thickness of the adhesive layer 222 is 1 μm or more, unevenness on the surface of the substrate 12 or mixed dust tends to be sufficiently embedded, and mechanical stress on the organic EL portion 18 due to these tends to be sufficiently embedded. It is possible to suppress the occurrence of dark spots by giving. When the thickness of the adhesive layer 222 is 100 μm or less, it tends to be less affected by the moisture infiltrating from the end face of the adhesive layer 222.

The material of the adhesive layer 222 is, for example, a pressure-sensitive adhesive resin. Examples of adhesive resins include acid-modified products of polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymers, acid-modified products of ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, and ethylene-methacrylic acid copolymers. It is a thermoplastic resin such as copolymer, polyamide, and synthetic rubber.

Next, as an example of the method for manufacturing the organic EL device 10 having the configuration shown in FIG. 1, a method for manufacturing the organic EL device 10 using the long flexible substrate 12 will be described.

In the method for manufacturing the organic EL device 10 of the present embodiment, the long sealing member 24 with a protective film shown in FIG. 2 is used.

The sealing member 24 with a protective film has a sealing member 22 and a protective film 241.
The protective film 241 is attached to the surface (the surface opposite to the metal layer 223) 222a of the adhesive layer 222 of the sealing member 22. The protective film 241 is a film for preventing dust from adhering to the adhesive layer 222 and the sealing members 22 from sticking to each other. The material of the protective film 241 is, for example, PET surface-treated with silicone, a fluorine compound, or the like. The thickness of the protective film 241 is, for example, 5 μm to 50 μm.

As shown in FIG. 3, the method for manufacturing the organic EL device 10 includes a device base material forming step S10, a drying step S20, a bonding step S30, and a cutting step S40.

[Device base material forming process]
In the device base material forming step S10, as schematically shown in FIG. 4, the anode 14, the extraction electrode 16, and the organic EL are in each of the plurality of device forming regions set in the longitudinal direction on the long substrate 12. An organic EL device base material (organic electronic device base material) 26 provided with a portion 18 and a cathode 20 is formed. FIG. 4 schematically shows a cross-sectional configuration when the substrate 12 is cut along a plane orthogonal to the longitudinal direction thereof in the device forming region.

As shown in FIG. 3, the device base material forming step S10 includes an anode (first electrode) forming step S11, an organic EL portion forming step S12, and a cathode (second electrode) forming step S13.

<Anode forming process>
In the anode forming step S11, the anode 14 is formed in each of a plurality of device forming regions set in the longitudinal direction of the long substrate 12. At this time, the extraction electrode 16 is also formed together with the anode 14 in each device formation region. The device forming region is a region corresponding to the product size of the organic EL device 10 to be manufactured.

The anode 14 and the extraction electrode 16 can be formed by a method known in the manufacture of the organic EL device 10. Examples of the method for forming the anode 14 include a vacuum film forming method, an ion plating method, a plating method, and a coating method. Examples of the coating method include an inkjet printing method, but other known coating methods may be used as long as the anode 14 can be formed. Known coating methods other than the inkjet printing method include, for example, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a spray coating method, a screen printing method, a flexographic printing method, and an offset printing method. And the nozzle printing method and the like.

The anode 14 and the extraction electrode 16 can be formed, for example, by forming a conductive film to be the anode 14 and the extraction electrode 16 and then patterning the conductive film in each pattern of the anode 14 and the extraction electrode 16. The anode 14 and the extraction electrode 16 may be manufactured by directly forming a conductive film corresponding to each pattern of the anode 14 and the extraction electrode 16.

<Organic EL part forming process>
In the organic EL portion forming step S12, the organic EL portion 18 is formed on the anode 14. In the form shown in FIG. 1, since the organic EL portion 18 has a light emitting layer 181. Therefore, the organic EL portion forming step S12 has a light emitting layer (functional layer) forming step S12A for forming the light emitting layer 181 on the anode 14. Examples of the method for forming the light emitting layer 181 include a vacuum film forming method and a coating method. Examples of the coating method include an inkjet printing method, but other known coating methods may be used as long as the coating method can form the light emitting layer 181. As a known coating method other than the inkjet printing method, the coating method exemplified in the description of the case where the anode 14 is formed by the coating method can be mentioned.

When the organic EL unit 18 includes a functional layer other than the light emitting layer 181, the functional layers may be formed in order from the anode 14 side according to the layer configuration of the organic EL unit 18. The method for forming each functional layer may be the same as that for the light emitting layer forming step S12A.

<Cathode formation process>
In the cathode forming step S13, the cathode 20 is formed on the organic EL portion 18. The cathode 20 can be formed in the same manner as the method for forming the anode 14.

In the device base material forming step S10, at least one of the anode forming step S11, the organic EL portion forming step S12, and the cathode forming step S13 may be carried out by a roll-to-roll method. For example, the organic EL portion forming step S12 may be carried out by a roll-to-roll method, or the organic EL portion forming step S12 and the cathode forming step S13 may be continuously carried out by a roll-to-roll method.

[Drying process]
In the drying step S20, the sealing member 22 is dried by drying the sealing member 24 with the protective film shown in FIG. In one embodiment, in the drying step S20, the water content of the adhesive layer 222 of the sealing member 22 is 600 ppm or less (ppm is based on mass and is the same in the present specification). The sealing member 22 is dried. The drying step S20 will be described in detail later.

[Lasting process]
In the bonding step S30, the sealing member 22 obtained by peeling the protective film 241 from the sealing member 24 dried in the drying step S20 is bonded to the organic EL device base material 26 via the adhesive layer 222. It fits. The bonding step S30 will be described in detail later.

[Cut process]
In the cutting step S40, the substrate 12 is cut for each device forming region while transporting the long organic EL device base material 26 to which the sealing member 22 is bonded in the bonding step S30 in the longitudinal direction. As a result, a plurality of product-sized organic EL devices 10 can be obtained from the long organic EL device base material 26 to which the sealing member 22 is bonded.

Next, the drying step S20 and the bonding step S30 will be described in detail with reference to FIG.
FIG. 5 is a drawing for explaining the drying step S20 and the bonding step S30. In FIG. 5, the organic EL device base material 26 and the sealing member 24 are schematically shown by a thick solid line. In the present embodiment, as shown in FIG. 5, after the drying step S20 is performed in the drying chamber 28, the bonding step S30 is performed in the bonding chamber 32 connected to the drying chamber 28 via the connecting portion 30. .. In FIG. 5, the organic EL device is manufactured by a roll-to-roll method.

For the sake of explanation, the roll on which the sealing member 24 with the protective film is wound is referred to as the first roll 34A, and the roll on which the long organic EL device base material 26 before the sealing member 22 is bonded is wound. Is referred to as a second roll 34B, and a roll on which the organic EL device base material 26 to which the sealing member 22 is bonded in the bonding step S30 is wound is referred to as a third roll 34C.

In the drying step S20, the sealing member 24 is unwound from the first roll 34A set in the feeding portion 36 in the drying chamber 28, and is conveyed while being guided by the guide roller R1 in the longitudinal direction of the sealing member 24. While transporting the sealing member 24 in this way, the sealing member 24 is irradiated with infrared rays from at least one infrared irradiation unit 38 arranged on the transport path to heat and dry the sealing member 24. FIG. 5 illustrates a case where the sealing member 24 is heated and dried by using a plurality of infrared irradiation units 38.

In the drying chamber 28, the transport path of the sealing member 24 may be folded back a plurality of times as shown in FIG. In this case, it is possible to secure the drying time while saving space for drying. The infrared irradiation unit 38 may be arranged on both sides of the sealing member 24, or may be arranged only on one side, for example, in the thickness direction of the sealing member 24.

The inside of the drying chamber 28 may be filled with, for example, a dew point of −40 ° C. or lower and an inert gas atmosphere (for example, a nitrogen gas atmosphere) in order to effectively perform drying. The inside of the drying chamber 28 may be set to a reduced pressure environment of 10 Pa or less in order to effectively perform drying.

The sealing member 24 dried in the drying chamber 28 passes through the connecting portion 30 and is carried into the bonding chamber 32, and the bonding step S30 is performed in the bonding chamber 32.

In the bonding step S30, the organic EL device base material 26 is fed out from the second roll 34B set in the feeding section 40 in the bonding chamber 32. After the unwound organic EL device base material 26 is conveyed in the longitudinal direction while being guided by the guide roller R2, it is wound around the winding portion 42 to form the third roll 34C from the drying chamber 28. The sealing member 22 obtained by peeling the protective film 241 from the sealing member 24 that has been carried in is bonded to the organic EL device base material 26.

Specifically, a pair of bonding rollers R3 are arranged in the bonding chamber 32 with a gap, and the adhesive layer 222 of the sealing member 22 and the organic EL device base material are arranged in the gap. The organic EL device base material 26 and the sealing member 22 are fed so that the anode 14, the organic EL portion 18, and the cathode 20 are opposed to each other in 26. Then, the organic EL device base material 26 and the sealing member 22 are pressed by the pair of bonding rollers R3. At this time, a heater is embedded in the bonding roller R3, and the sealing member 22 is bonded to the organic EL device base material 26 while warming the sealing member 22 by heating the bonding roller R3.

In order to feed the sealing member 22 into the pair of bonding rollers R3, the sealing member 24 conveyed from the drying chamber 28 is conveyed while being guided by the guide roller R4. A guide roller R5 is arranged in the transport path of the sealing member 22 by the guide roller R4 in the bonding chamber 32, and the protective film 241 is peeled from the sealing member 22 by the guide roller R5. The sealing member 22 obtained by peeling off the protective film 241 is conveyed by the guide roller R4 and sent to the pair of bonding rollers R3 in the above-mentioned state.

The protective film 241 peeled off by the guide roller R5 may be wound up by the film collecting unit 44.

Inside the connecting portion 30 and the bonding chamber 32, the water content of the adhesive layer 222 dried in the drying chamber 28 is maintained, and the organic EL device base material 26 to which the sealing member 22 is not bonded is maintained. It can be adjusted to prevent deterioration. For example, the inside of the connecting portion 30 and the bonding chamber 32 may have a dew point of −40 ° C. or lower and an inert gas atmosphere. Therefore, if the drying chamber 28 also has a dew point of −40 ° C. or lower and the atmosphere is an inert gas, the connecting portion 30 and the bonding chamber 32 may have the same indoor environment.
In FIG. 5, the feeding portion 36 is arranged in the drying chamber 28, but the feeding portion 36 may be arranged outside the drying chamber 28. Similarly, the feeding section 40, the winding section 42, and the film collecting section 44 may also be arranged outside the bonding chamber 32. However, a second roll 34B around which the long organic EL device base material 26 before the sealing member 22 is attached is installed in the feeding portion 40.
Therefore, when the feeding portion 40 is arranged outside the bonding chamber 32, the arrangement area of the feeding portion 40 and the transport path of the organic EL device base material 26 fed from the feeding portion 40 are deteriorated in the organic EL device base material 26. Can be configured to prevent. For example, the arrangement region of the feeding section 40 and the transport path of the organic EL device base material 26 fed from the feeding section 40 may be configured such that the dew point is −40 ° C. or lower and the inert gas atmosphere can be maintained.

After being conveyed to the connecting portion 30 and the bonding portion 32, the temperature of the connecting portion 30 and the bonding portion 32 of the sealing member 24 with a high-temperature protective film that has been heat-dried in the drying chamber is lower than that of the drying portion. The heat is gradually removed. In particular, it may be rapidly cooled by contact with the guide rollers R4, R5 and the like. At this time, since the coefficient of thermal expansion of each layer of the sealing member is different, in the conventional sealing member, stress due to the mismatch of shrinkage is generated in the plane of each layer, and the sealing member is deformed such as wrinkles. To do. When the sealing member deformed in this way is attached to the organic EL device base material, air bubbles are mixed in the deformed portion such as wrinkles, and the adhesion between the sealing member and the organic EL device base material is impaired. As a result, the sealing performance of the sealing member cannot be sufficiently exhibited, and the long-term storage property of the organic EL device deteriorates.

However, in the method for manufacturing an organic EL device of the present embodiment, the proof stress of the metal layer 223 in the sealing member is 100 N / mm ² to 200 N / mm ² , or the material of the metal layer 223 is work-hardened aluminum. Therefore, the deformation of the sealing material can be suppressed against the above stress. On the other hand, for example, when soft aluminum such as 1N30-O defined in JIS H4160 (generally, the yield strength of 1N30-O is 30 to 40 N / mm ² ) is used as the metal layer 223. Deformation of the sealing material cannot be sufficiently suppressed. When the proof stress of the metal layer 223 in the sealing member is 200 N / mm ² or less, the sealing member is not too hard and the sealing member has sufficient flexibility, so that the metal layer 223 can be easily transported by a roller.

In the method for manufacturing the organic EL device 10, the sealing member 24 formed by bonding the protective film 241 to the sealing member 22 is dried. Therefore, even if the tackiness of the adhesive layer 222 is increased by heating during drying, the adhesive layer 222 does not come into direct contact with the guide roller R1 or the like, so that the adhesive is attached to the guide roller R1 or the like. It can be prevented from adhering.

In the drying step S20, since the sealing member 22 is transported with the protective film 241 attached, dust does not adhere to the adhesive layer 222 during the transport process. Therefore, when the sealing member 22 is attached to the organic EL device base material 26, dust can be prevented from entering the organic EL device base material 26, and as a result, device defects caused by the dust do not occur.

In order to perform drying effectively, the thickness of the protective film 241 should be thin, but if it is too thin, the protective film 241 may be cut or the protective film 241 may be wrinkled during the transportation process. It becomes difficult to control. On the other hand, if the protective film 241 is too thick, the drying efficiency is lowered, so that the transport path of the sealing member 24 becomes unnecessarily long and the time required for the drying process also becomes long. Further, there is a problem that the first roll 34A around which the sealing member 24 is wound also becomes unnecessarily large. On the other hand, if the protective film 241 is, for example, 5 μm or more and 50 μm or less, the sealing member 24 can be easily transported and the drying efficiency can be improved. Further, the size of the first roll 34A can be reduced.

When the material of the adhesive adhesive layer 222 is a pressure-sensitive adhesive resin, the tackiness is likely to increase due to the heat in the drying step S20. Therefore, the method for manufacturing the organic EL device 10 described in the present embodiment is more effective when the sealing member 22 having the adhesive adhesive layer 222 containing the pressure-sensitive adhesive resin is used.

In the drying step S20, it is preferable to dry the sealing member 24 (more specifically, the sealing member 22) so that the water content of the adhesive layer 222 is 600 ppm or less. This is because the organic EL device 10 having further improved long-term storage stability can be manufactured by bonding the sealing member 22 in such a dry state to the organic EL device base material 26.

In the method for manufacturing an organic EL device described in the present embodiment, as described above, after the sealing member 24 with a protective film is dried, the dried sealing member 22 is attached to the organic EL device base material 26. ing. Therefore, it is possible to efficiently manufacture the organic EL device 10 having excellent long-term storage stability while improving the productivity. Further, by drying the sealing member 22 so that the water content is 600 ppm or less, the organic EL device 10 having even better long-term storage stability can be efficiently manufactured.

The various embodiments and examples of the present invention have been described above. However, the present invention is not limited to the various embodiments and examples described above, and various modifications can be made without departing from the spirit of the present invention.

FIG. 5 illustrates a form in which the drying chamber and the bonding chamber are connected by a connecting portion. However, the drying room and the bonding room do not have to be connected. In this case, the sealing member with a protective film dried in the drying chamber may be once wound into a roll, housed in an airtight container, and carried into the bonding chamber.

Although infrared heating was exemplified as a drying method in the drying step, the drying method of the sealing member with a protective film is not limited to infrared heating. For example, the guide roller that guides the sealing member with the protective film may be a heating roller, and the sealing member with the protective film may be dried by the heating roller, or dried by a heating method such as a halogen lamp heater, a laser, or microwave heating. You may.

In the above embodiment, the embodiment in which the anode, the organic EL portion, and the cathode are formed in order on the substrate has been described, but for example, the organic EL device may be manufactured from the substrate on which the anode is formed in advance. In this case, the method for manufacturing the organic EL device may include an organic EL portion forming step and a cathode forming step.
In the above embodiment, the manufacturing method by the roll-to-roll method using a long base material and a long sealing member has been described, but the base material and the sealing member are adjusted to a predetermined size in advance by cutting or the like. Organic electronic devices may be manufactured using the single-wafered ones.

For example, the peeling step is not limited to the case where it is carried out after the bonding step. For example, the peeling step may be carried out during the device main body forming step, or may be carried out between the device main body forming step and the bonding step. When it is carried out during the device main body forming step, for example, it may be carried out after forming an anode (first electrode). For example, it may be carried out during the organic functional layer forming step, or may be carried out between the organic functional layer forming step and the cathode forming step. In order to fix the flexible substrate to the support substrate in order to improve handling when forming the device main body or the like on the flexible substrate, the peeling step is performed at least after the anode (first electrode) forming step. It is preferable to carry out.

In the above embodiment, when a sealing member with a protective film having a protective film provided on the surface of the adhesive layer is used as the sealing member, the protective film may be peeled off before the drying step. As a sealing member, a member that does not originally have a protective film can also be used. As the sealing member having no protective film, for example, a sealing member wound in a roll shape so that the adhesive layer and the resin layer are in contact with each other can be used. In this case, the metal of the resin layer is used. The surface opposite to the layer may be subjected to a mold release treatment, if necessary.

In the explanation so far, the first electrode is used as an anode and the second electrode is used as a cathode, but the first electrode may be a cathode and the second electrode may be an anode.

The manufacturing method of the organic EL device, which is an example of the organic electronic device, has been described. However, the manufacturing method of the organic electronic device according to the present embodiment is an organic having an organic functional layer such as an organic solar cell, an organic photodetector, or an organic transistor. It can also be applied to electronic devices. When manufacturing an organic transistor, the first electrode is, for example, one of a source electrode, a drain electrode and a gate electrode, and the second electrode is other than the first electrode among the source electrode, the drain electrode and the gate electrode. It is an electrode of. The functional layer for manufacturing an organic transistor may be a gate insulating layer or an organic semiconductor layer.

[Example 1]
As the sealing member A, one having the following layer structure was used.
Protective film (thickness 12 μm) / adhesive layer (thickness 30 μm) / aluminum layer (thickness 30 μm, 1N30-H material, manufactured by Toyo Aluminum Co., Ltd.) / PET (thickness 38 μm)
The sealing member A was transported at a transport speed of 1 m / min, infrared-irradiated from the protective film side using a carbon heater so that the temperature of the sealing member A became 160 ° C., heated for 5 minutes, and then wound up. .. No deformation such as wrinkles was observed in the sealing member A.
When the protective film of the wound sealing member A was peeled off and bonded to the organic electronic device base material, no wrinkles were observed and a good bonded surface was obtained.

[Comparative Example 1]
An experiment was carried out in the same manner as in Example 1 except that the sealing member B in which the aluminum layer of the sealing member A was changed to a layer of 1N30-O material (thickness 30 μm, manufactured by Toyo Aluminum K.K., Ltd.) was used.
In the sealing member B after winding, wrinkles having a width of 5 mm were continuously generated in the transport direction, and deformation was observed.
When the protective film of the wound sealing member B was peeled off and bonded to the organic electronic device base material, air bubbles were mixed in the wrinkled portion, and a good bonded surface could not be obtained.

10 ... Organic EL device (organic electronic device), 12 ... Substrate, 14 ... Anode (first electrode), 20 ... Cathode (second electrode), 22 ... Sealing member, 24 ... Sealing member with protective film, 181 ... light emitting layer (functional layer), 222 ... adhesive adhesive layer, 223 ... metal layer, 224 ... resin layer, 241 ... protective film.

Claims

A step of forming an organic electronic device base material having a first electrode, an organic functional layer, and a second electrode in this order on the main surface of the support base material, and
A step of drying a sealing member in which a resin layer, a metal layer, and an adhesive adhesive layer are laminated in this order, and
It comprises a step of adhering the dried sealing member to an organic electronic device base material via the adhesive layer.
A method for manufacturing an organic electronic device, wherein the metal layer has a proof stress of 100 to 200 N / mm 2 .
The method for manufacturing an organic electronic device according to claim 1, wherein the material of the metal layer is work-hardened aluminum.
A step of forming an organic electronic device base material having a first electrode, an organic functional layer, and a second electrode in this order on the main surface of the support base material, and
A step of drying a sealing member in which a resin layer, a metal layer, and an adhesive adhesive layer are laminated in this order, and
It comprises a step of adhering the dried sealing member to an organic electronic device base material via the adhesive layer.
A method for manufacturing an organic electronic device, wherein the material of the metal layer is work-hardened aluminum.
The method for manufacturing an organic electronic device according to claim 3, wherein the metal layer has a proof stress of 100 to 200 N / mm 2 .
The method for manufacturing an organic electronic device according to any one of claims 1 to 4, wherein the material of the metal layer is 1N30-H material.
A protective film is provided on the surface of the adhesive layer of the sealing member, and in the step of bonding, the protective film is peeled off from the sealing member to attach the sealing member to an organic electronic device. The method for manufacturing an organic electronic device according to any one of claims 1 to 5, which is attached to a base material.